WO2012090764A1 - Pest control method and water storage-drainage system equipped with control agent - Google Patents
Pest control method and water storage-drainage system equipped with control agent Download PDFInfo
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- WO2012090764A1 WO2012090764A1 PCT/JP2011/079379 JP2011079379W WO2012090764A1 WO 2012090764 A1 WO2012090764 A1 WO 2012090764A1 JP 2011079379 W JP2011079379 W JP 2011079379W WO 2012090764 A1 WO2012090764 A1 WO 2012090764A1
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- WIPO (PCT)
- Prior art keywords
- water
- pest control
- silver
- storage
- control agent
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/14—Base exchange silicates, e.g. zeolites
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- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03F—SEWERS; CESSPOOLS
- E03F5/00—Sewerage structures
- E03F5/04—Gullies inlets, road sinks, floor drains with or without odour seals or sediment traps
- E03F5/0401—Gullies for use in roads or pavements
- E03F5/0403—Gullies for use in roads or pavements with a sediment trap
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- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03F—SEWERS; CESSPOOLS
- E03F7/00—Other installations or implements for operating sewer systems, e.g. for preventing or indicating stoppage; Emptying cesspools
- E03F7/06—Devices for restraining rats or other animals
Definitions
- the present invention relates to a method for controlling pests in water, particularly boufra (mosquito larvae), using a soluble glass capable of eluting silver ions into water or a resin molded article containing a silver-substituted inorganic ion exchanger. Further, the present invention relates to a storage and drainage facility provided with a storage and drainage member such as a septic tank and a water storage tank provided in a side ditch as an embodiment of the control method.
- a storage and drainage member such as a septic tank and a water storage tank provided in a side ditch
- the pest control method of the present invention is In addition, there is no fear of contamination by excessive metal ions, and it is a method capable of continuously controlling pests in water, and the storage and drainage equipment of the present invention is a facility that can efficiently carry out the above control method. is there.
- the place where water stays, especially the storage and drainage facility, will be a place for spawning mosquitoes from spring to autumn, and will be a place for growth of boufra, that is, a place for mosquitoes.
- the occurrence of mosquitoes causes discomfort to the local residents and is known to mediate many infectious diseases such as West Nile fever, malaria, dengue fever, Japanese encephalitis, chikungunya, etc., which is not preferable for public health.
- infectious diseases such as West Nile fever, malaria, dengue fever, Japanese encephalitis, chikungunya, etc.
- chikungunya etc.
- unpleasant insects that do not cause direct harm, such as those that stab livestock such as buoys, chironomids, and tobikelas, but clog the flow path when they occur in large quantities.
- a number of prevention tools using metallic copper have been proposed for the suppression of the generation of underwater bow flares.
- an anti-bowler generation tool that places a copper plate having a thickness of 1.5 mm or less in water such as a rainwater trout (see Patent Document 1).
- Patent Document 2 There is also a proposal of a method of putting copper or tin in a spawning container and dying or suppressing the growth of mosquito larvae such as human striped mosquitoes in the container (see Patent Document 2).
- This proposal also mentions that copper is preferable as a dissolved ion source that exhibits a growth inhibitory effect, but tin or silver ions having a strong insecticidal effect may be used.
- the effect of silver ions on the suppression of bowfura and the effectiveness of silver ions has not been known.
- Patent Document 3 an insecticidal sterilizer characterized in that a pipe made of copper or a copper alloy is housed in a container having a large number of communication holes.
- an electrolyzer for supplying silver ions, a sterilizing mat, a ball, and the like are also exemplified, but all relate to a sterilizing effect, and there is no description showing a bow ion suppressing effect of silver ions.
- a plurality of examples have been disclosed regarding the effect of copper ions on suppressing the bowfra, but a high copper ion concentration is required in order to exhibit the effect of suppressing copper on copper ions. Leaking high concentration of copper ions into the environment is not preferable in terms of environmental burden, and the amount of copper discharged is regulated by environmental standard values. In addition, it is difficult to control copper ions to elute copper ions stably, and it is practically difficult to supply a copper ion concentration that is not excessive or insufficient. Silver ions are considered safer than copper because there is no environmental standard setting in Japan. However, since the ionization tendency is lower than copper, elution of silver ions from metallic silver is less likely to occur than copper ions. Since it is expected that a large amount of silver will be required to obtain a good effect, there has never been an attempt to use metallic silver for the control of pests such as boufra.
- An object of the present invention is to provide a control method for controlling pests that lay eggs in water, such as boufra (mosquito larvae), in a simple and sustainable manner that does not cause environmental pollution.
- An object of the present invention is to provide a storage / drainage facility equipped with a pest control agent and a storage / drainage member constituting the storage / drainage facility, which can carry out the above control method simply and continuously.
- the present inventors have developed a pest control agent using a soluble glass capable of eluting silver ions over time in water, or a resin molded article containing a silver-substituted inorganic ion exchanger. It has been found that it can be controlled and controlled by installing it in a puddle where aquatic pests such as bow flares are generated or where puddles are generated, and storage with these pest control agents is also found.
- the present invention was completed by finding drainage facilities and storage drainage members.
- the pest control method of the present invention can be easily carried out by using silver glass that dissolves in water over time or a resin molded product kneaded with a silver-substituted inorganic ion exchanger as a pest control agent.
- the effect of continuously suppressing and controlling the growth of underwater pests such as boufras is obtained.
- the same level of effect can be obtained at a concentration lower than one-tenth of the copper ion as far as the concentration necessary for the effect of inhibiting the growth of boufra, compared to the conventionally known copper ion preparations.
- a large effect can be obtained with a smaller amount.
- the storage and drainage facility of the present invention is able to continuously suppress and control the growth of underwater pests such as bow flares that live in puddles generated in the facility, and keep the facility water clean. You can also.
- a bucket and rainwater as a storage / drainage member are examples of useful components of a storage / drainage system that exhibits the above effects.
- insects to be controlled in the present invention are insects that spawn or inhabit in the water and cause harm to humans. Chichaeka, Scutellaria, Tofukakuika, Anopheles, Aedes albopictus, Aedes albopictus, Aedes albopictus, Aedes aegypti Chironomid, chironomid chironomid, chironomid chironomid, lepidoptera, white-winged ephemera, white-tailed moth These include: Viquera, Nakaharashimatovicera, Murasakitobimushi, belonging to the order of Rhizobicidae, Fliesidae, Ashimadarabyu, Kiashiobyu, etc. In addition, algae, molds, fungi, and the like that are generated and attached to
- Mosquitoes are particularly effective among the pests to be controlled. And the bowfra in the present invention is a mosquito larva. Mosquitoes grow by transformation of eggs, larvae, pupae and adults. Mosquito eggs are laid in water or at the water's edge, and then grow in water until they become adults. The period of growth in the water from the egg to the cocoon is about 10 to 20 days. Since the effect in the present invention is exhibited in water, the effect is exerted on eggs, larvae, and pupae that are mosquito forms that exist in water.
- mosquitoes include the Anopheles subfamily such as Sinohada araka and Otsu hamada araka; Although it exists in Japan, since the kind of mosquito is not limited in the effect of the present invention, the same effect can be exerted against foreign mosquitoes.
- the pest control effect means an effect of suppressing the growth of pests, for example, boufra, which means that the boufra does not become an adult mosquito, and only delays growth. Rather, it aims to die in the form of a boufra.
- the place where a bow hula occurs is a pond, ground, stone, plant dent, bucket, fence, empty can, various containers, natural water pool due to rain or condensation on rainwater trout, etc., aquarium, artificial pond or pool, or water supply Various puddles such as puddles of water sprinkling and sewage accumulation are targeted.
- production place of these bow flares are object, and it is a puddle (water retention place) especially generate
- the pest control agent in the present invention uses silver which is superior in safety and health to copper and can elute silver ions into water, and has a solubility containing silver. It is at least one selected from glass (also referred to as silver glass) and a resin molded body in which a silver-substituted inorganic ion exchanger is contained in a resin having an official moisture content of 1 to 10. Although there are some differences in constituent materials between soluble glass and resin moldings, both have the same effect of controlling pests by releasing a certain amount of silver ions in water for a long period of time.
- the form of the resin molded body containing the soluble glass or the silver-substituted inorganic ion exchanger has a specific form in order to easily exhibit the growth inhibitory effect of the bowfra.
- the drug does not flow out of the water pool due to wind and rain, but is submerged in water. It is preferable to be submerged in water.
- the average mass per grain is preferably 0.5 g or more, and the specific gravity is preferably 1.05 or more, more preferably 1.2 or more and 5 or less. Specific gravity is defined by the mass ratio of a sample of the same volume and distilled water at 25 ° C.
- the particle diameter is, for example, the average of the maximum particle diameters of 50 control agents randomly selected regardless of the shape (for example, the diameter is a shape close to a sphere, the longest side length is a shape close to a rectangular parallelepiped). It can be represented by a value. Since the particles of the soluble glass or resin molded article of the pest control agent are too small to hold, it is essential that the particle size of the pest control agent in the present invention is 1 mm or more. .
- a water molded container or a water storage / drainage member is a resin molded body containing a silver-substituted inorganic ion exchanger
- a preferable upper limit is 1 m
- a more preferable particle size is 2 mm or more and 100 mm or less.
- pesticides such as resin moldings containing soluble glass or silver-substituted inorganic ion exchangers can be used for the first and subsequent times by replacing the elution amount of silver and water when first put into water after production.
- These pest control agents in the present invention are preferably soluble glass whose silver elution amount when water is replaced is within ⁇ 20% compared to the previous time.
- the silver elution amount does not change greatly, and it is preferably within ⁇ 20%.
- the soluble glass is preferable in that the weight loss is visibly easy to understand.
- the soluble glass that can be used in the present invention has solubility in water, and the preferable dissolution concentration of silver ions in deionized water at 25 ° C is 0.05 mg / g ⁇ L ⁇ day or more. 5 mg / g ⁇ L ⁇ day or less.
- the soluble glass that can be used in the present invention is one whose water does not change greatly even if the water is changed or depending on the conditions such as temperature and pH, and it is sustainable even if the water is changed due to rain. is there.
- composition of soluble glass that can be used in the present invention, the Ag 2 O 0.5 ⁇ 4 weight%, the K 2 O or Na 2 O 3 ⁇ 10 wt%, a SiO 2 0 ⁇ 60% by weight, B 2 O 3 or P 2 O 5 40 to 70 wt%, Al 2 O 3, MgO , BaO, at least one or more selected from the group consisting of ZnO containing 0-20%.
- Silver is a mosquito larvae suppressing active ingredient, Ag 2 O in effect can not be obtained unless using large amounts soluble glass in the amount of 0.5% or less, 4% or more Ag 2 O amount is vitrified Therefore, the Ag 2 O content is 0.5 to 4% by mass, preferably 1 to 3%, more preferably 1.5 to 2.5%.
- K 2 O or Na 2 O acting as a component for adjusting the solubility of the glass is easier to control the solubility of the glass for a long time than other alkali metals, and its content is preferably 3 to 10%, more preferably It is 4 to 9%, more preferably 5 to 8%.
- the more preferred among K 2 O or Na 2 O is K 2 O, can be improved solubility than soluble glass Preference containing Na 2 O, free of Na 2 O , K 2 O-containing soluble glass.
- SiO 2, P 2 O 5 and B 2 O 3 to form the skeletal structure of the glass controls the solubility of the glass in the overall balance of the proportions, generally the solubility and the proportion of SiO 2 is increased is reduced, B Solubility improves as the proportion of 2 O 3 increases.
- the preferred content of SiO 2 is 0-60%, more preferably 0-15%.
- a preferable content of B 2 O 3 is 42 to 70%, more preferably 44 to 67, and particularly preferably 44 to 65%.
- Al 2 O 3 forms the skeleton of glass with SiO 2 or B 2 O 3, the inclusion of Al 2 O 3 generally chemical durability improved when SiO 2 or B 2 O 3 is the main component Therefore, it is preferable to contain.
- the preferred content is 5% to 20%, more preferably 15 to 20%.
- MgO, BaO, and ZnO are not essential components because they enter between the glass skeleton components and have the effect of stabilizing the glass.
- the preferred content is 0 to 10%. Even if Ca, Ba, Zn, Co, Cu and the like are mixed as other components, the amount of the glass may be small so as not to affect the long term.
- an inexpensive industrial method for producing granular glass is to add hot liquid glass that has been heated and melted into water and rapidly cool it to form an irregularly shaped cullet, or pass between metal rollers to form a plate (flakes). It is a method to do.
- cullet is difficult to adjust the particle size and needs to be pulverized or classified because it contains fine particles or coarse particles of 2 mm or less.
- fine cracks are likely to occur, and crushing proceeds from the crack portion during use, so fragments and fine powder are generated, and the particle size is likely to change.
- flakes tend to have a certain particle size than cullet, but that is not sufficient, and there are many broken pieces of glass plate, which may be dangerous to use.
- the melted antibacterial glass for water treatment is molded with a cooling roller having a hemispherical or conical depression on one or both sides, thereby forming a hemispherical, conical or spherical shape.
- Granular glass can also be produced. By setting it as such a molded article, it is hard to break and it becomes easy to control solubility by realizing a certain shape and particle size.
- the manufacturing method of the soluble glass used in the present invention is a predetermined mixed amount of a compound containing necessary components such as oxides, hydroxides, borates, chlorides, nitrates, sulfates and carbonates. After mixing well, it can be obtained by heating and melting in a melting pot and quenching.
- the soluble glass obtained in this way is excellent in controlling the amount of elution of silver by adjusting the solubility, shape, and particle size.
- the inhibitory effect is expressed.
- the soluble glass itself dissolves and loses weight, the duration of the effect of suppressing the bow fluff can be easily seen by anyone.
- Those in which the soluble glass is colored are preferred because they are easily visible.
- the silver elution amount when the soluble glass capable of eluting silver ions in water in the present invention is immersed in water can be adjusted by the glass composition and the surface area of the molded body, and is 0.05 mg / g ⁇ L.
- ⁇ Preferably, it is not less than 5 mg / g ⁇ L ⁇ day and more preferably not less than 0.1 mg / g ⁇ L ⁇ day and not more than 0.5 mg / g ⁇ L ⁇ day. It is preferable that the dissolution amount in this range be maintained for 3 weeks or more, and for several months if possible.
- Estimated amount of soluble glass for realizing silver ion elution amount above the volume per liter of water soluble glass is immersed, a 3 cm 2 ⁇ 500 cm 2 as the sum of the surface area of soluble glass An amount is preferable, and an amount of 50 cm 2 to 300 cm 2 is more preferable.
- the specific surface area of soluble glass is preferably 3 ⁇ 500cm 2 / g, more preferably 5 ⁇ 200cm 2 / g, more preferably 10 ⁇ 50cm 2 / g.
- a spherical particle has a radius of about 0.05 to 1 cm.
- a specific surface area of 3 cm 2 / g is less than a (if the particle size is too large) slows dissolution rate of silver, the effective require more amount of control agent required for the control.
- the specific surface area is larger than 500 cm 2 / g (if the particle size is too small), the elution rate of silver is too fast and the control agent is consumed in a short period of time, so that the control effect may be insufficiently sustained.
- the form of use of the soluble glass that can be used in the present invention is not particularly limited, and can be used in the form of granules. For example, several g to several tens of g are filled and packed in a nonwoven fabric or net. It is also possible. It is more preferable that the packing is made of a nonwoven fabric and a net.
- the inside of the double packaging should be a fine nonwoven fabric to prevent leakage of soluble glass, and the outside should maintain the strength of the nonwoven fabric. Therefore, it is preferable to have a net shape that is strong and easy to pass water.
- As the material of the inner nonwoven fabric it is preferable to use a hydrophilic material because glass is easily dissolved, and examples thereof include nylon and polyester. Further, it is possible to store the soluble glass in a plastic container having holes or slits. It is also a preferable form that the soluble glass packed with a nonwoven fabric is stored in a plastic container so that it can be taken in and out.
- the resin molded body containing a silver-substituted inorganic ion exchanger in the present invention is preferably a silver-substituted inorganic ion exchanger in a resin having an official moisture content of 1% or more and 10% or less. Is a molded article made of a resin composition kneaded in an amount of 1 to 30% by mass.
- the silver-substituted inorganic ion exchanger is an inorganic cation exchanger powder obtained by ion exchange of silver.
- the silver content is 1% or more and 20% or less, more preferably 2% or more and 15% or less.
- inorganic cation exchangers include zeolite, zirconium phosphate, and titanium phosphate.
- zirconium phosphate represented by the following formula [1] is effective because it can stably ion-support silver at a high concentration. .
- M is at least one ion selected from alkali metal ions, alkaline earth metal ions, ammonium ions, hydrogen ions and oxonium ions, and a, b and c are 1.75 ⁇
- a molded article of a resin composition can be easily obtained by blending the silver-substituted inorganic ion exchanger of the present invention with a resin.
- Any known method can be adopted as a method for processing the resin molded body. For example, (1) using an additive for facilitating adhesion between the silver-substituted inorganic ion exchanger powder and the resin or a dispersant for improving the dispersibility of the silver-substituted inorganic ion exchanger powder, (2) A method of directly mixing a powdered resin with a mixer, (2) A method of mixing as described above, forming into a pellet shape with an extrusion molding machine, and then blending the molded product into the pellet-shaped resin, (3) A method in which the silver-substituted inorganic ion exchanger powder is molded into a high-concentration pellet using wax, and then the pellet-shaped molded product is blended into a pellet-shaped resin.
- the silver-substituted inorganic ion exchanger powder is polyol, etc.
- the molding machine for processing the resin molding containing the silver-substituted inorganic ion exchanger in the present invention there is no limitation on the molding machine for processing the resin molding containing the silver-substituted inorganic ion exchanger in the present invention, and an existing machine can be used.
- an injection molding machine, an extrusion molding machine, blow molding, a heat press, etc. are illustrated.
- an injection molding machine is preferable because it has a small thermal history in addition to the stability of the shape. This is because if the thermal history is large, the deterioration of the resin progresses, so that decomposition components of the resin other than silver may be dissolved in water.
- the mixer that can be used for producing the composition before molding include a kneader, an extrusion molding machine, and a mixing roll.
- the official moisture content of the resin used for the resin molded body in the present invention is an index indicating the moisture absorption rate of the resin determined based on the moisture absorption rate at a temperature of 20 ° C. and a relative humidity of 65%.
- the official moisture content of the resin used in the present invention is 1.0 or more and 10 or less, preferably 2 or more and 9 or less, more preferably 3 or more and 8.5 or less. If the official moisture content is 1 or less, sufficient persistence of silver elution of the resin molded product is not obtained, and if it is 10% or more, elution takes place in a short time, it is difficult to control the silver concentration, and the product value is reduced in appearance due to easy discoloration. There is also a risk.
- Polyamide is generally called nylon, and there are nylon 6, 66, 46, MDX6, 61, 9T, 610, 612, 11, 12, etc., and these can be used alone or in combination. .
- the specific gravity of the resin is preferably 1.1 or more. Since the specific gravity of polyamide is about 1.15, polyamide is preferable also in specific gravity.
- 6 nylon is particularly preferable from the viewpoint of versatility, moldability, controllability of silver elution amount, etc., and it can be used by mixing with other types of nylon. A compounding rate is preferable. Further, among the 6 nylons, those having a low density are preferable because they are more easily eluted.
- a dispersant such as metal soap can be used for the resin molded body containing the silver-substituted inorganic ion exchanger in the present invention.
- a preferred dispersant is a metal soap, such as zinc stearate, calcium stearate, magnesium stearate, and more preferably magnesium stearate.
- the silver-substituted inorganic ion exchanger used in the resin molded body containing the silver-substituted inorganic ion exchanger in the present invention has various additives as necessary in order to improve kneading into the resin and other physical properties. Can also be mixed.
- pigments such as zinc oxide and titanium oxide
- inorganic ion exchangers such as zirconium phosphate and zeolite
- dyes antioxidants, light stabilizers, weather stabilizers, flame retardants, antistatic agents, foaming agents
- Lubricants such as impact strengthening agents, glass fibers, metal soaps, moisture-proofing agents and extenders, coupling agents, nucleating agents, fluidity improvers, deodorants, wood powder, antifungal agents, antifouling agents, antirust agents, There are metal powders, UV absorbers, UV screening agents, etc.
- any known processing technique and machine can be used according to the characteristics of various resins, and heating, pressurizing, or depressurizing at an appropriate temperature or pressure.
- it can be easily prepared by a method of mixing, mixing or kneading, and their specific operation may be performed by a conventional method.
- the shape is not limited, and can be formed into various forms such as a spherical shape, a lump shape, a sponge shape, a film shape, a plate shape, a thread shape, a pipe shape, or a composite thereof, and can be appropriately designed according to the application. it can.
- the resin molded body containing the silver-substituted inorganic ion exchanger thus obtained can control the silver elution amount by adjusting the solubility, shape and particle size.
- the silver concentration in the water is eluted over time, and the growth inhibitory effect of boufra is expressed.
- the silver elution amount when the resin molded body capable of eluting silver ions in water in the present invention is immersed in water can be adjusted by the composition of the molded body and the surface area of the molded body, and 0.05 mg / g.
- ⁇ L ⁇ day to 5 mg / g ⁇ L ⁇ day is preferred, more preferably 0.1 mg / g ⁇ L ⁇ day to 0.5 mg / g ⁇ L ⁇ day. It is preferable that the dissolution amount in this range be maintained for 3 weeks or more, and for several months if possible.
- the specific surface area of the resin molded body is preferably 3 ⁇ 500cm 2 / g, more preferably 5 ⁇ 200cm 2 / g, more preferably 10 ⁇ 50cm 2 / g.
- a shape having a specific surface area of 3 to 50 cm 2 / g a spherical particle has a radius of about 0.05 to 1 cm.
- the plate is 10 cm square, the average thickness is about 0.3 to 6 mm.
- the specific surface area is less than 3 cm 2 / g, the elution rate of silver becomes slow, and a large amount of a control agent required for effective control is required.
- the specific surface area is larger than 500 cm 2 / g, the elution rate of silver is too fast and the control agent is consumed in a short period of time, so the sustainability of the control effect may be insufficient.
- the usage form of the resin molded body containing the silver-substituted inorganic ion exchanger in the present invention is not particularly limited, and the molded body can be used as it is. You may pack in a nonwoven fabric etc., and you may fill a cartridge-like container. It can be used by immersing or passing it in the water to be treated, and does not need to be always present in water. Even if it is once dried in air, its performance does not change greatly if it is returned to water again. What is necessary is just to adjust the standard of usage-amount suitably with the amount of silver substitution, and the target effect.
- the method for suppressing the growth of pests such as boufra in the present invention is likely to generate pests such as boufra when water is accumulated in a resin molded product containing soluble glass or a silver-substituted inorganic ion exchanger. It can be applied by installing it in a pit with a pit or actually a puddle, or a puddle where pests such as boufras are already generated.
- the amount used is about 1 g per liter, but can be appropriately prepared in consideration of the lifetime.
- the control agent When the control agent is used in water with no water in and out, it can be expected that a control effect will appear if the silver ion concentration in the gradually eluted water is 10 ppb or more, calculated from the silver content of the control agent.
- the silver ion concentration in the gradually eluted water is 10 ppb or more, calculated from the silver content of the control agent.
- the amount of the control agent to be added is preferably determined so that the silver elution concentration in water is 50 ppb / day or more and 5 ppm / day with respect to a fixed volume of water. . Specifically, if the elution amount of silver from the control agent is 0.1 (mg / L ⁇ g ⁇ day), the elution concentration of silver in an aqueous system with a volume of 1 L is from 50 ppb / day to 5 ppm / day.
- the amount of the control agent to be added is calculated to be 0.5 g to 50 g and can be used as a guide for the amount used in this way, but the amount used can be appropriately adjusted while observing the actual effect.
- control agent that elutes in a short period of time and exhibits an early control effect
- control agent that gradually elutes and maintains a control effect over a long period of time
- Examples of the occurrence of pests such as bow flares which are specific uses of the pest control method of the present invention, include pools, ponds, the ground, stones, plant depressions, buckets, empty cans, various containers, rainwater trouts, etc.
- Various puddles such as a puddle from natural water puddles due to rain and dew condensation, water pours from tap water, etc., and sewage stagnation are targeted.
- the effect of suppressing the growth of the bowfra of the present invention is intended for any place where a bowfra is generated.
- the pest control method of the present invention include rainwater troughs, rainwater infiltration troughs, rainwater storage tanks, rainwater manholes, side grooves, troughs provided in side grooves, and septic tanks. These members may retain water for several days or more, and it is intended by the present invention to control pests that are generated and live in the retained water.
- the material of the water storage / drainage member is not limited to plastics such as polyvinyl chloride and polypropylene, concrete, and pottery.
- the water storage / drainage member may be made of a resin containing a silver-substituted inorganic ion exchanger.
- Rainwater Masashi Rainwater Mas is a typical storage and drainage member in the present invention.
- the rainwater usually has a muddy part at the bottom. Often, water stays in the mud pool for days, creating pests and habitats.
- Many plastic storm drains are equipped with a bucket that can collect the muddy water staying in the mud pool for easy cleaning. Occurrence and habitat.
- a rainwater basin having a handle and a bucket that is easy to remove from and into the stormwater is particularly preferred.
- the shape of the bucket is generally cylindrical and the bottom is slightly smaller in diameter than the top, but is not limited to this.
- the bucket may have a hole or a slit.
- the storage / drainage facility of the present invention includes the pest control agent and the storage / drainage member.
- the pest control agent is granular, it is preferably stored and used in a pest control agent storage container.
- the pest control container is a container that can freely enter and leave the water and can release silver ions eluted from the pest control agent but prevent the pest control agent itself from flowing out. Several forms of the pest control container are illustrated.
- Non-woven bag-like container (2) Multi-layer container consisting of non-woven inner bag and open net outer bag (3) Plastic with one or more fine holes or narrow slits (4) Plastic container of “(3)” with non-woven inner bag
- the pest control container may be a disposable one that is discarded when the pest control agent is no longer consumed, or a pest
- the refillable thing which can replenish a control agent may be used.
- the inner bag made of nonwoven fabric may be replaced with a new one in the above “(4)”.
- the plastic include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, polyester, and ABS.
- the pest control agent storage container is preferably locked to the water storage / drainage member.
- the pesticide storage container may be directly locked to a storage and drainage member such as rainwater, or may be locked to a muddy water recovery bucket attached to the rainwater.
- a storage / drainage facility in which a pesticide storage container is detachably locked to a storage / drainage member is preferable because it is easy to maintain.
- the pesticide storage container may have a structure that is directly locked to the storage / drainage member or its accessory member, or a locking member such as a thread, string, rope, chain, wire, clip, nail, bolt, etc. It may be a structure which is locked via.
- a rainwater basin equipped with a bucket for collecting muddy water, in which a pesticide storage container is detachably locked is particularly preferable because of easy maintenance.
- a pest control agent storage container is detachably locked to a bucket.
- a plurality of pesticide storage containers may be locked in one or more forms. For example, by combining the following (3) and (4), even when the water stays in the bucket, mud accumulates in the bucket and the water stays at a position exceeding the height of the bucket But it can effectively control pests.
- the pesticide storage container is locked to the back surface of the bottom of the bucket.
- the pesticide storage container is suspended from the handle portion of the bucket.
- Silver ions have an effect of suppressing the growth of boufra at a low concentration of several tens of copper ions.
- the pest control method of the present invention suppresses the outflow by adjusting the particle size and specific gravity, is excellent in durability, and further continues to elute silver ions continuously, thus showing the growth inhibitory effect of boufra over a long period of time, Reduces the occurrence of mosquitoes.
- the elution amount of silver or copper ions was determined by adding 1 g of the sample to 1 L of deionized water at 25 ° C., and storing it for 24 hours, and then determining the concentration of silver or copper ions in the water by ICP (inductively coupled plasma emission spectrometer, Specifically, it was measured by Seiko Denshi Kogyo Co., Ltd. SPS7700 type), normalized to 1 g of sample, 1 liter of elution water and concentration per day, and displayed as elution amount (mg / g ⁇ L ⁇ day).
- ICP inductively coupled plasma emission spectrometer
- Table 1 shows the details of Samples 1 to 13 used in the tests in Examples and Comparative Examples.
- the meltable glass of Samples 1, 2, 5 to 9 shown in Table 1 is a metal cooling molding roller in which a glass raw material preparation is heated and melted at 1200 ° C., and a hemispherical depression having a diameter of 5 mm is arranged on one side. The resulting glass was cooled and molded, and the obtained glass was crushed and crushed, and further dry-crushed with a ball mill for 1 hour, followed by pulverizing fine powder with a metal mesh having an opening of 2.8 mm. Sample 5 was obtained by further pulverizing Sample 2 obtained using a ball mill.
- the silver-substituted inorganic ion exchangers used for Samples 3, 4, 10, and 11 shown in Table 1 are obtained by adding 10% of powdered zirconium phosphate or zeolite A to ion-exchanged water, On the other hand, silver substitution was performed by adding an aqueous silver nitrate solution to 11% with silver and stirring for 1 hour. Thereafter, the silver-substituted inorganic ion exchanger used in Samples 3, 4, 10, and 11 was obtained by filtration, washing with ion-exchanged water, drying at high temperature, and pulverizing.
- the composition of the silver-substituted zirconium phosphate is Ag 0.45 Na 0.47 H 0.2 Zr 1.95 Hf 0.02 (PO 4 ) 3 ⁇ 0.05H 2 O, and the silver-substituted zeolite is 0.15 Ag 2 O ⁇ 0.85Na 2 O ⁇ Al. It was 2 O 3 .2.03SiO 2 .0.7H 2 O.
- the glass composition is shown in Table 1 because the soluble glass has greatly different properties such as solubility depending on the composition.
- the soluble glass which elutes silver ions is called silver glass
- the soluble glass which elutes copper is called copper glass.
- Samples 3, 4, 8, and 10 were obtained by mixing the obtained soluble glass or silver-substituted inorganic ion exchanger powder with nylon or polyethylene resin powder, and then molding it with an extrusion molding machine. Cut to create.
- a plate crystal reagent was used as the silver nitrate of Sample 12.
- Table 2 shows the metal content (%), particle size (mm or ⁇ m), specific gravity, and metal elution amount (mg / g ⁇ L ⁇ day) of Samples 1 to 13.
- the particle diameter indicates an average value of the maximum particle diameters of 50 particles randomly selected regardless of the shape.
- Sample No. About 5 and 11 since it was too small and it was difficult to select and measure particles, volume-based median diameters measured with a laser diffraction particle size meter (Malvern Master Sizer 2000) were used.
- Table 3 shows the results of carrying out this water exchange test once a day and carrying out a test in which a bowfra was added again after 10 times in total.
- the test which does not put a sample was done similarly, and it was set as the comparative example 9.
- Table 3 shows the result of the test in which the water exchange test was performed once a day, and after 10 times in total, the bow-flas were added again.
- Example 6 On-site test of generation of bow flares using rainwater trough A test facility shown in Fig. 1 was prepared as a model of a storage and drainage facility. The handle 3 of the bucket 1 (capacity 2 liters) attached to the rainwater masu 4 contains 5 g of the sample 1 as the pest control agent 7, and the pest control storage container 8 made of a nylon nonwoven fabric is used as a locking thread. 9 was hung. For comparison, a test facility was also prepared in which an empty pesticide storage container without a pest control agent was suspended.
- control method of the present invention and the storage and drainage equipment equipped with the control agent can control pests that are generated and inhabit in the water staying in the storage and drainage equipment, and thus ensure a sanitary living environment for human livestock. Can prevent pest-borne infectious diseases.
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Abstract
[Problem] To provide a method whereby pests laying eggs in water, for example mosquito larvae, can be easily and continuously controlled without causing environmental pollution, and a water storage-drainage system.
[Solution] As the results of intensive studies to solve the aforesaid problem, the present inventors found that the growth of aquatic pests such as mosquito larvae can be inhibited and these pests can be controlled by placing a molded resin article, which contains a soluble glass capable of releasing silver ions in water with the passage of time or a silver-substituted inorganic ion exchanger, in a pool of water or an area where water likely pools, such a pool of water being a potential nursery of the aquatic pests, e.g., mosquito larvae, thereby completing the present invention.
Description
本発明は、銀イオンを水に溶出させることのできる溶解性ガラス、または銀置換無機イオン交換体を含有した樹脂成形体を用いた、水中の有害生物、特にボウフラ(蚊の幼虫)の防除方法に関し、さらに、該防除方法の実施形態としての、雨水ます、側溝に設けられたます、浄化槽、貯水槽などの貯排水部材を備える貯排水設備に関する。
本発明で用いる溶解性ガラス、または銀置換無機イオン交換体を含有した樹脂成形体は、水中で経時的に適量の銀イオンを溶出することが可能なため、本発明の有害生物の防除方法は、過剰の金属イオンによる汚染の恐れがなく、持続的に水中の有害生物の防除を行うことのできる方法であり、本発明の貯排水設備は、上記の防除方法を効率的に実施できる設備である。 The present invention relates to a method for controlling pests in water, particularly boufra (mosquito larvae), using a soluble glass capable of eluting silver ions into water or a resin molded article containing a silver-substituted inorganic ion exchanger. Further, the present invention relates to a storage and drainage facility provided with a storage and drainage member such as a septic tank and a water storage tank provided in a side ditch as an embodiment of the control method.
Since the resin molding containing the soluble glass or silver-substituted inorganic ion exchanger used in the present invention can elute an appropriate amount of silver ions over time in water, the pest control method of the present invention is In addition, there is no fear of contamination by excessive metal ions, and it is a method capable of continuously controlling pests in water, and the storage and drainage equipment of the present invention is a facility that can efficiently carry out the above control method. is there.
本発明で用いる溶解性ガラス、または銀置換無機イオン交換体を含有した樹脂成形体は、水中で経時的に適量の銀イオンを溶出することが可能なため、本発明の有害生物の防除方法は、過剰の金属イオンによる汚染の恐れがなく、持続的に水中の有害生物の防除を行うことのできる方法であり、本発明の貯排水設備は、上記の防除方法を効率的に実施できる設備である。 The present invention relates to a method for controlling pests in water, particularly boufra (mosquito larvae), using a soluble glass capable of eluting silver ions into water or a resin molded article containing a silver-substituted inorganic ion exchanger. Further, the present invention relates to a storage and drainage facility provided with a storage and drainage member such as a septic tank and a water storage tank provided in a side ditch as an embodiment of the control method.
Since the resin molding containing the soluble glass or silver-substituted inorganic ion exchanger used in the present invention can elute an appropriate amount of silver ions over time in water, the pest control method of the present invention is In addition, there is no fear of contamination by excessive metal ions, and it is a method capable of continuously controlling pests in water, and the storage and drainage equipment of the present invention is a facility that can efficiently carry out the above control method. is there.
水の滞留する場所、特に貯排水設備は、春から秋にかけて蚊の産卵場所となり、ボウフラの成育場所、即ち蚊の発生場所となる。蚊の発生は周辺住民に不快感を与えると共に、ウエストナイル熱、マラリア、デング熱、日本脳炎、チクングニヤなどの多くの伝染病を媒介することが知られており公衆衛生上も好ましくない。また、蚊の他にも、ブユなどの人畜を刺すものや、ユスリカやトビケラなど、直接の害はないが大量発生すると流路を詰まらせたりする不快害虫などが知られている。これらはいずれも水中に産卵するものなので、成長、羽化する前に水路や水の滞留する場所、浄化槽や雨水マスなどに殺虫剤を散布し、幼虫の段階で死滅させることが行われている。しかし、殺虫剤の効果は比較的短期間しか持続せず、また、流水により薬剤が流出するとその効果が持続できない上に、環境汚染を引き起こすという問題があった。
The place where water stays, especially the storage and drainage facility, will be a place for spawning mosquitoes from spring to autumn, and will be a place for growth of boufra, that is, a place for mosquitoes. The occurrence of mosquitoes causes discomfort to the local residents and is known to mediate many infectious diseases such as West Nile fever, malaria, dengue fever, Japanese encephalitis, chikungunya, etc., which is not preferable for public health. In addition to mosquitoes, there are also known unpleasant insects that do not cause direct harm, such as those that stab livestock such as buoys, chironomids, and tobikelas, but clog the flow path when they occur in large quantities. Since all of these lay eggs in the water, before they grow and emerge, they are sprayed with insecticides in waterways, places where water stays, septic tanks and rainwater trouts, and are killed at the larval stage. However, the effect of the insecticide lasts only for a relatively short period of time, and when the drug flows out by running water, the effect cannot be sustained and also causes environmental pollution.
水中のボウフラの発生抑制に関して、金属銅を使用した発生防止具等が複数提案されている。たとえば、厚さ1.5mm以下の銅板を雨水マス等の水中にいれるボウフラ発生防止具の提案がある(特許文献1参照)。また、銅またはスズを産卵容器内に入れ、容器内のヒトスジシマカなどの蚊の幼虫を死亡あるいは成長抑制させる方法の提案もある(特許文献2参照)。この提案には、成長抑制効果を発現する溶解イオン源には銅が好ましいが、殺虫効果の強いスズや銀イオンでも良いとの記載もある。しかし、銀イオンのボウフラ抑制効果に関する具体的な実施例はなく、銀イオンの有効性は知られていなかった。
A number of prevention tools using metallic copper have been proposed for the suppression of the generation of underwater bow flares. For example, there is a proposal for an anti-bowler generation tool that places a copper plate having a thickness of 1.5 mm or less in water such as a rainwater trout (see Patent Document 1). There is also a proposal of a method of putting copper or tin in a spawning container and dying or suppressing the growth of mosquito larvae such as human striped mosquitoes in the container (see Patent Document 2). This proposal also mentions that copper is preferable as a dissolved ion source that exhibits a growth inhibitory effect, but tin or silver ions having a strong insecticidal effect may be used. However, there is no specific example regarding the effect of silver ions on the suppression of bowfura, and the effectiveness of silver ions has not been known.
さらに、銅または銅合金製の管が、多数の連通孔を有する収容物の中に収容されていることを特徴とする殺虫殺菌装置が提案されている(特許文献3参照)。ここでは、銀イオンを供給する電解装置や殺菌マット、ボールなども例示されているが、すべて殺菌効果に関するものであり、銀イオンのボウフラ抑制効果を示す記載はない。
Furthermore, there has been proposed an insecticidal sterilizer characterized in that a pipe made of copper or a copper alloy is housed in a container having a large number of communication holes (see Patent Document 3). Here, an electrolyzer for supplying silver ions, a sterilizing mat, a ball, and the like are also exemplified, but all relate to a sterilizing effect, and there is no description showing a bow ion suppressing effect of silver ions.
銅イオンのボウフラ抑制効果に関しては、複数の事例が開示されているが、銅イオンでボウフラ抑制効果を発現するためには、高い銅イオン濃度が必要となる。高濃度の銅イオンを環境に漏出することは環境負荷上好ましくないため、銅は環境基準値により排出量が規制されている。また、金属銅は安定に銅イオンを溶出させる制御は難しく、過不足ない銅イオン濃度を供給することも現実的には難しい。銀イオンは、わが国では環境基準値の設定がなく、銅よりも安全であると考えられるが、銅よりもイオン化傾向が低いので、金属銀からの銀イオンの溶出は銅イオンよりもしにくく、十分な効果を得るためには多量の銀が必要になることが予想されるから、ボウフラ等の有害生物の防除に金属銀を用いる試みは、実際にはなされたことがなかった。
A plurality of examples have been disclosed regarding the effect of copper ions on suppressing the bowfra, but a high copper ion concentration is required in order to exhibit the effect of suppressing copper on copper ions. Leaking high concentration of copper ions into the environment is not preferable in terms of environmental burden, and the amount of copper discharged is regulated by environmental standard values. In addition, it is difficult to control copper ions to elute copper ions stably, and it is practically difficult to supply a copper ion concentration that is not excessive or insufficient. Silver ions are considered safer than copper because there is no environmental standard setting in Japan. However, since the ionization tendency is lower than copper, elution of silver ions from metallic silver is less likely to occur than copper ions. Since it is expected that a large amount of silver will be required to obtain a good effect, there has never been an attempt to use metallic silver for the control of pests such as boufra.
一方、一定速度で抗菌性の金属イオンを溶出するものとして、従来から銀、銅および亜鉛等の抗菌性金属を含有するガラスが、各種用途の樹脂組成物中に配合され、利用されている(例えば、特許文献4,5参照)。しかし、水中に浸漬して使用するこれらのガラス質抗菌剤は、細菌等に対する効果は確認されているものの、ボウフラ等の有害生物の防除効果に関する記載は一切ない。
細菌や黴類など微生物に対する抗菌効果を発現するために必要な銀イオンの濃度は知られているが、ボウフラなどの虫に対する効果、特に成長抑制のように数日かけて効果が発現する作用に対する銀イオンの有効性および必要な銀イオンの濃度に関する公知文献は見当たらず、具体的に検討された例はこれまでにない。
この他に、抗菌性の金属イオンを溶出する方法を用いて蚊の発生を防止する貯排水部材としては、銅イオン発生部材が係止された雨水ますが、例えば特許文献6、7に開示されているが、銀を用いることができることは知られていなかった。 On the other hand, as a material that elutes antibacterial metal ions at a constant rate, glass containing antibacterial metals such as silver, copper, and zinc has been conventionally blended and used in resin compositions for various purposes ( For example, seePatent Documents 4 and 5). However, although these glassy antibacterial agents used by immersing in water have been confirmed to have an effect on bacteria and the like, there is no description regarding the effect of controlling pests such as boufra.
The concentration of silver ions necessary to develop antibacterial effects against microorganisms such as bacteria and moss is known, but it is effective against insects such as boufra, especially against effects that take effect over several days such as growth inhibition. There is no known literature on the effectiveness of silver ions and the required concentration of silver ions, and no specific examples have been studied.
In addition to this, as a water storage / drainage member for preventing the generation of mosquitoes by using a method of eluting antibacterial metal ions, rainwater containing a copper ion generating member is locked, which is disclosed in Patent Documents 6 and 7, for example. However, it has not been known that silver can be used.
細菌や黴類など微生物に対する抗菌効果を発現するために必要な銀イオンの濃度は知られているが、ボウフラなどの虫に対する効果、特に成長抑制のように数日かけて効果が発現する作用に対する銀イオンの有効性および必要な銀イオンの濃度に関する公知文献は見当たらず、具体的に検討された例はこれまでにない。
この他に、抗菌性の金属イオンを溶出する方法を用いて蚊の発生を防止する貯排水部材としては、銅イオン発生部材が係止された雨水ますが、例えば特許文献6、7に開示されているが、銀を用いることができることは知られていなかった。 On the other hand, as a material that elutes antibacterial metal ions at a constant rate, glass containing antibacterial metals such as silver, copper, and zinc has been conventionally blended and used in resin compositions for various purposes ( For example, see
The concentration of silver ions necessary to develop antibacterial effects against microorganisms such as bacteria and moss is known, but it is effective against insects such as boufra, especially against effects that take effect over several days such as growth inhibition. There is no known literature on the effectiveness of silver ions and the required concentration of silver ions, and no specific examples have been studied.
In addition to this, as a water storage / drainage member for preventing the generation of mosquitoes by using a method of eluting antibacterial metal ions, rainwater containing a copper ion generating member is locked, which is disclosed in
本発明の課題は、ボウフラ(蚊の幼虫)などの、水中に産卵する有害生物の防除を、簡便に、持続的で環境汚染の恐れがない方法で行う防除方法を提供することにあり、さらに、上記の防除方法を、簡便に、持続的に実施できる、有害生物防除剤を備えた貯排水設備および、該貯排水設備を構成する貯排水部材を提供することにある。
An object of the present invention is to provide a control method for controlling pests that lay eggs in water, such as boufra (mosquito larvae), in a simple and sustainable manner that does not cause environmental pollution. An object of the present invention is to provide a storage / drainage facility equipped with a pest control agent and a storage / drainage member constituting the storage / drainage facility, which can carry out the above control method simply and continuously.
本発明者らは、上記課題を解決すべく鋭意検討した結果、水中で経時的に銀イオンを溶出できる溶解性ガラス、または銀置換無機イオン交換体を含有した樹脂成形体を、有害生物防除剤としてボウフラ等の水中有害生物の発生する水溜りまたは水溜りの発生する場所等に設置することでボウフラ等の成長を抑制し、防除できることを見出し、さらに、これらの有害生物防除剤を備えた貯排水設備および貯排水部材をも見出して本発明を完成した。
As a result of intensive studies to solve the above problems, the present inventors have developed a pest control agent using a soluble glass capable of eluting silver ions over time in water, or a resin molded article containing a silver-substituted inorganic ion exchanger. It has been found that it can be controlled and controlled by installing it in a puddle where aquatic pests such as bow flares are generated or where puddles are generated, and storage with these pest control agents is also found. The present invention was completed by finding drainage facilities and storage drainage members.
本発明の有害生物の防除方法は、水中で経時的に溶解する銀ガラス、または銀置換無機イオン交換体を練りこんだ樹脂成形体を有害生物防除剤として用いることで、いずれも簡便に実施でき、持続的にボウフラ等の水中有害生物の成長を抑制し、防除する効果が得られる。その効果の大きさは、ボウフラの成長抑制効果に必要な濃度でいえば銅イオンの10分の1以下の低濃度で同程度の効果が得られるため、従来知られた銅イオン製剤に比べて、より少ない量で大きな効果を得ることができる。さらに銀イオンには防菌,防黴,防藻の効果も期待できるため、水中を清浄な状態に保つこともできる。また、本発明の貯排水設備は、持続的に、設備中に発生する水たまりに生息するボウフラ等の水中有害生物の成長を抑制し、防除する効果が得られ、設備水中を清浄な状態に保つこともできる。貯排水部材としてのバケットおよび雨水ますは、上記効果を奏する貯排水設備の有用な構成要素の例である。
The pest control method of the present invention can be easily carried out by using silver glass that dissolves in water over time or a resin molded product kneaded with a silver-substituted inorganic ion exchanger as a pest control agent. The effect of continuously suppressing and controlling the growth of underwater pests such as boufras is obtained. As for the magnitude of the effect, the same level of effect can be obtained at a concentration lower than one-tenth of the copper ion as far as the concentration necessary for the effect of inhibiting the growth of boufra, compared to the conventionally known copper ion preparations. A large effect can be obtained with a smaller amount. Furthermore, since silver ions can be expected to have antibacterial, antifungal and antialgal effects, the water can be kept clean. In addition, the storage and drainage facility of the present invention is able to continuously suppress and control the growth of underwater pests such as bow flares that live in puddles generated in the facility, and keep the facility water clean. You can also. A bucket and rainwater as a storage / drainage member are examples of useful components of a storage / drainage system that exhibits the above effects.
以下本発明に関して説明する。なお、%は質量%である。また、体積の単位リットルを「L」とも表記する。
○防除の対象となる有害生物
本発明における防除対象となる有害生物としては、水中に産卵または生息し、人に害を及ぼす虫であり、具体的にはハエ目蚊科に属するアカイエカ、ネッタイイエカ、チカイエカ、コガタアカイエカ、トラフカクイカ、ハマダラカ、ヒトスジシマカ、ネッタイシマカ、トウゴウヤブカ、キンイロヤブカ、セスジヤブカ、オオクロヤブカ、アシマダラヌマカ、キンパラナガハシカ、シマハマダラカ、コガタハマダラカ、チョウバエ科に属するホシチョウバエ、オオショウバエ、ユスリカ科に属するセスジユスリカ、オオユスリカ、アカムシユスリカ、シマユスリカ、オオヤマチビユスリカ、カゲロウ目シロカゲロウ科に属するオオシロカゲロウ、トビケラ目シマトビケラ科に属するコガタシマトビケラ、オオシマトビケラ、ナカハラシマトビケラ、粘管目ヒメトビムシ科に属するムラサキトビムシ、ハエ目、長角亜目ブユ科に属するアシマダラブユ、キアシオオブユなどである。また、水中や容器壁に発生付着する藻類やカビ類や菌類等も含めることができる。 The present invention will be described below. In addition,% is the mass%. The unit liter of volume is also expressed as “L”.
○ Pests to be controlled The pests to be controlled in the present invention are insects that spawn or inhabit in the water and cause harm to humans. Chichaeka, Scutellaria, Tofukakuika, Anopheles, Aedes albopictus, Aedes albopictus, Aedes albopictus, Aedes aegypti Chironomid, chironomid chironomid, chironomid chironomid, lepidoptera, white-winged ephemera, white-tailed moth These include: Viquera, Nakaharashimatovicera, Murasakitobimushi, belonging to the order of Rhizobicidae, Fliesidae, Ashimadarabyu, Kiashiobyu, etc. In addition, algae, molds, fungi, and the like that are generated and attached to the water and the container wall can also be included.
○防除の対象となる有害生物
本発明における防除対象となる有害生物としては、水中に産卵または生息し、人に害を及ぼす虫であり、具体的にはハエ目蚊科に属するアカイエカ、ネッタイイエカ、チカイエカ、コガタアカイエカ、トラフカクイカ、ハマダラカ、ヒトスジシマカ、ネッタイシマカ、トウゴウヤブカ、キンイロヤブカ、セスジヤブカ、オオクロヤブカ、アシマダラヌマカ、キンパラナガハシカ、シマハマダラカ、コガタハマダラカ、チョウバエ科に属するホシチョウバエ、オオショウバエ、ユスリカ科に属するセスジユスリカ、オオユスリカ、アカムシユスリカ、シマユスリカ、オオヤマチビユスリカ、カゲロウ目シロカゲロウ科に属するオオシロカゲロウ、トビケラ目シマトビケラ科に属するコガタシマトビケラ、オオシマトビケラ、ナカハラシマトビケラ、粘管目ヒメトビムシ科に属するムラサキトビムシ、ハエ目、長角亜目ブユ科に属するアシマダラブユ、キアシオオブユなどである。また、水中や容器壁に発生付着する藻類やカビ類や菌類等も含めることができる。 The present invention will be described below. In addition,% is the mass%. The unit liter of volume is also expressed as “L”.
○ Pests to be controlled The pests to be controlled in the present invention are insects that spawn or inhabit in the water and cause harm to humans. Chichaeka, Scutellaria, Tofukakuika, Anopheles, Aedes albopictus, Aedes albopictus, Aedes albopictus, Aedes aegypti Chironomid, chironomid chironomid, chironomid chironomid, lepidoptera, white-winged ephemera, white-tailed moth These include: Viquera, Nakaharashimatovicera, Murasakitobimushi, belonging to the order of Rhizobicidae, Fliesidae, Ashimadarabyu, Kiashiobyu, etc. In addition, algae, molds, fungi, and the like that are generated and attached to the water and the container wall can also be included.
防除対象となる有害生物のなかでも、特に有効なのが蚊である。そして、本発明におけるボウフラとは、蚊の幼虫である。蚊は卵、幼虫、蛹、成虫の変態により成育する。蚊の卵は水中や水際に産み付けられその後、成虫になるまでは水中で生育する。卵から蛹までの水中で成育する期間は、凡そ10日~20日である。本発明における効果は水中で発揮されるため、水中で存在する蚊の形態である卵、幼虫および蛹に対して効果を発現する。蚊の種類には、シナハマダラカやオオツルハマダラカなどのハマダラカ亜科、ヤマトヤブカ、トウゴウヤブカ、チシマヤブカ、ネッタイシマカ、ヒトスジシマカ、オオクロヤブカ、チカイエカ、アカイエカネッタイイエカ、コガタアカイエカなどのナミカ亜科、トウダオウカなどのオオカ亜科が国内には存在するが、本発明のボウフラ防除効果においては蚊の種類は限定されないため、海外の種類の蚊に対しても同等の効果が発現可能である。
Mosquitoes are particularly effective among the pests to be controlled. And the bowfra in the present invention is a mosquito larva. Mosquitoes grow by transformation of eggs, larvae, pupae and adults. Mosquito eggs are laid in water or at the water's edge, and then grow in water until they become adults. The period of growth in the water from the egg to the cocoon is about 10 to 20 days. Since the effect in the present invention is exhibited in water, the effect is exerted on eggs, larvae, and pupae that are mosquito forms that exist in water. The types of mosquitoes include the Anopheles subfamily such as Sinohada araka and Otsu hamada araka; Although it exists in Japan, since the kind of mosquito is not limited in the effect of the present invention, the same effect can be exerted against foreign mosquitoes.
本発明において有害生物の防除効果とは、有害生物、例えばボウフラの成長抑制効果のことを意味し、ボウフラが成虫である蚊にならないようにすることを意味しており、単に成長を遅らせることだけではなく、ボウフラの形態のまま死滅することを目的としている。
ボウフラの発生場所は、池や地面や石、植物の窪み、バケツ、甕、空き缶、各種容器、雨水マスやなどへの雨や結露などによる天然の水溜り、水槽、人工池やプール、または水道水の散水などによる水溜り、下水の滞留箇所など様々な水溜りが対象となる。本発明の有害生物防除方法の対象場所に制限はないが、好ましくはこれらボウフラの発生場所が対象であり、特には、貯排水設備中に発生する水たまり(水の滞留場所)である。 In the present invention, the pest control effect means an effect of suppressing the growth of pests, for example, boufra, which means that the boufra does not become an adult mosquito, and only delays growth. Rather, it aims to die in the form of a boufra.
The place where a bow hula occurs is a pond, ground, stone, plant dent, bucket, fence, empty can, various containers, natural water pool due to rain or condensation on rainwater trout, etc., aquarium, artificial pond or pool, or water supply Various puddles such as puddles of water sprinkling and sewage accumulation are targeted. Although there is no restriction | limiting in the target place of the pest control method of this invention, Preferably the generation | occurrence | production place of these bow flares are object, and it is a puddle (water retention place) especially generate | occur | produced in a storage drainage facility.
ボウフラの発生場所は、池や地面や石、植物の窪み、バケツ、甕、空き缶、各種容器、雨水マスやなどへの雨や結露などによる天然の水溜り、水槽、人工池やプール、または水道水の散水などによる水溜り、下水の滞留箇所など様々な水溜りが対象となる。本発明の有害生物防除方法の対象場所に制限はないが、好ましくはこれらボウフラの発生場所が対象であり、特には、貯排水設備中に発生する水たまり(水の滞留場所)である。 In the present invention, the pest control effect means an effect of suppressing the growth of pests, for example, boufra, which means that the boufra does not become an adult mosquito, and only delays growth. Rather, it aims to die in the form of a boufra.
The place where a bow hula occurs is a pond, ground, stone, plant dent, bucket, fence, empty can, various containers, natural water pool due to rain or condensation on rainwater trout, etc., aquarium, artificial pond or pool, or water supply Various puddles such as puddles of water sprinkling and sewage accumulation are targeted. Although there is no restriction | limiting in the target place of the pest control method of this invention, Preferably the generation | occurrence | production place of these bow flares are object, and it is a puddle (water retention place) especially generate | occur | produced in a storage drainage facility.
銀イオンのボウフラ等の有害生物に対する成長抑制に及ぼす濃度の影響を検討した結果、銅イオンは1ppm程度の溶解濃度が必要であるのに対し、銀イオンでは銅イオンの数十分の1以下の数十ppb程度の溶解濃度でも十分なボウフラ成長抑制効果が発現することがわかった。ただし、ボウフラ成長抑制効果は金属イオン濃度のみに依存するわけでなく金属イオンの暴露時間にも左右され、数十ppbの低濃度であれば数日、数ppmの高濃度であれば短時間での作用となる。一般に、ボウフラの発生日時を特定することは不可能であるので、ボウフラを抑制したい場合は常に一定の銀イオン濃度を水中に供給し続けることが好ましい方法である。
As a result of examining the influence of the concentration of silver ions on growth inhibition of pests such as boufra, copper ions require a dissolution concentration of about 1 ppm, whereas silver ions require a concentration of 1 or less of several tens of minutes of copper ions. It has been found that even a dissolved concentration of about several tens of ppb exhibits a sufficient effect of suppressing the growth of boufra. However, the effect of suppressing the growth of the bowfla is not dependent only on the metal ion concentration, but also depends on the exposure time of the metal ions. In a low concentration of several tens of ppb, it takes several days, and in a high concentration of several ppm, it takes a short time. It becomes the action of. In general, since it is impossible to specify the date and time of occurrence of a bowfra, it is preferable to always supply a constant silver ion concentration in water when it is desired to suppress the bowfra.
○有害生物防除剤
本発明における有害生物防除剤は、銅よりも安全衛生の面で優れた銀を使用し、銀イオンを水に溶出させることのできるものであって、銀を含有する溶解性ガラス(銀ガラスともいう)、および公定水分率が1~10である樹脂に銀置換無機イオン交換体を含有させた樹脂成形体、の中から選択される少なくとも一つである。溶解性ガラスと樹脂成形体とは構成物質に一部差があるが、いずれも長期間、水中で一定量の銀イオンを放出し続けることによって有害生物を防除できるという効果が同一であり、形態や、銀イオンの溶出速度などに共通点があって、本発明の防除方法および貯排水設備において同様に用いることができるものである。
溶解性ガラス、または銀置換無機イオン交換体を含有した樹脂成形体の形態は、ボウフラの成長抑制効果を容易に発現するために特定の形態を有することが好ましい。例えば、水中で長期間安定に存在するためには、風雨などで水溜りより薬剤が流出せず、水中に沈んでいることが好ましく、この意味で、粉末状ではなく一定以上の大きさであり水中に沈んでいることが好ましい。具体的には、1粒当たりの平均質量が0.5g以上、比重は1.05以上であることが好ましく、さらに好ましくは比重が1.2以上5以下である。比重は25℃における同体積の試料と蒸留水の質量比で定義される。粒径は、例えば形状を問わずランダムに選択した粒子50個の防除剤の最大粒径(例えば球に近い形状であれば直径、直方体に近い形状であれば最も長い辺の長さ)の平均値で代表させることができる。有害生物防除剤の溶解性ガラスまたは樹脂成型体の粒子があまりにも小さいものは、保持することが困難であるから、本発明における有害生物防除剤では粒径が1mm以上であることが必須である。水容器や貯排水部材の少なくとも一部を銀置換無機イオン交換体を含有した樹脂成形体とする場合を考慮すると、大きさの上限は特にないが、あまりにも大きいものは成形困難であるので、好ましい上限は1mであり、さらに好ましい粒径は2mm以上100mm以下である。 ○ Pest control agent The pest control agent in the present invention uses silver which is superior in safety and health to copper and can elute silver ions into water, and has a solubility containing silver. It is at least one selected from glass (also referred to as silver glass) and a resin molded body in which a silver-substituted inorganic ion exchanger is contained in a resin having an official moisture content of 1 to 10. Although there are some differences in constituent materials between soluble glass and resin moldings, both have the same effect of controlling pests by releasing a certain amount of silver ions in water for a long period of time. In addition, there is a common point in the elution rate of silver ions and the like, and the same can be used in the control method and storage / drainage equipment of the present invention.
It is preferable that the form of the resin molded body containing the soluble glass or the silver-substituted inorganic ion exchanger has a specific form in order to easily exhibit the growth inhibitory effect of the bowfra. For example, in order to exist stably in water for a long period of time, it is preferable that the drug does not flow out of the water pool due to wind and rain, but is submerged in water. It is preferable to be submerged in water. Specifically, the average mass per grain is preferably 0.5 g or more, and the specific gravity is preferably 1.05 or more, more preferably 1.2 or more and 5 or less. Specific gravity is defined by the mass ratio of a sample of the same volume and distilled water at 25 ° C. The particle diameter is, for example, the average of the maximum particle diameters of 50 control agents randomly selected regardless of the shape (for example, the diameter is a shape close to a sphere, the longest side length is a shape close to a rectangular parallelepiped). It can be represented by a value. Since the particles of the soluble glass or resin molded article of the pest control agent are too small to hold, it is essential that the particle size of the pest control agent in the present invention is 1 mm or more. . Considering the case where a water molded container or a water storage / drainage member is a resin molded body containing a silver-substituted inorganic ion exchanger, there is no particular upper limit on the size, but too large ones are difficult to mold, A preferable upper limit is 1 m, and a more preferable particle size is 2 mm or more and 100 mm or less.
本発明における有害生物防除剤は、銅よりも安全衛生の面で優れた銀を使用し、銀イオンを水に溶出させることのできるものであって、銀を含有する溶解性ガラス(銀ガラスともいう)、および公定水分率が1~10である樹脂に銀置換無機イオン交換体を含有させた樹脂成形体、の中から選択される少なくとも一つである。溶解性ガラスと樹脂成形体とは構成物質に一部差があるが、いずれも長期間、水中で一定量の銀イオンを放出し続けることによって有害生物を防除できるという効果が同一であり、形態や、銀イオンの溶出速度などに共通点があって、本発明の防除方法および貯排水設備において同様に用いることができるものである。
溶解性ガラス、または銀置換無機イオン交換体を含有した樹脂成形体の形態は、ボウフラの成長抑制効果を容易に発現するために特定の形態を有することが好ましい。例えば、水中で長期間安定に存在するためには、風雨などで水溜りより薬剤が流出せず、水中に沈んでいることが好ましく、この意味で、粉末状ではなく一定以上の大きさであり水中に沈んでいることが好ましい。具体的には、1粒当たりの平均質量が0.5g以上、比重は1.05以上であることが好ましく、さらに好ましくは比重が1.2以上5以下である。比重は25℃における同体積の試料と蒸留水の質量比で定義される。粒径は、例えば形状を問わずランダムに選択した粒子50個の防除剤の最大粒径(例えば球に近い形状であれば直径、直方体に近い形状であれば最も長い辺の長さ)の平均値で代表させることができる。有害生物防除剤の溶解性ガラスまたは樹脂成型体の粒子があまりにも小さいものは、保持することが困難であるから、本発明における有害生物防除剤では粒径が1mm以上であることが必須である。水容器や貯排水部材の少なくとも一部を銀置換無機イオン交換体を含有した樹脂成形体とする場合を考慮すると、大きさの上限は特にないが、あまりにも大きいものは成形困難であるので、好ましい上限は1mであり、さらに好ましい粒径は2mm以上100mm以下である。 ○ Pest control agent The pest control agent in the present invention uses silver which is superior in safety and health to copper and can elute silver ions into water, and has a solubility containing silver. It is at least one selected from glass (also referred to as silver glass) and a resin molded body in which a silver-substituted inorganic ion exchanger is contained in a resin having an official moisture content of 1 to 10. Although there are some differences in constituent materials between soluble glass and resin moldings, both have the same effect of controlling pests by releasing a certain amount of silver ions in water for a long period of time. In addition, there is a common point in the elution rate of silver ions and the like, and the same can be used in the control method and storage / drainage equipment of the present invention.
It is preferable that the form of the resin molded body containing the soluble glass or the silver-substituted inorganic ion exchanger has a specific form in order to easily exhibit the growth inhibitory effect of the bowfra. For example, in order to exist stably in water for a long period of time, it is preferable that the drug does not flow out of the water pool due to wind and rain, but is submerged in water. It is preferable to be submerged in water. Specifically, the average mass per grain is preferably 0.5 g or more, and the specific gravity is preferably 1.05 or more, more preferably 1.2 or more and 5 or less. Specific gravity is defined by the mass ratio of a sample of the same volume and distilled water at 25 ° C. The particle diameter is, for example, the average of the maximum particle diameters of 50 control agents randomly selected regardless of the shape (for example, the diameter is a shape close to a sphere, the longest side length is a shape close to a rectangular parallelepiped). It can be represented by a value. Since the particles of the soluble glass or resin molded article of the pest control agent are too small to hold, it is essential that the particle size of the pest control agent in the present invention is 1 mm or more. . Considering the case where a water molded container or a water storage / drainage member is a resin molded body containing a silver-substituted inorganic ion exchanger, there is no particular upper limit on the size, but too large ones are difficult to mold, A preferable upper limit is 1 m, and a more preferable particle size is 2 mm or more and 100 mm or less.
また、溶解性ガラスまたは銀置換無機イオン交換体を含有した樹脂成形体などの有害生物防除剤は、製造後初めて水中に入れた際の銀の溶出量と水を入れ替えて2回目以降の溶出量が異なる場合がよくある。本発明におけるこれら有害生物防除剤は、水を入れ替えた際の銀の溶出量が前回と比較し±20%以内である溶解性ガラスであることが好ましい。また、屋外での使用で想定される水温やpHの変動があっても銀溶出量が大きく変化せず、±20%以内であることが好ましい。溶解性ガラスと樹脂成形体との比較では、効果に著しい差はないが、減量が目に見えてわかりやすい点で溶解性ガラスの方が好ましい。
In addition, pesticides such as resin moldings containing soluble glass or silver-substituted inorganic ion exchangers can be used for the first and subsequent times by replacing the elution amount of silver and water when first put into water after production. Are often different. These pest control agents in the present invention are preferably soluble glass whose silver elution amount when water is replaced is within ± 20% compared to the previous time. Moreover, even if there are fluctuations in water temperature and pH assumed for outdoor use, the silver elution amount does not change greatly, and it is preferably within ± 20%. In the comparison between the soluble glass and the resin molded body, there is no significant difference in the effect, but the soluble glass is preferable in that the weight loss is visibly easy to understand.
○溶解性ガラス
本発明で用いることのできる溶解性ガラスは水への溶解性があり、25℃での脱イオン水への銀イオンの好ましい溶解濃度は、0.05mg/g・L・日以上、5mg/g・L・日以下である。本発明で用いることのできる溶解性ガラスは、水を入れ替えたり、温度やpHなどの条件によっても大きく溶解度が変化しないものであり、雨により水が入れ替わったりしても持続性が発現するものである。 ○ Dissolvable glass The soluble glass that can be used in the present invention has solubility in water, and the preferable dissolution concentration of silver ions in deionized water at 25 ° C is 0.05 mg / g · L · day or more. 5 mg / g · L · day or less. The soluble glass that can be used in the present invention is one whose water does not change greatly even if the water is changed or depending on the conditions such as temperature and pH, and it is sustainable even if the water is changed due to rain. is there.
本発明で用いることのできる溶解性ガラスは水への溶解性があり、25℃での脱イオン水への銀イオンの好ましい溶解濃度は、0.05mg/g・L・日以上、5mg/g・L・日以下である。本発明で用いることのできる溶解性ガラスは、水を入れ替えたり、温度やpHなどの条件によっても大きく溶解度が変化しないものであり、雨により水が入れ替わったりしても持続性が発現するものである。 ○ Dissolvable glass The soluble glass that can be used in the present invention has solubility in water, and the preferable dissolution concentration of silver ions in deionized water at 25 ° C is 0.05 mg / g · L · day or more. 5 mg / g · L · day or less. The soluble glass that can be used in the present invention is one whose water does not change greatly even if the water is changed or depending on the conditions such as temperature and pH, and it is sustainable even if the water is changed due to rain. is there.
本発明で用いることのできる溶解性ガラスの成分組成は、Ag2Oを0.5~4質量%、K2OまたはNa2Oを3~10質量%、SiO2を0~60質量%、B2O3またはP2O5を40~70質量%、Al2O3、MgO、BaO、ZnOからなる群から選ばれる少なくとも1種以上が0~20%を含有する。ボウフラ抑制有効成分である銀は、Ag2Oで0.5%以下の配合量では大量に溶解性ガラスを使用しなければ効果が得られず、4%以上のAg2O配合量はガラス化することが困難で金属銀として析出してしまうため、Ag2O配合量は0.5~4質量%、好ましくは1~3%、より好ましくは1.5~2.5%である。
Composition of soluble glass that can be used in the present invention, the Ag 2 O 0.5 ~ 4 weight%, the K 2 O or Na 2 O 3 ~ 10 wt%, a SiO 2 0 ~ 60% by weight, B 2 O 3 or P 2 O 5 40 to 70 wt%, Al 2 O 3, MgO , BaO, at least one or more selected from the group consisting of ZnO containing 0-20%. Silver is a mosquito larvae suppressing active ingredient, Ag 2 O in effect can not be obtained unless using large amounts soluble glass in the amount of 0.5% or less, 4% or more Ag 2 O amount is vitrified Therefore, the Ag 2 O content is 0.5 to 4% by mass, preferably 1 to 3%, more preferably 1.5 to 2.5%.
ガラスの溶解性を調整する成分として働くK2OまたはNa2Oは、他のアルカリ金属よりガラスの溶解性を長期に渡り制御しやすく、その含有率は3~10%が好ましく、より好ましくは4~9%、さらに好ましくは5~8%である。K2OまたはNa2Oの中でより好ましいのはK2Oであり、溶解性を向上させることができるから、好ましいのはNa2Oを含む溶解性ガラスよりも、Na2Oを含まず、K2Oを含む溶解性ガラスである。ガラスの骨格構造を形成するSiO2、P2O5およびB2O3は、全体の比率のバランスでガラスの溶解性を制御し、一般にSiO2の割合が増えると溶解性が低下し、B2O3の割合が増えると溶解性が向上する。SiO2の好ましい含有率は、0~60%、より好ましくは0~15%である。B2O3の好ましい含有率は、42~70%、より好ましくは44~67、特に好ましくは44~65%である。Al2O3はSiO2やB2O3と共にガラスの骨格を形成し、SiO2やB2O3が主成分である場合にAl2O3を含有させると一般的に化学耐久性が向上するので、含有することが好ましい。しかし、あまり多く含有するとガラスの溶解性が小さくなりすぎてボウフラ成長抑制効果が発現しにくくなるから、好ましい含有量は5%~20%であり、さらに好ましくは15~20%である。
K 2 O or Na 2 O acting as a component for adjusting the solubility of the glass is easier to control the solubility of the glass for a long time than other alkali metals, and its content is preferably 3 to 10%, more preferably It is 4 to 9%, more preferably 5 to 8%. The more preferred among K 2 O or Na 2 O is K 2 O, can be improved solubility than soluble glass Preference containing Na 2 O, free of Na 2 O , K 2 O-containing soluble glass. SiO 2, P 2 O 5 and B 2 O 3 to form the skeletal structure of the glass, controls the solubility of the glass in the overall balance of the proportions, generally the solubility and the proportion of SiO 2 is increased is reduced, B Solubility improves as the proportion of 2 O 3 increases. The preferred content of SiO 2 is 0-60%, more preferably 0-15%. A preferable content of B 2 O 3 is 42 to 70%, more preferably 44 to 67, and particularly preferably 44 to 65%. Al 2 O 3 forms the skeleton of glass with SiO 2 or B 2 O 3, the inclusion of Al 2 O 3 generally chemical durability improved when SiO 2 or B 2 O 3 is the main component Therefore, it is preferable to contain. However, if the content is too large, the solubility of the glass becomes too small to make it difficult to exhibit the effect of suppressing the growth of bowflas. Therefore, the preferred content is 5% to 20%, more preferably 15 to 20%.
その他MgO、BaO、ZnOはガラス骨格成分の間に入り、ガラスを安定化させる作用があるので、必須成分ではないが含まれることが好ましい。好ましい含有量は、0~10%である。他の成分としてCa、Ba、Zn、Co、Cuなどが混在してもガラス溶解度が長期に渡り影響を及ぼさないような少量であればよい。
Other MgO, BaO, and ZnO are not essential components because they enter between the glass skeleton components and have the effect of stabilizing the glass. The preferred content is 0 to 10%. Even if Ca, Ba, Zn, Co, Cu and the like are mixed as other components, the amount of the glass may be small so as not to affect the long term.
一般に粒状ガラスの安価な工業的製法は、加熱溶解した高温の液状ガラスを水中に投入し急冷して不定形破砕状のカレットとするか、金属ローラー間を通すことで板状(フレーク状)とする方法である。しかし、カレットでは、粒度の調整が困難で2mm以下の微粒子や粗粒が含有されることで粉砕や分級の必要がある。また、表面に残留応力があるため微細クラックが発生し易く、使用時にクラック部分から破砕が進行していくので破片や細粉を発生し、粒度が変化し易いと言われている。一方、フレークはカレットよりは一定の粒度となりやすいがそれでも十分ではなく、割れたガラス板状の破片も多いため、使用するには危険な場合もある。フレーク状ガラスの製造方法の応用で、熔融した水処理用抗菌ガラスを片面または両面が半球状または円錐状の窪みを有する冷却成形ローラーで成形することで半球状、円錐状、球状などの形状の粒状ガラスを製造することもできる。このような成形物とすることで、割れにくく、一定の形状と粒度を実現することで溶解性の制御が容易になる。
In general, an inexpensive industrial method for producing granular glass is to add hot liquid glass that has been heated and melted into water and rapidly cool it to form an irregularly shaped cullet, or pass between metal rollers to form a plate (flakes). It is a method to do. However, cullet is difficult to adjust the particle size and needs to be pulverized or classified because it contains fine particles or coarse particles of 2 mm or less. Further, since there are residual stresses on the surface, fine cracks are likely to occur, and crushing proceeds from the crack portion during use, so fragments and fine powder are generated, and the particle size is likely to change. On the other hand, flakes tend to have a certain particle size than cullet, but that is not sufficient, and there are many broken pieces of glass plate, which may be dangerous to use. By application of the method for producing flake glass, the melted antibacterial glass for water treatment is molded with a cooling roller having a hemispherical or conical depression on one or both sides, thereby forming a hemispherical, conical or spherical shape. Granular glass can also be produced. By setting it as such a molded article, it is hard to break and it becomes easy to control solubility by realizing a certain shape and particle size.
本発明に用いる溶解性ガラスの製造方法は、酸化物、水酸化物、ホウ酸塩、塩化物、硝酸塩、硫酸塩、炭酸塩等の必要成分を含有している化合物を所定の混合量になるようによく混合した後、溶融釜で加熱溶融し、急冷することにより得ることができる。
The manufacturing method of the soluble glass used in the present invention is a predetermined mixed amount of a compound containing necessary components such as oxides, hydroxides, borates, chlorides, nitrates, sulfates and carbonates. After mixing well, it can be obtained by heating and melting in a melting pot and quenching.
この様にして得られた溶解性ガラスは、溶解度、形状および粒度を調整したことで銀溶出量の制御に優れており、適量水中に浸漬すると水中に銀濃度を経時的に溶出しボウフラの成長抑制効果を発現する。また、溶解性ガラス自体が溶解し減量することでボウフラ抑制効果の持続期間が誰にでも容易に目視でわかる。溶解性ガラスが着色されているものは視認が容易であり好ましい。本発明における銀イオンを水に溶出させることのできる溶解性ガラスを水に浸漬した時の銀溶出量は、ガラス組成と成形体の表面積とで調整することができ、0.05mg/g・L・日以上5mg/g・L・日以下が好ましく、より好ましくは0.1mg/g・L・日以上0.5mg/g・L・日以下である。この範囲の溶解量が3週間以上、可能であれば数ヶ月程度は持続することが好ましい。上記の銀イオン溶出量を実現するための溶解性ガラスの使用量の目安は、溶解性ガラスが浸漬される水の体積1リットルあたり、溶解性ガラスの表面積の合計として3cm2~500cm2となる量が好ましく、50cm2~300cm2となる量がより好ましい。
The soluble glass obtained in this way is excellent in controlling the amount of elution of silver by adjusting the solubility, shape, and particle size. The inhibitory effect is expressed. Moreover, since the soluble glass itself dissolves and loses weight, the duration of the effect of suppressing the bow fluff can be easily seen by anyone. Those in which the soluble glass is colored are preferred because they are easily visible. The silver elution amount when the soluble glass capable of eluting silver ions in water in the present invention is immersed in water can be adjusted by the glass composition and the surface area of the molded body, and is 0.05 mg / g · L. · Preferably, it is not less than 5 mg / g · L · day and more preferably not less than 0.1 mg / g · L · day and not more than 0.5 mg / g · L · day. It is preferable that the dissolution amount in this range be maintained for 3 weeks or more, and for several months if possible. Estimated amount of soluble glass for realizing silver ion elution amount above, the volume per liter of water soluble glass is immersed, a 3 cm 2 ~ 500 cm 2 as the sum of the surface area of soluble glass An amount is preferable, and an amount of 50 cm 2 to 300 cm 2 is more preferable.
溶解性ガラスの比表面積は、3~500cm2/gが好ましく、5~200cm2/gがより好ましく、10~50cm2/gがさらに好ましい。比表面積が3~50cm2/gとなる形状の例として、球状の粒子であれば半径0.05~1cm程度である。比表面積が3cm2/gより小さいと(粒径が大きすぎると)銀の溶出速度が遅くなり、効果的な防除のために要する防除剤の使用量を多く必要とする。比表面積が500cm2/gより大きいと(粒径が小さすぎると)銀の溶出速度が速すぎて防除剤が短期間で消費するため、防除効果の持続性が不十分となる場合がある。
The specific surface area of soluble glass is preferably 3 ~ 500cm 2 / g, more preferably 5 ~ 200cm 2 / g, more preferably 10 ~ 50cm 2 / g. As an example of a shape having a specific surface area of 3 to 50 cm 2 / g, a spherical particle has a radius of about 0.05 to 1 cm. A specific surface area of 3 cm 2 / g is less than a (if the particle size is too large) slows dissolution rate of silver, the effective require more amount of control agent required for the control. When the specific surface area is larger than 500 cm 2 / g (if the particle size is too small), the elution rate of silver is too fast and the control agent is consumed in a short period of time, so that the control effect may be insufficiently sustained.
本発明で用いることのできる溶解性ガラスの使用形態は特に制限はなく、粒状のまま使用することも可能であるが、例えば数g~数十gを不織布やネットに充填、梱包して使用することも可能である。梱包は不織布とネットの二重にしてあることがより好ましく、二重梱包の内側は、溶解性ガラスの漏出を防ぐため目が細かい不織布であることがよく、外側は不織布の強度を維持することが目的であるため、丈夫で水を通水しやすいネット状であることが好ましい。内側の不織布の材質は、親水性を有する材質を用いるとガラスが溶解しやすいので好ましく、例えばナイロンやポリエステルが挙げられる。また、孔やスリットのあいたプラスチック容器に溶解性ガラスを収納して使用することもできる。不織布で梱包された溶解性ガラスがプラスチック容器に出し入れ可能に収納されるのも好ましい形態である。
The form of use of the soluble glass that can be used in the present invention is not particularly limited, and can be used in the form of granules. For example, several g to several tens of g are filled and packed in a nonwoven fabric or net. It is also possible. It is more preferable that the packing is made of a nonwoven fabric and a net. The inside of the double packaging should be a fine nonwoven fabric to prevent leakage of soluble glass, and the outside should maintain the strength of the nonwoven fabric. Therefore, it is preferable to have a net shape that is strong and easy to pass water. As the material of the inner nonwoven fabric, it is preferable to use a hydrophilic material because glass is easily dissolved, and examples thereof include nylon and polyester. Further, it is possible to store the soluble glass in a plastic container having holes or slits. It is also a preferable form that the soluble glass packed with a nonwoven fabric is stored in a plastic container so that it can be taken in and out.
○銀置換無機イオン交換体を含有した樹脂成形体
本発明における銀置換無機イオン交換体を含有した樹脂成形体は、公定水分率1%以上10%以下の樹脂に銀置換無機イオン交換体を好ましくは1~30質量%練り込み加工した樹脂組成物からなる成形体である。
銀置換無機イオン交換体とは、銀をイオン交換した無機陽イオン交換体粉末である。銀の含有量は1%以上20%以下であり、より好ましくは2%以上15%以下である。銀含有量が1%以下ではボウフラ成長抑制効果が発現しにくく、20%以上無機イオン交換体に銀置換することは難しい。無機陽イオン交換体には、ゼオライト、リン酸ジルコニウム、リン酸チタンなどがあり、特に下記式〔1〕で示されるリン酸ジルコニウムは、高濃度で安定に銀をイオン交換担持できるため有効である。
MaZrbHfc(PO4)3・nH2O 〔1〕
上記式〔1〕において、Mはアルカリ金属イオン、アルカリ土類金属イオン、アンモニウムイオン、水素イオンおよびオキソニウムイオンから選ばれる少なくとも1種のイオンであり、a、bおよびcは、1.75<b+c<2.25で、Mが1価の場合はa+4(b+c)=9を満たす数であり、Mが2価の場合は、2a+4(b+c)=9を満たす数であり、a、bおよびcは正数であり、nは0または2以下の正数である Resin molded body containing silver-substituted inorganic ion exchanger The resin molded body containing a silver-substituted inorganic ion exchanger in the present invention is preferably a silver-substituted inorganic ion exchanger in a resin having an official moisture content of 1% or more and 10% or less. Is a molded article made of a resin composition kneaded in an amount of 1 to 30% by mass.
The silver-substituted inorganic ion exchanger is an inorganic cation exchanger powder obtained by ion exchange of silver. The silver content is 1% or more and 20% or less, more preferably 2% or more and 15% or less. If the silver content is 1% or less, the effect of inhibiting the growth of bowfra is difficult to develop, and it is difficult to substitute 20% or more of the inorganic ion exchanger with silver. Examples of inorganic cation exchangers include zeolite, zirconium phosphate, and titanium phosphate. In particular, the zirconium phosphate represented by the following formula [1] is effective because it can stably ion-support silver at a high concentration. .
M a Zr b Hf c (PO 4 ) 3 · nH 2 O [1]
In the above formula [1], M is at least one ion selected from alkali metal ions, alkaline earth metal ions, ammonium ions, hydrogen ions and oxonium ions, and a, b and c are 1.75 < When b + c <2.25 and M is monovalent, it is a number satisfying a + 4 (b + c) = 9, and when M is divalent, it is a number satisfying 2a + 4 (b + c) = 9, and a, b and c is a positive number, and n is a positive number of 0 or 2 or less
本発明における銀置換無機イオン交換体を含有した樹脂成形体は、公定水分率1%以上10%以下の樹脂に銀置換無機イオン交換体を好ましくは1~30質量%練り込み加工した樹脂組成物からなる成形体である。
銀置換無機イオン交換体とは、銀をイオン交換した無機陽イオン交換体粉末である。銀の含有量は1%以上20%以下であり、より好ましくは2%以上15%以下である。銀含有量が1%以下ではボウフラ成長抑制効果が発現しにくく、20%以上無機イオン交換体に銀置換することは難しい。無機陽イオン交換体には、ゼオライト、リン酸ジルコニウム、リン酸チタンなどがあり、特に下記式〔1〕で示されるリン酸ジルコニウムは、高濃度で安定に銀をイオン交換担持できるため有効である。
MaZrbHfc(PO4)3・nH2O 〔1〕
上記式〔1〕において、Mはアルカリ金属イオン、アルカリ土類金属イオン、アンモニウムイオン、水素イオンおよびオキソニウムイオンから選ばれる少なくとも1種のイオンであり、a、bおよびcは、1.75<b+c<2.25で、Mが1価の場合はa+4(b+c)=9を満たす数であり、Mが2価の場合は、2a+4(b+c)=9を満たす数であり、a、bおよびcは正数であり、nは0または2以下の正数である Resin molded body containing silver-substituted inorganic ion exchanger The resin molded body containing a silver-substituted inorganic ion exchanger in the present invention is preferably a silver-substituted inorganic ion exchanger in a resin having an official moisture content of 1% or more and 10% or less. Is a molded article made of a resin composition kneaded in an amount of 1 to 30% by mass.
The silver-substituted inorganic ion exchanger is an inorganic cation exchanger powder obtained by ion exchange of silver. The silver content is 1% or more and 20% or less, more preferably 2% or more and 15% or less. If the silver content is 1% or less, the effect of inhibiting the growth of bowfra is difficult to develop, and it is difficult to substitute 20% or more of the inorganic ion exchanger with silver. Examples of inorganic cation exchangers include zeolite, zirconium phosphate, and titanium phosphate. In particular, the zirconium phosphate represented by the following formula [1] is effective because it can stably ion-support silver at a high concentration. .
M a Zr b Hf c (PO 4 ) 3 · nH 2 O [1]
In the above formula [1], M is at least one ion selected from alkali metal ions, alkaline earth metal ions, ammonium ions, hydrogen ions and oxonium ions, and a, b and c are 1.75 < When b + c <2.25 and M is monovalent, it is a number satisfying a + 4 (b + c) = 9, and when M is divalent, it is a number satisfying 2a + 4 (b + c) = 9, and a, b and c is a positive number, and n is a positive number of 0 or 2 or less
本発明の銀置換無機イオン交換体を樹脂と配合することにより樹脂組成物の成形体を容易に得ることができる。樹脂成形体の加工方法は、公知の方法がどれも採用できる。例えば、(1)銀置換無機イオン交換体粉末と樹脂とが付着しやすくするための添着剤や銀置換無機イオン交換体粉末の分散性を向上させるための分散剤を使用し、ペレット状樹脂またはパウダー状樹脂をミキサーで直接混合する方法、(2)前記のようにして混合して、押し出し成形機にてペレット状に成形した後、その成形物をペレット状樹脂に配合する方法、(3)銀置換無機イオン交換体粉末をワックスを用いて高濃度のペレット状に成形後、そのペレット状成形物をペレット状樹脂に配合する方法、(4)銀置換無機イオン交換体粉末をポリオ-ルなどの高粘度の液状物に分散混合したペ-スト状組成物を調製後、このペーストをペレット状樹脂に配合する方法などがある。
A molded article of a resin composition can be easily obtained by blending the silver-substituted inorganic ion exchanger of the present invention with a resin. Any known method can be adopted as a method for processing the resin molded body. For example, (1) using an additive for facilitating adhesion between the silver-substituted inorganic ion exchanger powder and the resin or a dispersant for improving the dispersibility of the silver-substituted inorganic ion exchanger powder, (2) A method of directly mixing a powdered resin with a mixer, (2) A method of mixing as described above, forming into a pellet shape with an extrusion molding machine, and then blending the molded product into the pellet-shaped resin, (3) A method in which the silver-substituted inorganic ion exchanger powder is molded into a high-concentration pellet using wax, and then the pellet-shaped molded product is blended into a pellet-shaped resin. (4) The silver-substituted inorganic ion exchanger powder is polyol, etc. There is a method of preparing a paste-like composition dispersed and mixed in a high-viscosity liquid material and then blending this paste into a pellet-like resin.
本発明における銀置換無機イオン交換体を含有する樹脂成形体を加工するための成形機には制限はなく、既存の機械が使用できる。例えば、射出成形機、押し出し成形機、ブロー成形、熱プレスなどが例示される。この中でも射出成形機が形状の安定性に加え、熱履歴が少ないため好ましい。熱履歴が多いと樹脂の劣化が進行することで、銀以外の樹脂の分解成分などが水中に溶け出すおそれがあるためである。成形前の組成物の製造に使用できる混合機としては、ニーダー、押出成形機、ミキシングロールなどが挙げられる。
There is no limitation on the molding machine for processing the resin molding containing the silver-substituted inorganic ion exchanger in the present invention, and an existing machine can be used. For example, an injection molding machine, an extrusion molding machine, blow molding, a heat press, etc. are illustrated. Among these, an injection molding machine is preferable because it has a small thermal history in addition to the stability of the shape. This is because if the thermal history is large, the deterioration of the resin progresses, so that decomposition components of the resin other than silver may be dissolved in water. Examples of the mixer that can be used for producing the composition before molding include a kneader, an extrusion molding machine, and a mixing roll.
本発明における樹脂成形体に使用される樹脂の公定水分率とは、温度20℃、相対湿度65%での吸湿率に基づいて定められる樹脂の吸湿率を示す指標である。本発明に用いられる樹脂の公定水分率は、1.0以上10以下であり、好ましくは2以上9以下、より好ましくは3以上8.5以下である。公定水分率が1以下では樹脂成形体の銀溶出の持続性が十分得られず、10%以上では短時間で溶出し銀濃度の制御が難しく、変色しやすくなることで外観上製品価値を低下するおそれもある。
The official moisture content of the resin used for the resin molded body in the present invention is an index indicating the moisture absorption rate of the resin determined based on the moisture absorption rate at a temperature of 20 ° C. and a relative humidity of 65%. The official moisture content of the resin used in the present invention is 1.0 or more and 10 or less, preferably 2 or more and 9 or less, more preferably 3 or more and 8.5 or less. If the official moisture content is 1 or less, sufficient persistence of silver elution of the resin molded product is not obtained, and if it is 10% or more, elution takes place in a short time, it is difficult to control the silver concentration, and the product value is reduced in appearance due to easy discoloration. There is also a risk.
一般的な樹脂の公定水分率としては、ポリプロピレン0.0、ポリエチレン0.0、塩ビ0.0、ビニリデン0.0、ポリエステル0.3-0.4、ウレタン1、アクリル1.2-2.0、ポリアセタール2.0、ポリアミド3.5-5.0、アセテート6-7、レーヨン12-14であり、公定水分率の値から最も好ましい樹脂はポリアミドである。ポリアミドは一般にナイロンとも呼ばれ、その種類にはナイロン6、66、46、MDX6、61、9T、610、612、11、12などがあり、これらの単独または混合して使用することも可能である。さらに水に沈ませることが望ましいことから、樹脂の比重は1.1以上が好ましい。ポリアミドの比重は1.15程度であることから比重においてもポリアミドが好ましい。このなかで汎用性、成形性、銀溶出量の制御性などから特に好ましくは、6ナイロンであり、他の種類のナイロンと混合して使用することも可能であり、その場合は50%以上の配合率が好ましい。さらに、6ナイロンの中でも低密度のものほど溶出しやすいため好ましい。
As the official moisture content of general resins, polypropylene 0.0, polyethylene 0.0, vinyl chloride 0.0, vinylidene 0.0, polyester 0.3-0.4, urethane 1, acrylic 1.2-2. 0, polyacetal 2.0, polyamide 3.5-5.0, acetate 6-7, rayon 12-14, and the most preferred resin from the value of official moisture content is polyamide. Polyamide is generally called nylon, and there are nylon 6, 66, 46, MDX6, 61, 9T, 610, 612, 11, 12, etc., and these can be used alone or in combination. . Furthermore, since it is desirable to submerge it in water, the specific gravity of the resin is preferably 1.1 or more. Since the specific gravity of polyamide is about 1.15, polyamide is preferable also in specific gravity. Among these, 6 nylon is particularly preferable from the viewpoint of versatility, moldability, controllability of silver elution amount, etc., and it can be used by mixing with other types of nylon. A compounding rate is preferable. Further, among the 6 nylons, those having a low density are preferable because they are more easily eluted.
本発明における銀置換無機イオン交換体を含有する樹脂成形体には、金属石鹸などの分散剤を用いることができる。好ましい分散剤は金属石鹸であり、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸マグネシウムなどで、より好ましくはステアリン酸マグネシウムである。
A dispersant such as metal soap can be used for the resin molded body containing the silver-substituted inorganic ion exchanger in the present invention. A preferred dispersant is a metal soap, such as zinc stearate, calcium stearate, magnesium stearate, and more preferably magnesium stearate.
本発明における銀置換無機イオン交換体を含有する樹脂成形体に用いる銀置換無機イオン交換体には、樹脂への練り込み加工性やその他の物性を改善するため、必要に応じて種々の添加剤を混合することもできる。具体例としては酸化亜鉛や酸化チタンなどの顔料、リン酸ジルコニウムやゼオライトなどの無機イオン交換体、染料、酸化防止剤、耐光安定剤、耐候安定剤、難燃剤、帯電防止剤、発泡剤、耐衝撃強化剤、ガラス繊維、金属石鹸などの滑剤、防湿剤および増量剤、カップリング剤、核剤、流動性改良剤、消臭剤、木粉、防黴剤、防汚剤、防錆剤、金属粉、紫外線吸収剤、紫外線遮蔽剤などがある。
The silver-substituted inorganic ion exchanger used in the resin molded body containing the silver-substituted inorganic ion exchanger in the present invention has various additives as necessary in order to improve kneading into the resin and other physical properties. Can also be mixed. Specific examples include pigments such as zinc oxide and titanium oxide, inorganic ion exchangers such as zirconium phosphate and zeolite, dyes, antioxidants, light stabilizers, weather stabilizers, flame retardants, antistatic agents, foaming agents, Lubricants such as impact strengthening agents, glass fibers, metal soaps, moisture-proofing agents and extenders, coupling agents, nucleating agents, fluidity improvers, deodorants, wood powder, antifungal agents, antifouling agents, antirust agents, There are metal powders, UV absorbers, UV screening agents, etc.
本発明における銀置換無機イオン交換体を含有する樹脂成形体には、各種樹脂の特性に合わせてあらゆる公知の加工技術と機械が使用可能であり、適当な温度または圧力で加熱および加圧または減圧しながら混合、混入または混練りの方法によって容易に調製することができ、それらの具体的操作は常法により行えば良い。また、その形状に制限はなく、球状、塊状、スポンジ状、フィルム状、板状、糸状またはパイプ状或いはこれらの複合体など、種々の形態に成形加工でき、用途に応じて適宜設計することができる。
In the resin molding containing the silver-substituted inorganic ion exchanger in the present invention, any known processing technique and machine can be used according to the characteristics of various resins, and heating, pressurizing, or depressurizing at an appropriate temperature or pressure. However, it can be easily prepared by a method of mixing, mixing or kneading, and their specific operation may be performed by a conventional method. The shape is not limited, and can be formed into various forms such as a spherical shape, a lump shape, a sponge shape, a film shape, a plate shape, a thread shape, a pipe shape, or a composite thereof, and can be appropriately designed according to the application. it can.
この様にして得られた銀置換無機イオン交換体を含有する樹脂成形体は、溶解度、形状および粒度を調整することにより銀溶出量の制御が可能である。適量水中に浸漬すると水中に銀濃度を経時的に溶出しボウフラの成長抑制効果を発現する。本発明における銀イオンを水に溶出させることのできる樹脂成形体を水に浸漬した時の銀溶出量は、成形体の組成と成形体の表面積とで調整することができ、0.05mg/g・L・日以上5mg/g・L・日以下が好ましく、より好ましくは0.1mg/g・L・日以上0.5mg/g・L・日以下である。この範囲の溶解量が3週間以上、可能であれば数ヶ月程度は持続することが好ましい。
上記の銀イオン溶出量を実現するための樹脂成形体の使用量の目安は、樹脂成形体が浸漬される水の体積1リットルあたり、樹脂成形体の表面積として3cm2~500cm2となる量が好ましく、50cm2~300cm2となる量がより好ましい。 The resin molded body containing the silver-substituted inorganic ion exchanger thus obtained can control the silver elution amount by adjusting the solubility, shape and particle size. When immersed in water in an appropriate amount, the silver concentration in the water is eluted over time, and the growth inhibitory effect of boufra is expressed. The silver elution amount when the resin molded body capable of eluting silver ions in water in the present invention is immersed in water can be adjusted by the composition of the molded body and the surface area of the molded body, and 0.05 mg / g. · L · day to 5 mg / g · L · day is preferred, more preferably 0.1 mg / g · L · day to 0.5 mg / g · L · day. It is preferable that the dissolution amount in this range be maintained for 3 weeks or more, and for several months if possible.
Estimated amount of resin molding for realizing silver ion elution amount above, the volume per liter of water which the resin molded article is immersed, the amount to be 3 cm 2 ~ 500 cm 2 as the surface area of the resin molding An amount of 50 cm 2 to 300 cm 2 is more preferable.
上記の銀イオン溶出量を実現するための樹脂成形体の使用量の目安は、樹脂成形体が浸漬される水の体積1リットルあたり、樹脂成形体の表面積として3cm2~500cm2となる量が好ましく、50cm2~300cm2となる量がより好ましい。 The resin molded body containing the silver-substituted inorganic ion exchanger thus obtained can control the silver elution amount by adjusting the solubility, shape and particle size. When immersed in water in an appropriate amount, the silver concentration in the water is eluted over time, and the growth inhibitory effect of boufra is expressed. The silver elution amount when the resin molded body capable of eluting silver ions in water in the present invention is immersed in water can be adjusted by the composition of the molded body and the surface area of the molded body, and 0.05 mg / g. · L · day to 5 mg / g · L · day is preferred, more preferably 0.1 mg / g · L · day to 0.5 mg / g · L · day. It is preferable that the dissolution amount in this range be maintained for 3 weeks or more, and for several months if possible.
Estimated amount of resin molding for realizing silver ion elution amount above, the volume per liter of water which the resin molded article is immersed, the amount to be 3 cm 2 ~ 500 cm 2 as the surface area of the resin molding An amount of 50 cm 2 to 300 cm 2 is more preferable.
樹脂成形体の比表面積は、3~500cm2/gが好ましく、5~200cm2/gがより好ましく、10~50cm2/gがさらに好ましい。比表面積が3~50cm2/gとなる形状の例として、球状の粒子であれば半径0.05~1cm程度である。別の形状の例として、10cm角の板状であれば平均厚さは0.3~6mm程度である。比表面積が3cm2/gより小さいと銀の溶出速度が遅くなり、効果的な防除のために要する防除剤の使用量を多く必要とする。比表面積が500cm2/gより大きいと銀の溶出速度が速すぎて防除剤が短期間で消費するため、防除効果の持続性が不十分となる場合がある。
The specific surface area of the resin molded body is preferably 3 ~ 500cm 2 / g, more preferably 5 ~ 200cm 2 / g, more preferably 10 ~ 50cm 2 / g. As an example of a shape having a specific surface area of 3 to 50 cm 2 / g, a spherical particle has a radius of about 0.05 to 1 cm. As an example of another shape, if the plate is 10 cm square, the average thickness is about 0.3 to 6 mm. When the specific surface area is less than 3 cm 2 / g, the elution rate of silver becomes slow, and a large amount of a control agent required for effective control is required. When the specific surface area is larger than 500 cm 2 / g, the elution rate of silver is too fast and the control agent is consumed in a short period of time, so the sustainability of the control effect may be insufficient.
本発明における銀置換無機イオン交換体を含有する樹脂成形体の使用形態には特に制限はなく、成形体そのままで使用することも可能であるほか、上記溶解性ガラスの使用例と同様にメッシュや不織布などに梱包しても、カートリッジ状の容器に充填してもよい。処理したい水に浸漬または通水することで使用可能であり、常時水中に存在させる必要はなく、空気中で一旦乾いても再度水中に戻せばその性能は大きく変化しない。使用量の目安は銀置換量や目的とする効果により適宜調整すればよい。
The usage form of the resin molded body containing the silver-substituted inorganic ion exchanger in the present invention is not particularly limited, and the molded body can be used as it is. You may pack in a nonwoven fabric etc., and you may fill a cartridge-like container. It can be used by immersing or passing it in the water to be treated, and does not need to be always present in water. Even if it is once dried in air, its performance does not change greatly if it is returned to water again. What is necessary is just to adjust the standard of usage-amount suitably with the amount of silver substitution, and the target effect.
○使用方法
本発明におけるボウフラ等の有害生物の成長抑制方法は、溶解性ガラスまたは銀置換無機イオン交換体を含有する樹脂成形体を水が溜まった際にボウフラ等の有害生物が発生する可能性のある窪みや現に水溜り、既にボウフラ等の有害生物が発生している水溜りなどに設置することで適用可能である。使用量は1L当たり1g程度であるが、寿命などを勘案して適宜調製することができる。水の出入りが全くない水に防除剤を用いる場合、防除剤の銀含有率から算出して、徐々に溶出した水中の銀イオン濃度が10ppb以上になれば防除効果が顕れることが期待できるが、現実環境下で、水中有害生物が問題になるような水域では、水の出入りが全くなくい状況は考えにくい。そうすると、水の出入りがあっても有害生物の成長速度に追いつくだけの速さで銀を溶出し、なおかつ、経済的理由からできるだけ少量の防除剤で長期間の防除を行うことが好ましい。この意味で、防除剤の使用量としては、一定体積の水に対して、水中への銀溶出濃度が50ppb/日以上5ppm/日になるように、添加する防除剤の量を決めることが好ましい。具体的には、防除剤からの銀の溶出量が0.1(mg/L・g・日)だとすると、1Lの体積の水系への銀溶出濃度が50ppb/日以上5ppm/日になるために添加する防除剤の量は0.5g~50gと算出され、このような考え方で使用量の目安とすることができるが、実際の効果も観察しながら適宜使用量を加減することができる。
銀の溶出量が異なる複数種類の有害生物防除剤を併用するのも好ましく、短期間で溶出して早期に防除効果を奏する防除剤と徐々に溶出して長期間にわたって防除効果を持続する防除剤とを併用することにより、防除をさらに効果的なものにすることもできる。 ○ Usage method The method for suppressing the growth of pests such as boufra in the present invention is likely to generate pests such as boufra when water is accumulated in a resin molded product containing soluble glass or a silver-substituted inorganic ion exchanger. It can be applied by installing it in a pit with a pit or actually a puddle, or a puddle where pests such as boufras are already generated. The amount used is about 1 g per liter, but can be appropriately prepared in consideration of the lifetime. When the control agent is used in water with no water in and out, it can be expected that a control effect will appear if the silver ion concentration in the gradually eluted water is 10 ppb or more, calculated from the silver content of the control agent. In a real environment where water pests are a problem, it is difficult to imagine a situation where there is no water access. In this case, it is preferable to elute silver at a rate sufficient to catch up with the growth rate of pests even when water enters and exits, and for long-term control with as little control agent as possible for economic reasons. In this sense, the amount of the control agent to be added is preferably determined so that the silver elution concentration in water is 50 ppb / day or more and 5 ppm / day with respect to a fixed volume of water. . Specifically, if the elution amount of silver from the control agent is 0.1 (mg / L · g · day), the elution concentration of silver in an aqueous system with a volume of 1 L is from 50 ppb / day to 5 ppm / day. The amount of the control agent to be added is calculated to be 0.5 g to 50 g and can be used as a guide for the amount used in this way, but the amount used can be appropriately adjusted while observing the actual effect.
It is also preferable to use a combination of multiple types of pest control agents with different silver elution amounts, a control agent that elutes in a short period of time and exhibits an early control effect, and a control agent that gradually elutes and maintains a control effect over a long period of time By using together, the control can be made more effective.
本発明におけるボウフラ等の有害生物の成長抑制方法は、溶解性ガラスまたは銀置換無機イオン交換体を含有する樹脂成形体を水が溜まった際にボウフラ等の有害生物が発生する可能性のある窪みや現に水溜り、既にボウフラ等の有害生物が発生している水溜りなどに設置することで適用可能である。使用量は1L当たり1g程度であるが、寿命などを勘案して適宜調製することができる。水の出入りが全くない水に防除剤を用いる場合、防除剤の銀含有率から算出して、徐々に溶出した水中の銀イオン濃度が10ppb以上になれば防除効果が顕れることが期待できるが、現実環境下で、水中有害生物が問題になるような水域では、水の出入りが全くなくい状況は考えにくい。そうすると、水の出入りがあっても有害生物の成長速度に追いつくだけの速さで銀を溶出し、なおかつ、経済的理由からできるだけ少量の防除剤で長期間の防除を行うことが好ましい。この意味で、防除剤の使用量としては、一定体積の水に対して、水中への銀溶出濃度が50ppb/日以上5ppm/日になるように、添加する防除剤の量を決めることが好ましい。具体的には、防除剤からの銀の溶出量が0.1(mg/L・g・日)だとすると、1Lの体積の水系への銀溶出濃度が50ppb/日以上5ppm/日になるために添加する防除剤の量は0.5g~50gと算出され、このような考え方で使用量の目安とすることができるが、実際の効果も観察しながら適宜使用量を加減することができる。
銀の溶出量が異なる複数種類の有害生物防除剤を併用するのも好ましく、短期間で溶出して早期に防除効果を奏する防除剤と徐々に溶出して長期間にわたって防除効果を持続する防除剤とを併用することにより、防除をさらに効果的なものにすることもできる。 ○ Usage method The method for suppressing the growth of pests such as boufra in the present invention is likely to generate pests such as boufra when water is accumulated in a resin molded product containing soluble glass or a silver-substituted inorganic ion exchanger. It can be applied by installing it in a pit with a pit or actually a puddle, or a puddle where pests such as boufras are already generated. The amount used is about 1 g per liter, but can be appropriately prepared in consideration of the lifetime. When the control agent is used in water with no water in and out, it can be expected that a control effect will appear if the silver ion concentration in the gradually eluted water is 10 ppb or more, calculated from the silver content of the control agent. In a real environment where water pests are a problem, it is difficult to imagine a situation where there is no water access. In this case, it is preferable to elute silver at a rate sufficient to catch up with the growth rate of pests even when water enters and exits, and for long-term control with as little control agent as possible for economic reasons. In this sense, the amount of the control agent to be added is preferably determined so that the silver elution concentration in water is 50 ppb / day or more and 5 ppm / day with respect to a fixed volume of water. . Specifically, if the elution amount of silver from the control agent is 0.1 (mg / L · g · day), the elution concentration of silver in an aqueous system with a volume of 1 L is from 50 ppb / day to 5 ppm / day. The amount of the control agent to be added is calculated to be 0.5 g to 50 g and can be used as a guide for the amount used in this way, but the amount used can be appropriately adjusted while observing the actual effect.
It is also preferable to use a combination of multiple types of pest control agents with different silver elution amounts, a control agent that elutes in a short period of time and exhibits an early control effect, and a control agent that gradually elutes and maintains a control effect over a long period of time By using together, the control can be made more effective.
○用途
本発明の有害生物防除方法の具体的用途であるボウフラ等の有害生物の発生場所を例示すると、プールや池や地面や石、植物の窪み、バケツ、空き缶、各種容器、雨水マスなどへの雨や結露などによる天然の水溜りまたは水道水の散水などによる水溜り、下水の滞留箇所など様々な水溜りが対象となる。本発明のボウフラ成長抑制効果はあらゆるボウフラの発生場所が対象である。本発明の有害生物防除方法の具体的用途として、雨水ます、雨水浸透ます、雨水貯留槽、雨水マンホール、側溝、側溝に設けられたます、浄化槽などの貯排水部材を挙げることができる。これらの部材には数日間以上水が滞留することがあり、滞留した水の中に発生、生息しようとする有害生物の防除が本発明の意図するものである。貯排水部材の材質は、ポリ塩化ビニル、ポリプロピレンなどのプラスチック、コンクリート、陶器など限定されない。貯排水部材が銀置換無機イオン交換体を含有する樹脂からなるものであってもよい。 ○ Applications Examples of the occurrence of pests such as bow flares, which are specific uses of the pest control method of the present invention, include pools, ponds, the ground, stones, plant depressions, buckets, empty cans, various containers, rainwater trouts, etc. Various puddles such as a puddle from natural water puddles due to rain and dew condensation, water pours from tap water, etc., and sewage stagnation are targeted. The effect of suppressing the growth of the bowfra of the present invention is intended for any place where a bowfra is generated. Specific examples of the pest control method of the present invention include rainwater troughs, rainwater infiltration troughs, rainwater storage tanks, rainwater manholes, side grooves, troughs provided in side grooves, and septic tanks. These members may retain water for several days or more, and it is intended by the present invention to control pests that are generated and live in the retained water. The material of the water storage / drainage member is not limited to plastics such as polyvinyl chloride and polypropylene, concrete, and pottery. The water storage / drainage member may be made of a resin containing a silver-substituted inorganic ion exchanger.
本発明の有害生物防除方法の具体的用途であるボウフラ等の有害生物の発生場所を例示すると、プールや池や地面や石、植物の窪み、バケツ、空き缶、各種容器、雨水マスなどへの雨や結露などによる天然の水溜りまたは水道水の散水などによる水溜り、下水の滞留箇所など様々な水溜りが対象となる。本発明のボウフラ成長抑制効果はあらゆるボウフラの発生場所が対象である。本発明の有害生物防除方法の具体的用途として、雨水ます、雨水浸透ます、雨水貯留槽、雨水マンホール、側溝、側溝に設けられたます、浄化槽などの貯排水部材を挙げることができる。これらの部材には数日間以上水が滞留することがあり、滞留した水の中に発生、生息しようとする有害生物の防除が本発明の意図するものである。貯排水部材の材質は、ポリ塩化ビニル、ポリプロピレンなどのプラスチック、コンクリート、陶器など限定されない。貯排水部材が銀置換無機イオン交換体を含有する樹脂からなるものであってもよい。 ○ Applications Examples of the occurrence of pests such as bow flares, which are specific uses of the pest control method of the present invention, include pools, ponds, the ground, stones, plant depressions, buckets, empty cans, various containers, rainwater trouts, etc. Various puddles such as a puddle from natural water puddles due to rain and dew condensation, water pours from tap water, etc., and sewage stagnation are targeted. The effect of suppressing the growth of the bowfra of the present invention is intended for any place where a bowfra is generated. Specific examples of the pest control method of the present invention include rainwater troughs, rainwater infiltration troughs, rainwater storage tanks, rainwater manholes, side grooves, troughs provided in side grooves, and septic tanks. These members may retain water for several days or more, and it is intended by the present invention to control pests that are generated and live in the retained water. The material of the water storage / drainage member is not limited to plastics such as polyvinyl chloride and polypropylene, concrete, and pottery. The water storage / drainage member may be made of a resin containing a silver-substituted inorganic ion exchanger.
○雨水ます
雨水ますは、本発明における代表的な貯排水部材である。雨水ますは通常底部に泥だめ部を備える。泥だめ部にはしばしば何日間も水が滞留し、有害生物が発生、生息する場所となることが少なくない。プラスチック製の雨水ますは、清掃を容易にするために泥だめ部に滞留した泥水を回収できるバケットを備えるものも多いが、バケット内にも泥だめ部と同様に水が滞留し、有害生物が発生、生息する場所となる。持ち手を備え、雨水ますからの出し入れが容易となっているバケットを備える雨水ますは特に好ましいものである。
バケットの形状は概ね円筒状で底部が上部よりやや径が小さくなっているものが標準的であるがこれに限定されない。バケットは孔やスリットがあいたものであってもよい。 ○ Rainwater Masashi Rainwater Mas is a typical storage and drainage member in the present invention. The rainwater usually has a muddy part at the bottom. Often, water stays in the mud pool for days, creating pests and habitats. Many plastic storm drains are equipped with a bucket that can collect the muddy water staying in the mud pool for easy cleaning. Occurrence and habitat. A rainwater basin having a handle and a bucket that is easy to remove from and into the stormwater is particularly preferred.
The shape of the bucket is generally cylindrical and the bottom is slightly smaller in diameter than the top, but is not limited to this. The bucket may have a hole or a slit.
雨水ますは、本発明における代表的な貯排水部材である。雨水ますは通常底部に泥だめ部を備える。泥だめ部にはしばしば何日間も水が滞留し、有害生物が発生、生息する場所となることが少なくない。プラスチック製の雨水ますは、清掃を容易にするために泥だめ部に滞留した泥水を回収できるバケットを備えるものも多いが、バケット内にも泥だめ部と同様に水が滞留し、有害生物が発生、生息する場所となる。持ち手を備え、雨水ますからの出し入れが容易となっているバケットを備える雨水ますは特に好ましいものである。
バケットの形状は概ね円筒状で底部が上部よりやや径が小さくなっているものが標準的であるがこれに限定されない。バケットは孔やスリットがあいたものであってもよい。 ○ Rainwater Masashi Rainwater Mas is a typical storage and drainage member in the present invention. The rainwater usually has a muddy part at the bottom. Often, water stays in the mud pool for days, creating pests and habitats. Many plastic storm drains are equipped with a bucket that can collect the muddy water staying in the mud pool for easy cleaning. Occurrence and habitat. A rainwater basin having a handle and a bucket that is easy to remove from and into the stormwater is particularly preferred.
The shape of the bucket is generally cylindrical and the bottom is slightly smaller in diameter than the top, but is not limited to this. The bucket may have a hole or a slit.
○貯排水設備
本発明の貯排水設備は、上記の有害生物防除剤および貯排水部材を備える。有害生物防除剤は、粒状である場合は、有害生物防除剤収納容器に収納されて使用されることが好ましい。有害生物防除剤収納容器は、水の出入りが自由であって有害生物防除剤から水に溶出した銀イオンは流出可能だが有害生物防除剤自体が流出しないように保持できる容器である。有害生物防除剤容器の形態をいくつか例示する。
(1)不織布製の袋状の容器
(2)不織布製の内袋と目の粗いネット製の外袋からなる複層の容器
(3)1個以上の細かい孔または幅の狭いスリットのあいたプラスチック製の容器
(4)不織布製の内袋を備えた「(3)」のプラスチック容器
有害生物防除剤容器は、有害生物防除剤が消費されてなくなったら廃棄する使い捨てのものでもよいし、有害生物防除剤を補充できる詰め替え可能のものでもよい。有害生物防除剤が消費されてなくなったら上記「(4)」において不織布製の内袋ごと新しいものに取り替えるという形態とすることもできる。プラスチックとしては、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ポリカーボネート、ポリエステル、ABSなどが挙げられる。 ○ Storage / drainage facility The storage / drainage facility of the present invention includes the pest control agent and the storage / drainage member. When the pest control agent is granular, it is preferably stored and used in a pest control agent storage container. The pest control container is a container that can freely enter and leave the water and can release silver ions eluted from the pest control agent but prevent the pest control agent itself from flowing out. Several forms of the pest control container are illustrated.
(1) Non-woven bag-like container (2) Multi-layer container consisting of non-woven inner bag and open net outer bag (3) Plastic with one or more fine holes or narrow slits (4) Plastic container of “(3)” with non-woven inner bag The pest control container may be a disposable one that is discarded when the pest control agent is no longer consumed, or a pest The refillable thing which can replenish a control agent may be used. When the pest control agent is no longer consumed, the inner bag made of nonwoven fabric may be replaced with a new one in the above “(4)”. Examples of the plastic include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, polyester, and ABS.
本発明の貯排水設備は、上記の有害生物防除剤および貯排水部材を備える。有害生物防除剤は、粒状である場合は、有害生物防除剤収納容器に収納されて使用されることが好ましい。有害生物防除剤収納容器は、水の出入りが自由であって有害生物防除剤から水に溶出した銀イオンは流出可能だが有害生物防除剤自体が流出しないように保持できる容器である。有害生物防除剤容器の形態をいくつか例示する。
(1)不織布製の袋状の容器
(2)不織布製の内袋と目の粗いネット製の外袋からなる複層の容器
(3)1個以上の細かい孔または幅の狭いスリットのあいたプラスチック製の容器
(4)不織布製の内袋を備えた「(3)」のプラスチック容器
有害生物防除剤容器は、有害生物防除剤が消費されてなくなったら廃棄する使い捨てのものでもよいし、有害生物防除剤を補充できる詰め替え可能のものでもよい。有害生物防除剤が消費されてなくなったら上記「(4)」において不織布製の内袋ごと新しいものに取り替えるという形態とすることもできる。プラスチックとしては、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ポリカーボネート、ポリエステル、ABSなどが挙げられる。 ○ Storage / drainage facility The storage / drainage facility of the present invention includes the pest control agent and the storage / drainage member. When the pest control agent is granular, it is preferably stored and used in a pest control agent storage container. The pest control container is a container that can freely enter and leave the water and can release silver ions eluted from the pest control agent but prevent the pest control agent itself from flowing out. Several forms of the pest control container are illustrated.
(1) Non-woven bag-like container (2) Multi-layer container consisting of non-woven inner bag and open net outer bag (3) Plastic with one or more fine holes or narrow slits (4) Plastic container of “(3)” with non-woven inner bag The pest control container may be a disposable one that is discarded when the pest control agent is no longer consumed, or a pest The refillable thing which can replenish a control agent may be used. When the pest control agent is no longer consumed, the inner bag made of nonwoven fabric may be replaced with a new one in the above “(4)”. Examples of the plastic include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, polyester, and ABS.
有害生物防除剤収納容器は貯排水部材に係止されることが好ましい。有害生物防除剤収納容器は雨水ますなどの貯排水部材に直接係止されてもよいし、雨水ますに付属する泥水回収用のバケットに係止されてもよい。
有害生物防除剤収納容器が着脱自在に貯排水部材に係止された貯排水設備は、メンテナンスが容易であり好ましいものである。有害生物防除剤収納容器が直接貯排水部材またはその付属部材に係止される構造であってもよいし、糸、紐、綱、鎖、ワイヤ、クリップ、釘、ボルトなどの係止用部材を介して係止される構造であってもよい。 The pest control agent storage container is preferably locked to the water storage / drainage member. The pesticide storage container may be directly locked to a storage and drainage member such as rainwater, or may be locked to a muddy water recovery bucket attached to the rainwater.
A storage / drainage facility in which a pesticide storage container is detachably locked to a storage / drainage member is preferable because it is easy to maintain. The pesticide storage container may have a structure that is directly locked to the storage / drainage member or its accessory member, or a locking member such as a thread, string, rope, chain, wire, clip, nail, bolt, etc. It may be a structure which is locked via.
有害生物防除剤収納容器が着脱自在に貯排水部材に係止された貯排水設備は、メンテナンスが容易であり好ましいものである。有害生物防除剤収納容器が直接貯排水部材またはその付属部材に係止される構造であってもよいし、糸、紐、綱、鎖、ワイヤ、クリップ、釘、ボルトなどの係止用部材を介して係止される構造であってもよい。 The pest control agent storage container is preferably locked to the water storage / drainage member. The pesticide storage container may be directly locked to a storage and drainage member such as rainwater, or may be locked to a muddy water recovery bucket attached to the rainwater.
A storage / drainage facility in which a pesticide storage container is detachably locked to a storage / drainage member is preferable because it is easy to maintain. The pesticide storage container may have a structure that is directly locked to the storage / drainage member or its accessory member, or a locking member such as a thread, string, rope, chain, wire, clip, nail, bolt, etc. It may be a structure which is locked via.
有害生物防除剤収納容器が着脱自在に係止された、泥水回収用のバケットを備えた雨水ますは、特にメンテナンスが容易なため好ましいものである。バケットに有害生物防除剤収納容器が着脱自在に係止された形態をいくつか例示する。複数の有害生物防除剤収納容器が1種以上の形態で係止されたものであってもよい。例えば下記の(3)および(4)を組み合わせることにより、水がバケット内に滞留している状態でも、バケット内に泥が堆積してバケットの高さを超える位置に水が滞留している状態でも効果的に有害生物を防除できる。
(1)バケットの底部の裏面に有害生物防除剤収納容器を係止する。
(2)バケットの底部の表面に有害生物防除剤収納容器を係止する。
(3)バケットの円筒状部分の内面に有害生物防除剤収納容器を係止する。
(4)バケットの持ち手部分から有害生物防除剤収納容器を吊るす形で係止する。 A rainwater basin equipped with a bucket for collecting muddy water, in which a pesticide storage container is detachably locked, is particularly preferable because of easy maintenance. Several forms in which a pest control agent storage container is detachably locked to a bucket are illustrated. A plurality of pesticide storage containers may be locked in one or more forms. For example, by combining the following (3) and (4), even when the water stays in the bucket, mud accumulates in the bucket and the water stays at a position exceeding the height of the bucket But it can effectively control pests.
(1) The pesticide storage container is locked to the back surface of the bottom of the bucket.
(2) Lock the pesticide storage container on the bottom surface of the bucket.
(3) Lock the pesticide storage container on the inner surface of the cylindrical portion of the bucket.
(4) The pesticide storage container is suspended from the handle portion of the bucket.
(1)バケットの底部の裏面に有害生物防除剤収納容器を係止する。
(2)バケットの底部の表面に有害生物防除剤収納容器を係止する。
(3)バケットの円筒状部分の内面に有害生物防除剤収納容器を係止する。
(4)バケットの持ち手部分から有害生物防除剤収納容器を吊るす形で係止する。 A rainwater basin equipped with a bucket for collecting muddy water, in which a pesticide storage container is detachably locked, is particularly preferable because of easy maintenance. Several forms in which a pest control agent storage container is detachably locked to a bucket are illustrated. A plurality of pesticide storage containers may be locked in one or more forms. For example, by combining the following (3) and (4), even when the water stays in the bucket, mud accumulates in the bucket and the water stays at a position exceeding the height of the bucket But it can effectively control pests.
(1) The pesticide storage container is locked to the back surface of the bottom of the bucket.
(2) Lock the pesticide storage container on the bottom surface of the bucket.
(3) Lock the pesticide storage container on the inner surface of the cylindrical portion of the bucket.
(4) The pesticide storage container is suspended from the handle portion of the bucket.
<作用>
銀イオンは銅イオンの数十分の1の低濃度でボウフラの成長抑制効果がある。主に屋外の水溜りで発生するボウフラを持続的に抑制するためには、流出等しない形態、酸性雨や紫外線などに対する耐久性、水が入れ替わっても継続して銀溶解性が発現する持続性を有するものでないと使用ができない。本発明の有害生物防除方法は、粒度と比重を調整することで流出を抑制し、耐久性に優れ、さらに銀イオンを持続的に溶出し続けるので、長期間にわたりボウフラの成長抑制効果を示し、蚊の発生を低減できる。 <Action>
Silver ions have an effect of suppressing the growth of boufra at a low concentration of several tens of copper ions. In order to continuously suppress bow flares that occur mainly in outdoor puddles, forms that do not run out, durability against acid rain, ultraviolet rays, etc., and sustainability that continuously develops silver solubility even when water is replaced. It can not be used unless it has. The pest control method of the present invention suppresses the outflow by adjusting the particle size and specific gravity, is excellent in durability, and further continues to elute silver ions continuously, thus showing the growth inhibitory effect of boufra over a long period of time, Reduces the occurrence of mosquitoes.
銀イオンは銅イオンの数十分の1の低濃度でボウフラの成長抑制効果がある。主に屋外の水溜りで発生するボウフラを持続的に抑制するためには、流出等しない形態、酸性雨や紫外線などに対する耐久性、水が入れ替わっても継続して銀溶解性が発現する持続性を有するものでないと使用ができない。本発明の有害生物防除方法は、粒度と比重を調整することで流出を抑制し、耐久性に優れ、さらに銀イオンを持続的に溶出し続けるので、長期間にわたりボウフラの成長抑制効果を示し、蚊の発生を低減できる。 <Action>
Silver ions have an effect of suppressing the growth of boufra at a low concentration of several tens of copper ions. In order to continuously suppress bow flares that occur mainly in outdoor puddles, forms that do not run out, durability against acid rain, ultraviolet rays, etc., and sustainability that continuously develops silver solubility even when water is replaced. It can not be used unless it has. The pest control method of the present invention suppresses the outflow by adjusting the particle size and specific gravity, is excellent in durability, and further continues to elute silver ions continuously, thus showing the growth inhibitory effect of boufra over a long period of time, Reduces the occurrence of mosquitoes.
以下、本発明を実施例により説明するが、本発明はこれに限定されるものではない。
銀または銅イオンの溶出量は、25℃の1Lの脱イオン水に試料を1g添加し、24時間静置保存したのちの水中の銀または銅イオンの濃度をICP(誘導結合プラズマ発光分析装置、具体的にはセイコー電子工業株式会社製 SPS7700型)にて測定し、試料1g、溶出水1リットルおよび1日あたりの濃度に規格化して溶出量(mg/g・L・日)として表示した。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
The elution amount of silver or copper ions was determined by adding 1 g of the sample to 1 L of deionized water at 25 ° C., and storing it for 24 hours, and then determining the concentration of silver or copper ions in the water by ICP (inductively coupled plasma emission spectrometer, Specifically, it was measured by Seiko Denshi Kogyo Co., Ltd. SPS7700 type), normalized to 1 g of sample, 1 liter of elution water and concentration per day, and displayed as elution amount (mg / g · L · day).
銀または銅イオンの溶出量は、25℃の1Lの脱イオン水に試料を1g添加し、24時間静置保存したのちの水中の銀または銅イオンの濃度をICP(誘導結合プラズマ発光分析装置、具体的にはセイコー電子工業株式会社製 SPS7700型)にて測定し、試料1g、溶出水1リットルおよび1日あたりの濃度に規格化して溶出量(mg/g・L・日)として表示した。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
The elution amount of silver or copper ions was determined by adding 1 g of the sample to 1 L of deionized water at 25 ° C., and storing it for 24 hours, and then determining the concentration of silver or copper ions in the water by ICP (inductively coupled plasma emission spectrometer, Specifically, it was measured by Seiko Denshi Kogyo Co., Ltd. SPS7700 type), normalized to 1 g of sample, 1 liter of elution water and concentration per day, and displayed as elution amount (mg / g · L · day).
<参考例>
表1に実施例および比較例で試験に供した試料1~13の明細を示した。
表1に示した試料1、2、5~9の溶解性ガラスは、ガラス原料調合物を1200℃で加熱溶融後、直径5mmの半球状の窪みを片面に配した金属製の冷却成形ローラーを用いて、冷却、成形し、得られたガラスを叩いて破砕したものを、さらにボ-ルミルにて1時間乾式破砕した後、目開き2.8mmの金網で微粉をふるい落として作成した。試料5は、得られた試料2をさらにボールミルを用いて微粉砕して得た。 <Reference example>
Table 1 shows the details of Samples 1 to 13 used in the tests in Examples and Comparative Examples.
The meltable glass of Samples 1, 2, 5 to 9 shown in Table 1 is a metal cooling molding roller in which a glass raw material preparation is heated and melted at 1200 ° C., and a hemispherical depression having a diameter of 5 mm is arranged on one side. The resulting glass was cooled and molded, and the obtained glass was crushed and crushed, and further dry-crushed with a ball mill for 1 hour, followed by pulverizing fine powder with a metal mesh having an opening of 2.8 mm. Sample 5 was obtained by further pulverizing Sample 2 obtained using a ball mill.
表1に実施例および比較例で試験に供した試料1~13の明細を示した。
表1に示した試料1、2、5~9の溶解性ガラスは、ガラス原料調合物を1200℃で加熱溶融後、直径5mmの半球状の窪みを片面に配した金属製の冷却成形ローラーを用いて、冷却、成形し、得られたガラスを叩いて破砕したものを、さらにボ-ルミルにて1時間乾式破砕した後、目開き2.8mmの金網で微粉をふるい落として作成した。試料5は、得られた試料2をさらにボールミルを用いて微粉砕して得た。 <Reference example>
Table 1 shows the details of Samples 1 to 13 used in the tests in Examples and Comparative Examples.
The meltable glass of
表1に示した試料3、4,10,11に用いた銀置換無機イオン交換体は、粉末状のリン酸ジルコニウムまたはA型ゼオライトをイオン交換水に10%添加し、さらに無機イオン交換体に対し銀で11%となるように硝酸銀水溶液を加え、1時間攪拌することで銀置換を行った。その後、ろ過、イオン交換水で水洗し、高温で乾燥し、粉砕することで試料3、4,10,11に用いた銀置換無機イオン交換体を得た。銀置換リン酸ジルコニウムの組成は、Ag0.45Na0.47H0.2Zr1.95Hf0.02(PO4)3・0.05H2Oであり、銀置換ゼオライトは0.15Ag2O・0.85Na2O・Al2O3・2.03SiO2・0.7H2Oであった。溶解性ガラスは組成によって溶解性などの物性が大きく異なるため、ガラス組成を表1に示した。なお、銀イオンを溶出する溶解性ガラスを銀ガラス、銅を溶出する溶解性ガラスを銅ガラスと呼ぶ。試料3、4、8、10は、得られた溶解性ガラスまたは銀置換無機イオン交換体粉末をナイロンまたはポリエチレン樹脂粉末と混合後、押し出し成形機で成形したものを直径3mm×4mm厚の円柱状にカットして作成した。試料12の硝酸銀は板状結晶の試薬を用いた。
The silver-substituted inorganic ion exchangers used for Samples 3, 4, 10, and 11 shown in Table 1 are obtained by adding 10% of powdered zirconium phosphate or zeolite A to ion-exchanged water, On the other hand, silver substitution was performed by adding an aqueous silver nitrate solution to 11% with silver and stirring for 1 hour. Thereafter, the silver-substituted inorganic ion exchanger used in Samples 3, 4, 10, and 11 was obtained by filtration, washing with ion-exchanged water, drying at high temperature, and pulverizing. The composition of the silver-substituted zirconium phosphate is Ag 0.45 Na 0.47 H 0.2 Zr 1.95 Hf 0.02 (PO 4 ) 3 · 0.05H 2 O, and the silver-substituted zeolite is 0.15 Ag 2 O · 0.85Na 2 O · Al. It was 2 O 3 .2.03SiO 2 .0.7H 2 O. The glass composition is shown in Table 1 because the soluble glass has greatly different properties such as solubility depending on the composition. In addition, the soluble glass which elutes silver ions is called silver glass, and the soluble glass which elutes copper is called copper glass. Samples 3, 4, 8, and 10 were obtained by mixing the obtained soluble glass or silver-substituted inorganic ion exchanger powder with nylon or polyethylene resin powder, and then molding it with an extrusion molding machine. Cut to create. As the silver nitrate of Sample 12, a plate crystal reagent was used.
<ボウフラの防除試験>
ポリカップに100mLの市販のミネラルウォーターを入れ、さらに参考例で示した各種防除材の試料を表3に示す量で各々入れた。各水溶液中に、ヒトスジシマカの孵化3時間後の1齢幼虫を10頭ずつ投入した。試験ポリカップは黒色容器内に入れ、26~27℃暗所保管とし、5日後に死亡虫数を測定した結果を表3に示した。試験後に市販のミネラルウォーター100mlを継ぎ足し、容器から水を溢れさせることで水の一部入れ替えを行った。なお、一部試料ではこの操作で容器からの水の溢れに伴って試料が容器外に漏出するのが確認されたが、漏出の防止は行わずそのままとした。この水入れ替え試験を毎日1回行い、計10回おこなった後に、再度ボウフラを加えた試験を同様に実施した結果を表3に示した。なお、試料をいれない試験も同様におこなって比較例9とした。 <Cutting test of bow-flas>
100 mL of commercially available mineral water was put into a polycup, and samples of various control materials shown in Reference Examples were added in the amounts shown in Table 3, respectively. Ten 1-year-old larvae 3 hours after hatching of Aedes albopictus were put into each aqueous solution. The test polycup was placed in a black container and stored in the dark at 26 to 27 ° C. The results of measuring the number of dead insects after 5 days are shown in Table 3. After the test, 100 ml of commercially available mineral water was added, and water was partially replaced by overflowing water from the container. In some samples, it was confirmed that the sample leaked out of the container due to the overflow of water from the container in this operation, but the leakage was not prevented and left as it was. Table 3 shows the results of carrying out this water exchange test once a day and carrying out a test in which a bowfra was added again after 10 times in total. In addition, the test which does not put a sample was done similarly, and it was set as the comparative example 9.
ポリカップに100mLの市販のミネラルウォーターを入れ、さらに参考例で示した各種防除材の試料を表3に示す量で各々入れた。各水溶液中に、ヒトスジシマカの孵化3時間後の1齢幼虫を10頭ずつ投入した。試験ポリカップは黒色容器内に入れ、26~27℃暗所保管とし、5日後に死亡虫数を測定した結果を表3に示した。試験後に市販のミネラルウォーター100mlを継ぎ足し、容器から水を溢れさせることで水の一部入れ替えを行った。なお、一部試料ではこの操作で容器からの水の溢れに伴って試料が容器外に漏出するのが確認されたが、漏出の防止は行わずそのままとした。この水入れ替え試験を毎日1回行い、計10回おこなった後に、再度ボウフラを加えた試験を同様に実施した結果を表3に示した。なお、試料をいれない試験も同様におこなって比較例9とした。 <Cutting test of bow-flas>
100 mL of commercially available mineral water was put into a polycup, and samples of various control materials shown in Reference Examples were added in the amounts shown in Table 3, respectively. Ten 1-year-
実施例1~4は、初期および水入れ替え後にもボウフラの成長を抑制する効果が極めて高かった。比較例2、3の銅ガラスおよび比較例8銅板は銀と比較し溶出濃度自体は高く設定してもボウフラの成長抑制効果は低かった。また、粉末状や水に沈まない比較例1、4、6、7は初期の効果は低くはないが、10回水入れ替え後の効果は著しく低下し、持続的な効果が得られなかった。
In Examples 1 to 4, the effect of suppressing the growth of boufra was extremely high even at the initial stage and after water replacement. The copper glass of Comparative Examples 2 and 3 and the copper plate of Comparative Example 8 were low in the effect of suppressing the growth of bow flares even when the elution concentration itself was set higher than that of silver. Further, Comparative Examples 1, 4, 6, and 7 that do not sink in powder form or water are not low in initial effect, but the effect after 10 times of water replacement is remarkably lowered, and a sustained effect cannot be obtained.
公定水分率が1より小さいポリエチレンに有効成分が分散された成形体からなる防除剤を使用した比較例4、5について、初期よりも10回水入れ替え後の効果が低下した現象は、成形体表面付近の有効成分である銀が初期に消費され、成形体の内部の銀は分散媒であるポリエチレンの疎水性(低い公定水分率)のために有効に利用されにくいことも影響しているかと推察される。公定水分率が1~10の範囲にあるナイロンに有効成分が分散された成形体からなる防除剤を使用した実施例3、4について、10回水入れ替え後も防除効果が持続した現象は、成形体表面付近の有効成分である銀が初期に消費されても、成形体の内部の銀が分散媒であるナイロンの親水性(高い公定水分率)のために有効に利用されやすいことも影響しているかと推察される。
Regarding Comparative Examples 4 and 5 using a control agent comprising a molded product in which an active ingredient is dispersed in polyethylene having an official moisture content of less than 1, the phenomenon in which the effect after water replacement 10 times lower than the initial level is the surface of the molded product It is inferred that silver, which is an active ingredient in the vicinity, is consumed in the initial stage, and that the silver inside the molded body is also difficult to use effectively due to the hydrophobicity (low official moisture content) of polyethylene as a dispersion medium. Is done. Regarding Examples 3 and 4 using a control agent made of a molded product in which an active ingredient is dispersed in nylon having an official moisture content in the range of 1 to 10, the phenomenon in which the control effect was maintained after 10 times of water replacement was Even if silver, which is an active ingredient near the body surface, is consumed at the initial stage, it is also affected by the fact that silver inside the molded body is easily used effectively due to the hydrophilicity (high official moisture content) of nylon, which is a dispersion medium. It is inferred that
<実施例6>雨水ますを使用したボウフラの発生実地試験
貯排水設備のモデルとして、図1に示す試験設備を準備した。雨水ます4に付属するバケット1(容量2リットル)の持ち手3に、有害生物防除剤7として5gの試料1を収納した、ナイロン製不織布からなる有害生物防除剤収納容器8を係止用糸9で吊り下げた。比較用に有害生物防除剤が収納されていない空の有害生物防除剤収納容器を吊り下げた試験設備も準備した。 <Example 6> On-site test of generation of bow flares using rainwater trough A test facility shown in Fig. 1 was prepared as a model of a storage and drainage facility. Thehandle 3 of the bucket 1 (capacity 2 liters) attached to the rainwater masu 4 contains 5 g of the sample 1 as the pest control agent 7, and the pest control storage container 8 made of a nylon nonwoven fabric is used as a locking thread. 9 was hung. For comparison, a test facility was also prepared in which an empty pesticide storage container without a pest control agent was suspended.
貯排水設備のモデルとして、図1に示す試験設備を準備した。雨水ます4に付属するバケット1(容量2リットル)の持ち手3に、有害生物防除剤7として5gの試料1を収納した、ナイロン製不織布からなる有害生物防除剤収納容器8を係止用糸9で吊り下げた。比較用に有害生物防除剤が収納されていない空の有害生物防除剤収納容器を吊り下げた試験設備も準備した。 <Example 6> On-site test of generation of bow flares using rainwater trough A test facility shown in Fig. 1 was prepared as a model of a storage and drainage facility. The
上記バケット1に約2リットルの水を入れ、屋外の日陰に設置した雨水ますに装着した。雨により貯水の流出や異物の混入などがあったが、約3ヶ月に渡り屋外でそのまま放置した。3ヶ月間に2週間に一度バケット内のボウフラの発生を観察した結果、試料1を使用しないバケットにはボウフラの発生が3度確認されたが、試料1を入れたバケットでボウフラの発生は1度も確認できなかった。
Approx. 2 liters of water was put into the above bucket 1 and attached to a rainwater basin installed in the shade outdoors. The rain caused storage water to flow out and foreign matter, but it was left outdoors for about 3 months. As a result of observing the occurrence of a bowler in the bucket once every two weeks in three months, the occurrence of a bowler was confirmed three times in a bucket not using the sample 1, but the occurrence of a bowler was 1 in the bucket containing the sample 1. I could not confirm it again.
本発明の防除方法および、防除剤を備えた貯排水設備は、貯排水設備に滞留する水中に発生、生息する有害生物を防除することができるので、人畜の衛生的な生活環境を確保することができ、有害生物の媒介する伝染病を予防することができる。
The control method of the present invention and the storage and drainage equipment equipped with the control agent can control pests that are generated and inhabit in the water staying in the storage and drainage equipment, and thus ensure a sanitary living environment for human livestock. Can prevent pest-borne infectious diseases.
1 バケット
2 バケット本体
3 持ち手
4 雨水ます
5 ます本体
6 点検筒
7 有害生物防除剤
8 有害生物防除剤収納容器
9 係止部材 DESCRIPTION OF SYMBOLS 1Bucket 2 Bucket main body 3 Handle 4 Rainwater masu 5 Mass main body 6 Inspection cylinder 7 Pest control agent 8 Pest control agent storage container 9 Locking member
2 バケット本体
3 持ち手
4 雨水ます
5 ます本体
6 点検筒
7 有害生物防除剤
8 有害生物防除剤収納容器
9 係止部材 DESCRIPTION OF SYMBOLS 1
Claims (14)
- 有害生物防除剤として、銀イオンを水に溶出させることのできる溶解性ガラス、または公定水分率が1~10の樹脂に銀置換無機イオン交換体を含有させた樹脂成形体、の中から選択される少なくとも一つを用い、粒径が1mm以上の有害生物防除剤を水と接触させることにより、水中の有害生物を防除する、有害生物防除方法。 The pest control agent is selected from a soluble glass that can elute silver ions into water, or a resin molded product containing a silver-substituted inorganic ion exchanger in a resin having an official moisture content of 1 to 10. A pest control method for controlling pests in water by bringing a pest control agent having a particle diameter of 1 mm or more into contact with water.
- 有害生物防除剤からの、水中への銀溶出量が0.05mg/g・L・日以上、5mg/g・L・日以下である、請求項1に記載の有害生物防除方法。 The method for controlling pests according to claim 1, wherein the amount of silver elution into the water from the pest control agent is 0.05 mg / g · L · day or more and 5 mg / g · L · day or less.
- 水中への銀溶出濃度が50ppb/日以上5ppm/日以下である、請求項1または2に記載の有害生物防除方法。 The pest control method according to claim 1 or 2, wherein the silver elution concentration in water is 50 ppb / day or more and 5 ppm / day or less.
- 有害生物防除剤が水中に沈むものであり、有害生物防除剤を水中に投入することにより水中の有害生物を防除する、請求項1~3のいずれかに記載の有害生物防除方法。 The pest control method according to any one of claims 1 to 3, wherein the pest control agent is submerged in water, and the pest control agent in the water is controlled by introducing the pest control agent into the water.
- 有害生物防除剤が、比重1.05以上5以下であり、なおかつ比表面積が3cm2/g~500cm2/gの粒状または成形体である、請求項1~4のいずれかに記載の有害生物防除方法。 The pest according to any one of claims 1 to 4, wherein the pest control agent is a granule or a molded article having a specific gravity of 1.05 to 5 and a specific surface area of 3 cm 2 / g to 500 cm 2 / g. Control method.
- 水中の有害生物がボウフラである、請求項1~5のいずれかに記載の有害生物防除方法。 The method for controlling pests according to any one of claims 1 to 5, wherein the pests in the water are boufra.
- 請求項1~6のいずれかに記載の、有害生物防除方法を用いた貯排水部材を備えた貯排水設備。 A storage and drainage facility comprising a storage and drainage member using the pest control method according to any one of claims 1 to 6.
- 水の出入りが自由であって有害生物防除剤から水に溶出した銀イオンは流出可能だが有害生物防除剤自体が流出しないように保持できる有害生物防除剤収納容器を備え、有害生物防除剤が有害生物防除剤収納容器に収納された、請求項7に記載の貯排水設備。 Silver ions eluted into the water from the pest control agent are free to enter and exit, but a pest control agent storage container that can hold the pest control agent so that it does not flow out is provided, and the pest control agent is harmful The storage and drainage facility according to claim 7, which is stored in a biocontrol agent storage container.
- 有害生物防除剤収納容器は、有害生物防除剤の交換または補充が可能な構造を有する請求項8に記載の貯排水設備。 The storage and drainage facility according to claim 8, wherein the pest control agent storage container has a structure capable of replacing or replenishing the pest control agent.
- 有害生物防除剤収納容器が、着脱自在に貯排水部材に係止された請求項8または9に記載の貯排水設備。 10. The storage / drainage facility according to claim 8 or 9, wherein the pest control container is detachably locked to the storage / drainage member.
- 貯排水部材が雨水ますである請求項7~10のいずれかに記載の貯排水設備。 The storage and drainage facility according to any one of claims 7 to 10, wherein the storage and drainage member is rainwater.
- 雨水ますは、底部に溜まる滞留物排出用バケットを備えるものであり、
有害生物防除剤収納容器が、着脱自在にバケットに係止された請求項11に記載の貯排水設備。 The rainwater masu is equipped with a stagnant discharge bucket that collects at the bottom,
The storage / drainage facility according to claim 11, wherein the pesticide storage container is detachably locked to the bucket. - 有害生物防除剤収納容器を着脱自在に係止できる、請求項12に記載の貯排水設備に使用されるバケット。 The bucket used for the storage and drainage facility according to claim 12, wherein the pesticide storage container can be detachably locked.
- 請求項13に記載のバケットを備え、請求項12に記載の貯排水設備に使用される雨水ます。
It is provided with the bucket according to claim 13, and rainwater used in the storage and drainage facility according to claim 12.
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JP2010289070A JP5631194B2 (en) | 2010-12-27 | 2010-12-27 | How to control Bow Fra |
JP2010289069A JP5634857B2 (en) | 2010-12-27 | 2010-12-27 | A storage and drainage facility equipped with a bowfla control agent |
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US11891788B1 (en) * | 2021-02-23 | 2024-02-06 | Executive High Reach Maintenance, Inc. | Sewer cleanout cap and related methods |
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