WO2018038091A1 - Composite-type solid water treatment product - Google Patents

Composite-type solid water treatment product Download PDF

Info

Publication number
WO2018038091A1
WO2018038091A1 PCT/JP2017/029898 JP2017029898W WO2018038091A1 WO 2018038091 A1 WO2018038091 A1 WO 2018038091A1 JP 2017029898 W JP2017029898 W JP 2017029898W WO 2018038091 A1 WO2018038091 A1 WO 2018038091A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid
water treatment
agent
treatment product
isothiazolin
Prior art date
Application number
PCT/JP2017/029898
Other languages
French (fr)
Japanese (ja)
Inventor
隆志 居安
靖 村野
雄介 的場
Original Assignee
栗田工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 栗田工業株式会社 filed Critical 栗田工業株式会社
Priority to CN201780038585.8A priority Critical patent/CN109415233B/en
Priority to SG11201811348WA priority patent/SG11201811348WA/en
Priority to MYPI2018002634A priority patent/MY198348A/en
Publication of WO2018038091A1 publication Critical patent/WO2018038091A1/en
Priority to PH12018502690A priority patent/PH12018502690B1/en

Links

Images

Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/50Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/76Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F25/00Component parts of trickle coolers
    • F28F25/02Component parts of trickle coolers for distributing, circulating, and accumulating liquid

Definitions

  • the present invention is a water treatment product used in various water systems such as industrial water, cooling water, cold / hot water, boiler water, process water, waste water, etc., and is a composite solid water for simultaneously using a plurality of types of water treatment agents. Regarding processing products.
  • Patent Document 1 An active ingredient can be gradually released into an aqueous system.
  • a solid water treatment agent having the following has been proposed.
  • the water treatment agent in the various aqueous systems it is sometimes more effective to use two or more types in combination than to use only one type of compound as an active ingredient.
  • a halogenated hydantoin compound (halogen oxidant) and an isothiazolone compound are used as liquid water treatment agents in predetermined process water. Pumping is described.
  • the combined use of the halogen-based oxidizing agent and the isothiazolone-based compound provides a bactericidal action, particularly an excellent bactericidal action against Legionella spp.
  • JP2015-93260A Japanese Patent Laid-Open No. 11-47755 JP 2007-31850 A
  • halogen-based oxidizing agents particularly chlorine-based oxidizing agents, and isothiazolone-based compounds generate chlorine gas remarkably when they are brought into direct contact with each other. Therefore, even when it is formulated as a solid water treatment agent as described in Patent Document 1, it is difficult to make a single agent. Further, from the viewpoint of safety, it is not preferable to make direct contact even during use.
  • the present invention has been made in order to solve the above-mentioned problems, and it is possible to safely use a halogen-based oxidizing agent and an active ingredient having reactivity therewith, and to have an excellent drug effect by using these active ingredients in combination. It is an object of the present invention to provide a composite type solid water treatment product that can maintain the water resistance and is excellent in handling convenience.
  • the composite solid water treatment product of the present invention is a container in which a halogen-based oxidizing agent that is a water treatment agent and an organic disinfectant having reactivity therewith are formulated, and each solid agent can be used in a predetermined form.
  • a halogen-based oxidizing agent that is a water treatment agent and an organic disinfectant having reactivity therewith
  • each solid agent can be used in a predetermined form.
  • the drug effect of both solid preparations can be exhibited safely and at the same time easy to handle.
  • a solid water treatment product which is used after being eluted in the water to be treated, and is a halogenated oxidant solid agent (A) containing a halogenated hydantoin compound as an active ingredient, and reactivity with the halogenated oxidant.
  • a solid agent (B) containing an organic disinfectant having, and one or two or more elution containers for containing the solid agent (A) and the solid agent (B) without contacting each other, Composite type solid water treatment product.
  • the halogenated hydantoin compound is at least one selected from 1-bromo-3-chloro-5,5-dimethylhydantoin and 1,3-dichloro-5,5-dimethylhydantoin.
  • the isothiazoline-based compound may be 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-methyl-4-isothiazoline.
  • the halogen-containing oxidizing agent contains 1-bromo-3-chloro-5,5-dimethylhydantoin as an active ingredient, and the organic fungicide contains 5-chloro-2-methyl-4-
  • the composite solid water treatment product according to any one of [1] to [4] above, which contains isothiazolin-3-one.
  • the solid agent (B) contains one or more selected from triazole compounds, phosphonic acid compounds, and sulfamic acid compounds.
  • the solid agent (A) and the solid agent (B) are accommodated in separate elution containers, and each elution container is disposed in a cooling tower, and the container main body and the container main body
  • the container main body includes one or more storage chambers that store the solid agent (A) or (B), which is a solid drug, and a partition wall that divides the interior into a non-storage chamber that does not store the solid drug.
  • the composite solid water treatment product according to any one of [1] to [9], wherein the product has one or more partition wall communication passages through which water can flow.
  • the halogen-based oxidizing agent and the active ingredient having reactivity therewith can be safely maintained and the excellent drug effect by the combined use of these active ingredients can be maintained.
  • the composite solid water treatment product of the present invention is also excellent in convenience in handling reactive chemicals at the same time.
  • the composite type solid water treatment product of the present invention is a solid water treatment product comprising two kinds of solid agents and using these solid agents by eluting them into the water to be treated.
  • a solid agent (A) of a halogen-based oxidizing agent containing a halogenated hydantoin-based compound as an active ingredient a solid agent (B) containing an organic disinfectant having reactivity with the halogen-based oxidizing agent, and the solid agent It has 1 or 2 or more elution containers which accommodate (A) and the said solid agent (B), without mutually contacting.
  • Solid agent (A) is a halogen-based oxidant, and has an effect of sterilization and slime suppression in the water treatment agent.
  • the halogen-based oxidant those containing a halogenated hydantoin compound as an active ingredient are used.
  • the halogenated hydantoin-based compound is a solid organic halogen-based oxidizing agent, and releases an active halogen having strong oxidizing power when in contact with water. Further, from the viewpoint of solubility in water and the like, it is suitable for releasing active halogen continuously over a long period of time.
  • the halogen-based oxidizing agents that are commercially available as sustained-release tablets include calcium hypochlorite, sodium chlorite, dichloroisocyanuric acid, trichloroisocyanuric acid, and the like as active ingredients.
  • halogenated hydantoin compound as an active ingredient have a relatively low elution rate. From this, it can be said that the halogenated hydantoin compound is most suitable from the viewpoint of maintaining an excellent drug effect by the combined use with a solid agent containing an organic fungicide. Moreover, the halogenated hydantoin compounds are preferable from the viewpoint of safety during handling because they generate relatively little odor when they come into contact with water.
  • halogenated hydantoin compound examples include 1-bromo-3-chloro-5,5-dimethylhydantoin (hereinafter abbreviated as BCDMH), 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1-bromo-3-chloro-5,5-diethylhydantoin, 1,3-dichloro-5,5-diethylhydantoin, 1-bromo-3-chloro-5 -Methyl-5-ethylhydantoin and the like. These may be used alone or in combination of two or more. Of these, BCDMH and 1,3-dichloro-5,5-dimethylhydantoin are preferred from the viewpoints of balance with the solid agent (B) of the dissolution rate when contacted with water and availability.
  • BCDMH 1-bromo-3-chloro-5,5-dimethylhydan
  • the form of the halogen-based oxidizing agent as described above is not particularly limited, but is in the form of tablets or granules such as pellets and tablets from the viewpoint of ease of adjustment of the amount used and ease of handling. It is preferable that the tablet is more preferable from the viewpoint of workability and the like when being accommodated in the container.
  • the manufacturing method of a tablet is not specifically limited, It can manufacture by a well-known method. Usually, it is produced by pressure molding using additives such as excipients and binders. The dissolution rate of the tablet in the water to be treated can be adjusted by adjusting the type and amount of the excipient and binder.
  • a commercial item can also be used as a solid agent (A).
  • the solid agent (A) has a content of the halogen-based oxidant so that effective chlorine (Cl 2 ) In terms of conversion, it is preferably 10% by mass or more, more preferably 30 to 90% by mass, and still more preferably 40 to 70% by mass.
  • the concentration of effective halogen (Cl 2 equivalent) in the water to be treated by the solid agent (A) is preferably 0.1 mg / L or more, more preferably 0.1 to 5 mg. / L, more preferably 0.1 to 2 mg / L.
  • Solid agent (B) contains an organic disinfectant having reactivity with the halogen-based oxidizing agent.
  • the organic disinfectant has reactivity with the halogen-based oxidizing agent. Since the reaction with the halogen-based oxidant generates a toxic halogen-based substance such as chlorine gas, it is difficult to mix with the halogen-based oxidant to form a single agent. For this reason, in order to formulate an organic disinfectant, it is necessary to use a separate agent from the halogen-based oxidizing agent. Therefore, in the present invention, the solid agent (B) is formulated separately from the solid agent (A).
  • the active ingredient in the organic fungicide preferably contains an isothiazoline compound from the viewpoint of sterilization performance when used in combination with a halogen oxidizing agent.
  • the isothiazoline compound include 5-chloro-2-methyl-4-isothiazolin-3-one (hereinafter abbreviated as Cl-MIT), 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-methyl-4-isothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2- Ethyl-4-isothiazolin-3-one, 5-chloro-2-t-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4, Examples include 5-dichloro-2-cyclohexyl-4-isothiazolin
  • Cl-MIT is preferred from the viewpoints of solubility in water, sterilization performance, and availability.
  • a solid agent (A) of a halogen-based oxidizing agent containing BCDMH as an active ingredient, and a solid agent (B) containing an organic fungicide containing Cl-MIT as an active ingredient is preferable.
  • the active ingredient is Cl-MIT
  • the elution amount of the organic fungicide solid agent (B), which is an active ingredient is the halogen-based oxidizing agent of the solid agent (A).
  • the concentration of Cl-MIT (unit: mg / L) in the treated water is higher than the effective halogen (Cl 2 equivalent) concentration (unit: mg / L) of BCDMH in the treated water. It is preferably 0.00001 to 100 times, more preferably 0.01 to 30 times, and still more preferably 0.1 to 1 times.
  • the concentration of Cl-MIT in the water to be treated is preferably 0.0001 to 5 mg / L, more preferably 0.001 to 3 mg / L, and still more preferably 0.001 to 2 mg / L.
  • Solid agent (B) may contain other known compounds used from the viewpoint of anticorrosion and scale prevention in the water treatment agent in addition to the organic fungicide.
  • flocculants composed of triazole compounds, phosphonic acid compounds, sulfamic acid compounds, amethrin, 2,2-dibromo-3-nitrilopropionamide, bronopol, zinc pyrithione, thiabendazole, acrylic acid and maleic acid based low molecular weight polymers Etc. These may be one type or two or more types. However, the addition amount of these compounds shall be the range which does not prevent the bactericidal action by solid agent (A) and (B).
  • the form of the solid agent (B) is not particularly limited in the same manner as the form of the solid agent (A), but from the viewpoint of ease of adjustment of the amount used, ease of handling, and the like, pellets and tablets From the viewpoints of workability and the like when accommodated in a container, the tablet is more preferable.
  • the manufacturing method of a tablet is not specifically limited, It can manufacture by a well-known method. Usually, it is produced by pressure molding using additives such as excipients and binders. The dissolution rate of the tablet in the water to be treated can be adjusted by adjusting the type and amount of the excipient and binder. As these additives, for example, magnesium stearate, silica, magnesium oxide and the like are used.
  • a commercial item can also be used as a solid agent (B) which uses the above organic type fungicides as an active ingredient.
  • the solid agent (B) preferably has an organic fungicide content of 1 to 40% by weight, more preferably 2 to 35% by weight, from the viewpoint of allowing the organic fungicide to have an appropriate dissolution rate. %, More preferably 5 to 30% by mass.
  • the container which accommodates the solid agent (A) and the solid agent (B) can accommodate both without contacting each other.
  • a toxic halogen-based substance such as chlorine gas is generated as described above. Therefore, when eluting the solid agent (A) and the solid agent (B) into the water to be treated, the solid agent (A) and the solid agent (B) are accommodated in a container so that they can be kept out of contact with each other.
  • the solid agent (A) and the solid agent (B) may be accommodated in one container having a partition, It may be contained in two or more separate containers.
  • the drug effect of each active ingredient can be maintained for a long time rather than being put into the water to be treated in an exposed state.
  • drug effects such as synergistic bactericidal action by the combined use of both can be maintained.
  • the composite solid water treatment product can be suitably used for water treatment of cooling water in a cooling tower.
  • the solid agent (A) and the solid agent (B) are accommodated in separate elution containers, and the elution containers are arranged in a cooling tower.
  • the form of the elution container is not particularly limited, but for example, the form shown in FIGS. 1 and 2 is preferable.
  • the elution containers 10 and 20 shown in FIGS. 1 and 2 include a container body 1 and a partition wall 2 that partitions the inside of the container body 1.
  • the inside of the container main body 1 includes one or more storage chambers 3 for storing the solid medicines 11 and 21 (solid agent (A) or (B)) and a non-storage chamber that does not store the solid water treatment agent by the partition wall 2. It is divided into four.
  • the container main body 1 has one or more container communication paths 5 through which cooling water can flow between the outside of the container main body 1 and the non-accommodating chamber 4.
  • the partition wall 2 has one or more partition wall communication paths 6 through which cooling water can flow between the storage chamber 3 and the non-storage chamber 4.
  • the elution container 20 shown in FIG. 2 has two storage chambers 3 for storing the solid medicine 21. Further, the container communication path 5 is formed so that the elution container 20 has a smaller total cross-sectional area of the flow channel than the elution container 10 and is suitable for the case where it is desired to further suppress the elution rate of the solid drug. Structure.
  • the shape of the container body 1 and the shape, arrangement, number, and the like of the storage chamber 3, the non-storage chamber 4, the container communication path 5, and the partition wall communication path 6 are only those described in FIGS. It is not limited to.
  • the solid agents (A) and (B) to be used can be appropriately determined according to the form, bactericidal performance, elution rate, the arrangement environment of the composite solid water treatment product in the cooling tower, and the like. It is preferable that the elution container is transparent so that the accommodation state of the solid agent (A) or (B) can be visually observed from the outside. Further, from the viewpoint of ease of handling, cost, etc., it is preferably made of plastic.
  • FIG. 3 shows an example of a composite solid water treatment product in which the elution container 10 shown in FIG. 1 and the elution container 20 shown in FIG.
  • solid agent (A) and (B) are tablets of a predetermined size and solid agent (A) is more easily eluted than solid agent (B) when contacted with water
  • the solid agent (B) is accommodated in the elution vessel 10 and the solid agent (A) is accommodated in the elution vessel 20 that can more easily suppress the elution rate.
  • the composite-type solid water treatment product shown in FIG. 3 is configured so that the elution containers 10 and 20 can be fitted into the frame 30 and both can be held.
  • FIG. 3 shows an example of a composite solid water treatment product in which the elution container 10 shown in FIG. 1 and the elution container 20 shown in FIG.
  • the frame body 30 is preferably made of foamed plastic such as polystyrene foam. Thereby, it is easy to carry a lightweight and complex type solid water treatment product as one body, and it can also be used by floating in the cooling water pit in the cooling tower.
  • the cooling water flows into the non-accommodating chamber 4 through the container communication path 5, and from the inside of the non-accommodating chamber 4 through the partition wall flow path 6 to the accommodating chamber 3. Flows in.
  • the solid medicines 11 and 21 (solid agent (A) or (B)) in the storage chamber 3 are eluted in contact with the cooling water that has flowed in.
  • Each cooling water (eluent) from which the solid drug 11 or 21 is eluted flows out of the elution container through the container communication path 5.
  • solid agent (A) and (B) can be used together in the state which kept the fixed space
  • Sustainability evaluation test is for elution containing a halogen-based oxidant on a silencing mat in a countercurrent (round) open cooling tower with a cooling capacity of 20 USRT, operating for 8 hours / day, and a cooling water temperature of 30 ° C. This was done by placing the container, taking out the halogen-based oxidant remaining in the container every predetermined number of elapsed days, measuring its weight, and confirming the change in the residual weight with the passage of days. .
  • the details of the container and the halogen-based oxidizing agent used are as follows.
  • container A container made of polypropylene of the type having two storage chambers as shown in FIG. 2. External size: major axis 12.7 cm, minor axis 8.0 cm Container communication path 5 (however, the position is partially different from the description in FIG.
  • BCDMH is excellent in sustained release, as a halogen-based oxidizing agent, the balance of dissolution rate for maintaining the drug effect by the combined use with a solid agent containing an active ingredient having reactivity therewith. It can be said that it is preferable from the viewpoint of achieving the above.
  • the bactericidal rate was calculated
  • the bactericidal rate when only Cl-MIT (0.5 mg / L) was added was 97.4%, whereas BCDMH (1 mg / L) and Cl-MIT (0.5 ml / L) ) was used in combination, the sterilization rate was 100%. From this, the improvement effect of the bactericidal action against Legionella spp. By the combined use of BCDMH and Cl-MIT was confirmed.

Abstract

A composite-type solid water treatment product is provided which safely uses a halogen oxidizing agent and an active component that has reactivity thereto, which can sustain the excellent drug effect obtained by joint use of these active components, and which is very convenient to handle. In this solid water treatment product, used by eluting into water being treated, a solid preparation of a halogen oxidizing agent (A) which has a halogenated hydantoin compound as the active component, and a solid preparation (B) which contains an organic fungicide that has reactivity with the aforementioned halogen oxidizing agent are housed inside of an elution container without contacting one another.

Description

複合型固形水処理製品Combined solid water treatment products
 本発明は、工業用水や冷却水、冷温水、ボイラ水、工程水、排水等の各種水系において用いられる水処理製品であって、複数種の水処理剤を同時使用するための複合型固形水処理製品に関する。 The present invention is a water treatment product used in various water systems such as industrial water, cooling water, cold / hot water, boiler water, process water, waste water, etc., and is a composite solid water for simultaneously using a plurality of types of water treatment agents. Regarding processing products.
 工業用水や冷却水、冷温水、ボイラ水、工程水、排水等の各種水系では、これらの水系で用いられている金属部材の腐食防止及びスケール防止、また、水系内での細菌や藻類等の微生物の発生防止等のために、防食剤やスケール防止剤、殺菌剤、殺藻剤等の種々の水処理剤が使用されている。
 このような目的で使用される水処理剤は、多くの場合、長期間にわたって高い薬剤効果を持続できることが求められる。このため、通常、液体水処理剤を、薬注ポンプ等を用いて被処理水系に連続的に注入することにより、薬剤効果を持続させる方法が採用されている。
In various water systems such as industrial water, cooling water, cold / hot water, boiler water, process water, waste water, etc., corrosion prevention and scale prevention of metal members used in these water systems, bacteria and algae in the water system, etc. In order to prevent the generation of microorganisms, various water treatment agents such as anticorrosives, scale inhibitors, bactericides, and algicides are used.
Water treatment agents used for such purposes are often required to be able to maintain a high drug effect over a long period of time. For this reason, the method of maintaining a chemical | medical agent effect is normally employ | adopted by continuously inject | pouring a liquid water processing agent into a to-be-processed water system using a chemical injection pump etc.
 しかしながら、設備上、薬注ポンプ等による水処理剤の注入が困難な施設もあり、このような場合には、薬剤効果を持続させるための他の手段が必要である。
 また、薬注ポンプ等の装置を設置することができる場合であっても、例えば、小型の冷却塔においては、これらの装置を設置することは、コストや装置のメンテナンス等の負担が大きい。
However, in some facilities, it is difficult to inject the water treatment agent with a chemical pump or the like, and in such a case, another means for maintaining the drug effect is necessary.
Even when a device such as a chemical injection pump can be installed, for example, in a small cooling tower, installing these devices has a large burden of cost and device maintenance.
 したがって、より簡便な手段で薬剤効果を持続できる方法が求められており、その手段の1つとして、例えば、特許文献1において、有効成分を水系中に徐々に放出することができる、徐放性を有する固形水処理剤が提案されている。 Therefore, there is a demand for a method that can sustain the drug effect by a simpler means. As one of the means, for example, in Patent Document 1, an active ingredient can be gradually released into an aqueous system. A solid water treatment agent having the following has been proposed.
 一方、前記各種水系における水処理剤としては、有効成分として1種類の化合物のみを用いるよりも、2種類以上を組み合わせて使用する方が、より効果的である場合がある。例えば、特許文献2及び3には、微生物の繁殖によるスライムの発生を抑制する観点から、ハロゲン化ヒダントイン系化合物(ハロゲン系酸化剤)とイソチアゾロン系化合物とを液体水処理剤として所定の工程水にポンプで注入することが記載されている。
 このように、ハロゲン系酸化剤とイソチアゾロン系化合物との併用は、殺菌作用、特に、レジオネラ属菌に対して優れた殺菌作用が得られる。
On the other hand, as the water treatment agent in the various aqueous systems, it is sometimes more effective to use two or more types in combination than to use only one type of compound as an active ingredient. For example, in Patent Documents 2 and 3, from the viewpoint of suppressing slime generation due to the growth of microorganisms, a halogenated hydantoin compound (halogen oxidant) and an isothiazolone compound are used as liquid water treatment agents in predetermined process water. Pumping is described.
Thus, the combined use of the halogen-based oxidizing agent and the isothiazolone-based compound provides a bactericidal action, particularly an excellent bactericidal action against Legionella spp.
特開2015-93260号公報JP2015-93260A 特開平11-47755号公報Japanese Patent Laid-Open No. 11-47755 特開2007-319850号公報JP 2007-31850 A
 このため、ハロゲン系酸化剤とイソチアゾロン系化合物との両化合物を別個に添加するのではなく、一剤化して用いることができれば、取り扱い上、便利である。
 しかしながら、ハロゲン系酸化剤、特に塩素系酸化剤と、イソチアゾロン系化合物とは、直に接触させると塩素ガスを著しく発生するため、使用前に一剤化することは好ましくない。したがって、上記特許文献1に記載されているような固形水処理剤として製剤化する場合においても、一剤化することは困難である。
 さらに、安全性の観点からは、使用時においても、直に接触することは好ましくない。
For this reason, it is convenient in handling if both the halogen-based oxidizing agent and the isothiazolone-based compound can be used as one agent rather than separately added.
However, halogen-based oxidizing agents, particularly chlorine-based oxidizing agents, and isothiazolone-based compounds generate chlorine gas remarkably when they are brought into direct contact with each other. Therefore, even when it is formulated as a solid water treatment agent as described in Patent Document 1, it is difficult to make a single agent.
Further, from the viewpoint of safety, it is not preferable to make direct contact even during use.
 したがって、2種以上の有効成分が、反応性を有し、取り扱い時に危険な生成物を生じるような場合であっても、これらの有効成分の併用による優れた薬剤効果を持続させることができ、かつ、取り扱い上の利便性にも優れた水処理製品が求められている。 Therefore, even when two or more kinds of active ingredients are reactive and produce dangerous products during handling, it is possible to maintain an excellent drug effect by the combined use of these active ingredients, There is also a need for water treatment products that are excellent in handling convenience.
 本発明は、上記のような課題を解決するためになされたものであり、ハロゲン系酸化剤及びこれと反応性を有する有効成分を安全に、かつ、これらの有効成分の併用による優れた薬剤効果を持続させることができ、しかも、取り扱い上の利便性にも優れた複合型固形水処理製品を提供することを目的とするものである。 The present invention has been made in order to solve the above-mentioned problems, and it is possible to safely use a halogen-based oxidizing agent and an active ingredient having reactivity therewith, and to have an excellent drug effect by using these active ingredients in combination. It is an object of the present invention to provide a composite type solid water treatment product that can maintain the water resistance and is excellent in handling convenience.
 本発明の複合型固形水処理製品は、水処理剤であるハロゲン系酸化剤及びこれとの反応性を有する有機系殺菌剤をそれぞれ製剤化し、各固形剤を所定の態様で使用できるような容器と組み合わせることによって、両固形剤の薬剤効果を安全に発揮させることができ、同時に取り扱いやすいものとすることができるものである。 The composite solid water treatment product of the present invention is a container in which a halogen-based oxidizing agent that is a water treatment agent and an organic disinfectant having reactivity therewith are formulated, and each solid agent can be used in a predetermined form. In combination, the drug effect of both solid preparations can be exhibited safely and at the same time easy to handle.
 すなわち、本発明は、以下の[1]~[10]を提供するものである。
[1]被処理水中に溶出させて使用する固形水処理製品であって、ハロゲン化ヒダントイン系化合物を有効成分とするハロゲン系酸化剤の固形剤(A)、前記ハロゲン系酸化剤との反応性を有する有機系殺菌剤を含む固形剤(B)、及び前記固形剤(A)と前記固形剤(B)とを互いに接触することなく収容する1つ又は2つ以上の溶出用容器を有する、複合型固形水処理製品。
[2]前記ハロゲン化ヒダントイン系化合物が、1-ブロモ-3-クロロ-5,5-ジメチルヒダントイン、及び1,3-ジクロロ-5,5-ジメチルヒダントインのうちから選ばれる1種以上である、上記[1]に記載の複合型固形水処理製品。
[3]前記有機系殺菌剤が、有効成分としてイソチアゾリン系化合物を含む、上記[1]又は[2]に記載の複合型固形水処理製品。
[4]前記イソチアゾリン系化合物が、5-クロロ-2-メチル-4-イソチアゾリン-3-オン、2-メチル-4-イソチアゾリン-3-オン、4,5-ジクロロ-2-メチル-4-イソチアゾリン-3-オン、2-エチル-4-イソチアゾリン-3-オン、2-n-オクチル-4-イソチアゾリン-3-オン、5-クロロ-2-エチル-4-イソチアゾリン-3-オン、5-クロロ-2-t-オクチル-4-イソチアゾリン-3-オン、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン、4,5-ジクロロ-2-シクロヘキシル-4-イソチアゾリン-3-オン及び1,2-ベンゾイソチアゾリン-3-オンのうちから選ばれる1種以上である、上記[3]に記載の複合型固形水処理製品。
[5]前記ハロゲン系酸化剤が、有効成分として1-ブロモ-3-クロロ-5,5-ジメチルヒダントインを含み、前記有機系殺菌剤が、有効成分として5-クロロ-2-メチル-4-イソチアゾリン-3-オンを含む、上記[1]~[4]のいずれか1項に記載の複合型固形水処理製品。
[6]前記固形剤(B)が、トリアゾール系化合物、ホスホン酸系化合物、及びスルファミン酸系化合物のうちから選ばれるいずれか1種以上を含む、上記[1]~[5]のいずれか1項に記載の複合型固形水処理製品。
That is, the present invention provides the following [1] to [10].
[1] A solid water treatment product which is used after being eluted in the water to be treated, and is a halogenated oxidant solid agent (A) containing a halogenated hydantoin compound as an active ingredient, and reactivity with the halogenated oxidant. A solid agent (B) containing an organic disinfectant having, and one or two or more elution containers for containing the solid agent (A) and the solid agent (B) without contacting each other, Composite type solid water treatment product.
[2] The halogenated hydantoin compound is at least one selected from 1-bromo-3-chloro-5,5-dimethylhydantoin and 1,3-dichloro-5,5-dimethylhydantoin. The composite solid water treatment product according to the above [1].
[3] The combined solid water treatment product according to the above [1] or [2], wherein the organic disinfectant contains an isothiazoline compound as an active ingredient.
[4] The isothiazoline-based compound may be 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-methyl-4-isothiazoline. -3-one, 2-ethyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, 5-chloro -2-t-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-cyclohexyl-4-isothiazoline-3 The composite solid water treatment product according to [3] above, which is at least one selected from -one and 1,2-benzisothiazolin-3-one.
[5] The halogen-containing oxidizing agent contains 1-bromo-3-chloro-5,5-dimethylhydantoin as an active ingredient, and the organic fungicide contains 5-chloro-2-methyl-4- The composite solid water treatment product according to any one of [1] to [4] above, which contains isothiazolin-3-one.
[6] Any one of the above-mentioned [1] to [5], wherein the solid agent (B) contains one or more selected from triazole compounds, phosphonic acid compounds, and sulfamic acid compounds. The composite type solid water treatment product according to Item.
[7]前記固形剤(A)が錠剤である、上記[1]~[6]のいずれか1項に記載の複合型固形水処理製品。
[8]前記固形剤(B)が錠剤である、上記[1]~[7]のいずれか1項に記載の複合型固形水処理製品。
[9]前記被処理水が冷却塔内の冷却水である、上記[1]~[8]のいずれか1項に記載の複合型固形水処理製品。
[10]前記固形剤(A)と前記固形剤(B)とが、それぞれ別々の溶出用容器に収容され、前記各溶出用容器は、冷却塔内に配置され、容器本体と前記容器本体の内部を、固形薬剤である前記固形剤(A)又は(B)を収容する1つ以上の収容室と、前記固形薬剤を収容しない非収容室とに区画する区画壁とを備え、前記容器本体は、該容器本体の外部と前記非収容室とを冷却水が流通可能な1つ以上の容器連通路を有し、前記区画壁は、前記収容室と前記非収容室との間を冷却水が流通可能な1つ以上の区画壁連通路を有する、上記[1]~[9]のいずれか1項に記載の複合型固形水処理製品。
[7] The composite solid water treatment product according to any one of [1] to [6], wherein the solid agent (A) is a tablet.
[8] The composite solid water treatment product according to any one of [1] to [7] above, wherein the solid preparation (B) is a tablet.
[9] The composite solid water treatment product according to any one of [1] to [8], wherein the water to be treated is cooling water in a cooling tower.
[10] The solid agent (A) and the solid agent (B) are accommodated in separate elution containers, and each elution container is disposed in a cooling tower, and the container main body and the container main body The container main body includes one or more storage chambers that store the solid agent (A) or (B), which is a solid drug, and a partition wall that divides the interior into a non-storage chamber that does not store the solid drug. Has one or more container communication passages through which cooling water can flow between the outside of the container body and the non-accommodating chamber, and the partition wall is provided with cooling water between the accommodating chamber and the non-accommodating chamber. The composite solid water treatment product according to any one of [1] to [9], wherein the product has one or more partition wall communication passages through which water can flow.
 本発明の複合型固形水処理製品によれば、ハロゲン系酸化剤及びこれと反応性を有する有効成分を安全に、かつ、これらの有効成分の併用による優れた薬剤効果を持続させることができる。
 また、本発明の複合型固形水処理製品は、反応性を有する薬剤を、同時に取り扱う上での利便性にも優れている。
According to the composite type solid water treatment product of the present invention, the halogen-based oxidizing agent and the active ingredient having reactivity therewith can be safely maintained and the excellent drug effect by the combined use of these active ingredients can be maintained.
In addition, the composite solid water treatment product of the present invention is also excellent in convenience in handling reactive chemicals at the same time.
本発明の複合型固形水処理製品の一の実施形態に係る溶出用容器の概略を示す縦断面図である。It is a longitudinal cross-sectional view which shows the outline of the container for elution which concerns on one Embodiment of the composite type solid water treatment product of this invention. 本発明の複合型固形水処理製品の他の実施形態に係る溶出用容器の概略を示す縦断面図である。It is a longitudinal cross-sectional view which shows the outline of the container for elution which concerns on other embodiment of the composite type solid water treatment product of this invention. 本発明の複合型固形水処理製品の一の実施形態の概略を示す側面図である。It is a side view which shows the outline of one Embodiment of the composite type solid water treatment product of this invention.
 以下、本発明について詳細に説明する。
 本発明の複合型固形水処理製品は、2種の固形剤からなり、被処理水中にこれらの固形剤を溶出させて使用する固形水処理製品である。そして、ハロゲン化ヒダントイン系化合物を有効成分とするハロゲン系酸化剤の固形剤(A)、前記ハロゲン系酸化剤との反応性を有する有機系殺菌剤を含む固形剤(B)、及び前記固形剤(A)と前記固形剤(B)とを互いに接触することなく収容する1つ又は2つ以上の溶出用容器を有するものである。
 水処理剤をこのような構成の複合型製品とすることにより、反応性を有する薬剤同士を、それぞれ製剤化し、安全に同時に取り扱うことができ、また、両薬剤の併用による優れた薬剤効果を高い持続性で発揮させることができる。
Hereinafter, the present invention will be described in detail.
The composite type solid water treatment product of the present invention is a solid water treatment product comprising two kinds of solid agents and using these solid agents by eluting them into the water to be treated. Further, a solid agent (A) of a halogen-based oxidizing agent containing a halogenated hydantoin-based compound as an active ingredient, a solid agent (B) containing an organic disinfectant having reactivity with the halogen-based oxidizing agent, and the solid agent It has 1 or 2 or more elution containers which accommodate (A) and the said solid agent (B), without mutually contacting.
By making the water treatment agent into a composite product with such a configuration, it is possible to formulate each of the reactive drugs and handle them safely at the same time. Also, the combination of both drugs is highly effective. Can be demonstrated with sustainability.
[固形剤(A)]
 固形剤(A)は、ハロゲン系酸化剤であり、水処理剤において殺菌消毒やスライム抑制の作用を奏するものである。本発明においては、ハロゲン系酸化剤としては、ハロゲン化ヒダントイン系化合物を有効成分とするものを用いる。
[Solid agent (A)]
The solid agent (A) is a halogen-based oxidant, and has an effect of sterilization and slime suppression in the water treatment agent. In the present invention, as the halogen-based oxidant, those containing a halogenated hydantoin compound as an active ingredient are used.
 ハロゲン化ヒダントイン系化合物は、固体の有機ハロゲン系酸化剤であり、水と接触すると、強力な酸化力を有する活性ハロゲンを放出する。
 また、水に対する溶解性等の観点から、活性ハロゲンを長期間にわたって持続的に放出させる上で好適である。徐放性錠剤として市販されているハロゲン系酸化剤としては、ハロゲン化ヒダントイン系化合物以外にも、次亜塩素酸カルシウム、亜塩素酸ナトリウム、ジクロロイソシアヌル酸、トリクロロイソシアヌル酸等を有効成分とするものがあるが、これらのうち、ハロゲン化ヒダントイン系化合物を有効成分とするものが、比較的溶出速度が小さいことを見出した。このことから、ハロゲン化ヒダントイン系化合物が、有機系殺菌剤を含む固形剤との併用による優れた薬剤効果を持続させる観点から最も好適であると言える。しかも、ハロゲン化ヒダントイン系化合物は、水と接触した際に生じる臭気も比較的少ないため、取り扱い時の安全性の観点からも好ましい。
The halogenated hydantoin-based compound is a solid organic halogen-based oxidizing agent, and releases an active halogen having strong oxidizing power when in contact with water.
Further, from the viewpoint of solubility in water and the like, it is suitable for releasing active halogen continuously over a long period of time. In addition to halogenated hydantoin compounds, the halogen-based oxidizing agents that are commercially available as sustained-release tablets include calcium hypochlorite, sodium chlorite, dichloroisocyanuric acid, trichloroisocyanuric acid, and the like as active ingredients. Among them, it has been found that those containing a halogenated hydantoin compound as an active ingredient have a relatively low elution rate. From this, it can be said that the halogenated hydantoin compound is most suitable from the viewpoint of maintaining an excellent drug effect by the combined use with a solid agent containing an organic fungicide. Moreover, the halogenated hydantoin compounds are preferable from the viewpoint of safety during handling because they generate relatively little odor when they come into contact with water.
 ハロゲン化ヒダントイン系化合物としては、具体的には、1-ブロモ-3-クロロ-5,5-ジメチルヒダントイン(以下、BCDMHと略称する。)、1,3-ジクロロ-5,5-ジメチルヒダントイン、1,3-ジブロモ-5,5-ジメチルヒダントイン、1-ブロモ-3-クロロ-5,5-ジエチルヒダントイン、1,3-ジクロロ-5,5-ジエチルヒダントイン、1-ブロモ-3-クロロ-5-メチル-5-エチルヒダントイン等が挙げられる。これらは、1種単独で用いても、2種以上を併用してもよい。これらのうち、水と接触した場合の溶出速度の固形剤(B)とのバランスや入手容易性等の観点から、BCDMH、及び1,3-ジクロロ-5,5-ジメチルヒダントインが好ましい。 Specific examples of the halogenated hydantoin compound include 1-bromo-3-chloro-5,5-dimethylhydantoin (hereinafter abbreviated as BCDMH), 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1-bromo-3-chloro-5,5-diethylhydantoin, 1,3-dichloro-5,5-diethylhydantoin, 1-bromo-3-chloro-5 -Methyl-5-ethylhydantoin and the like. These may be used alone or in combination of two or more. Of these, BCDMH and 1,3-dichloro-5,5-dimethylhydantoin are preferred from the viewpoints of balance with the solid agent (B) of the dissolution rate when contacted with water and availability.
 上記のようなハロゲン系酸化剤の形態は、特に限定されるものではないが、使用量の調整のしやすさや取り扱い容易性等の観点から、ペレット状やタブレット状等の錠剤又は顆粒状であることが好ましく、容器内への収容の際の作業性等の観点から、錠剤であることがより好ましい。錠剤の製造方法は、特に限定されるものではなく、公知の方法により製造することができる。通常は、賦形剤や結合剤等の添加剤を用いて、加圧成形することにより作製される。賦形剤や結合剤の種類や添加量を調整することにより、被処理水中への錠剤の溶出速度を調節することができる。
 固形剤(A)としては、市販品を用いることもできる。
The form of the halogen-based oxidizing agent as described above is not particularly limited, but is in the form of tablets or granules such as pellets and tablets from the viewpoint of ease of adjustment of the amount used and ease of handling. It is preferable that the tablet is more preferable from the viewpoint of workability and the like when being accommodated in the container. The manufacturing method of a tablet is not specifically limited, It can manufacture by a well-known method. Usually, it is produced by pressure molding using additives such as excipients and binders. The dissolution rate of the tablet in the water to be treated can be adjusted by adjusting the type and amount of the excipient and binder.
A commercial item can also be used as a solid agent (A).
 固形剤(A)は、ハロゲン系酸化剤が適度な溶出速度となるようにする観点から、ハロゲン系酸化剤の含有量は、有効ハロゲン成分をすべて有効塩素とみなした場合、有効塩素(Cl2)換算で10質量%以上であることが好ましく、より好ましくは30~90質量%、さらに好ましくは40~70質量%である。
 レジオネラ属菌に対する殺菌作用の観点から、固形剤(A)による被処理水中の有効ハロゲン(Cl2換算)濃度は、0.1mg/L以上であることが好ましく、より好ましくは0.1~5mg/L、さらに好ましくは0.1~2mg/Lである。
From the viewpoint of allowing the halogen-based oxidant to have an appropriate elution rate, the solid agent (A) has a content of the halogen-based oxidant so that effective chlorine (Cl 2 ) In terms of conversion, it is preferably 10% by mass or more, more preferably 30 to 90% by mass, and still more preferably 40 to 70% by mass.
From the viewpoint of bactericidal action against Legionella, the concentration of effective halogen (Cl 2 equivalent) in the water to be treated by the solid agent (A) is preferably 0.1 mg / L or more, more preferably 0.1 to 5 mg. / L, more preferably 0.1 to 2 mg / L.
[固形剤(B)]
 固形剤(B)は、前記ハロゲン系酸化剤との反応性を有する有機系殺菌剤を含むものである。このような固形剤をハロゲン系酸化剤と併用することにより、殺菌作用の相乗効果が得られる。
 有機系殺菌剤は、前記ハロゲン系酸化剤との反応性を有するものである。ハロゲン系酸化剤との反応により、塩素ガス等の有毒なハロゲン系物質を生じるため、ハロゲン系酸化剤と混合して一剤化することは困難である。このため、有機系殺菌剤を製剤化するには、ハロゲン系酸化剤とは、別個の薬剤とする必要がある。したがって、本発明では、固形剤(B)は、固形剤(A)とは別に製剤化されたものを用いる。
[Solid agent (B)]
The solid agent (B) contains an organic disinfectant having reactivity with the halogen-based oxidizing agent. By using such a solid agent in combination with a halogen-based oxidizing agent, a synergistic effect of bactericidal action can be obtained.
The organic disinfectant has reactivity with the halogen-based oxidizing agent. Since the reaction with the halogen-based oxidant generates a toxic halogen-based substance such as chlorine gas, it is difficult to mix with the halogen-based oxidant to form a single agent. For this reason, in order to formulate an organic disinfectant, it is necessary to use a separate agent from the halogen-based oxidizing agent. Therefore, in the present invention, the solid agent (B) is formulated separately from the solid agent (A).
 前記有機系殺菌剤における有効成分としては、ハロゲン系酸化剤との併用による殺菌性能の観点から、イソチアゾリン系化合物を含むことが好ましい。
 イソチアゾリン系化合物としては、具体的には、5-クロロ-2-メチル-4-イソチアゾリン-3-オン(以下、Cl-MITと略称する。)、2-メチル-4-イソチアゾリン-3-オン、4,5-ジクロロ-2-メチル-4-イソチアゾリン-3-オン、2-エチル-4-イソチアゾリン-3-オン、2-n-オクチル-4-イソチアゾリン-3-オン、5-クロロ-2-エチル-4-イソチアゾリン-3-オン、5-クロロ-2-t-オクチル-4-イソチアゾリン-3-オン、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン、4,5-ジクロロ-2-シクロヘキシル-4-イソチアゾリン-3-オン、1,2-ベンゾイソチアゾリン-3-オン等が挙げられる。これらは、1種単独で用いても、2種以上を併用してもよい。これらのうち、水に対する溶解性、殺菌性能及び入手容易性の観点から、Cl-MITが好ましい。特に、レジオネラ属菌に対する殺菌作用の観点から、有効成分としてBCDMHを含むハロゲン系酸化剤の固形剤(A)と、有効成分としてCl-MITを含む有機系殺菌剤を含む固形剤(B)との組み合わせが好ましい。
The active ingredient in the organic fungicide preferably contains an isothiazoline compound from the viewpoint of sterilization performance when used in combination with a halogen oxidizing agent.
Specific examples of the isothiazoline compound include 5-chloro-2-methyl-4-isothiazolin-3-one (hereinafter abbreviated as Cl-MIT), 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-methyl-4-isothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2- Ethyl-4-isothiazolin-3-one, 5-chloro-2-t-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4, Examples include 5-dichloro-2-cyclohexyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, and the like. These may be used alone or in combination of two or more. Of these, Cl-MIT is preferred from the viewpoints of solubility in water, sterilization performance, and availability. In particular, from the viewpoint of bactericidal action against Legionella spp., A solid agent (A) of a halogen-based oxidizing agent containing BCDMH as an active ingredient, and a solid agent (B) containing an organic fungicide containing Cl-MIT as an active ingredient, The combination of is preferable.
 有効成分である有機系殺菌剤の固形剤(B)の溶出量は、優れた殺菌作用を得る観点から、例えば、有効成分がCl-MITであり、固形剤(A)のハロゲン系酸化剤の有効成分がBCDMHである場合、被処理水中のBCDMHの有効ハロゲン(Cl2換算)濃度(単位:mg/L)に対して、被処理水中のCl-MITの濃度(単位:mg/L)が0.00001~100倍であることが好ましく、より好ましくは0.01~30倍、さらに好ましくは0.1~1倍である。なお、被処理水中のCl-MITの濃度は、0.0001~5mg/Lであることが好ましく、より好ましくは0.001~3mg/L、さらに好ましくは0.001~2mg/Lである。 From the viewpoint of obtaining an excellent bactericidal action, for example, the active ingredient is Cl-MIT, and the elution amount of the organic fungicide solid agent (B), which is an active ingredient, is the halogen-based oxidizing agent of the solid agent (A). When the active ingredient is BCDMH, the concentration of Cl-MIT (unit: mg / L) in the treated water is higher than the effective halogen (Cl 2 equivalent) concentration (unit: mg / L) of BCDMH in the treated water. It is preferably 0.00001 to 100 times, more preferably 0.01 to 30 times, and still more preferably 0.1 to 1 times. The concentration of Cl-MIT in the water to be treated is preferably 0.0001 to 5 mg / L, more preferably 0.001 to 3 mg / L, and still more preferably 0.001 to 2 mg / L.
 固形剤(B)は、前記有機系殺菌剤以外にも、水処理剤において防食やスケール防止等の観点から使用される他の公知の化合物を含んでいてもよい。例えば、トリアゾール系化合物、ホスホン酸系化合物、スルファミン酸系化合物、アメトリン、2,2-ジブロモ-3-ニトリロプロピオンアミド、ブロノポール、ジンクピリチオン、チアベンダゾール、アクリル酸系やマレイン酸系の低分子量ポリマーによる凝集剤等が挙げられる。これらは、1種でも2種以上であってもよい。ただし、これらの化合物の添加量は、固形剤(A)及び(B)による殺菌作用を妨げない範囲とする。 Solid agent (B) may contain other known compounds used from the viewpoint of anticorrosion and scale prevention in the water treatment agent in addition to the organic fungicide. For example, flocculants composed of triazole compounds, phosphonic acid compounds, sulfamic acid compounds, amethrin, 2,2-dibromo-3-nitrilopropionamide, bronopol, zinc pyrithione, thiabendazole, acrylic acid and maleic acid based low molecular weight polymers Etc. These may be one type or two or more types. However, the addition amount of these compounds shall be the range which does not prevent the bactericidal action by solid agent (A) and (B).
 固形剤(B)の形態も、固形剤(A)の形態と同様に、特に限定されるものではないが、使用量の調整のしやすさや取り扱い容易性等の観点から、ペレット状やタブレット状等の錠剤又は顆粒状であることが好ましく、容器内への収容の際の作業性等の観点から、錠剤であることがより好ましい。錠剤の製造方法は、特に限定されるものではなく、公知の方法により製造することができる。通常は、賦形剤や結合剤等の添加剤を用いて、加圧成形することにより作製される。賦形剤や結合剤の種類や添加量を調整することにより、被処理水中への錠剤の溶出速度を調節することができる。これらの添加剤としては、例えば、ステアリン酸マグネシウム、シリカ、酸化マグネシウム等が用いられる。
 上記のような有機系殺菌剤を有効成分とする固形剤(B)としては、市販品を用いることもできる。
The form of the solid agent (B) is not particularly limited in the same manner as the form of the solid agent (A), but from the viewpoint of ease of adjustment of the amount used, ease of handling, and the like, pellets and tablets From the viewpoints of workability and the like when accommodated in a container, the tablet is more preferable. The manufacturing method of a tablet is not specifically limited, It can manufacture by a well-known method. Usually, it is produced by pressure molding using additives such as excipients and binders. The dissolution rate of the tablet in the water to be treated can be adjusted by adjusting the type and amount of the excipient and binder. As these additives, for example, magnesium stearate, silica, magnesium oxide and the like are used.
A commercial item can also be used as a solid agent (B) which uses the above organic type fungicides as an active ingredient.
 固形剤(B)は、有機系殺菌剤が適度な溶出速度となるようにする観点から、有機系殺菌剤の含有量が1~40質量%であることが好ましく、より好ましくは2~35質量%、さらに好ましくは5~30質量%である。 The solid agent (B) preferably has an organic fungicide content of 1 to 40% by weight, more preferably 2 to 35% by weight, from the viewpoint of allowing the organic fungicide to have an appropriate dissolution rate. %, More preferably 5 to 30% by mass.
[溶出用容器]
 固形剤(A)及び固形剤(B)を収容する容器は、その内部に両者を互いに接触することなく収容できるものである。固形剤(A)と固形剤(B)とが接触した状態で水処理を行うと、上述したように、塩素ガス等の有毒なハロゲン系物質を生じる。したがって、固形剤(A)及び固形剤(B)を被処理水中に溶出させる際は、互いに接触しない状態を保つことができるように容器内に収容する。
 固形剤(A)と固形剤(B)とが互いに接触しない状態であればよく、固形剤(A)及び固形剤(B)は、隔壁を有する1つの容器内に収容されてもよく、また、2つ以上の別々の容器に収容されてもよい。
 また、固形剤(A)及び固形剤(B)を溶出用容器内に収容することにより、剥き出しの状態で被処理水中に投入するよりも、各有効成分の薬剤効果を長時間にわたって持続させることができ、さらに、両者の併用による相乗的な殺菌作用等の薬剤効果を持続させることができる。
[Elution container]
The container which accommodates the solid agent (A) and the solid agent (B) can accommodate both without contacting each other. When the water treatment is performed in a state where the solid agent (A) and the solid agent (B) are in contact with each other, a toxic halogen-based substance such as chlorine gas is generated as described above. Therefore, when eluting the solid agent (A) and the solid agent (B) into the water to be treated, the solid agent (A) and the solid agent (B) are accommodated in a container so that they can be kept out of contact with each other.
As long as the solid agent (A) and the solid agent (B) are not in contact with each other, the solid agent (A) and the solid agent (B) may be accommodated in one container having a partition, It may be contained in two or more separate containers.
Moreover, by storing the solid agent (A) and the solid agent (B) in the elution container, the drug effect of each active ingredient can be maintained for a long time rather than being put into the water to be treated in an exposed state. In addition, drug effects such as synergistic bactericidal action by the combined use of both can be maintained.
 前記複合型固形水処理製品は、冷却塔内の冷却水の水処理に好適に用いることができる。
 この場合、固形剤(A)と固形剤(B)とは、それぞれ別々の溶出用容器に収容され、前記各溶出用容器は、冷却塔内に配置されることが好ましい。溶出用容器の形態は、特に限定されるものはないが、例えば、図1及び図2に示すような形態のものが好ましい。図1及び図2に示す溶出用容器10,20は、容器本体1と、該容器本体1の内部を区画する区画壁2とを備えている。容器本体1の内部は、区画壁2によって、固形薬剤11,21(固形剤(A)又は(B))を収容する1つ以上の収容室3と、固形水処理剤を収容しない非収容室4とに区画されている。
 容器本体1は、該容器本体1の外部と非収容室4との間を冷却水が流通可能な1つ以上の容器連通路5を有している。一方、区画壁2は、収容室3と非収容室4との間を冷却水が流通可能な1つ以上の区画壁連通路6を有している。
The composite solid water treatment product can be suitably used for water treatment of cooling water in a cooling tower.
In this case, it is preferable that the solid agent (A) and the solid agent (B) are accommodated in separate elution containers, and the elution containers are arranged in a cooling tower. The form of the elution container is not particularly limited, but for example, the form shown in FIGS. 1 and 2 is preferable. The elution containers 10 and 20 shown in FIGS. 1 and 2 include a container body 1 and a partition wall 2 that partitions the inside of the container body 1. The inside of the container main body 1 includes one or more storage chambers 3 for storing the solid medicines 11 and 21 (solid agent (A) or (B)) and a non-storage chamber that does not store the solid water treatment agent by the partition wall 2. It is divided into four.
The container main body 1 has one or more container communication paths 5 through which cooling water can flow between the outside of the container main body 1 and the non-accommodating chamber 4. On the other hand, the partition wall 2 has one or more partition wall communication paths 6 through which cooling water can flow between the storage chamber 3 and the non-storage chamber 4.
 図2に示す溶出用容器20は、固形薬剤21を収容する収容室3を2つ有しているものである。また、容器連通路5は、溶出用容器20の方が、溶出用容器10よりも流路総断面積が小さくなるように形成されており、固形薬剤の溶出速度を、より抑制したい場合に適した構造としている。
 なお、容器本体1の形状、また、収容室3、非収容室4、容器連通路5及び区画壁連通路6の形状や配置、数等の形態は、図1及び図2に記載のもののみに限定されない。使用する固形剤(A)及び(B)の形態や殺菌性能、溶出速度、該複合型固形水処理製品の冷却塔内における配置環境等に応じて、適宜定めることができる。
 溶出用容器は、固形剤(A)又は(B)の収容状態が外部から目視観察できるように、透明性を有するものであることが好ましい。また、取り扱い容易性やコスト等の観点から、プラスチック製であることが好ましい。
The elution container 20 shown in FIG. 2 has two storage chambers 3 for storing the solid medicine 21. Further, the container communication path 5 is formed so that the elution container 20 has a smaller total cross-sectional area of the flow channel than the elution container 10 and is suitable for the case where it is desired to further suppress the elution rate of the solid drug. Structure.
The shape of the container body 1 and the shape, arrangement, number, and the like of the storage chamber 3, the non-storage chamber 4, the container communication path 5, and the partition wall communication path 6 are only those described in FIGS. It is not limited to. The solid agents (A) and (B) to be used can be appropriately determined according to the form, bactericidal performance, elution rate, the arrangement environment of the composite solid water treatment product in the cooling tower, and the like.
It is preferable that the elution container is transparent so that the accommodation state of the solid agent (A) or (B) can be visually observed from the outside. Further, from the viewpoint of ease of handling, cost, etc., it is preferably made of plastic.
 図3に、図1に示すような溶出用容器10及び図2に示すような溶出用容器20を用いて、これらを一体化させるようにセットとした複合型固形水処理製品の一例を示す。
 例えば、固形剤(A)及び(B)がいずれも所定のサイズの錠剤であり、水と接触した際に、固形剤(A)の方が固形剤(B)よりも溶出しやすい場合、両者の溶出速度を制御する観点から、溶出用容器10に固形剤(B)を収容し、溶出速度をより抑制しやすい溶出用容器20に固形剤(A)を収容する。
 図3に示す複合型固形水処理製品は、枠体30に、溶出用容器10,20を嵌め込んで両者を保持することができるように構成されている。図3においては、2つの溶出用容器10と1つの溶出用容器20とを一体化させている。
 枠体30は、発泡スチロール等の発泡プラスチック製であることが好ましい。これにより、軽量で複合型固形水処理製品を一体として持ち運びやすく、また、冷却塔内の冷却水ピットに浮かせて使用することもできる。
FIG. 3 shows an example of a composite solid water treatment product in which the elution container 10 shown in FIG. 1 and the elution container 20 shown in FIG.
For example, when both solid agent (A) and (B) are tablets of a predetermined size and solid agent (A) is more easily eluted than solid agent (B) when contacted with water, From the viewpoint of controlling the elution rate, the solid agent (B) is accommodated in the elution vessel 10 and the solid agent (A) is accommodated in the elution vessel 20 that can more easily suppress the elution rate.
The composite-type solid water treatment product shown in FIG. 3 is configured so that the elution containers 10 and 20 can be fitted into the frame 30 and both can be held. In FIG. 3, two elution containers 10 and one elution container 20 are integrated.
The frame body 30 is preferably made of foamed plastic such as polystyrene foam. Thereby, it is easy to carry a lightweight and complex type solid water treatment product as one body, and it can also be used by floating in the cooling water pit in the cooling tower.
 このような複合型固形水処理製品によれば、冷却水が、容器連通路5を通って非収容室4内に流入し、非収容室4内から区画壁流通路6を通って収容室3内に流入する。収容室3内の固形薬剤11,21(固形剤(A)又は(B))は、流入してきた冷却水と接触して溶出する。これらの固形薬剤11又は21が溶出した各冷却水(溶出液)が、容器連通路5を通って溶出用容器外へ流出する。これにより、固形剤(A)及び(B)を互いに一定の間隔を保持した状態で併用し、冷却塔内の冷却水中に溶出させることができる。 According to such a composite type solid water treatment product, the cooling water flows into the non-accommodating chamber 4 through the container communication path 5, and from the inside of the non-accommodating chamber 4 through the partition wall flow path 6 to the accommodating chamber 3. Flows in. The solid medicines 11 and 21 (solid agent (A) or (B)) in the storage chamber 3 are eluted in contact with the cooling water that has flowed in. Each cooling water (eluent) from which the solid drug 11 or 21 is eluted flows out of the elution container through the container communication path 5. Thereby, solid agent (A) and (B) can be used together in the state which kept the fixed space | interval mutually, and can be eluted in the cooling water in a cooling tower.
 以下、本発明を実施例により具体的に説明するが、本発明は下記実施例により限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.
[持続性評価試験]
 下記に示す各ハロゲン系酸化剤について、図2に示すようなタイプの溶出用容器を用いて、持続性評価試験を行った。
 持続性評価試験は、冷凍能力20USRT、8時間/日稼働、冷却水の水温30℃の向流型(丸形)開放式冷却塔内の消音マット上に、ハロゲン系酸化剤を収容した溶出用容器を載置し、所定の経過日数ごとに、容器内に残留しているハロゲン系酸化剤を取り出して、その重量を測定し、日数の経過に伴う残留重量の変化を確認することにより行った。
 使用した容器及びハロゲン系酸化剤の詳細は、以下のとおりである。
(容器)
 図2に示すような2つの収容室を有するタイプのポリプロピレン製の容器
・外形サイズ:長径12.7cm、短径8.0cm
・容器連通路5(ただし、図2の記載とは、一部、位置が異なる。):
  天部に、直径5.5mmの丸孔8個、孔総面積1.9cm2
  側周部に、直径5mmの丸孔6個、丸孔の中心位置が底部内面より高さ12mm、
  底部に、直径2.5mmの丸孔2個
・区画壁連通路6:筒状体の区画壁2の下端と底部内面との隙間7mm
(ハロゲン系酸化剤)
 直径31mm、高さ17.5mm、20gの円形錠剤;収容室1つ当たり3錠重ね
・固形薬剤1:BCDMH
・固形薬剤2:次亜塩素酸カルシウム
・固形薬剤3:トリクロロイソシアヌル酸
[Sustainability evaluation test]
About each halogen-type oxidizing agent shown below, the sustainability evaluation test was done using the container for an elution as shown in FIG.
Sustainability evaluation test is for elution containing a halogen-based oxidant on a silencing mat in a countercurrent (round) open cooling tower with a cooling capacity of 20 USRT, operating for 8 hours / day, and a cooling water temperature of 30 ° C. This was done by placing the container, taking out the halogen-based oxidant remaining in the container every predetermined number of elapsed days, measuring its weight, and confirming the change in the residual weight with the passage of days. .
The details of the container and the halogen-based oxidizing agent used are as follows.
(container)
A container made of polypropylene of the type having two storage chambers as shown in FIG. 2. External size: major axis 12.7 cm, minor axis 8.0 cm
Container communication path 5 (however, the position is partially different from the description in FIG. 2):
On the top, 8 round holes with a diameter of 5.5mm, total hole area 1.9cm 2
On the side periphery, 6 round holes with a diameter of 5 mm, the center position of the round hole is 12 mm higher than the bottom inner surface,
Two round holes with a diameter of 2.5 mm at the bottom and a partition wall communication path 6: a clearance of 7 mm between the lower end of the cylindrical partition wall 2 and the inner surface of the bottom
(Halogen-based oxidizer)
Round tablet with a diameter of 31 mm, a height of 17.5 mm, and 20 g; 3 tablets stacked per storage room. Solid drug 1: BCDMH
-Solid drug 2: Calcium hypochlorite-Solid drug 3: Trichloroisocyanuric acid
 試験の結果、容器内のハロゲン系酸化剤は、次亜塩素酸カルシウム(固形薬剤2)が約2日間、トリクロロイソシアヌル酸(固形薬剤3)が約25日間で、いずれも溶け切った。なお、トリクロロイソシアヌル酸(固形薬剤3)は、試験中の臭気が強かった。
 これに対して、1-ブロモ-3-クロロ-5,5-ジメチルヒダントイン(固形薬剤1)は、約3ヶ月間にわたって徐々に溶出することが認められた。また、トリクロロイソシアヌル酸(固形薬剤3)よりも臭気が少なかった。
 このように、BCDMHは、徐放性に優れていることから、ハロゲン系酸化剤として、これと反応性を有する有効成分を含む固形剤との併用による薬剤効果を持続させるための溶出速度のバランスを図る観点から、好適であると言える。
As a result of the test, as for the halogen-based oxidizing agent in the container, calcium hypochlorite (solid drug 2) was dissolved for about 2 days and trichloroisocyanuric acid (solid drug 3) was melted for about 25 days. Trichloroisocyanuric acid (solid drug 3) had a strong odor during the test.
In contrast, 1-bromo-3-chloro-5,5-dimethylhydantoin (solid drug 1) was found to elute gradually over about 3 months. Moreover, there was less odor than trichloroisocyanuric acid (solid chemical | medical agent 3).
Thus, since BCDMH is excellent in sustained release, as a halogen-based oxidizing agent, the balance of dissolution rate for maintaining the drug effect by the combined use with a solid agent containing an active ingredient having reactivity therewith. It can be said that it is preferable from the viewpoint of achieving the above.
[殺菌作用の確認試験]
 BCDMHとCl-MITとの併用によるレジオネラ属菌に対する殺菌作用を確認する試験を以下の条件にて行った。
(試験条件)
・初発菌数:1×106~1×107CFU/100mL
・接触時間:24時間
・試験水pH7.0(リン酸緩衝液)
・試験水量:100mL
・培養温度:36℃
・BCDMH:有効ハロゲン(Cl2換算)濃度0.0005質量%水溶液
・Cl-MIT:0.01質量%水溶液
[Confirmation test of bactericidal action]
A test for confirming the bactericidal action against Legionella by the combined use of BCDMH and Cl-MIT was conducted under the following conditions.
(Test conditions)
・ Initial number of bacteria: 1 × 10 6 to 1 × 10 7 CFU / 100 mL
Contact time: 24 hours Test water pH 7.0 (phosphate buffer)
・ Test water volume: 100 mL
・ Culture temperature: 36 ℃
BCDMH: Effective halogen (Cl 2 equivalent) concentration 0.0005 mass% aqueous solution Cl-MIT: 0.01 mass% aqueous solution
 薬剤未添加の場合(ブランク)の24時間試験後の試験水中の菌数1.2×109CFU/100mLを基準として殺菌率を求めた。
 その結果、Cl-MIT(0.5mg/L)のみを添加した場合の殺菌率が97.4%であったのに対して、BCDMH(1mg/L)とCl-MIT(0.5ml/L)とを併用した場合は、殺菌率が100%であった。このことから、BCDMHとCl-MITとの併用によるレジオネラ属菌に対する殺菌作用の向上効果が確認された。
The bactericidal rate was calculated | required on the basis of the microbe count 1.2 * 10 < 9 > CFU / 100mL in the test water after a 24-hour test when a chemical | medical agent is not added (blank).
As a result, the bactericidal rate when only Cl-MIT (0.5 mg / L) was added was 97.4%, whereas BCDMH (1 mg / L) and Cl-MIT (0.5 ml / L) ) Was used in combination, the sterilization rate was 100%. From this, the improvement effect of the bactericidal action against Legionella spp. By the combined use of BCDMH and Cl-MIT was confirmed.
 1     容器本体
 2     区隔壁
 3     収容室
 4     非収容室
 5     容器連通路
 6     区画壁連通路
 10,20 溶出用容器
 11,21 固形薬剤
 30    枠体
DESCRIPTION OF SYMBOLS 1 Container main body 2 Compartment partition 3 Storage chamber 4 Non-accommodation chamber 5 Container communication path 6 Partition wall communication path 10,20 Elution container 11,21 Solid medicine 30 Frame

Claims (10)

  1.  被処理水中に溶出させて使用する固形水処理製品であって、
     ハロゲン化ヒダントイン系化合物を有効成分とするハロゲン系酸化剤の固形剤(A)、前記ハロゲン系酸化剤との反応性を有する有機系殺菌剤を含む固形剤(B)、及び前記固形剤(A)と前記固形剤(B)とを互いに接触することなく収容する1つ又は2つ以上の溶出用容器を有する、複合型固形水処理製品。
    A solid water treatment product that is used by elution in the water to be treated,
    A halogenated oxidant solid agent (A) containing a halogenated hydantoin compound as an active ingredient, a solid agent (B) containing an organic disinfectant having reactivity with the halogenated oxidant, and the solid agent (A ) And the solid agent (B) are contained in one or two or more elution containers that do not come into contact with each other.
  2.  前記ハロゲン化ヒダントイン系化合物が、1-ブロモ-3-クロロ-5,5-ジメチルヒダントイン、及び1,3-ジクロロ-5,5-ジメチルヒダントインのうちから選ばれる1種以上である、請求項1に記載の複合型固形水処理製品。 2. The halogenated hydantoin compound is one or more selected from 1-bromo-3-chloro-5,5-dimethylhydantoin and 1,3-dichloro-5,5-dimethylhydantoin. The combined solid water treatment product according to 1.
  3.  前記有機系殺菌剤が、有効成分としてイソチアゾリン系化合物を含む、請求項1又は2に記載の複合型固形水処理製品。 The composite solid water treatment product according to claim 1 or 2, wherein the organic disinfectant contains an isothiazoline compound as an active ingredient.
  4.  前記イソチアゾリン系化合物が、5-クロロ-2-メチル-4-イソチアゾリン-3-オン、2-メチル-4-イソチアゾリン-3-オン、4,5-ジクロロ-2-メチル-4-イソチアゾリン-3-オン、2-エチル-4-イソチアゾリン-3-オン、2-n-オクチル-4-イソチアゾリン-3-オン、5-クロロ-2-エチル-4-イソチアゾリン-3-オン、5-クロロ-2-t-オクチル-4-イソチアゾリン-3-オン、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン、4,5-ジクロロ-2-シクロヘキシル-4-イソチアゾリン-3-オン及び1,2-ベンゾイソチアゾリン-3-オンのうちから選ばれる1種以上である、請求項3に記載の複合型固形水処理製品。 The isothiazoline-based compound is 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-methyl-4-isothiazoline-3- ON, 2-ethyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, 5-chloro-2- t-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3-one and The composite-type solid water treatment product according to claim 3, wherein the product is one or more selected from 1,2-benzisothiazolin-3-one.
  5.  前記ハロゲン系酸化剤が、有効成分として1-ブロモ-3-クロロ-5,5-ジメチルヒダントインを含み、
     前記有機系殺菌剤が、有効成分として5-クロロ-2-メチル-4-イソチアゾリン-3-オンを含む、請求項1~4のいずれか1項に記載の複合型固形水処理製品。
    The halogen-based oxidizing agent contains 1-bromo-3-chloro-5,5-dimethylhydantoin as an active ingredient;
    The composite solid water treatment product according to any one of claims 1 to 4, wherein the organic disinfectant contains 5-chloro-2-methyl-4-isothiazolin-3-one as an active ingredient.
  6.  前記固形剤(B)が、トリアゾール系化合物、ホスホン酸系化合物、及びスルファミン酸系化合物のうちから選ばれるいずれか1種以上を含む、請求項1~5のいずれか1項に記載の複合型固形水処理製品。 The composite type according to any one of claims 1 to 5, wherein the solid agent (B) contains at least one selected from triazole compounds, phosphonic acid compounds, and sulfamic acid compounds. Solid water treatment product.
  7.  前記固形剤(A)が錠剤である、請求項1~6のいずれか1項に記載の複合型固形水処理製品。 The composite solid water treatment product according to any one of claims 1 to 6, wherein the solid agent (A) is a tablet.
  8.  前記固形剤(B)が錠剤である、請求項1~7のいずれか1項に記載の複合型固形水処理製品。 The composite solid water treatment product according to any one of claims 1 to 7, wherein the solid preparation (B) is a tablet.
  9.  前記被処理水が冷却塔内の冷却水である、請求項1~8のいずれか1項に記載の複合型固形水処理製品。 The composite solid water treatment product according to any one of claims 1 to 8, wherein the treated water is cooling water in a cooling tower.
  10.  前記固形剤(A)と前記固形剤(B)とが、それぞれ別々の溶出用容器に収容され、
     前記各溶出用容器は、冷却塔内に配置され、容器本体と前記容器本体の内部を、固形薬剤である前記固形剤(A)又は(B)を収容する1つ以上の収容室と、前記固形薬剤を収容しない非収容室とに区画する区画壁とを備え、
     前記容器本体は、該容器本体の外部と前記非収容室との間を冷却水が流通可能な1つ以上の容器連通路を有し、前記区画壁は、前記収容室と前記非収容室との間を冷却水が流通可能な1つ以上の区画壁連通路を有する、請求項1~9のいずれか1項に記載の複合型固形水処理製品。
    The solid agent (A) and the solid agent (B) are accommodated in separate elution containers,
    Each of the elution containers is disposed in a cooling tower, and the container main body and the inside of the container main body include one or more storage chambers that store the solid agent (A) or (B) that is a solid drug, A partition wall that divides into a non-contained chamber that does not contain a solid drug,
    The container main body has one or more container communication paths through which cooling water can flow between the outside of the container main body and the non-contained chamber, and the partition wall includes the accommodating chamber and the non-contained chamber. The composite solid water treatment product according to any one of claims 1 to 9, further comprising one or more partition wall communication passages through which cooling water can flow.
PCT/JP2017/029898 2016-08-23 2017-08-22 Composite-type solid water treatment product WO2018038091A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201780038585.8A CN109415233B (en) 2016-08-23 2017-08-22 Composite solid water treatment product
SG11201811348WA SG11201811348WA (en) 2016-08-23 2017-08-22 Composite-type solid water treatment product
MYPI2018002634A MY198348A (en) 2016-08-23 2017-08-22 Composite-type solid water treatment product
PH12018502690A PH12018502690B1 (en) 2016-08-23 2018-12-19 Composite-type solid water treatment product

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016162518A JP6394659B2 (en) 2016-08-23 2016-08-23 Combined solid water treatment products
JP2016-162518 2016-08-23

Publications (1)

Publication Number Publication Date
WO2018038091A1 true WO2018038091A1 (en) 2018-03-01

Family

ID=61245049

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/029898 WO2018038091A1 (en) 2016-08-23 2017-08-22 Composite-type solid water treatment product

Country Status (7)

Country Link
JP (1) JP6394659B2 (en)
CN (1) CN109415233B (en)
MY (1) MY198348A (en)
PH (1) PH12018502690B1 (en)
SG (1) SG11201811348WA (en)
TW (1) TWI726142B (en)
WO (1) WO2018038091A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018180402A1 (en) * 2017-03-30 2018-10-04 栗田工業株式会社 Solid chemical agent housing body and water treatment method
JP2021092346A (en) * 2019-12-10 2021-06-17 株式会社振研 Method for suppressing scale generated from cooling water of cooling tower

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USD860387S1 (en) 2017-03-09 2019-09-17 Kurita Water Industries Ltd. Vessel for a solid water treatment agent

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63252597A (en) * 1987-04-09 1988-10-19 Kurita Seizosho:Kk Apparatus for adding solid chemical agent to cooling water of cooling tower
JPH0235983A (en) * 1988-07-22 1990-02-06 Somar Corp Slow release water treatment apparatus
JPH0459707A (en) * 1990-06-26 1992-02-26 Kurita Water Ind Ltd Slime-controlling agent
JPH07277912A (en) * 1994-04-01 1995-10-24 Nissan Chem Ind Ltd Stable solid halogen agent composition and tablet of solid halogen agent
JPH1147755A (en) * 1997-07-29 1999-02-23 Hakuto Co Ltd Slime controlling agent and method
JPH11263702A (en) * 1997-12-11 1999-09-28 Rohm & Haas Co Sustained-release composition
JP2001072502A (en) * 1999-09-03 2001-03-21 Nippon Soda Co Ltd Slimicide
JP2004293897A (en) * 2003-03-26 2004-10-21 Touzai Kagaku Sangyo Kk Agent housing container for cooling water of cooling tower
JP2005041813A (en) * 2003-07-22 2005-02-17 Shikoku Chem Corp Halogenated hydantoin molding
JP2008505883A (en) * 2004-07-08 2008-02-28 ブローミン コンパウンズ リミテッド New solid composition for water sterilization
JP2009001556A (en) * 2007-05-21 2009-01-08 Nippon Nohyaku Co Ltd Material including microbicide
JP2014176850A (en) * 2014-06-17 2014-09-25 Aquas Corp Method for treating open circulation cooling water system

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61185397A (en) * 1985-02-13 1986-08-19 Ebara Infuiruko Eng Service Kk Apparatus for adding chemical agent
GB8707004D0 (en) * 1987-03-24 1987-04-29 Alcan Int Ltd Inhibiting corrosion in apparatus
US6133300A (en) * 1999-10-15 2000-10-17 Troy Technology Corporation, Inc. Antimicrobial mixtures of 1,3-bis(hydroxymethyl)-5,5-dimethylhydantoin and 1,2-benzisothiazolin-3-one
GB0718420D0 (en) * 2007-09-21 2007-10-31 Reckitt Benckiser Inc Improvements in dispensing devices

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63252597A (en) * 1987-04-09 1988-10-19 Kurita Seizosho:Kk Apparatus for adding solid chemical agent to cooling water of cooling tower
JPH0235983A (en) * 1988-07-22 1990-02-06 Somar Corp Slow release water treatment apparatus
JPH0459707A (en) * 1990-06-26 1992-02-26 Kurita Water Ind Ltd Slime-controlling agent
JPH07277912A (en) * 1994-04-01 1995-10-24 Nissan Chem Ind Ltd Stable solid halogen agent composition and tablet of solid halogen agent
JPH1147755A (en) * 1997-07-29 1999-02-23 Hakuto Co Ltd Slime controlling agent and method
JPH11263702A (en) * 1997-12-11 1999-09-28 Rohm & Haas Co Sustained-release composition
JP2001072502A (en) * 1999-09-03 2001-03-21 Nippon Soda Co Ltd Slimicide
JP2004293897A (en) * 2003-03-26 2004-10-21 Touzai Kagaku Sangyo Kk Agent housing container for cooling water of cooling tower
JP2005041813A (en) * 2003-07-22 2005-02-17 Shikoku Chem Corp Halogenated hydantoin molding
JP2008505883A (en) * 2004-07-08 2008-02-28 ブローミン コンパウンズ リミテッド New solid composition for water sterilization
JP2009001556A (en) * 2007-05-21 2009-01-08 Nippon Nohyaku Co Ltd Material including microbicide
JP2014176850A (en) * 2014-06-17 2014-09-25 Aquas Corp Method for treating open circulation cooling water system

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018180402A1 (en) * 2017-03-30 2018-10-04 栗田工業株式会社 Solid chemical agent housing body and water treatment method
JP2021092346A (en) * 2019-12-10 2021-06-17 株式会社振研 Method for suppressing scale generated from cooling water of cooling tower

Also Published As

Publication number Publication date
MY198348A (en) 2023-08-28
JP6394659B2 (en) 2018-09-26
TWI726142B (en) 2021-05-01
PH12018502690A1 (en) 2019-10-14
TW201829319A (en) 2018-08-16
CN109415233B (en) 2020-08-25
SG11201811348WA (en) 2019-01-30
JP2018030063A (en) 2018-03-01
CN109415233A (en) 2019-03-01
PH12018502690B1 (en) 2019-10-14

Similar Documents

Publication Publication Date Title
WO2018038091A1 (en) Composite-type solid water treatment product
US20070029263A1 (en) Multi-functional oxidizing composition
SA518400529B1 (en) Hand disinfectant
US8591748B2 (en) Water treatment
US7993545B2 (en) Tablet composition for the in-situ generation of chlorine dioxide for use in antimicrobial applications
CA2683081A1 (en) Calcium hypochlorite compositions comprising zinc salts and lime
US20090232903A1 (en) Biocide compositions
US8017032B2 (en) Tablet composition for the in-situ generation of chlorine dioxide for use in antimicrobial applications
GB2437489A (en) Disinfectant mixture of a donor of freely available chlorine (e.g. hypochlorite) and a buffering agent or acid, optionally in the form of an aqueous solution
TWI743178B (en) Container and container set for solid water treatment agent and water treatment method
US7780857B2 (en) Solid composition for treating water
CA2545338C (en) Multi-functional oxidizing composition
JP2018167239A (en) Solid chemical agent accommodation body and water treatment method
Abdou et al. Identification of the Chlorine-and Bromine-Based Biocides-Task 1 of the NESC Assessment of Biocide Impacts on Life Support (LS) and Extravehicular Activity (EVA) Architectures
UA75335C2 (en) A method for water disinfection and a composition for realizing the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17843571

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17843571

Country of ref document: EP

Kind code of ref document: A1