JP2018030063A - Composite solid water-treated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite solid water-treated product that safely uses a halogen oxidizing agent and an active ingredient having reactivity therewith, while maintaining the excellent efficacy produced from the combination of these active ingredients, and also offers excellent convenience in handleability.SOLUTION: A composite solid water-treated product is eluted and used in water to be treated. In the solid water-treated product, a solid agent of a halogen oxidizing agent containing a halogenated hydantoin compound as an active ingredient (A) and a solid agent containing an organic bactericide having reactivity with the halogen oxidizing agent (B) are stored in an elution container without brought into contact with each other.SELECTED DRAWING: None

Description

  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.

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.

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.

  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.

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.

JP2015-93260A Japanese Patent Laid-Open No. 11-47755 JP 2007-31850 A

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.

  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.

  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. In combination, the drug effect of both solid preparations can be exhibited safely and at the same time easy to handle.

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 one or more 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 is 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 combined solid water treatment product according to the above [3], 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 the above [1] to [4], comprising isothiazolin-3-one.
[6] Any one of the above-mentioned [1] to [5], wherein the solid agent (B) contains any 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] The composite solid water treatment product according to any one of [1] to [6], wherein the solid agent (A) is a tablet.
[8] The combined solid water treatment product according to any one of [1] to [7], wherein the solid agent (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 type solid water treatment product according to any one of the above [1] to [9], which has one or more partition wall communication passages through which water can flow.

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.

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. 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. It is a side view which shows the outline of one Embodiment of the composite type solid water treatment product of this invention.

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.

[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.

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.

  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. Among these, BCDMH and 1,3-dichloro-5,5-dimethylhydantoin are preferable from the viewpoints of balance with the solid agent (B) of the elution rate when contacted with water and availability.

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).

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 spp., The effective halogen (Cl ₂ equivalent) concentration 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)]
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).

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-based 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 and 1,2-benzisothiazolin-3-one. These may be used alone or in combination of two or more. Among these, Cl-MIT is preferable 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.

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 (unit: mg / L) of Cl-MIT in the treated water is relative to the effective halogen (Cl ₂ equivalent) concentration (unit: mg / L) of BCDMH in the treated water. It is preferable that it is 0.00001-100 times, More preferably, it is 0.01-30 times, More preferably, it is 0.1-1 times. In addition, it is preferable that the density | concentration of Cl-MIT in to-be-processed water is 0.0001-5 mg / L, More preferably, it is 0.001-3 mg / L, More preferably, it is 0.001-2 mg / L.

  The solid agent (B) may contain other known compounds used in the water treatment agent from the viewpoint of anticorrosion and scale prevention, in addition to the organic fungicide. For example, triazole compounds, phosphonic acid compounds, sulfamic acid compounds, ametrine, 2,2-dibromo-3-nitrilopropionamide, bronopol, zinc pyrithione, thiabendazole, acrylic acid and maleic acid based flocculants 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 mass, more preferably 2 to 35% from the viewpoint of allowing the organic fungicide to have an appropriate elution rate. %, More preferably 5 to 30% by mass.

[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.

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.

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.
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.

  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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by the following Example.

[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

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.

[Confirmation test of bactericidal action]
A test for confirming the bactericidal action against Legionella by the combined use of BCDMH and Cl-MIT was performed 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

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 with respect to Legionella genus bacteria by combined use with BCDMH and Cl-MIT was confirmed.

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)

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.   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.   The combined solid water treatment product according to claim 1 or 2, wherein the organic disinfectant contains an isothiazoline compound as an active ingredient.   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. The halogen-based oxidizing agent contains 1-bromo-3-chloro-5,5-dimethylhydantoin as an active ingredient,
The composite type solid water treatment product according to any one of claims 1 to 4, wherein the organic fungicide contains 5-chloro-2-methyl-4-isothiazolin-3-one as an active ingredient.   The composite type according to any one of claims 1 to 5, wherein the solid agent (B) contains any one or more selected from triazole compounds, phosphonic acid compounds, and sulfamic acid compounds. Solid water treatment product.   The combined solid water treatment product according to claim 1, wherein the solid agent (A) is a tablet.   The combined solid water treatment product according to claim 1, wherein the solid agent (B) is a tablet.   The composite solid water treatment product according to any one of claims 1 to 8, wherein the water to be treated is cooling water in a cooling tower. 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 type solid water treatment product according to any one of claims 1 to 9, which has one or more partition wall communication passages through which cooling water can flow.

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