CN112996756B - Water treatment agent - Google Patents

Abstract

The present invention provides a water treatment agent in which the effect of hypobromous acid is well exhibited when added to a water system. The present invention is a water treatment agent containing the following components (a) to (c) and having a pH of 10 or more, and/or a water treatment agent containing an alkaline agent, a chloramine compound and a bromide salt, wherein (a ) chloramine compound, (b) bromide salt, (c) 1 mass% to 18 mass% of a carboxyl polymer having a carboxyl group content rate of 0.8g‑COOH/g‑polymer or less, a water treatment agent , the total chlorine detection rate after production is more than 95% and the free chlorine content rate in the total chlorine concentration is less than 0.05% (calculated as _Cl2 ). The molar ratio of the chloramine compound to the bromide salt is preferably 1:0.1-1.0.

Description

water treatment agent

Technical field

This technology involves water treatment technology such as water treatment agents.

Background technique

In various water systems such as water storage systems, pulp process water systems, dust collection water systems, and scrubber water systems, in order to prevent biological adhesion, prevent slime, or kill microorganisms (such as bacteria, fungi, Algae, etc.), use hypohalous acid (such as hypochlorous acid, hypobromous acid, etc.). As an example, the above-mentioned effect is obtained by circulating hypohalous acid in open-circulation cooling water or the like. Among the above-mentioned hypohalous acids, hypobromous acid has a higher bactericidal power than hypochlorous acid, so the use of hypobromous acid in water systems has attracted attention.

For example, Patent Document 1 describes a method for sterilizing water, in which a chlorine-based oxidizing agent and a stabilized hypobromous acid composition are added to the water, and the stabilized hypobromous acid composition contains a bromine-based oxidizing agent, or a bromine compound and a chlorine-based oxidizing agent. Reactants of oxidizing agents, and sulfamic acid compounds.

For example, Patent Document 2 proposes a method for preparing a biocide in order to control pollution caused by microorganisms in water systems. The preparation method includes: (a) combining unstabilized sodium hypochlorite with sulfamate as a stabilizer. The step of preparing a stabilized alkali metal or alkaline earth metal hypochlorite having a pH of at least 11 by mixing an acid in an alkaline solution; (b) the step of preparing sodium bromide as a source of bromide ions; and (c) The step of adding the bromide ion source prepared in the aforementioned step (b) to the stabilized alkali metal or alkaline earth metal hypochlorite prepared in the aforementioned step (a) (for example, refer to claim 1 and paragraphs [0047] etc.).

In addition, for example, Patent Document 3 proposes a method of producing a stabilized bromine solution as a method of producing a stabilized bromine solution for controlling biological adhesion, which method includes: a. making sodium bromide as a bromine source The step of combining the solution with a solid sulfamate as a stabilizer to form a mixture; b. The step of slowly adding a sodium hypochlorite solution as an oxidizing agent to the aforementioned mixture; and then, c. Slowly adding hydroxide as an alkali source to the aforementioned mixture. sodium solution, a step of adjusting the pH of the mixture to at least 13 (for example, refer to claim 1 and paragraph [0022], etc.).

existing technical documents

patent documents

Patent Document 1: Japanese Patent Application Publication No. 2016-209837

Patent Document 2: Japanese Patent Publication No. 2005-519089

Patent Document 3: Japanese Patent Publication No. 2002-540297

Patent Document 4: Japanese Patent Application Publication No. 2014-140056

Contents of the invention

Invent the problem to be solved

The main purpose of this technology is to provide a water treatment technology in which the effect of hypobromous acid is well exhibited when added to a water system.

solutions to problems

The present inventors conducted intensive research in order to solve the above-mentioned problems, and as a result found that it is possible to provide a water treatment technology in which the effect of hypobromous acid can be effectively exhibited when added to a water system, and completed the present technology.

That is, this technology is as follows.

[1] A water treatment agent containing the following components (a) to (c) and having a pH of 10 or more:

(a)Chloramine compounds,

(b) Bromide salt,

(c) 1 to 18 mass% of a carboxyl polymer having a carboxyl group content rate of 0.8 g-COOH/g-polymer or less.

[2] The water treatment agent according to the above [1], wherein the molar ratio of the chloramine compound to the bromide salt is 1:0.1 to 1.0.

[3] The water treatment agent according to the above [1] or [2], which is at least one of slime control, corrosion prevention, and scale prevention.

[4] The water treatment agent according to any one of the above [1] to [3], wherein the (a) chloramine compound and the (b) bromide salt in the water treatment agent are It is obtained by mixing a mixed solution of an alkaline agent, a stabilizer and a bromide salt with an oxidizing agent.

[5] The water treatment agent according to any one of the above [1] to [4], wherein the total chlorine detection rate after production of the water treatment agent is 95% or more and the free chlorine in the total chlorine concentration The content rate is 0.05% or less in terms of _Cl2 .

[6] A method for producing a water treatment agent, which includes mixing a mixed solution of an alkali agent, a stabilizer, and a bromide salt with an oxidizing agent.

[7] The method for producing a water treatment agent according to the above [6], wherein the stabilizer is a sulfamic acid compound.

[8] The method for producing a water treatment agent according to the above [6] or [7], wherein the oxidizing agent is a chlorine-based oxidizing agent.

[9] The method for producing a water treatment agent according to any one of [6] to [8] above, wherein the pH of the mixed solution is 13 or more.

[10] The method for producing a water treatment agent according to any one of [6] to [9] above, wherein the mixed solution is a solution in which powdered bromide salt is mixed as the bromide salt.

[11] The method for producing a water treatment agent according to any one of the above [6] to [10], wherein the carboxyl polymer is further mixed to 1% by mass to 18% by mass, and the carboxyl group in the carboxyl polymer is The content rate is 0.8g-COOH/g-polymer or less.

[12] A water treatment agent containing an alkali agent, a chloramine compound and a bromide salt,

The total chlorine detection rate after manufacture of the water treatment agent is 95% or more and the free chlorine content rate in the total chlorine concentration is 0.05% or less in terms of _Cl2 .

[13] The water treatment agent according to the above [12], which is obtained by mixing a mixed solution of an alkaline agent, a stabilizer, and a bromide salt with an oxidizing agent.

[14] The water treatment agent according to the above [13], wherein the pH of the water treatment agent is 13 or more.

Effect of invention

According to this technology, it is possible to provide a water treatment technology in which the effect of hypobromous acid is well exhibited when added to a water system. It should be noted that the effects described here are not necessarily limited, and may be any effects described in this specification.

Description of the drawings

Figure 1 shows the time-dependent changes in the total oxidizing agent concentration in the water system (pH 8 to 9) when each sample 1 to 4 is added. Sample 1: chloramine compound (×), sample 2: chloramine compound + bromide (△), sample 3: chloramine compound + carboxyl polymer (□), sample 4: chloramine compound + carboxyl polymer substance + bromide (◇). The carboxyl polymer has a carboxyl group content of 0.77 g-COOH/g-polymer. The concentration when only the chloramine compound is added is 100%.

Figure 2 shows hypobromous acid in the water system when each water treatment agent is added to the water system (pH 8 to 9) while changing the carboxyl group content ratio (g-COOH/g-polymer) of the carboxyl polymer in the water treatment agent. The relationship between concentration (%) and total oxidant concentration (%). The concentration of carboxyl polymer in the water system is 5 mg-polymer/L, measured 48 hours after addition. The hypobromous acid concentration when no carboxyl polymer is added is set to 100%.

Figure 3 shows hypobromous acid in the water system when each water treatment agent is added to the water system (pH 8 to 9) while changing the carboxyl group content ratio (g-COOH/g-polymer) of the carboxyl polymer in the water treatment agent. The relationship between concentration (%) and total oxidant concentration (%). The concentration of carboxyl polymer in the water system is 30 mg-polymer/L, measured 48 hours after addition. The hypobromous acid concentration when no carboxyl polymer is added is set to 100%.

Figure 4 shows the concentration of the carboxyl polymer in the water system (mg/L) and the hypobromous acid concentration when the content of the carboxyl polymer in the water treatment agent is changed and each water treatment agent is added to the water system (pH 8 to 9). (%)Relationship. The hypobromous acid concentration when no carboxyl polymer is added is set to 100%.

Fig. 5 shows the change over time of the hypobromous acid concentration (mg/L as _Cl2 ) in the water system when the water treatment agent of the present technology is added to the water system (pH 8 to 9).

FIG. 6 shows each water treatment agent of Test Example 29 (Example 1), Test Example 30, and Test Example 31 (Comparative Example 1 and Comparative Example 2) when a fixed time has elapsed after the production of each water treatment agent. Changes in total chlorine detection rate (%).

Detailed ways

Hereinafter, the method for implementing this technology will be described. It should be noted that the embodiment described below is an example of a representative embodiment of the present technology, and the scope of the present technology is not to be interpreted in a limiting manner.

It should be noted that in this specification, percentages are expressed in terms of mass unless otherwise specified. In addition, the upper limit and lower limit of each numerical range can be arbitrarily combined as needed.

<1. Overview of this technology>

The main purpose of this technology is to provide a water treatment technology in which the effect of hypobromous acid is well exhibited when added to a water system.

Furthermore, the present technology can provide the water treatment technology of the first embodiment of the present technology and the water treatment technology of the second embodiment of the present technology. This makes it possible to provide a water treatment technology in which the effect of hypobromous acid is well exhibited when added to a water system.

The first embodiment of the present technology can provide a water treatment agent, etc., which contains the following components (a) to (c) and has a pH of 10 or more: (a) chloramine compound, (b) bromide salt, (c) ) The carboxyl group content rate in the polymer is 0.8 g-COOH/g-polymer or less and 1 to 18 mass% of the carboxyl polymer.

According to the first embodiment, it is possible to provide a water treatment technology such as a one-liquid type water treatment agent in which the effect of hypobromous acid is well exerted when added to a water system and the chemical effects of other compounds are also well exerted.

A second embodiment of the present technology is a method for producing a water treatment agent in which a mixed solution of an alkali agent, a stabilizer, and a bromide salt is mixed with an oxidant, and a water treatment agent obtained by the method, and A water treatment agent containing an alkaline agent, a chloramine compound and a bromide salt, which can provide a total chlorine detection rate of more than 95% after manufacture and a free chlorine content rate of 0.05% in the total chlorine concentration (calculated as _Cl2 ) The following water treatment agents, etc.

According to the second embodiment, it is possible to provide a water treatment technology such as a water treatment agent that exhibits a good effect of hypobromous acid when added to a water system and has excellent quality stability of the agent.

Furthermore, this technology can be combined with the technology of the first embodiment and the second embodiment. This makes it possible to provide a water treatment technology in which the effect of hypobromous acid is well exerted when added to a water system, and furthermore, this water treatment technology has a single liquid that can form other compounds and can also exert a good effect. Advantages of type and/or excellent quality and stability of pharmaceuticals.

In addition, this technology can also be applied to a water treatment device or a water treatment system in which the effect of hypobromous acid is expected. It is also possible to provide a water treatment device or water treatment system of the present technology, which is configured so that the first embodiment and/or the second embodiment of the present technology can be combined with a conventional water treatment device or water treatment system in which the effect of bromic acid is expected. implemented in the system. The water treatment device or water treatment system of the present technology preferably includes: a storage device for each component used in the present technology; a device for adding each component or mixing the components; and a mixing device or pipe for mixing each component (for example, using stirring or Convection mixing, etc.) etc. The water treatment device or water treatment system of the present technology may further include a control unit or control device described below. In addition, it is also possible to provide a device for adding water treatment agents or components according to the present technology.

In addition, the water treatment method that exhibits the effect of hypobromous acid of the present technology can also be used to control the addition timing, addition amount, mixing ratio, etc. of each component or water treatment agent used in the present technology including a central processing unit (Central Processing). Unit, CPU) and other control units (such as computers, etc.). In addition, the method of this technology can also be stored as a program in a device equipped with a recording medium (non-volatile memory (Universal Serial Bus (USB) memory, etc.)), a hard disk drive (Hard Disk Drive, HDD), an optical disk ( In hardware resources such as Compact Disc, CD), etc., it is realized by the aforementioned control unit. It is also possible to provide a control device or an adding device that is controlled by the control unit to add a chemical to the water to be treated. Furthermore, this technology can also provide the water treatment system or water treatment apparatus provided with the said control device, the said addition device, etc.

The water treatment technology according to the first embodiment of the present technology and the water treatment technology according to the second embodiment of the present technology will be described in detail below. In addition, in the description of the present technology, in the first embodiment and the second embodiment, overlapping structures, components, etc. are appropriately omitted.

<2. Water treatment agent according to the first embodiment of the present technology>

Hereinafter, a mode for implementing the first embodiment of the present technology will be described. It should be noted that the embodiment described below is an example of a representative embodiment showing the first embodiment of the present technology, and the scope of the first embodiment of the present technology is not to be interpreted in a limiting manner.

The main purpose of the first embodiment of the present technology is to provide a water treatment agent such as a single-liquid type water treatment agent in which the effect of hypobromous acid is well exerted when added to a water system and the chemical effects of other compounds are also well exerted. technology.

Generally, polymers having carboxyl groups (hereinafter also referred to as "carboxyl polymers") are used as chemicals for slime control, anti-corrosion, anti-fouling, etc., so the present inventors expected to use chloramine compounds and bromine compounds as agents. When a single-liquid water treatment agent is prepared by blending a carboxyl polymer (for example, a maleic acid-based or acrylic acid-based polymer) into a compound salt and added to the water system, hypobromous acid exerts good effects except for hypobromous acid. In addition to the effect of the carboxyl polymer, the pharmaceutical effect of the carboxyl polymer can also be exerted.

However, the present inventors discovered that when a water treatment agent in which a carboxyl polymer is blended with a chloramine compound and a bromide salt is added to a water system, the decomposition of hypobromous acid in the water system proceeds rapidly due to the carboxyl polymer, and the water system The stability of the hypobromous acid in the product over time decreases, and the effect of hypobromous acid is not sustained (see Figure 1). However, the present inventors dared to conduct in-depth research on a one-pack type water treatment agent that can exert the chemical effect of a carboxyl polymer in addition to the effect exerted by hypobromous acid in a water system.

As a result, the present inventors found that by adjusting the characteristics and content of the carboxyl polymer in a water treatment agent containing a chloramine compound and a bromide salt, a unit capable of obtaining good stability over time when added to a water system can be obtained. Liquid water treatment agent. Furthermore, the present inventors discovered that in addition to the effect of hypobromous acid, the pharmaceutical effect of the carboxyl polymer can also be favorably exerted, and completed the present technology.

That is, this technology can adopt the following.

The first embodiment of the present technology can provide a water treatment agent containing the following components (a) to (c) and having a pH of 10 or more.

(a)Chloramine compounds

(b) Bromide salt

(c) 1 to 18 mass% of a carboxyl polymer having a carboxyl group content rate of 0.8 g-COOH/g-polymer or less.

In addition, the molar ratio of the chloramine compound and the bromide salt is preferably 1:0.1 to 1.0.

In addition, the water treatment agent is preferably at least one for slime control, anti-corrosion, or anti-scaling.

The water treatment agent according to the first embodiment of the present technology contains a chloramine compound and a bromide salt that generate hypobromous acid, and further contains a specific amount of a specific carboxyl polymer, and the water treatment agent is adjusted to an alkaline range. This is a one-liquid water treatment agent, and hypobromous acid is not easily generated in this water treatment agent over time. As a result, the water treatment agent according to the first embodiment of the present technology has excellent chemical quality stability over time. Therefore, even if it is distributed on the market as a single-liquid type, stable quality can be maintained even if the water treatment agent is transferred after a fixed period of storage. Even when the one-liquid type water treatment agent according to the first embodiment of the technology is used in a water system, good effects can be expected.

Furthermore, by containing a specific amount of a specific carboxyl polymer, the water treatment agent according to the first embodiment of the present technology can control hypobromide in the water system when the water treatment agent according to the first embodiment of the present technology is added to the water system. Acid production. Therefore, the water treatment agent according to the first embodiment of the present technology can be controlled so that hypobromous acid is not rapidly generated in a short period of time in the water system. Furthermore, the water treatment agent according to the first embodiment of the present technology can gradually generate hypobromous acid in the water system over time, and therefore can maintain the effect of hypobromous acid in the water system for a longer period of time.

On the other hand, the water treatment agent according to the first embodiment of the present technology is a one-liquid type agent and can also be used as a slow release water treatment agent. If hypobromous acid is rapidly released in the water system, it will easily lead to corrosion or deterioration in the water system. However, since the water treatment agent according to the first embodiment of the present technology can control the generation rate of hypobromous acid slowly, it can reduce the amount of hypobromous acid in the water system. corrosion or deterioration, and the effects caused by hypobromous acid (e.g., bactericidal effect, etc.) can be obtained continuously over a long period of time. Therefore, it is more advantageous to apply the water treatment agent according to the first embodiment of the present technology to an open circulation device having a cooling water system, a water storage system, a dust collection water system, a scrubber water system, or the like.

Furthermore, the carboxyl polymer used in the first embodiment of the present technology is a component that can be used as a slime control agent, an anti-corrosion agent, an anti-scaling agent, and the like. Therefore, when the water treatment agent according to the first embodiment of the present technology is added to a water system, the effect of hypobromous acid can be well exhibited, and the chemical effect of the carboxyl polymer as another compound can also be well exhibited.

The present inventors established the following hypothesis regarding the mechanism of generating hypobromous acid in the water system when the water treatment agent according to the first embodiment of the present technology is used, and further conducted in-depth research on the mechanism of action of the first embodiment of the present technology.

The water treatment agent according to the first embodiment of the present technology is preferably a single-liquid type agent, and is preferably designed in the form of a chloramine compound (hereinafter referred to as a chloramine compound) and bromide ions, which are a combination of a sulfamic acid compound and hypochlorous acid. exists and contains a specific amount of the aforementioned specific carboxyl polymer. In the first embodiment of the present technology, it is important to use a carboxyl polymer whose characteristics are adjusted, so the carboxyl group content rate in the carboxyl polymer is adjusted to a predetermined range. In addition, it is important to contain a specific amount of this specific carboxyl polymer in a one-pack type agent and to use it in an aqueous system. The first embodiment of the present technology is preferably a water treatment agent adjusted to a state in which the pH is raised and excess sulfamic acid coexists. This can be controlled so that the reaction of generating hypobromous acid from the chloramine compound hardly occurs.

Furthermore, when the water treatment agent according to the first embodiment of the present technology is added to the water system, the chloramine compound and the bromide salt react to generate sulfamic acid, hypobromous acid, and the like. This enables the sterilization effect caused by hypobromous acid and the like generated in the water system to be exerted, and the medicinal effect of the carboxyl polymer that is difficult to achieve with conventional single-liquid water treatment agents can also be exerted, and furthermore, the secondary effect can be continuously exerted. The effect of bromic acid.

＜2-(a) Chloramine compound＞

The chloramine compound used in the first embodiment of the present technology is not particularly limited. For example, it is preferable to react hypochlorous acid (HOCl) with a compound having a primary amino group (XNH) through the reaction shown in the following reaction formulas (1) and (2). ₂ ) A compound (XNHCl) obtained by the reaction in which the hydrogen atom of the amino group is replaced by a chlorine atom. This compound has a weak oxidation effect on metals, films, etc. in the water system, so it can inhibit the progression of corrosion or film deterioration, and can be continuously and/or continuously used in the water system.

The chloramine compound used in the first embodiment of the present technology is not particularly limited, but it is preferable to use any one of a compound having a primary amino group, ammonia, and an ammonium salt (hereinafter, these are also referred to as "NH _2- based compounds" ) is produced and obtained by mixing with hypochlorous acid and/or hypochlorite.

The compound having a primary amino group is not particularly limited, and examples thereof include aliphatic amines, aromatic amines, sulfamic acid, sulfanilic acid, sulfamoylbenzoic acid, and amino acids. Examples of the ammonium salt include ammonium chloride, ammonium sulfate, and the like. One selected from the group consisting of these may be used alone, or two or more types may be mixed and used.

Among these NH ₂ compounds, sulfamic acid is preferred (NH ₂ SO ₂ OH is more preferred). If sulfamic acid is used to generate monochlorosulfamic acid, it will become a stable chloramine compound.

Examples of the sulfamic acid compound include compounds represented by the following general formula [1] or salts thereof.

(Wherein, in the general formula [1], R ¹ and R ² are each independently hydrogen or a hydrocarbon having 1 to 8 carbon atoms.)

Examples of such sulfamic acid compounds include, in addition to sulfamic acid in which both R ¹ and R ² are hydrogen, N-methylsulfamic acid, N,N-dimethylsulfamic acid, and N-phenyl. Sulfamic acid, etc. One selected from the group consisting of these may be used alone, or two or more types may be mixed and used.

The salt of the compound used in the first embodiment of the present technology is not particularly limited, and examples thereof include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts, strontium salts, and barium salts; manganese salts, and copper salts. Salts, zinc salts, iron salts, cobalt salts, nickel salts and other metal salts; ammonium salts, guanidinium salts and other amine salts or amino acid salts, etc., one selected from the group consisting of these, or a combination of two or more can be suitably used. use. Among these, an alkali metal salt (preferably sodium) is preferred from the viewpoint of cost and ease of operation.

These salts mentioned above can be used as salts of sulfamic acid compounds.

Examples of the sulfamate compound used in the first embodiment of the present technology include sodium sulfamate, potassium sulfamate, calcium sulfamate, strontium sulfamate, barium sulfamate, iron sulfamate, amino Zinc sulfonate, etc. One selected from the group consisting of these may be used alone, or two or more types may be mixed and used.

In the first embodiment of the present technology, one selected from the group consisting of sulfamic acid and these sulfamate salts may be used alone, or two or more species may be used in combination.

On the other hand, as the hypochlorite that reacts with the NH ₂ -based compound, alkali metal salts of hypochlorous acid such as sodium hypochlorite; alkaline earth metal salts of hypochlorous acid such as calcium hypochlorite, etc. can be used. One selected from the group consisting of these may be used alone, or two or more types may be mixed and used.

When an NH ₂ -based compound and hypochlorous acid and/or hypochlorite are mixed to generate a chloramine compound, from the viewpoint of the production efficiency and stability of chloramine, the NH ₂ -based compound and hypochlorous acid and/or hypochlorite are The chlorate is preferably used so that the molar ratio of available chlorine (Cl ₂ ) derived from hypochlorous acid and/or hypochlorite to the nitrogen atom N derived from the NH ₂ -based compound, that is, the Cl ₂ /N molar ratio becomes 0.1 to 0.1 1 method is used. If the Cl ₂ /N molar ratio is below the above upper limit, the generation of free chlorine can be suppressed. If it is above the above lower limit, the reduction in the chloramine generation efficiency relative to the NH ₂ -based compound used can be suppressed.

The content of the chloramine compound in the water treatment agent according to the first embodiment is preferably 4% by mass or more, more preferably 6% by mass or more, and even more preferably 8% by mass or more as the lower limit. The limit value is preferably 24% by mass or less, more preferably 22% by mass or less, and even more preferably 20% by mass or less. The numerical range is preferably 4% by mass to 24% by mass, more preferably 6% by mass to 22% by mass, and even more preferably 8% by mass to 20% by mass.

＜2-(b) Bromide salt＞

The bromide salt used in the first embodiment of the present technology is not particularly limited, and examples thereof include alkali metal bromide salts, ammonium bromide salts, hydrobromic acid, and amine bromide salts, and a group selected from these can be used. one or more than two of them.

Examples of the alkali metal bromide salt include sodium bromide, potassium bromide, lithium bromide, etc., but are not limited thereto.

Examples of the aforementioned amine bromide salt (linear, branched, or cyclic alkyl or alkenyl group having 1 to 6 carbon atoms) include diethylamine hydrogen bromide, allylamine hydrogen bromide, and cyclohexylamine hydrogen bromide. , monomethylamine hydrogen bromide, dimethylamine hydrogen bromide, trimethylamine hydrogen bromide, n-butylamine hydrogen bromide or ethylamine hydrogen bromide, etc., but are not limited thereto.

As the aforementioned bromide salt, one or two or more types selected from the group consisting of these can be used.

Regarding the content of the bromide salt in the water treatment agent of the first embodiment, in terms of bromide conversion, the lower limit thereof is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and still more preferably 1.0 mass% or more. , In addition, the upper limit is preferably 10 mass% or less, more preferably 9 mass% or less, and still more preferably 8 mass% or less. As this numerical range, 0.1 mass % to 10 mass % is preferable, 0.5 mass % to 9 mass % is more preferable, and 1.0 mass % to 8 mass % is still more preferable.

<Measurement method for bromide (Br ^- )>

Bromide (Br ^- ) in this technology can be analyzed and the concentration can be measured based on the method of Japanese Industrial Standards (JIS)-K0101 (1998) 28.4.

＜pH measurement method＞

The pH in this technology can be measured at room temperature of 25°C using a general pH meter (for example, "Portable pH Meter D-54 (pH/mV (ORP)/COND/Resistivity) manufactured by Horiba Manufacturing Co., Ltd. /Salt/TDS)" or subsequent models) to measure.

＜2-(c)carboxypolymer＞

The carboxyl polymer used in the first embodiment of the present technology is not particularly limited as long as it is a polymer compound having a specific amount of carboxyl groups.

Furthermore, the carboxyl polymer used in the first embodiment of the present technology preferably has a carboxyl group content rate in the carboxyl polymer (hereinafter also referred to as “in the polymer”) of a specific rate. Therefore, when the water treatment agent according to the first embodiment of the present technology is added to a water system, it is possible to exhibit the effects unique to the carboxyl polymer and to effectively exhibit hypobromous acid generated in the water system without decomposing it very much. Effect of Bromic Acid.

Here, the present inventors discovered that by controlling the carboxyl group content rate in the carboxyl polymer and the carboxyl group concentration in the water system, hypobromous acid in the water system can be controlled so as not to be decomposed. Furthermore, the present inventors also found that the content of the carboxyl polymer contained in the water treatment agent can be specified by studying the correlation between the carboxyl group content rate in the carboxyl polymer and the carboxyl group concentration in the water system.

Thus, the present inventors were able to design a one-liquid water treatment agent containing the component (a) chloramine compound and the component (b) bromide salt, and containing a specific amount of the component (c) a specific carboxyl polymer. This water treatment agent is a single-liquid type and can also inhibit the decomposition of other components due to mixing of components. This water treatment agent can stably maintain its quality, and when added to a water system, it can effectively exhibit the respective effects of hypobromous acid and carboxyl polymer. Furthermore, by using a specific amount of this specific carboxyl polymer in a water system, the effect of hypobromous acid can be exerted continuously and for a longer period of time. Therefore, the water treatment agent according to the first embodiment of the present technology is effective from the viewpoint of reducing the number of additions to the water system due to slow release properties, simplifying the work process due to use of a single-liquid type, and reducing the decomposition of hypobromous acid. It is also excellent from the viewpoint of continuously expressing effects or reducing costs.

Therefore, the carboxyl polymer according to the first embodiment of the present technology preferably has a carboxyl group content rate of 0.8 g-COOH/g-polymer or less, and the carboxyl polymer is 1 mass in the water treatment agent according to the first embodiment. %~18% by mass.

[Carboxyl group content in polymer]

In the water treatment agent according to the first embodiment of the present technology, the upper limit of the carboxyl group content in the polymer is preferably 0.8 g-COOH/g-polymer or less, and more preferably 0.77 g-COOH/g. -polymer or less, more preferably 0.72g-COOH/g-polymer or less, and the lower limit thereof is preferably 0.1g-COOH/g-polymer or more, more preferably 0.2g-COOH/g-polymer or more . This numerical range is more preferably 0.8 g-COOH/g-polymer to 0.1 g-COOH/g-polymer, and further preferably 0.77 g-COOH/g-polymer to 0.2 g-COOH/g-polymer.

<Measurement method of carboxyl group content (g-COOH/g-polymer)>

Carbon derived from carboxyl groups (180 ppm to 182 ppm) can be quantified using 13C-Nuclear Magnetic Resonance (NMR) spectroscopy (carbon 13 nuclear magnetic resonance) (measurement temperature: 30°C). Sodium 3-(trimethylsilyl)propionate can be used as a standard substance to quantify the carbon derived from the carboxyl group based on the concentration of sodium 3-(trimethylsilyl)propionate. In addition, the influence of the nuclear Overhauser effect (NOE) can be removed through gated decoupling (1J(C, H)).

The lower limit of the content of the carboxyl polymer in the water treatment agent of the first embodiment is preferably 0.5% by mass or more, more preferably 0.75% by mass or more, still more preferably 1.0% by mass or more, still more preferably 1.5% by mass. As mentioned above, the upper limit is preferably 25 mass% or less, more preferably 20 mass% or less, still more preferably 18 mass% or less, still more preferably 15 mass% or less. The numerical range is preferably 0.5% by mass to 25% by mass, more preferably 0.75% by mass to 20% by mass, and even more preferably 1% by mass to 18% by mass from the viewpoint of cost, work efficiency, effect expression, etc.

<Measurement method of weight average molecular weight of water-soluble polymer>

The weight average molecular weight of the water-soluble polymer used in this technology can be measured by gel permeation chromatography (GPC) analysis using standard polystyrene as a standard material (for example, refer to Patent Document 4 (Reference 1): Japanese Patent Application Publication No. 2014-140056, etc.).

The type of carboxyl polymer used in the first embodiment of the present technology is not particularly limited. Examples thereof include water-soluble homopolymers and/or copolymers having a carboxyl group. More specifically, examples include maleic acid. Polymer, (meth)acrylic polymer. In addition, the "polymer" means a polymer containing a monomer and a copolymer.

More specific examples of the carboxyl polymer include maleic acid homopolymer, (meth)acrylic acid homopolymer, and copolymerization of an unsaturated monomer copolymerizable with maleic acid or (meth)acrylic acid. It is possible to use one type selected from the group consisting of these, or a combination of two or more types.

The carboxyl polymer in the first embodiment of the present technology preferably contains a maleic acid-based polymer and/or a (meth)acrylic acid-based polymer. The content ratio (content) of the maleic acid-based polymer and/or (meth)acrylic acid-based polymer in the carboxyl polymer is preferably 50 mass% or more, more preferably 80 mass% or more, still more preferably 90 mass% or more, and further More preferably it is 95% by mass or more, particularly preferably 99% by mass or more, and most preferably substantially 100% by mass. The higher the content ratio of the carboxyl polymer, the more expected effects of the present technology can be easily obtained.

Examples of the unsaturated monomer copolymerizable with maleic acid or (meth)acrylic acid monomers include 2-acrylamide-2-methylpropanesulfonic acid, 2-hydroxy-3-aryloxy- 1-Propane sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, acrylamide, ethylene, propylene, isopropylene, butylene, isobutylene, hexene, 2-ethylhexene, pentene, isopentene, octene , isooctene, vinyl alcohol, vinyl methyl ether, vinyl ethyl ether, etc. and their salts.

Examples include one or more monomers selected from the group consisting of homopolymers, copolymers, and copolymers of the foregoing monomers and isobutylene, which are obtained using one or two or more monomers selected from these monomers. Two or more polymers.

When chemical effects such as anti-corrosion effects are expected for the aforementioned carboxyl polymer, the weight average molecular weight is preferably 10 to the third power to the fourth power, more specifically, it is preferably in the range of 200 to 50,000, and more preferably 500 to 30,000. within the range, more preferably within the range of 800 to 30,000, still more preferably 1,000 to 20,000. In order to obtain chemical effects such as anti-corrosion effects, the weight average molecular weight is preferably 500 or more. From the viewpoint of operability, in order to reduce the viscosity of the aqueous solution, the weight average molecular weight is preferably 20,000 or less, and more preferably 16,000 or less.

The weight average molecular weight of the carboxyl polymer can be measured by the aforementioned <Measurement method of weight average molecular weight of water-soluble polymer>.

From the viewpoint of obtaining chemical effects such as anti-corrosion effects, the amount of the carboxyl polymer added to the water system is preferably such that the concentration in the water system becomes 1 mg-polymer/L to 100 mg-polymer/L, and more preferably The amount is 2 mg-polymer/L to 50 mg-polymer/L, and more preferably 5 mg-polymer/L to 30 mg-polymer/L.

<The pH of the water treatment agent according to the first embodiment of the present technology>

From the viewpoint of the stability of the agent over time, the pH of the water treatment agent according to the first embodiment of the present technology is in an alkaline range, more preferably 10 or more, still more preferably 11 or more, still more preferably 12 or more, particularly preferably 13 or more. . By adjusting the agent to an alkaline range using a pH adjuster (especially an alkaline agent), the production of hypobromous acid in the water treatment agent can be suppressed, and the stability over time can be maintained or improved.

<Contents and mass content ratios of each component in the water treatment agent according to the first embodiment of the present technology>

[Molar ratio of the aforementioned chloramine compound and bromide salt]

In the water treatment agent according to the first embodiment of the present technology, it is preferable to adjust the molar ratio of the chloramine compound to the bromide salt. When the chloramine compound is 1, the molar ratio of the chloramine compound to the bromide salt is preferably 1. : 0.05 to 3.0, more preferably 1: 0.1 to 1.5, still more preferably 1: 0.1 to 1.0, still more preferably 1: 0.2 to 1.0.

In the water treatment agent according to the first embodiment of the present technology, the preferable range of the carboxyl group content in the polymer is as shown above [Carboxyl group content in the polymer], and more preferably 0.3 to 0.72 (g-COOH/g-polymerization things).

Within the preferred range of the carboxyl group content in the polymer, the hypobromous acid concentration (%) in the water system is not particularly limited, but is preferably 75% or more, more preferably 80% or more, even more preferably 85% or more. Furthermore, it is more preferable to prepare the water treatment agent of the first embodiment of the present technology so that 90% or more of the water treatment agent is used, or to add the water treatment agent of the first embodiment of the present technology or each component used in the water treatment agent.

Within the preferred range of the carboxyl group content in the polymer, the total oxidant concentration (%) in the water system is not particularly limited, but is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. The water treatment agent according to the first embodiment of the present technology is prepared or the water treatment agent according to the first embodiment of the present technology is added.

The water treatment agent according to the first embodiment of the present technology has excellent stability over time by using a specific amount of a specific carboxyl polymer as described above. The total oxidant concentration of the water treatment agent according to the first embodiment of the present technology after a fixed period has elapsed is preferably 98% or more, and more preferably 99% or more when stored at 20° C. for 20 days during static storage in a constant temperature bath. , In addition, when stored at 50° C. for 20 days, it can be preferably 85% or more, and more preferably 90% or more.

In addition, as described above, the water treatment agent according to the first embodiment of the present technology can obtain excellent slow release properties by adjusting the characteristics and specific usage amount of the carboxyl polymer. The water treatment agent according to the first embodiment of the present technology can be adjusted so that the hypobromous acid concentration 48 hours after addition to the water system is preferably 0.25 mg/L (based on Cl ₂ ) to 1.5 mg/L (based on Cl ₂ ), or more Preferably, it is 0.5 mg/L (based on Cl ₂ ) to 1 mg/L (based on Cl ₂ ).

Furthermore, the first embodiment of the present technology may adopt the technology of the second embodiment of the present technology described later.

By combining the technology of the first embodiment and the technology of the second embodiment, it is possible to provide a single-liquid type in which the effect of hypobromous acid is well exerted when added to a water system and the pharmaceutical effects of other compounds are also favorably exerted. Water treatment technology, this single-liquid water treatment technology has the advantage of excellent quality stability of chemicals.

As an example of the technology employing the second embodiment of the present technology described below, for example, the above-mentioned (a) chloramine compound and the above-mentioned (b) bromide salt in the first embodiment of the present technology may be a mixture of an alkali. A mixture containing the aforementioned (a) and (b) obtained by mixing a mixed solution of an agent, a stabilizer and a bromide salt with an oxidizing agent. By using the obtained mixture containing the above (a) and (b), the water treatment agent according to the first embodiment of the present technology can also have a total chlorine detection rate after production of 95% or more and a free chlorine concentration in the total chlorine concentration. The chlorine content is 0.05% (calculated as _Cl2 ) or less.

<2-(d) Optional components of the first embodiment of the present technology>

In addition, the water treatment agent of 1st Embodiment of this technology can be used together with arbitrary chemicals within the range which does not impair the effect of this technology. Examples of arbitrary chemicals include, but are not limited to, anticorrosive agents (corrosion inhibitors), antiscalants, slime control agents, solvents or dispersion media such as water, dispersant enzymes, bactericides, and defoaming agents. In addition, various chemicals commonly used for water treatment can also be used. One, or two or more types of these groups may be appropriately selected.

In addition, the water treatment agent according to the first embodiment of the present technology can be obtained by suitably mixing each component or each agent of the above-mentioned essential components or optional components. In addition, it can be obtained according to a general manufacturing method of a water treatment agent or the present technology described below. manufactured using the manufacturing method of the second embodiment.

＜Anti-corrosion agents (corrosion inhibitors)＞

The anti-corrosion agent (corrosion inhibitor) other than the above-mentioned carboxyl polymer is not particularly limited, but an anti-corrosion agent for cooling water system is preferred. Azoles such as benzotriazole and toluenetriazole are preferred.

＜Anti-scaling agent＞

The antifouling agent other than the above-mentioned carboxyl polymer is not particularly limited. For example, phosphoric acid antifouling agents and/or phosphonic acid antifouling agents are known.

Examples of the antifouling agent include orthophosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate, 2-phosphono-1,2,4-tricarboxybutane, and 1-hydroxyethylene-1,1-di Phosphonic acid and aminotrimethylenephosphonic acid, 1-hydroxyethylene-1,1-diphosphonic acid (also known as: 1-hydroxyethane-1,1-diylbisphosphonic acid, HEDP), 2-phosphonoyl Butane-1,2,4-tricarboxylic acid (PBTC), etc. One type, or two or more types selected from the group consisting of these may be used.

The content of the anti-corrosion agent and/or anti-scaling agent in the water treatment agent according to the first embodiment of the present technology is not particularly limited, but is preferably 0.5% by mass to 30% by mass, and further preferably 1% by mass to 20% by mass.

<2-2. The method of using the water treatment agent according to the first embodiment of the present technology and the water treatment method using the water treatment agent>

The water treatment agent according to the first embodiment of the present technology is expected to have the medicinal effect of the specific carboxyl polymer mentioned above in addition to the effect of hypobromous acid (for example, bactericidal effect, slime control effect, etc.). For example, It is used for at least one of slime control, corrosion prevention, scale prevention, etc.

The first embodiment of the present technology can provide the use or use method of the water treatment agent according to the first embodiment of the present technology. Examples of the purpose of use include water treatment in the water system, sterilization methods in the water system, and viscosity removal in the water system. Mud control methods, anti-corrosion methods in water systems, or membrane anti-scaling methods in water systems, etc.

In addition, the first embodiment of the present technology can also provide a water treatment method, a sterilization method, a slime control method, an anti-corrosion method, or an anti-scaling method in which the water treatment agent of the first embodiment of the present technology is added to a water system. In addition, it is appropriate to omit the structure which overlaps with the structure demonstrated in the water treatment agent of this technology mentioned above.

From the viewpoint of stability over time, the pH of the aqueous system in the method of the first embodiment of the present technology is in an alkaline range, more preferably 7 to 10, and even more preferably 8 to 9.

In addition, another aspect of the first embodiment of the present technology can provide a water treatment method in which the following components (a) to (c) are added to the water system at the same time or at different times and/or at the same place or at different places: Sterilization methods, slime control methods, anti-corrosion methods or anti-scaling methods. (a) chloramine compound; (b) bromide salt; (c) 1 mass % to 18 mass % of a carboxyl polymer having a carboxyl group content rate of 0.8 g-COOH/g-polymer or less.

In the first embodiment of the present technology, the timing at which the chemicals or components in the water system are added is not particularly limited, and they may be added at the same time or separately. The place where the chemicals or components in the water system are added is not particularly limited and can be added to the same place or different places. In addition, each of the components (a) to (c) can be added to a water system and mixed to exhibit the effects expected in the first embodiment of the present technology. In addition, each of the components can also be added to form a water treatment agent by mixing. into the water system.

For example, in the case of membrane slime control or fouling prevention, it is preferable to add chemicals before membrane treatment. In addition, if it is used for slime control, sterilization, and corrosion prevention of pipes in the water system, the effects of this technology can be obtained at any time and in any place in the water system.

The object of the first embodiment of the present technology is preferably a cooling water system, and more preferably, the cooling water system is a cooling water system equipped with metal or metal pipes such as a cooling tank, a cooling tower, and a heat exchanger.

In addition, in the method of the first embodiment of the present technology, it is preferable to add such that the molar ratio of the component (a) chloramine compound to the component (b) bromide salt becomes 1:0.1 to 1.0. This molar ratio can be the same as the molar ratio in the aforementioned water treatment agent.

In the method of the first embodiment of the present technology, it is preferable that the component (c) carboxyl polymer is added so as to have a predetermined concentration in the water system. The predetermined concentration in the aqueous system is not particularly limited. The lower limit is preferably 0.5 mg/L or more, more preferably 1 mg/L or more, and still more preferably 2 mg/L or more. The upper limit is preferably 0.5 mg/L or more, and even more preferably 2 mg/L or more. 500 mg/L or less, more preferably 80 mg/L or less, still more preferably 60 mg/L or less, even more preferably 50 mg/L or less, particularly preferably 40 mg/L or less.

In addition, in the method of the first embodiment of the present technology, the concentration of the aforementioned component (c) carboxyl polymer in the water system is preferably 1 mg/L to 80 mg/L, more preferably 2 mg/L to 60 mg/L, and even more preferably 2 mg. /L～50mg/L.

It should be noted that the first embodiment of the present technology can also be used as a water treatment agent set. In the case of a water treatment agent set, each component (a) to component (c) may be stored in a different container. In addition, two mixed components and one component may be stored in different containers. In addition, optional components may be appropriately blended in each container. The use or method of the water treatment agent set can be performed in the same manner as the use or method of the above-mentioned water treatment agent.

<3. The manufacturing method and water treatment agent of the water treatment agent according to the second embodiment of the present technology>

Hereinafter, a mode for implementing the second embodiment of the present technology will be described. It should be noted that the embodiment described below shows an example of a representative embodiment of the second embodiment of the present technology, and therefore the scope of the second embodiment of the present technology is not to be interpreted in a limiting manner.

The main object of the second embodiment of the present technology is to provide a water treatment agent that exhibits a good effect of hypobromous acid when added to a water system and has excellent quality stability of the agent.

The present inventors conducted in-depth research and found that, with respect to a water treatment agent obtained by mixing an oxidant in a mixed solution of an alkali agent, a stabilizer, and a bromide salt, even after a fixed time has elapsed after production, total chlorine detection The rate is also maintained high and the content rate of free chlorine in the total chlorine concentration is also maintained low. That is, the present inventors were able to obtain a water treatment agent that exhibits a good effect of hypobromous acid when added to a water system and has excellent quality stability of the agent, and completed the present technology.

That is, this technology can adopt the following.

A second embodiment of the present technology provides a method for producing a water treatment agent, which includes mixing a mixed solution of an alkaline agent, a stabilizer, and a bromide salt with an oxidizing agent.

The aforementioned stabilizer is preferably a sulfamic acid compound.

The oxidizing agent is preferably a chlorine-based oxidizing agent.

The pH of the mixed solution is preferably 13 or higher.

The mixed solution preferably contains powdered bromide salt as the bromide salt.

In addition, the second embodiment of the present technology is a water treatment agent containing an alkaline agent, a chloramine compound and a bromide salt, which can provide a post-production total chlorine detection rate of 95% or more and a free chlorine content rate in the total chlorine concentration. Water treatment agent below 0.05% (calculated as _Cl2 ).

The water treatment agent according to the second embodiment of the present technology is preferably obtained by mixing a mixed solution of an alkali agent, a stabilizer, and a bromide salt with an oxidizing agent.

The pH of the water treatment agent according to the second embodiment of the present technology is preferably 13 or more.

<3-1. Water treatment agent and manufacturing method thereof according to the second embodiment of the present technology>

A second embodiment of the present technology provides a method for producing a water treatment agent, characterized by mixing a mixed solution of an alkaline agent, a stabilizer, and a bromide salt with an oxidizing agent. When obtaining a mixed solution of alkali agent, stabilizer and bromide salt, the order of mixing the alkali agent, stabilizer and bromide salt can be any order and is not particularly limited.

In addition, the second embodiment of the present technology can provide a water treatment agent obtained by mixing an oxidizing agent in a mixed solution in which an alkaline agent, a stabilizer, and a bromide salt are mixed.

In addition, the second embodiment of the present technology is a water treatment agent containing an alkaline agent, a chloramine compound, and a bromide salt, which can provide a post-production total chlorine detection rate that is higher than a certain level and/or a free chlorine concentration in the total chlorine concentration. A water treatment agent with a chlorine content below a certain level.

Therefore, the second embodiment of the present technology can provide a water treatment agent that exhibits a good effect of hypobromous acid when added to a water system and has excellent quality stability of the agent.

<3-2. Manufacturing method of water treatment agent according to the second embodiment of the present technology>

The present inventors studied the biocide preparation method of Patent Document 2 (Japanese Patent Publication No. 2005-519089). Specifically, in Patent Document 2, hypochlorite and sulfamic acid are mixed with a sodium hydroxide solution to prepare a hypochlorite solution with a pH of at least 11 or higher, and sodium bromide is finally mixed into the solution to obtain a stable hypochlorite solution. Bromate solution as biocide.

However, it was found that when powdery sodium bromide is mixed using the biocide preparation method of Patent Document 2, unstable hypobromous acid with high oxidizing power is generated. The inventors of the present invention have found that when the stability of hypobromous acid decreases in this way, the effect of the active ingredient contained in the biocide tends to decrease. The present inventors verified the reason and found that when powdered sodium bromide is added to a hypochlorous acid solution, a thick bromide solution is generated in a part of the solution when the powder is dissolved. The present inventors believe that unstable hypobromous acid is generated by reaction with hypochlorous acid that coexists when the concentrated portion of the bromide solution is generated.

On the other hand, the present inventor also studied the method of adding sodium bromide not as a powder but as a liquid in the preparation method of the biocide in Patent Document 2. However, the present inventor found that since it is necessary to add sodium bromide Since water is added as an aqueous solution at the same time, there is a problem that the concentration that can be compounded decreases.

In addition, the present inventors studied a method for producing a stabilized bromine solution for controlling biological adhesion disclosed in Patent Document 3 (Japanese Patent Publication No. 2002-540297). Specifically, in Patent Document 3, a sodium bromide solution and a solid sulfamate are mixed, and then a sodium hypochlorite solution and a sodium hydroxide solution are added to obtain a stabilized bromine solution.

The present inventors believe that according to the method of Patent Document 3, when the solution is prepared, a concentrated bromide solution is not generated in a part of the solution, and therefore the generation of hypobromous acid can be suppressed. However, in the method of Patent Document 3, since an oxidizing agent is mixed with an aqueous solution containing sodium bromide and sulfamic acid, the pH of the oxidizing agent decreases. The present inventors discovered that when the pH of an oxidizing agent is lowered, an unstable component with high oxidizing power (such as dichlorosulfamate or bromochlorosulfamate, etc.) is generated. Due to this unstable component, there is a presence of the stabilized bromine solution contained in the solution. The problem of reduced effectiveness of active ingredients.

Moreover, the present inventors further conducted in-depth research and found that in a water treatment agent obtained by using an alkali agent, a stabilizer, a bromide salt, and an oxidizing agent, the water treatment agent was obtained by adding a mixture of an alkali agent, a stabilizer, and a bromide salt to a mixed solution. As shown in [Examples] described below, the water treatment agent obtained by mixing an oxidizing agent has a higher total chlorine detection rate, total chlorine concentration, and total chlorine concentration than the water treatment agents of Patent Document 2 and Patent Document 3. The free chlorine content is excellent from a comprehensive viewpoint. That is, when the water treatment agent of the second embodiment of the present technology obtained in this way is added to a water system, the effect of hypobromous acid is favorably exerted and the quality stability of the agent is excellent.

Conventionally, as shown in Patent Document 2 and Patent Document 3, when producing a water treatment agent containing a chloramine compound and a bromide salt, the order in which the bromide salt is mixed into the solution is maintained first or last. The reason is considered to be that a stable chloramine compound is obtained from an alkali agent - a stabilizer - an oxidizing agent, and therefore the mixing of these agents is regarded as an integral process. The inventors of the present invention were able to break through this conventional insistence, and thus were able to obtain an excellent water treatment agent according to the second embodiment of the present technology. The mixing sequence discovered was also unpredictable from the conventional technology.

That is, the method of manufacturing a water treatment agent according to the second embodiment of the present technology is characterized by mixing a mixed solution in which an alkali agent, a stabilizer, and a bromide salt are mixed with an oxidizing agent. Furthermore, the method for manufacturing a water treatment agent according to the second embodiment of the present technology has the advantage of obtaining a one-liquid water treatment agent that can stably maintain the quality of the agent for a long period of time.

<Measurement method of free chlorine concentration, combined chlorine concentration and total chlorine concentration>

In this technology, the free chlorine concentration, combined chlorine concentration, and total chlorine concentration can be determined by the DPD method using N,N-diethyl-1,4-phenylenediamine as shown in JIS K0400-33-10:1999. The concentration of Cl ₂ is measured. In JIS K 0400-33-10:1999, the following definition is proposed.

That is, free chlorine is chlorine that exists in the form of hypochlorous acid, hypochlorite ions, or dissolved chlorine. Combined chlorine is chlorine that exists in the form of chloramine, organic chloramine, etc., and is not included in the above-mentioned free chlorine, but is the total chlorine measured by the DPD method. Total chlorine is defined as chlorine present as free chlorine, combined chlorine, or both.

＜Total chlorine detection rate (%) and free chlorine content rate (%)＞

In this technology, the so-called "total chlorine detection rate (%)" refers to the remaining rate (%) of the total chlorine concentration as an active ingredient in the water treatment agent. It can be determined by "the actual measured value of the total chlorine concentration (%) in the water treatment agent Calculated by (calculated as _Cl2 )/theoretical value of the total chlorine concentration in the water treatment agent (% calculated as _Cl2 )" × 100 (%). The theoretical value of the total chlorine concentration is the calculated value of the total chlorine concentration formed in the water treatment agent when the oxidant and the stabilizer are mixed during manufacture.

In addition, in this technology, "the content rate of free chlorine in the total chlorine concentration (% (calculated as Cl ₂ ))" can be calculated by [concentration of free chlorine in the water treatment agent (% calculated as Cl ₂ )/in the water treatment agent The total chlorine concentration (% as _Cl2 )] × 100% is calculated.

In addition, the <Measurement method of bromide (Br ^- )> and <Measurement method of pH> in the second embodiment may be the same as the <Measurement method of bromide (Br ^- )> and <Measurement of pH> described in the first embodiment. Method > Proceed in the same way.

<2-2-1. Raw materials (alkali agent, stabilizer, bromide salt and oxidizing agent)>

The alkaline agent, stabilizer, bromide salt, and oxidizing agent used as raw materials in the manufacturing method of the second embodiment of the present technology are as follows.

＜3-2-1(a) Alkali agent＞

The alkaline agent used in the second embodiment of the present technology is not particularly limited, and examples thereof include alkaline inorganic salts, alkaline organic salts, and the like.

Examples include alkali metals (such as lithium, sodium, potassium, etc.), alkaline earth metals (such as calcium, magnesium, barium, etc.), salt oxides (such as sodium oxide, calcium oxide, etc.), salt hydroxides (such as sodium hydroxide, Potassium hydroxide, magnesium hydroxide, calcium hydroxide, etc.), carbonate (sodium carbonate, potassium carbonate, calcium carbonate, etc.), etc., one or two or more types selected from the group consisting of these can be used.

The oxide, salt hydroxide, and carbonate are preferably alkali metals or alkaline earth metals. One type selected from the group consisting of these may be used, or two or more types may be used in combination.

Among the above-mentioned alkaline agents, alkaline inorganic salts are preferred, and among these, salt hydroxides are more preferred from the viewpoint of workability and cost. Among these salt hydroxides, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are more preferred, and from the viewpoint of cost, sodium hydroxide is even more preferred.

In addition, the acidic agent used for adjusting the pH of the water treatment agent according to the second embodiment of the present technology is not particularly limited, and examples thereof include acidic inorganic salts, acidic organic salts, and the like. Examples include citric acid, phosphoric acid, tartaric acid, acetic acid, boric acid, phthalic acid, maleic acid, succinic acid, and the like, and one or two or more selected from the group consisting of these can be used.

<3-2-1(b) Stabilizer>

The stabilizer used in the second embodiment of the present technology is not particularly limited, but is preferably a chlorine stabilizer that generates a combined chlorine agent by reaction with an oxidizing agent (preferably an inorganic chlorine agent).

Examples of the chlorine stabilizer include compounds having a primary amino group, any one of ammonia and ammonium salts (hereinafter, these are also referred to as "NH _2- based compounds"), and any one selected from these can be used. or two or more.

The compound having a primary amino group is not particularly limited, and examples thereof include aliphatic amines, aromatic amines, sulfamic acid, sulfamic acid, sulfamoylbenzoic acid, amino acids, etc., and compounds selected from the group consisting of these can be used. One or more than two kinds.

Examples of the ammonium salt include ammonium chloride, ammonium sulfate, and the like, and one or two or more types selected from the group consisting of these can be used.

More specific examples of the chlorine stabilizer include sulfamic acid compounds; isocycyanuric acid; hydantoins such as 5,5'-dimethylhydantoin; urea, biuret, and carbamic acid Methyl ester, ethyl carbamate, acetamide, nicotinamide, methane sulfonamide, toluene sulfonamide and other amide compounds; maleimide, succinimide, phthalimide and other imide compounds; glycine , alanine, histidine, lysine and other amino acids; amine compounds such as methylamine, hydroxylamine, morpholine, piperazine, imidazole and histamine; ammonia; ammonium salts such as ammonium sulfate, etc., and those selected from these can be used One or more than two types in the group.

Among the aforementioned chlorine-based stabilizers, sulfamic acid compounds are preferred from the viewpoint of environmental load. Examples of the sulfamic acid compound include sulfamic acid, sulfamic acid derivatives, and salts thereof, and they can be used. One or more than two types are selected from the group consisting of these.

Among the aforementioned chlorine stabilizers (preferably NH ₂ -based compounds), sulfamic acid is preferred (NH ₂ SO ₂ OH is more preferred). It is preferable to use sulfamic acid to generate monochlorosulfamic acid because it becomes a stable chloramine compound.

Examples of the sulfamic acid compound include the compound represented by the general formula [1] shown in the first embodiment of the present technology or a salt thereof.

The salt of the compound used in the stabilizer is not particularly limited, and the above-mentioned “salt of the compound used in the first embodiment of the present technology” can be used. Among these, an alkali metal salt (preferably sodium) is preferred from the viewpoint of cost and ease of operation.

The sulfamic acid compound used in the second embodiment of the present technology is not particularly limited, and the above-mentioned “sulfamic acid compound used in the first embodiment of the present technology” can be used.

Among the aforementioned stabilizers, sulfamate is more preferred.

<3-2-1(c) Bromide salt>

The bromide salt used in the second embodiment of the present technology is not particularly limited, and the above-mentioned “bromide salt used in the first embodiment of the present technology” can be used.

In addition, the alkali metal bromide salt and amine bromide salt used in the second embodiment of the present technology are not particularly limited, and the aforementioned alkali metal bromide salt used in the first embodiment of the present technology can be used. ” and “the aforementioned amine bromide salt”.

In addition, the form of the bromide salt when mixed into the solution may be either in the state of a chloride solution or in the state of powdered chloride salt. However, from the viewpoint of increasing the concentration of the active ingredient, it is preferable to use powdered bromide. .

<3-2-1(d) Oxidizing agent>

The oxidizing agent used in the second embodiment of the present technology is not particularly limited, and is preferably a halogen-based oxidizing agent. The halogen-based oxidizing agent is not particularly limited, and the chloramine compound can be obtained from the chlorine-based oxidizing agent and the chlorine-based stabilizer. In particular, a chlorine-based oxidizing agent is preferred.

The chlorine-based oxidizing agent used in the second embodiment of the present technology is not particularly limited, and examples thereof include chlorine gas, chlorine dioxide, hypochlorous acid or its salts, chlorous acid or its salts, chloric acid or its salts, and perchloric acid. or its salt, chlorinated isocyanuric acid or its salt, etc., one or two or more selected from the group consisting of these can be used.

Among these, specific examples of salt-form substances are not particularly limited, but include: alkali metal hypochlorite salts such as sodium hypochlorite and potassium hypochlorite; alkaline earth metal hypochlorite salts such as calcium hypochlorite and barium hypochlorite; Alkali metal salts of chlorite such as sodium chlorite and potassium chlorite; alkaline earth metal salts of chlorite such as barium chlorite; other metal salts of chlorite such as nickel chlorite; chlorine such as ammonium chlorate, sodium chlorate, potassium chlorate Acid and alkali metal salts; alkaline earth metal chlorate salts such as calcium chlorate and barium chlorate, etc., and one or two or more types selected from the group consisting of these can be used.

Among the aforementioned chlorine-based oxidizing agents, one or two or more types selected from the group consisting of hypochlorite, chlorine dioxide, and chlorine gas are preferred, and among these, hypochlorite is more preferred from the viewpoint of ease of operation.

<3-2-2. Manufacturing method of water treatment agent according to the second embodiment of the present technology>

The method for producing a water treatment agent according to the second embodiment of the present technology preferably mixes at least a mixed solution of an alkali agent, a stabilizer, and a bromide salt (hereinafter also referred to as a “three-agent mixed solution”) and an oxidizing agent. Furthermore, it is more preferable to add an oxidizing agent to the mixed solution of three kinds of chemicals and mix them. Mixing of the oxidizing agent can be carried out by referring to <3-2-2-2. Oxidizing agent mixing step> described later.

Example 1 of the manufacturing method according to the second embodiment of the present technology preferably includes at least a step of mixing an oxidizing agent in a mixed solution in which an alkali agent, a stabilizer, and a bromide salt are mixed. The step of mixing the oxidizing agent can be performed in the same manner as <3-2-2-2. Oxidizing agent mixing step> described below.

The aforementioned three medicament mixed solutions may be prepared in advance, or may be prepared in the same manufacturing line or in different manufacturing lines. The three-drug mixed solution may be, for example, a solution prepared in <3-2-2-1 Step of Preparing a Mixed Solution of Mixed Alkaline Agent, Stabilizer, and Bromide Salt> described later.

From the viewpoint of the quality stability of the water treatment agent, it is more preferable to mix the three chemicals and then quickly mix the oxidizing agent into the mixed liquid of the three chemicals to obtain the water treatment agent.

In addition, from the viewpoint of work efficiency and the ease of adjusting active ingredients in the water treatment agent, Example 2 of the manufacturing method of the second embodiment of the present technology more preferably includes preparing and mixing an alkali agent and a stabilizer. and a mixed solution of bromide salts, and a step of mixing an oxidizing agent in the mixed solution of the three chemicals.

The solvent of the solution used in the second embodiment of the present technology is not particularly limited as long as it can dissolve an alkali agent, a stabilizer, a bromide salt, and an oxidizing agent. From the viewpoints of safety, operability, and cost, water is preferred. The water may contain other solvents within a range that does not impair the effect of the present technology, but preferably 99% or more of the solvent is water. Examples of other solvents include hydrophilic organic solvents. Examples of the hydrophilic organic solvents include glycols (eg, ethylene glycol, diethylene glycol, etc.) and glycol ethers (eg, diethylene glycol). Monomethyl ether, etc.), glycol dimethyl ethers (glyme), ketones, esters (such as methyl acetate, etc.), alcohols (such as ethanol, aminoethanol, etc.), amides (such as N, N- dimethylacetamide, etc.), among which glycols, glycol ethers, esters, and alcohols are preferred. One type, or two or more types selected from the group consisting of these may be used.

In the manufacturing method of the second embodiment of the present technology, the blending amount of the solvent (preferably water) is not particularly limited. In the water treatment agent of the second embodiment, it is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 50% by mass. It is preferable to mix it so that it may be 10 mass % - 40 mass %.

The manufacturing conditions of the manufacturing method according to the second embodiment of the present technology can be carried out with reference to known manufacturing conditions. For example, it can be carried out in batches or continuous steps, and can also be carried out at a temperature of about 4°C to 40°C.

Hereinafter, an example of the manufacturing method of the water treatment agent according to the second embodiment of the present technology will be described using the manufacturing method of Example 2 of the embodiment of the present technology. However, the manufacturing method of the second embodiment of the present technology is not limited to this description. . In addition, the manufacturing method according to the second embodiment of the present technology can omit the preparation process of the three-drug mixed solution.

The manufacturing method of Example 2 of the second embodiment of the present technology includes the steps of preparing a mixed solution of three chemicals and the step of mixing an oxidizing agent in the mixed solution.

<3-2-2-1. The process of preparing a mixed solution of an alkali agent, a stabilizer and a bromide salt>

In the "process of preparing a mixed solution in which an alkali agent, a stabilizer, and a bromide salt are mixed" (hereinafter, also referred to as a "three-agent mixed solution preparation process") in the production of the second embodiment of the present technology, the mixing The order of the components of the alkaline agent, stabilizer and bromide salt is not particularly limited.

The three-drug mixed solution according to the second embodiment of the present technology can be obtained by adding and mixing the three agents of an alkali agent, a stabilizer, and a bromide salt at the same time or separately. More specifically, the three pharmaceuticals may be added in sequence, the remaining pharmaceuticals may be mixed after mixing two pharmaceuticals, or the three pharmaceuticals may be mixed at the same time.

When the above three chemicals are added in order, for example, (1) in the order of alkali agent, stabilizer and bromide salt, (2) in the order of alkali agent, bromide salt and stabilizer, (3) In the order of stabilizer, bromide salt and alkali agent, (4) In the order of stabilizer, alkali agent and bromide salt, (5) In the order of bromide salt, stabilizer and alkali agent, (6) In the order of bromide salt, The order of compound salt, alkali agent and stabilizer, etc.

In the three-drug mixing preparation process according to the second embodiment of the present technology, it is preferable to first mix an alkali agent in the solution. As will be described later, the pH of the solution can be adjusted to an alkaline range using an alkaline agent. Specifically, the pH is preferably 11 or more, more preferably 12 or more, and even more preferably 13 or more. By making the solution into an alkaline region, the quality stability of each chemical mixed in the solution is also improved.

By sequentially or appropriately blending chemicals in a solution adjusted to an alkaline range, a water treatment agent with excellent quality stability can be obtained.

In addition, in the mixing and preparation process of three chemicals according to the second embodiment of the present technology, it is more preferable to mix the alkali agent, the stabilizer and the bromide salt in this order, or the alkali agent, the bromide salt and the stabilizer in this order.

The processing temperature in the three-drug mixed solution preparation process of the second embodiment of the present technology is not particularly limited, and this process can be performed under temperature conditions of about 4°C to 40°C. In addition, the mixing mechanism in the preparation process of the three-drug mixed solution can be a known mechanism (for example, a stirring mechanism, etc.) that can mix each drug and the solution.

From the viewpoint of maintaining the quality stability of the water treatment agent according to the second embodiment of the present technology, the pH of the three-drug mixed solution prepared above is preferably adjusted by using the alkali agent. pH. The pH of the three-drug mixed solution is more preferably 10 or more, still more preferably 11 or more, still more preferably 12 or more, and particularly preferably 13 or more. By thus adjusting the pH of the three-agent mixed solution, the pH of the finally obtained water treatment agent according to the second embodiment of the present technology can be brought into an alkaline range, thereby making it possible to make good use of the water treatment agent according to the second embodiment of the present technology. The effect of the active ingredients of the treatment agent. In addition, in order to adjust the pH of the water treatment agent of the second embodiment, an alkaline agent may be added appropriately within a range that does not impair the effect of the present technology.

In addition, from the viewpoint of maintaining the quality stability of the water treatment agent according to the second embodiment of the present technology, the respective concentrations of the stabilizer and the bromide salt contained in the three-drug mixed solution prepared above can be determined by Adjust the following mixing amount.

The blending amount of the stabilizer (preferably a chlorine-based stabilizer) used in the preparation of the aforementioned three-drug mixed solution is not particularly limited. In the aforementioned three-drug mixed solution, 5% to 80% is preferred, and 10% to 70% is more preferred. %, more preferably 16% to 60%.

The blending amount of the stabilizer (preferably a chlorine-based stabilizer) used in the preparation of the aforementioned three-drug mixed solution is not particularly limited. When the oxidizing agent is an inorganic chlorine agent, from the viewpoint of sufficient reactivity, it is preferably 1 mol to 5 mol, and more preferably 1 mol to 1 mol of the oxidizing component contained in the inorganic chlorine agent. 4 mol, more preferably 1.2 mol to 3 mol. Therefore, even if it is a one-liquid type water treatment agent, the active ingredient can be well maintained.

The blending amount of the bromide salt used in the preparation of the aforementioned three-drug mixed solution is not particularly limited. In the aforementioned three-drug mixed solution, 3% to 50% is preferred, 6% to 40% is more preferred, and 12% is further preferred. ~30%.

＜3-2-2-2. Oxidizing agent mixing process＞

In the "step of mixing an oxidizing agent into the aforementioned three chemical agent mixture solutions" (hereinafter also referred to as the "oxidizing agent mixing step") in the production of the second embodiment of the present technology, the alkali agent prepared in the aforementioned step, Mix the oxidizing agent with the solution of stabilizer and bromide salt. Thus, a mixed solution of four kinds of chemicals can be obtained.

Moreover, when the four chemicals are mixed, the stabilizer and the oxidizing agent react to generate a halamine compound (preferably a chloramine compound), and water containing a halamine compound (preferably a chloramine compound) and a bromide salt can be prepared in an alkaline region treatment agent.

The blending amount of the oxidizing agent when mixing the three-drug mixed solution is not particularly limited. In the four-drug mixed solution, it is preferably 20% to 55%, more preferably 30% to 55%, and even more preferably 40% to 40%. 50%.

In addition, the mixing mass ratio of the aforementioned three-drug mixed solution and the oxidizing agent is not particularly limited, but relative to the three-drug mixed solution 1, the oxidizing agent is preferably 0.5 to 1.5, and more preferably 0.7 to 1.3.

The water treatment agent obtained by the manufacturing method of the second embodiment of the present technology exhibits the effect of hypobromous acid favorably when added to a water system and has excellent quality stability of the agent. Furthermore, even if the one-liquid medicine obtained by this manufacturing method is stored for a long period of time in the one-liquid state, it can exert the target effect and maintain constant quality.

The water treatment agent obtained by the production method of the second embodiment of the present technology contains an alkaline agent, a halamine compound (preferably a chloramine compound), and a bromide salt. The total chlorine detection rate (%) in the water treatment agent after production The free chlorine concentration is preferably 95% or more and/or the free chlorine concentration is 0.05% (in terms of _Cl2 ) or less of the total chlorine concentration and can be maintained for a long time because it can suppress the decrease in the concentration of the active ingredient after production.

The content of the stabilizer in the water treatment agent according to the second embodiment of the present technology is adjusted to have a lower limit of preferably 3% or more, more preferably 5% or more, even more preferably 8% or more, and an upper limit thereof. The value is preferably 40% or less, more preferably 35% or less, still more preferably 30% or less, and the more preferred numerical range is more preferably 5% to 35%, even more preferably 8% to 30%.

The content of the bromide salt in the water treatment agent according to the second embodiment of the present technology is adjusted to have a lower limit of preferably 1% or more, more preferably 3% or more, and still more preferably 6% or more, and the upper limit thereof is The limit value is preferably 25% or less, more preferably 20% or less, still more preferably 15% or less, and the more preferred numerical range is more preferably 3% to 20%, further preferably 6% to 15%.

The content of the oxidizing agent in the water treatment agent according to the second embodiment of the present technology is adjusted to a lower limit of preferably 20% or more, more preferably 30% or more, and still more preferably 40% or more, and an upper limit thereof. , preferably 60% or less, more preferably 55% or less, even more preferably 50% or less, and the more preferred numerical range is more preferably 30% to 55%, even more preferably 40% to 50%.

The "total chlorine detection rate (%)" in the water treatment agent according to the second embodiment is more preferably 96% or more, still more preferably 97% or more, and still more preferably 97.5% or more.

In the water treatment agent of the second embodiment, the “free chlorine content rate (% (in terms of Cl ₂ )) of the total chlorine concentration” is more preferably 0.05% or less, further preferably 0.04% or less.

When using the water treatment agent of the second embodiment, the "total chlorine concentration (% as _Cl2 )" is more preferably 4.1% or more, still more preferably 4.2% or more, still more preferably 4.3% or more. According to the manufacturing method of the second embodiment of the present technology, it is considered that the total chlorine concentration (% in terms of _Cl2 ) in the water treatment agent of the second embodiment can be increased to 4.4% to 4.7%. Therefore, as the The upper limit value may be 4.7% or less, 4.6% or less, 4.5% or less, or 4.4% or less.

In addition, from the viewpoint of reducing decomposition of active ingredients and efficiently adding them to the water system, the total chlorine detection rate (%), total chlorine concentration (%) in the water treatment agent according to the second embodiment of the present technology is expressed as Cl ₂ ) and the content rate of free chlorine in the total chlorine concentration is preferably between 4 hours after production and 4 hours of storage, and more preferably 1 hour after production. Even if the water treatment agent according to the second embodiment of the present technology is not used immediately 0 hours after production, the total chlorine detection rate and total chlorine concentration are high and stable from about 4 hours after production. Therefore, even if a water treatment agent manufacturing device is not installed near the water system addition site, transportation and other measures can be taken. In addition, if it is a water treatment agent obtained by the manufacturing method of the second embodiment of the present technology, the total chlorine detection rate (%) and total chlorine concentration (%) in the water treatment agent can be suppressed in about three months after production. (calculated as _Cl2 ), and can inhibit the sharp increase in the free chlorine concentration in the total chlorine concentration.

In addition, storage conditions when storing the water treatment agent according to the second embodiment of the present technology after production are not particularly limited, but storage at normal temperature or storage in a dark place at normal temperature is preferred, and temperature management at about 4°C to 40°C is more preferred.

In addition, the water treatment agent of the second embodiment obtained by the manufacturing method of the second embodiment of the present technology can be marketed at normal temperatures of about 4°C to 40°C, even at normal temperatures for a long period of time (for example, about 3 months after production) Storage can also prevent the concentration of active ingredients from decreasing. In addition, the water treatment agent according to the second embodiment of the present technology can prevent the generation of a thick bromide solution during the mixing process in the manufacturing process, thereby suppressing the generation of hypochlorine in the obtained water treatment agent according to the second embodiment. acid, reducing the decrease in the concentration of active ingredients, thus providing products with stable quality.

Compared with the water treatment agent of Patent Document 2 or the water treatment agent of Patent Document 3, the water treatment agent obtained by the production method of the second embodiment of the present technology has a higher total chlorine concentration after production and a substantially lower free chlorine concentration. In the following, the target effect can be well exhibited and the quality stability of the pharmaceutical agent is also excellent.

It should be noted that in this technology, the quality stability of a pharmaceutical means that the active ingredient in the pharmaceutical is difficult to decompose when the pharmaceutical is stored for a fixed period, and the concentration of the active ingredient is maintained within a certain range. More specifically, it is desirable that hypochlorous acid is less likely to be generated in the pharmaceutical agent and that the concentration of the active ingredient is less reduced.

In the water treatment agent according to the second embodiment of the present technology, it is preferable to adjust the molar ratio of the chloramine compound to the bromide salt. When the chloramine compound is 1, the molar ratio of the chloramine compound to the bromide salt is preferably 1. : 0.05 to 3.0, more preferably 1: 0.1 to 1.5, still more preferably 1: 0.1 to 1.0, still more preferably 1: 0.2 to 1.0. In addition, in the manufacturing method of the water treatment agent of 2nd Embodiment of this technology, it is also possible to adjust suitably to this molar ratio.

The water treatment agent according to the second embodiment of the present technology has excellent quality stability of the agent, and when added to the water system, it can produce good results based on the alkali agent, halamine compound (preferably chloramine compound) and bromide salt in the agent. Effectively exert the effect of hypochlorous acid. Furthermore, the water treatment agent according to the second embodiment of the present technology can gradually generate hypobromous acid in the water system over time, and therefore can maintain the effect of hypobromous acid in the water system for a longer period of time and more continuously.

On the other hand, the water treatment agent according to the second embodiment of the present technology is a one-liquid type agent and can also be used as a slow release water treatment agent. If hypobromous acid is rapidly released in the water system, it will easily cause corrosion or deterioration in the water system. However, since the water treatment agent according to the second embodiment of the present technology can control the generation rate of hypobromous acid slowly, it can reduce the amount of hypobromous acid in the water system. corrosion or deterioration, and the effects caused by hypobromous acid (e.g., bactericidal effect, etc.) can be obtained continuously over a long period of time. Therefore, it is more advantageous to apply the water treatment agent according to the second embodiment of the present technology to an open circulation device having a cooling water system, a water storage system, a dust collection water system, a scrubber water system, or the like.

<3-2-3. Optional components of the second embodiment of the present technology>

In any manufacturing process of the water treatment agent according to the second embodiment of the present technology, any chemical as an arbitrary component may be mixed within a range that does not impair the effect of the present technology.

Examples of arbitrary chemicals include, but are not limited to, anticorrosive agents (corrosion inhibitors), antiscalants, slime control agents, solvents or dispersion media such as water, dispersant enzymes, bactericides, and defoaming agents. , In addition, various chemicals commonly used for water treatment can also be used. One type, or two or more types selected from the group consisting of these may be used. As any medicine, the medicine described in the first embodiment can be suitably used.

＜Anti-corrosion agents (corrosion inhibitors)＞

The anti-corrosion agent (corrosion inhibitor) is not particularly limited, but is preferably an anti-corrosion agent for cooling water systems. For example, polymers such as carboxyl polymers and azoles such as benzotriazole and toluenetriazole are preferred.

The type of the carboxyl polymer is not particularly limited, and examples thereof include water-soluble homopolymers and/or copolymers having a carboxyl group. More specific examples include maleic acid-based polymers and (meth)acrylic acid polymers. Polymer-like. In addition, the "polymer" means a polymer containing a monomer and a copolymer.

More specific examples of the carboxyl polymer include maleic acid homopolymer, (meth)acrylic acid homopolymer, and copolymerization of an unsaturated monomer copolymerizable with maleic acid or (meth)acrylic acid. It is possible to use one type selected from the group consisting of these, or a combination of two or more types.

The carboxyl polymer in the second embodiment of the present technology preferably contains a maleic acid-based polymer and/or a (meth)acrylic acid-based polymer. The content ratio (content) of the maleic acid-based polymer and/or (meth)acrylic acid-based polymer in the carboxyl polymer is preferably 50 mass% or more, more preferably 80 mass% or more, still more preferably 90 mass% or more, and further More preferably, it is 95 mass % or more, and especially preferably 99 mass % or more. The higher the content ratio of the carboxyl polymer is, the more likely it is to obtain the expected effects of the present technology.

Examples of the unsaturated monomer copolymerizable with maleic acid or (meth)acrylic acid monomers include 2-acrylamide-2-methylpropanesulfonic acid, 2-hydroxy-3-aryloxy- 1-Propane sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, acrylamide, ethylene, propylene, isopropylene, butylene, isobutylene, hexene, 2-ethylhexene, pentene, isopentene, octene , isooctene, vinyl alcohol, vinyl methyl ether, vinyl ethyl ether, etc. and their salts.

Examples include those obtained using one or two or more monomers selected from the group consisting of these monomers, and selected from the group consisting of homopolymers, copolymers, and copolymers of the aforementioned monomers and isobutylene. One or more than two polymers.

When chemical effects such as anti-corrosion effects are expected for the aforementioned carboxyl polymer, the weight average molecular weight is preferably 10 to the third power to the fourth power, more specifically, it is preferably in the range of 200 to 50,000, and more preferably 500 to 30,000. within the range, more preferably within the range of 800 to 30,000, still more preferably 1,000 to 20,000.

The carboxyl polymer used in the first embodiment of the present technology and the usage amount can be used as the aforementioned carboxyl polymer. Furthermore, in the second embodiment, the mixture obtained by mixing a mixed solution of an alkali agent, a stabilizer and a bromide salt with an oxidizing agent is preferably a mixture containing a chloramine compound and a bromide salt, and more preferably, the mixture is mixed with the above-mentioned The carboxyl polymer is mixed to provide a water treatment agent or a water treatment agent set using the components (a) to (c) of the first embodiment. Therefore, in addition to the effects of the second embodiment of the present technology, as shown in the first embodiment of the present technology, it is possible to provide a one-liquid type water treatment in which the chemical effects of other compounds can also be favorably exerted. technology.

The <method for measuring the weight average molecular weight of the water-soluble polymer> in the second embodiment can be performed in the same manner as the <method for measuring the weight average molecular weight of the water-soluble polymer> described in the first embodiment.

＜Anti-scaling agent＞

The antifouling agent used in the second embodiment of the present technology is not particularly limited, and the <antifouling agent> used in the first embodiment of the present technology described above can be used.

The content of the anti-corrosion agent and/or anti-scaling agent in the water treatment agent according to the second embodiment of the present technology is not particularly limited, but is preferably 0.5% by mass to 30% by mass, and more preferably 1% by mass to 20% by mass.

<3-3. The method of using the water treatment agent according to the second embodiment of the present technology and the water treatment method using the water treatment agent>

The water treatment agent according to the second embodiment of the present technology is expected to have the effects of hypobromous acid (for example, bactericidal effect, slime control effect, etc.) as described above, and can be used, for example, as a slime control agent, an anti-corrosion agent, or an anti-scaler agent. of at least any use.

The second embodiment of the present technology can provide the use or use method of the water treatment agent of the second embodiment of the present technology. Examples of the purpose of use include water treatment in the water system, sterilization methods in the water system, and viscosity removal in the water system. Mud control methods, anti-corrosion methods in water systems, or membrane anti-scaling methods in water systems, etc.

In addition, the second embodiment of the present technology can also provide a water treatment method, a sterilization method, a slime control method, an anti-corrosion method, or an anti-scaling method in which the water treatment agent of the second embodiment of the present technology is added to a water system. In addition, it is appropriate to omit the structure which overlaps with the structure demonstrated in the water treatment agent of this technology mentioned above.

From the viewpoint of stability over time, the pH of the aqueous system in the method of the second embodiment of the present technology is in an alkaline range, more preferably 7 to 10, and even more preferably 8 to 9. In addition, the water temperature of the water system is not particularly limited, but is usually about 4°C to 40°C.

The amount of the water treatment agent added to the water system according to the second embodiment of the present technology is not particularly limited and can be appropriately adjusted according to various water systems to be treated. However, it is usually preferably a concentration of 1 mg/L to each water system to be treated. 1000mg/L can be added continuously or intermittently.

In the second embodiment of the present technology, the timing at which the chemicals or components in the water system are added is not particularly limited, and they may be added at the same time or separately. The place where the chemicals or components in the water system are added is not particularly limited and can be added to the same place or different places.

For example, when the membrane is used for slime control or scale prevention, it is preferable to add the chemical before membrane treatment. In addition, if it is used for slime control, sterilization, and corrosion prevention of pipes in the water system, the effects of this technology can be obtained at any time and in any place in the water system.

The object of the second embodiment of the present technology is preferably a cooling water system, and more preferably, the cooling water system is a cooling water system equipped with metal or metal pipes such as a cooling tank, a cooling tower, and a heat exchanger.

In addition, in the 2nd Embodiment of this technology, it can also be used as the water treatment agent set which respectively contains the water treatment agent of the 2nd Embodiment of this technology, and arbitrary components.

For example, a water treatment agent set containing (a) a chloramine compound and (b) a bromide salt contained in one container A and obtained by the method for producing a water treatment agent according to the second embodiment can be provided. and a carboxyl polymer containing a carboxyl group content of 0.8 g-COOH/g-polymer or less in the polymer (c) contained in one container B. When these are mixed, the carboxyl group polymer becomes 1% by mass. ~18% by mass, pH is 10 or above.

In the case of a water treatment agent set, each component may be stored in a different container, or two mixed components and one component may be stored in different containers. In addition, optional components may be appropriately blended in each container. The use or method of the water treatment agent set can be performed in the same manner as the use or method of the above-mentioned water treatment agent.

This technology may also adopt the following configuration.

·[1] A water treatment agent containing the following components (a) to (c) and having a pH of 10 or more:

(a)Chloramine compounds,

(b) Bromide salt,

(c) 1 to 18 mass% of a carboxyl polymer having a carboxyl group content rate of 0.8 g-COOH/g-polymer or less.

·[2] The water treatment agent according to the above [1], wherein the molar ratio of the chloramine compound and the bromide salt is 1:0.1 to 1.0.

·[3] The water treatment agent according to the above [1] or [2], which is at least any one of slime control, corrosion prevention, and scale prevention.

·[4] The water treatment agent according to any one of the above [1] to [3], wherein the water treatment agent is treated with a mixed solution of an alkali agent, a stabilizer, and a bromide salt and an oxidizing agent. Mixed and obtained.

·[5] The water treatment agent according to any one of the above [1] to [4], wherein the total chlorine detection rate after production of the water treatment agent is 95% or more and the free chlorine concentration in the total chlorine concentration The chlorine content is 0.05% (calculated as _Cl2 ) or less.

·[6] The water treatment agent according to any one of the above [1] to [5], wherein the carboxyl polymer contains a maleic acid-based polymer and/or a (meth)acrylic acid-based polymer, It is preferable that the carboxyl polymer contains 50% by mass or more.

·[7] The water treatment agent according to any one of the above [1] to [6], wherein the pH of the water treatment agent is 13 or more.

·[8] The water treatment agent according to any one of the above [1] to [7], wherein the bromide salt is selected from the group consisting of alkali metal bromide salts, ammonium bromide salts, hydrobromic acid, and bromide salts. One or more than two kinds of amine salts.

·[9] A water treatment method, sterilization method, slime control method, anti-corrosion method or anti-scaling method, in which the water treatment agent described in any one of the above [1] to [8] is added to the water system.

·[10] The method according to the above [9], wherein the water treatment agent is added to the water system so that the carboxyl group concentration in the water system becomes 1 mg/L to 100 mg/L.

·[11] A water treatment method, sterilization method, slime control method, anti-corrosion method or anti-scaling method, wherein the following components (a) to (c) are used at the same time or at different times and/or at Add the same place or different places to the water system:

(a)Chloramine compounds,

(b) Bromide salt,

(c) 1 to 18 mass% of a carboxyl polymer having a carboxyl group content rate of 0.8 g-COOH/g-polymer or less.

·[12] The method according to any one of the above [10] to [12], wherein the molar ratio of the component (a) chloramine compound to the component (b) bromide salt is 1: The component (c) is added so that the carboxyl group concentration in the water system becomes 5 mg/L to 50 mg/L.

·[13] The method according to any one of the above [9] to [12], wherein the water system is a cooling water system, and preferably the cooling water system is equipped with a cooling tank, a cooling tower, a heat exchanger and other metal or Metal pipe cooling water system.

In addition, this technology can also adopt the following structure.

·[14] A method for producing a water treatment agent, characterized by mixing a mixed solution of an alkaline agent, a stabilizer, and a bromide salt with an oxidizing agent. It is preferable to add an oxidizing agent to the mixed liquid and mix it.

·[15] The method for producing a water treatment agent according to the above [14], wherein the stabilizer is a sulfamic acid compound. The sulfamic acid compound is preferably a compound represented by the general formula (1) or a salt thereof. Among these, sulfamic acid or a salt thereof is more preferred.

·[16] The method for producing a water treatment agent according to the above [14] or [15], wherein the oxidizing agent is a chlorine-based oxidizing agent. The chlorine-based oxidizing agent is preferably one or more selected from the group consisting of hypochlorite, chlorine dioxide and chlorine gas.

·[17] The method for producing a water treatment agent according to any one of [14] to [16], wherein the pH of the mixed solution is 12 or more (preferably 13 or more). When mixing the oxidizing agent, it is preferable to adjust the pH of the mixed solution.

·[18] The method for producing a water treatment agent according to any one of [14] to [17] above, wherein the mixed solution is a solution in which powdered bromide salt is mixed as the bromide salt.

·[19] The method for producing a water treatment agent according to any one of the above [14] to [18], wherein the carboxyl polymer is further mixed to 1% by mass to 18% by mass, and the carboxyl polymer is The carboxyl group content rate is 0.8g-COOH/g-polymer or less. It is preferable to further mix the mixed liquid and the carboxyl polymer.

·[20] The method for producing a water treatment agent according to any one of the above [14] to [19], wherein the solution in which an alkali agent, a stabilizer and a bromide salt are mixed is obtained by mixing the alkali agent into The solution is followed by mixing the stabilizer and/or bromide salt at the same time or separately.

·[21] The method for producing a water treatment agent according to any one of the above [14] to [20], wherein when the chloramine compound is set to 1, the chloramine compound and bromine in the water treatment agent are The molar ratio of the compound salt is adjusted to 1:0.05~3.0.

·[22] A water treatment agent obtained by the method for producing a water treatment agent according to any one of the above [14] to [21]. Preferably, the water treatment agent contains an alkaline agent, a halamine compound (preferably a chloramine compound), and a bromide salt.

·[23] A water treatment agent containing an alkaline agent, a chloramine compound and a bromide salt, with a post-production total chlorine detection rate of 95% or more and a free chlorine content rate of 0.05% in the total chlorine concentration (in terms of Cl ₂ total) or less. Furthermore, it is preferable that the total chlorine concentration after production is 4.1% (as _Cl2 ) or more.

·[24] The water treatment agent according to the above [22] or [23], which is obtained by mixing a mixed solution of an alkali agent, a stabilizer, and a bromide salt with an oxidizing agent.

·[25] The water treatment agent according to any one of the above [22] to [24], which is further mixed to form a carboxyl polymer of 1% to 18% by mass, and the carboxyl group content in the carboxyl polymer is It is less than 0.8g-COOH/g-polymer.

The carboxyl polymer preferably contains a maleic acid-based polymer and/or a (meth)acrylic acid-based polymer, and more preferably 50% by mass or more of the carboxyl polymer.

·[26] The water treatment agent according to any one of the above [21] to [24], wherein the pH of the water treatment agent is 13 or more.

·[27] The water treatment agent according to any one of the above [21] to [26], wherein the water treatment agent is a slow release preparation of hypobromous acid.

·[28] The water treatment agent according to any one of the above [21] to [27], which further contains an anticorrosion agent and/or an antiscalant. It is preferable to contain 0.5% by mass to 30% by mass of an anticorrosion agent and/or an antifouling agent.

·[29] A water treatment method, sterilization method, slime control method, anti-corrosion method or anti-scaling method, in which the water treatment agent described in any one of the aforementioned [14] to [21] is added to the water system. The water treatment agent obtained by the manufacturing method or the water treatment agent described in any one of the above [22] to [28].

Preferably used in water treatment plants. Applied to open circulation devices with cooling water system or hot water storage system, dust collection water system, washing tower water system, etc.

The water treatment agent is preferably added continuously or intermittently at a concentration of 1 mg/L to 1000 mg/L to each water system to be treated.

·[30] A water treatment device or water treatment system, including a device or system for adding a water treatment agent or each component used in the water treatment agent,

The water treatment agent is the water treatment agent according to any one of the above [1] to [14], or the water treatment agent according to any one of the above [23] to [28].

The water treatment device or water treatment system may further include a device or system for storage, and/or may also include a device or pipe or system for mixing. Furthermore, a control device or a control system for controlling the method described in any one of the above [9] to [13] and/or the method described in the above [29] may be included.

In addition, each component used in the water treatment agent described in any one of the above [1] to [14], and any one of the above [22] to [28] may be suitably blended and used. Ingredients used in water treatment agents. The effect of hypobromous acid can also be exerted by mixing each component and adding it to the water system in the form of a water treatment agent. In addition, the effect of hypobromous acid can also be exerted by adding each component to a water system at the same time or sequentially, and mixing these components in the water system.

Example

The embodiments of the present technology will be described with reference to the following test examples, examples, comparative examples, and the like. It should be noted that the scope of the present technology is not limited to test examples, working examples, and the like.

<Test Example 1 to Test Example 28 (First Embodiment)>

[Test Example 1 to Test Example 4: Combination of Each Component: Sample 1 to Sample 4]

In Figure 1, each sample 1 to 4 is added to open circulation cooling water (pH 8 to 9) so that the sample (water treatment agent) becomes 0.8 g/water L, and the total oxidant concentration in the water system is shown. time changes.

The water treatment agent (×) of Sample 1 in Test Example 1 contains a chloramine compound concentration of 9%.

The water treatment agent (Δ) of Sample 2 in Test Example 2 contains a chloramine compound concentration of 9% and a bromide concentration of 3.9%.

The water treatment agent (□) of Sample 3 in Test Example 3 contains a chloramine compound concentration of 9% and a carboxyl polymer concentration of 1.6%.

The water treatment agent (◇) of Sample 4 in Test Example 4 contains a chloramine compound concentration of 9%, a carboxyl polymer concentration of 1.6%, a bromide concentration of 3.9%, and a pH of 13.

In addition, the chloramine compound used in Test Example 1 to Test Example 28 was obtained by reacting hypochlorous acid and sulfamic acid (HN ₂ SO ₂ OH), and the Cl ₂ /N molar ratio was 0.1 to 1. method of preparation.

In addition, the bromide salt used in Test Examples 1 to 28 is potassium bromide.

In addition, the carboxyl polymer used in Test Examples 1 to 4 was a maleic acid polymer (99% by mass or more), and the carboxyl group content in this polymer was 0.77 g-COOH/g-polymer. The weight average molecular weight is 3900.

The carboxyl group content in the carboxyl polymer is measured by the above <Measurement method of carboxyl group content (g-COOH/g-polymer)>.

The weight average molecular weight of the carboxyl polymer is measured by the above <Measurement method of weight average molecular weight of water-soluble polymer>.

Each measurement method used in each [Test Example] is as follows.

<Total oxidizing agent concentration>: The total of chloramine, hypochlorous acid, and hypobromous acid is measured using DPD total reagent. The total oxidant concentration is expressed in terms of chlorine conversion, mg/L, and _Cl2 .

<Hypobromous acid>: After reacting free chlorine and glycine, the remaining hypobromous acid is measured using DPD free reagent. The concentration of hypobromous acid is calculated in terms of chlorine and expressed in mg/L and _Cl2 .

In addition, the DPD method used in this technology is performed in accordance with the DPD method using N,N-diethyl-1,4-phenylenediamine in JIS K 0400-33-10:1999.

FIG. 1 shows the change with time in the total oxidizing agent concentration when the concentration when only the chloramine compound is added is 100% and the carboxyl polymer and the bromide are coexisting.

When carboxyl polymer and bromide were added to the chloramine compound alone, no difference in the residual rate was observed. However, when both carboxyl polymer and bromide were added to the chloramine compound, the residual rate decreased by more than 10%.

When only a chloramine compound coexists with a brominating agent and a carboxyl polymer, the residual rate is significantly reduced. Therefore, it is considered that the hypobromous acid generated in the water system reacts with the carboxyl polymer and decomposes.

In this way, the pharmacological effect of the carboxyl polymer can be expected in the water treatment agent of Sample 4. However, although Sample 4 is designed to utilize hypobromous acid, which is stronger than hypochlorous acid, the stability of hypobromous acid over time in a water system is not very good, so it is considered that the effect of hypobromous acid (such as the sterilizing effect etc.) also lacks sustainability. Therefore, in Sample 4, it is considered that it is difficult to provide a one-pack type water treatment agent that can exhibit the effect of hypobromous acid satisfactorily when added to a water system and can also exert the chemical effects of other compounds satisfactorily.

[Test Examples 5 to 16: Carboxyl Group Content of Carboxy Polymer]

Each water treatment agent used in Test Examples 5 to 16 contained a chloramine compound concentration of 9%, a carboxyl polymer concentration of 1.6%, and a bromide concentration of 3.9%. Water treatment agents prepared using those with pH 13 as raw materials were used.

The carboxyl polymer used in each water treatment agent used in Test Examples 5 to 16 was a maleic acid polymer, and a polymer having a weight average molecular weight in the range of 1,000 to 16,000 was used.

At this time, as the carboxyl polymer of each water treatment agent, the carboxyl group content ratio (g-COOH/g-polymer) in the carboxyl polymer shown in Table 1 and Table 2 was used.

Specifically, the carboxyl group content rate in the carboxyl polymer in each water treatment agent of Test Examples 5 to 16 was measured. The results were as follows: Test Examples 5 and 11: 0.63 g-COOH/g-polymer, Test Example 6 and 12: 0.43g-COOH/g-polymer, Test Examples 7 and 13: 0.49g-COOH/g-polymer, Test Examples 8 and 14: 0.52g-COOH/g-polymer, Test Examples 9 and 15: 0.71g-COOH/g-polymer, Test Examples 10 and 16: 0.77g-COOH/g-polymer.

Furthermore, each water treatment agent was prepared so that the carboxyl polymer concentration in the water treatment agent would be 5 mg-polymer/L when added to 1 L of water, and was used in Test Examples 5 to 10 respectively. .

In addition, each water treatment agent was prepared so that the carboxyl polymer concentration in the water treatment agent would be 30 mg-polymer/L when added to 1 L of water, and was used in Test Examples 11 to 16 respectively. .

When the chloramine compound is set to 1, the molar ratio of the chloramine compound to the bromide salt in each water treatment agent used in Test Examples 5 to 16 is 1:0.2 to 1.0.

In Test Examples 5 to 10, each water treatment agent was added to the open-circulation cooling water (pH 8 to 9) so that the carboxyl polymer concentration became 5 mg-polymer/L, and the times in the water system after 48 hours were measured. Bromic acid concentration (mg/L, calculated as _Cl2 ). The results are shown in Figure 2 and Table 1.

In Test Examples 11 to 16, each water treatment agent was added to open circulation cooling water (pH 8 to 9) so that the carboxyl polymer concentration became 30 mg-polymer/L, and the water treatment agent was measured after 48 hours. Bromic acid concentration (mg/L, calculated as _Cl2 ). The results are shown in Figure 3 and Table 2.

[Table 1]

Table 1

[Table 2]

Table 2

[Test Example 17 to Test Example 27: Carboxyl Polymer Concentration in Water System]

Using the water treatment agent used in Test Example 5 as a raw material and changing the carboxyl polymer concentration in the water system shown in Table 3, each water treatment agent used in Test Examples 17 to 29 was obtained.

In Test Examples 17 to 27, each water treatment agent was added to the open circulation cooling water (pH 8 to 9) so that the carboxyl polymer concentration (mg-polymer/L) in the water system was as shown in Table 3 below. . After adding each water treatment agent, measure the hypobromous acid concentration (mg/L, calculated as _Cl2 ) in the water system 48 hours later. The results are shown in Figure 4 and Table 3.

[table 3]

table 3

＜Summary＞

The results of Test Examples 5 to 16 are shown in Figures 2 and 3, and Tables 1 and 2. The results of Test Examples 17 to 27 are shown in Figure 4 and Table 3.

When the carboxyl polymer used in the water treatment agent has a carboxyl group content ratio of 0.77 in the polymer, the concentration of hypobromous acid in the added aqueous system can be maintained at approximately 80%. Furthermore, from the viewpoint that the concentration of added aqueous hypobromous acid can be 90% or more, the carboxyl group content in the polymer is more preferably 0.35 to 0.75.

In addition, when the water treatment agent is added to the water system and the concentration of the carboxyl polymer in the water system is 5 mg-polymer/L to 30 mg-polymer/L, the total oxidant concentration (%) and hypobromous acid concentration in the water system ( %) high and good.

Furthermore, from the viewpoint of effect and cost, the amount of the water treatment agent added to the water system is preferably 40 mg/L to 200 mg/L. Furthermore, as mentioned above, when the concentration of the carboxyl polymer in the water system when the water treatment agent is added to the water system is considered to be preferably 5 mg-polymer/L to 30 mg-polymer/L, the carboxyl group contained in the water treatment agent polymerizes The substance concentration is preferably set to 18% by mass or less (more preferably 15% by mass or less), and from the viewpoint of cost, work efficiency, or effect expression, it is ideally set to 1% by mass or more (more preferably 1.5% by mass). mass% or more). This can be calculated by, for example, [polymer concentration in water system 30 mg - polymer/L]/[amount of water treatment agent added to water system 200 mg/L] = polymer content in water treatment agent 0.15 mg - polymer/mg (i.e., 15% by mass).

In addition, even if the maleic acid polymer used in the water treatment agent of Test Example 7 was replaced with an acrylic acid polymer (carboxyl group content in the polymer: 0.5 g-COOH/g-polymer; weight average molecular weight: 1,000 to 16,000) The same effect as the water treatment agent of Test Example 7 can also be obtained with the water treatment agent.

In addition, the total oxidizing agent concentration of each water treatment agent in Test Examples 5 to 16 was 98% or more when stored at 20°C for 20 days in a constant temperature bath, and was stored at 50°C for 20 days. time is more than 90%.

[Test Example 28: Slow release properties and weight average molecular weight of carboxyl polymer]

As shown in Table 4, the water treatment agent used in Test Example 5 was added to the open circulation cooling water (pH 8 to 9) so that the carboxyl polymer concentration became 0.2 g/L, and the hypobromide in the water system was measured over time. Acid concentration (mg/L, calculated as _Cl2 ).

In addition, the carboxyl polymer having a weight average molecular weight of 3,900 used in the water treatment agent of Test Example 5 was replaced with those having a weight average molecular weight of 800, 14,000, and 20,000, respectively, and the same test was performed. Even with these carboxyl polymers having a weight average molecular weight in the range of 10 to the 4th power, a hypochlorous acid concentration that is approximately the same as in the case of a carboxyl polymer having a weight average molecular weight of 3,900 can be obtained. When a carboxyl polymer with a weight average molecular weight of about 1,000 to 20,000 is used, a more excellent hypobromous acid concentration (about 40% to 60%) can be achieved.

The content of carboxyl groups in the polymer is measured by the above <Measurement method of carboxyl group content (g-COOH/g-polymer)>.

The weight average molecular weight of the carboxyl polymer is measured by the above <Measurement method of weight average molecular weight of water-soluble polymer>.

The water treatment agent of the first embodiment can be adjusted so that the hypobromous acid concentration 48 hours after addition to the water system is preferably 0.25 mg/L (based on Cl ₂ ) to 1.5 mg/L (based on Cl ₂ ), more preferably 0.5 mg. /L (calculated as Cl ₂ ) ~ 1mg/L (calculated as Cl ₂ ).

[Table 4]

Table 4

<Test Example 29 to Test Example 31 (Second Embodiment)>

Each measurement method used in each [Test Example] is as follows.

<Total oxidizing agent concentration>: The total amount of chloramine, hypochlorous acid, and hypobromous acid is measured using DPD total reagent. The total oxidant concentration is expressed in terms of chlorine conversion, mg/L, and _Cl2 .

<Hypobromous acid>: After reacting free chlorine and glycine, the remaining hypobromous acid is measured using DPD free reagent. The concentration of hypobromous acid is calculated in terms of chlorine and expressed in mg/L and _Cl2 .

In addition, the DPD method used in this technology is performed in accordance with the DPD method using N,N-diethyl-1,4-phenylenediamine in JIS K 0400-33-10:1999.

[Test Examples: Test Example 29 (Example 1), Test Example 30 (Comparative Example 1), and Test Example 31 (Comparative Example 2)]

In this test, each component in Table 5 was mixed with water (about 10°C to 20°C) according to the mixing order shown in Table 5 to prepare each single-liquid water treatment agent.

At this time, the water treatment agent immediately after production (0 hours) was blended with the water treatment agent in Table 5 so that it became 20 mass % of water (remainder), 10 mass % of sodium sulfamate, 5 mass % of sodium bromide, and pH 14. Ingredients shown. Use sodium hydroxide as the alkaline agent and powdered sodium bromide as the sodium bromide. Sodium hypochlorite was used so that hypochlorous acid (free form) became 1 mol with respect to 1.5 mol of sulfamic acid (free form).

In addition, in Test Example 29 (Example 1), Test Example 30, and Test Example 31 (Comparative Examples 1 and 2), when sodium sulfamate and sodium hypochlorite are mixed, the calculated amount of the water treatment agent produced is The theoretical value of total chlorine concentration (%) (as _Cl2 ) is 4.4%. The "total chlorine detection rate (%)" of each of Test Example 29 (Example 1), Test Example 30, and Test Example 31 (Comparative Example 1 and Comparative Example 2) shown in Table 2 and Figure 5 passed the "Water Treatment Agent It is calculated by "the actual measured value of the total chlorine concentration in the water treatment agent (% in Cl ₂ )/the theoretical value of the total chlorine concentration in the water treatment agent (% in Cl ₂ )" × 100 (%).

Regarding the manufacturing method of the water treatment agent of Test Example 29 (Example 1):

Add 500 g of sodium hydroxide to 1.0 L of water and mix to adjust the pH to 14 or higher to obtain an alkali agent mixed aqueous solution.

To this alkali agent mixed aqueous solution, 400 g of sodium sulfamate was added, and then 250 g of powdered sodium bromide was added and mixed to obtain a mixed aqueous solution of three kinds of agents.

2000g of sodium hypochlorite was added to the mixed aqueous solution of the three chemicals and mixed to obtain a water treatment agent. It was prepared by adding sodium hypochlorite so that sulfamic acid (free form) became 1.5 mol with respect to 1 mol of hypochlorous acid (free form).

It should be noted that the sodium sulfamate was produced by Tokyo Chemical Industry Co., Ltd., the powdered sodium bromide was produced by Tokyo Chemical Industry Co., Ltd., and the sodium hypochlorite was produced by Nippon Light Metal Co., Ltd.

The concentration of each component in the single-liquid water treatment agent is as described above.

In addition, "the content rate of free chlorine in the total chlorine concentration (%)" is calculated by [the concentration of free chlorine in the water treatment agent (% as _Cl2 )/the total chlorine concentration in the water treatment agent (% as _Cl2 ) ]×100(%) is calculated.

In addition, as the water treatment agent in Test Example 32 (Example 2), when preparing a mixed aqueous solution of three chemicals, the order of adding sodium sulfamate and powdered sodium bromide was changed. That is, powdered sodium bromide is added to the alkali agent mixed aqueous solution, and sodium sulfamate is added and mixed to prepare a three-drug mixed aqueous solution. Four hours after production, the total chlorine concentration in the water treatment agent of Test Example 32 (Example 2) was 4.3 (% as _Cl2 ), and the free chlorine content rate in the total chlorine concentration was 0.04 (%). Calculated as _Cl2 ). Therefore, the water treatment agent of Test Example 32 (Example 2) has substantially the same quality stability as the water treatment agent of Test Example 29 (Example 1).

Each water treatment agent (Test Example 29 (Example 1), Test Example 30, and Test Example 31 (Comparative Example 1 and Comparative Example 2)) was stored at a temperature of the aqueous solution of approximately 15°C to 25°C for a fixed period of time after production. The total chlorine concentration and free chlorine in each water treatment agent were measured at each elapsed time (1 hour, 2 hours, 3 hours, and 4 hours) after production, and the results are shown in Table 6.

[table 5]

Table 5: Manufacturing steps of each water treatment agent

[Table 6]

Table 6: Total chlorine concentration in each water treatment agent and free chlorine content rate in the total chlorine concentration

[Table 7]

Table 7: Total chlorine detection rate in each water treatment agent

The theoretical value of the total chlorine concentration is set to 4.4 (%) (calculated as _Cl2 ).

As shown in Test Example 29 (Example 1) in Tables 5 to 7, a mixed solution containing chemicals other than bromide salts is prepared, and a bromide salt is added to the mixed solution and mixed to obtain a chloramine-containing solution. According to this production procedure, a single-liquid water treatment agent of a compound + bromide ion can exhibit the effect of hypobromous acid well when added to a water system, and on the other hand, it is possible to obtain a water treatment agent that has excellent quality stability of the chemical.

Specifically, the water treatment agent of Test Example 29 (Example 1) had a total chlorine detection rate (%) of approximately 98% and a total chlorine concentration (% in _Cl2 ) of 4.3% after 4 hours after production. became stable, and the free chlorine content rate in the total chlorine concentration also became stable at 0.04%. It is considered that by reaching this steady state, the active ingredient in the water treatment agent becomes a stable state, and therefore this stable state is considered to last for several weeks or more.

On the other hand, in the water treatment agent of Test Example 31 (Comparative Example 2), the decrease in the total chlorine concentration continues even after 4 hours after production, and it is considered that the total chlorine detection rate will be significantly lower than the total chlorine detection rate of 60% and the total chlorine concentration (% Calculated as _Cl2 ) 2.8%. In addition, after 4 hours after production of the water treatment agent of Test Example 30 (Comparative Example 1), the total chlorine detection rate was approximately 93% and the total chlorine concentration (% in _Cl2 ) was 4.1% and became stable. The free chlorine content rate in the chlorine concentration is also 0.05% and becomes stable.

The loss in the total chlorine detection rate of the water treatment agent of Test Example 29 (Example 1) was about 3% after 1 hour and 4 hours after production, but the water treatment agent of Test Example 30 (Comparative Example 1) The loss of total chlorine detection rate is approximately 7%. When comparing the loss rate of the total chlorine concentration in the water treatment agent of Test Example 29 (Example 1) with the loss rate of the total chlorine concentration of the water treatment agent of Test Example 30 (Comparative Example 1), Test Example 29 (Execution The water treatment agent of Example 1) can suppress the loss rate to less than half and maintain a state substantially close to 100%. Therefore, it can be said that the quality stability is very excellent.

In this way, the water treatment agent according to the second embodiment of the present technology can maintain a high level of active ingredients. Therefore, when added to a water system, the effect of hypobromous acid is well exerted and the quality stability of the agent is excellent.

In addition, the total chlorine concentration (% in Cl2) of the water treatment agent of Test Example 30 (Comparative Example 1) after ₂ hours has elapsed is 4.1% or less, but the total chlorine concentration of the water treatment agent according to the second embodiment of the present technology The concentration (% as _Cl2 ) remains at least 4.2% or higher even after 2 hours. The water treatment agent obtained by the manufacturing method of the second embodiment of the present technology can be said to be a novel water treatment agent.

The water treatment agent according to the second embodiment of the present technology produced according to the above-described procedure has excellent quality stability of the agent and can significantly suppress the decrease of active ingredients. Therefore, when added to a water system, hypobromous acid can be generated at a high concentration. Therefore, the water treatment agent according to the second embodiment of the present technology can generate hypobromous acid at a higher concentration when added to a water system than other water treatment agents, that is, it can exhibit the effect of hypobromous acid favorably. Therefore, the water treatment agent according to the second embodiment of the present technology can further exhibit the effects of hypobromous acid such as high bactericidal effect and high slime prevention effect.

In addition, the water treatment agent according to the second embodiment of the present technology does not incorporate a special device or other chemicals to exhibit such effects, but can exhibit such excellent effects by designing the mixing order of each component. That is, the manufacturing method of the second embodiment of the present technology thus introduced and the water treatment agent obtained by this manufacturing method can achieve cost reduction, work efficiency, and quality stability improvement. From this point of view, the present technology The second embodiment can also be said to have discovered an unpredictable structure and an unpredictable effect resulting therefrom.

Claims (8)

1. A water treatment agent containing the following components (a) to (c) and having a pH of 10 or more: (a) Chloramine compound 6 to 24% by mass, (b) Bromide salt, (c) 1 mass % to 18 mass % of a carboxyl polymer having a carboxyl group content rate of 0.1 g-COOH/g-polymer or more and 0.71 g-COOH/g-polymer or less, Wherein, the (c) carboxyl polymer is a maleic acid-based polymer and/or a (meth)acrylic acid-based polymer. 2. The water treatment agent according to claim 1, wherein the molar ratio of the chloramine compound to the bromide salt is 1:0.1-1.0. 3. The water treatment agent according to claim 1 or 2, wherein the water treatment agent is for at least any one of slime control, corrosion prevention, and scale prevention. 4. The water treatment agent according to claim 1 or 2, wherein the (a) chloramine compound and the (b) bromide salt in the water treatment agent are a mixture of an alkali agent and a stabilizer. It is obtained by mixing a mixed solution of bromide salt and an oxidizing agent. 5. The water treatment agent according to claim 1 or 2, wherein the total chlorine detection rate after manufacture of the water treatment agent is 95% or more and the free chlorine content rate in the total chlorine concentration is 0.05 in terms of _Cl2 . %the following. 6. A method for manufacturing a water treatment agent, which includes mixing a mixed solution of an alkali agent, a stabilizer and a bromide salt with an oxidizing agent, Wherein, the stabilizer and the bromide salt are mixed in an aqueous solution adjusted to a pH of 13 or above using the alkali agent to prepare the mixed solution; 1.2 to 3 moles of the stabilizer are blended relative to 1 mole of the oxidizing agent; The stabilizer is a sulfamic acid compound; The oxidizing agent is hypochlorous acid or its salt, The pH of the water treatment agent is 13 or above. 7. The method for producing a water treatment agent according to claim 6, wherein the mixed solution is a solution in which a powdery bromide salt is mixed as the bromide salt. 8. The method for producing a water treatment agent according to claim 6 or 7, wherein the carboxyl polymer is further mixed to 1% by mass to 18% by mass, and the carboxyl group content in the carboxyl polymer is 0.1 g-COOH/ g-polymer or more and 0.8g-COOH/g-polymer or less.