JP6447687B1 - One-component water treatment agent and method for producing the same - Google Patents

Abstract

Disclosed is a one-component water treatment agent containing a combined chlorine-type fungicide and an organic fungicide, which has excellent storage stability and has an excellent effect as a slime control agent, an antiseptic, and the like, and a method for producing the same. To do. SOLUTION: A one-component water treatment agent having a pH of 2 to 6 containing an inorganic chlorine agent, a chlorine stabilizer, an organic fungicide, a pH adjuster, an organic solvent and water as a blending component is added to water at least. A pH adjuster, a chlorine stabilizer, an inorganic chlorine agent, an organic solvent and an organic fungicide are added in this order, and the mixture is stirred and mixed at 40 ° C. or lower. [Selection figure] None

Description

  The present invention relates to a one-pack type water treatment agent suitable as a slime control agent, preservative, and the like, and a method for producing the same in a paper pulp process water system, a cooling water system, a reverse osmosis membrane treated water system, and the like.

In the pulp and paper process water system, cooling water system, reverse osmosis membrane treated water system, etc., the growth of microorganisms and algae present in the water causes slime to be generated and attached in the system, resulting in poor water permeability due to blockage of pipes and membranes. May cause. In particular, in the pulp and paper process water system, malodor and drainage failure due to rot such as starch slurry and coating liquid are likely to occur, and thus it is required to prevent such harmful effects.
For this reason, in these aqueous systems, water treatment agents such as slime control agents and preservatives are added and used.

As such a water treatment agent, an inorganic chlorine agent, a combined chlorine type fungicide combining this with sulfamic acid or the like, or 2,2-dibromo-2-nitroethanol (hereinafter abbreviated as “DBNE”). Slime control agents (organic fungicides) are known.
Patent Document 1 describes that slime control and antiseptic can be efficiently performed by using a combined chlorine-type fungicide as described above and a slime control agent in combination.

However, combined chlorine type disinfectants are generally strongly alkaline, and when mixed with acidic organic disinfectants such as DBNE, decomposition reactions occur, and there is a risk of fever and gas generation. It could not be used as a mixed solution.
For this reason, it is necessary to separately provide a chemical injection device such as a tank or pump for the combined chlorine type organic disinfectant and the organic disinfectant in the water system to be treated, and the problem that the operation and management of the chemical solution injection on the site becomes complicated Had.

  For this, for example, it is conceivable to suppress the decomposition reaction of the combined chlorine type bactericide by the acidic organic bactericide by using a bonded chlorine type bactericide that is stable even in the acidic state. As such a combined chlorine type disinfectant, for example, in Patent Document 2, by adding an acrylic acid copolymer to a combined chlorine type disinfectant (inorganic chlorine agent and chlorine stabilizer), the acid is stable. It has been proposed to obtain a simple composition.

Japanese Patent Laying-Open No. 2015-226905 JP 2016-210739 A

However, in order to improve the operability at the time of injecting a chemical solution into the aqueous system to be treated, a combined chlorine-type disinfectant as described in Patent Document 2 and an organic disinfectant will be combined into a single agent. However, precipitation and precipitation of organic fungicides may occur, and active ingredients may be decomposed (see Comparative Example 1 described later).
As described above, even when a combined chlorine type fungicide as described in Patent Document 2 is used, it is difficult to use it in combination with an organic fungicide.

  Therefore, from the viewpoint of improving the operability of injecting chemical solution in the field, it is required to stably combine the combined chlorine type germicide and the organic germicide.

  The present invention has been made in order to solve the above-described problems, and provides a combined chlorine-type fungicide and an organic fungicide having excellent storage stability and excellent effects as a slime control agent, an antiseptic, and the like. An object of the present invention is to provide a one-component water treatment agent and a method for producing the same.

  The present invention is based on the finding that a combined chlorine-type fungicide and an organic fungicide can be stably combined into one agent by combining with a predetermined pH adjuster and an organic solvent.

That is, the present invention provides the following [1] to [4].
[1] A one-component water treatment agent that contains an inorganic chlorine agent, a chlorine stabilizer, an organic fungicide, a pH adjuster, an organic solvent, and water as blending components and has a pH of 2 to 6.
[2] The one-component water treatment agent according to [1], wherein the organic solvent is one or more selected from glycols, glycol ethers, esters, and alcohols.
[3] The pH adjusting agent includes a strong acid, a strong base, a mixture of a weak acid and a conjugate acid thereof having a pH buffering capacity, or a mixture of a weak base and a conjugate acid thereof having a pH buffering ability. The one-pack type water treatment agent according to the above [1] or [2].
[4] A method for producing the one-component water treatment agent according to any one of [1] to [3] above, wherein water is at least a pH adjuster, a chlorine stabilizer, and inorganic chlorine. An agent, an organic solvent, and an organic disinfectant are added in this order, and stirred and mixed at 40 ° C. or lower to obtain a one-component water treatment agent having a pH of 2 to 6.

According to the present invention, it is possible to obtain a one-pack type water treatment agent in which a combined chlorine-type fungicide and an organic fungicide are stably made into one agent. The one-component water treatment agent is excellent in storage stability and exhibits excellent effects as a slime control agent, preservative and the like.
Therefore, the one-pack type water treatment agent of the present invention can contribute to the improvement of the operability of the chemical solution injection in the field in the water system to be treated.
Moreover, according to the manufacturing method of this invention, the said 1 liquid type water treatment agent can be manufactured suitably.

Hereinafter, the present invention will be described in detail.
The one-component water treatment agent of the present invention is characterized in that it contains an inorganic chlorinating agent, a chlorine stabilizer, an organic disinfectant, a pH adjuster, an organic solvent, and water as ingredients, and has a pH of 2-6. .
By setting it as such a mixing | blending, the water treatment agent which made the inorganic type chlorine agent, the chlorine stabilizer, and the organic type germicide stably one agent can be obtained.

(Inorganic chlorine agent)
Inorganic chlorine agents produce bound chlorine type fungicides by reaction with chlorine stabilizers.
Examples of the inorganic chlorinating agent include chlorine gas, chlorine dioxide, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, and salts thereof. These may be used alone or in combination of two or more. Of these, hypochlorous acid or a salt thereof is preferable, and hypochlorite is more preferably used. The hypochlorite is not particularly limited, and examples thereof include sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, and barium hypochlorite. Among these, sodium hypochlorite is preferable from the viewpoint of availability.
The blending amount of the inorganic chlorine agent in the one-pack type water treatment agent is not particularly limited, but is preferably 0.5 to 20% by mass as an effective chlorine component, and more preferably 1 to 10% by mass. %, More preferably 1 to 5% by mass. In the present invention, the amount of the inorganic chlorinating agent is considered to correspond to the initial concentration of the effective chlorine component of the combined chlorinated fungicide in the one-pack type water treatment agent.

(Chlorine stabilizer)
A chlorine stabilizer produces a combined chlorine-type fungicide by reaction with an inorganic chlorine agent.
Examples of the chlorine stabilizer include sulfamic acid and derivatives thereof; isocyanuric acid; hydantoins such as 5,5′-dimethylhydantoin, urea, biuret, methyl carbamate, ethyl carbamate, acetamide, nicotinamide, methanesulfone. Amide compounds such as amide and toluenesulfonamide; Imide compounds such as maleimide, succinimide and phthalimide; Amino acids such as glycine, alanine, histidine and lysine; Amine compounds such as methylamine, hydroxylamine, morpholine, piperazine, imidazole and histamine Ammonia; ammonium salts such as ammonium sulfate; These may be used alone or in combination of two or more. Of these, sulfamic acid, sulfamic acid derivatives, and salts thereof are preferable from the viewpoint of environmental load and the like.

Examples of the sulfamic acid derivative include N-methylsulfamic acid, N, N-dimethylsulfamic acid, N-phenylsulfamic acid and the like.
Examples of salts of sulfamic acid and sulfamic acid derivatives include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salt, strontium salt and barium salt, manganese salt, copper salt, zinc salt, iron Other metal salts such as salts, cobalt salts, nickel salts; ammonium salts and the like.
From the viewpoint of sufficient reactivity with the inorganic chlorinating agent, the blending amount of the chlorine stabilizer in the one-pack type water treatment agent is 1 to 5 mol with respect to 1 mol of chlorine atoms contained in the inorganic chlorinating agent. It is preferable that there is, more preferably 1-4 mol, and still more preferably 1.2-3 mol.

(Organic fungicide)
The organic fungicide can be used in combination with the combined chlorine fungicide to obtain a synergistic effect of bactericidal action, and can effectively perform slime control and preserving.
The organic fungicide is not particularly limited, but 2,2-dibromo-2-nitroethanol (DBNE), 2-bromo-2-nitro-1,3-propanediol (abbreviation “BNP”) 2,2-dibromo-3-nitrilopropionamide (abbreviation “DBNPA”), 5-chloro-2-methyl-4-isothiazolin-3-one (abbreviation “Cl-MIT”) and metal salts thereof, 2-methyl -4-isothiazolin-3-one (abbreviation “MIT”) and metal salts thereof, orthophthalaldehyde (abbreviation “OPA”), glutaraldehyde, 4,5-dichloro-1,2-dithiolane-3-one, 1, 4-bis (bromoacetoxy) -2-butene (abbreviation “BBAB”), 1,2-bis (bromoacetoxy) ethane (abbreviation “BBAE”), 4,5-dichloro-2- Cutyl-4-isothiazolin-3-one (abbreviation “DCOIT”), 1,2-benzisothiazolin-3-one (abbreviation “BIT”), methylenebisthiocyanate (abbreviation “MBTC”), dichloroglyoxime (abbreviation “DCG”) )), Tetrakishydroxymethylphosphonium sulfate (abbreviated as “THPS”), and the like. These may be used alone or in combination of two or more. Of these, DBNE, BNP, DBNPA, Cl-MIT, and MIT are preferable, and DBNE and BNP are more preferable, from the viewpoint of being stably integrated with the combined chlorine-type fungicide.

  The blending amount of the organic fungicide in the one-pack type water treatment agent is appropriately adjusted according to the desired performance of the water treatment agent, but from the viewpoint of improving the bactericidal action in combination with the combined chlorine type fungicide, It is preferable that it is 0.01-5 mol with respect to 1 mol of inorganic type chlorine agents, More preferably, it is 0.1-4 mol, More preferably, it is 0.2-2 mol.

(PH adjuster)
The pH adjuster plays a role of adjusting the pH for stably combining the combined chlorine-type disinfectant and the organic disinfectant so that the pH of the one-part water treatment agent is 2-6. It is for adjustment.
As a pH adjuster, 1 type (s) or 2 or more types of strong acids, such as hydrochloric acid and a sulfuric acid, or 1 type or 2 types or more of strong bases, such as sodium hydroxide and potassium hydroxide, can be used.
Moreover, as a pH adjuster, it is preferable to use what has a buffer capacity from a viewpoint of stability of pH. Specifically, one or more of a mixture of a weak acid and its conjugate base having pH buffering ability, or one or two of a mixture of a weak base and its conjugate acid having pH buffering ability A solution containing the above is preferably used. Examples of the weak acid include citric acid, phosphoric acid, tartaric acid, acetic acid, boric acid, glycine, phthalic acid, formic acid, 3,3-dimethylglutaric acid, phenylacetic acid, succinic acid, maleic acid, diethyl barbituric acid, trans -Homoaconitinic acid and the like. Examples of the weak base include trishydroxymethylaminomethane. In these solutions, it is preferable to use a buffer solution adjusted with the strong acid or the strong base so that the one-component water treatment agent has a desired pH within a range of pH 2-6. In addition, you may add these strong acids and strong bases in order to adjust so that it may become desired pH in the last process of manufacture of a one-pack type water treatment agent.
As a mixture containing a mixture of a weak acid and its conjugate base, for example, a solution containing an organic acid such as citric acid or acetic acid, phosphoric acid, or a salt of at least one of these with a strong base is preferably used. For example, the pH can be suitably adjusted by adding sodium hydroxide to a mixed aqueous solution of citric acid and disodium hydrogen phosphate.

The pH of the one-pack type water treatment agent is adjusted to be 2 to 6 from the viewpoint of the stable unitization of the combined chlorine-type fungicide and the organic fungicide, but it improves the storage stability. From the viewpoint, the pH is preferably 3 to 5.
When the pH is less than 2, the decomposition reaction of the combined chlorine-type fungicide is promoted. On the other hand, when the pH exceeds 6, the decomposition reaction of the organic fungicide is promoted.
The pH adjuster is added so that the pH of the one-component water treatment agent falls within the above range, but a good pH buffering action is obtained, and the performance of the active ingredient of the one-component water treatment agent is sufficient. From the viewpoint of being exhibited, the amount of the one-component water treatment agent is preferably about 0.5 to 20% by mass, and more preferably 1 to 10% by mass.

(Organic solvent)
The organic solvent is added to suppress decomposition, precipitation and precipitation of the organic fungicide.
As the organic solvent, when the water system to be treated is an industrial cooling water system or a papermaking pulp process water system, especially starch slurry, the dispersibility and solubility of the active ingredient of the one-pack type water treatment agent are taken into consideration. It is preferable to use a solvent having hydrophilicity.
Examples of hydrophilic organic solvents include glycols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, methyl cellosolve, phenyl cellosolve, and tripropylene Glycol ethers such as glycol monomethyl ether; glymes such as monoglyme and diglyme; ketones such as acetone and diacetone alcohol; methyl acetate, ethyl acetate, 3-methoxybutyl acetate, 2-ethoxymethyl acetate, 2-ethoxyethyl acetate , Propylene carbonate, dimethyl glutarate, dimethyl succinate, dimethyl adipate, etc. Ester ethers, ethanol, amino and alcohols such as ethanol and propanol; N, such as an acid amides such as N- dimethylacetamide. Of these, glycols, glycol ethers, esters, and alcohols are preferable from the viewpoint of stable unitization of a combined chlorine-type fungicide and an organic fungicide and safety.
The blending amount of the organic solvent in the one-pack type water treatment agent is 5 from the viewpoints of stable unitization of the combined chlorine-type fungicide and the organic fungicide, the uniformity of the one-pack type water treatment agent, and the like. It is preferable that it is -50 mass%, More preferably, it is 10-40 mass%.

(water)
Water is contained as a solvent in the one-component water treatment agent together with the organic solvent from the viewpoint of solubility and dispersibility of the active ingredient of the one-component water treatment agent. It also plays a role in improving the solubility and dispersibility in the aqueous system to be treated.
From the above viewpoint, the amount of water in the one-component water treatment agent is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass.
In addition, when each said compounding component in a one-pack type water treatment agent is an aqueous solution, a water dispersion liquid, etc. previously, water can also contain what originates in these.

(Other ingredients)
In the one-pack type water treatment agent, an inorganic chlorine agent, within a range that does not hinder the stable formation of a combined chlorine-type fungicide and organic fungicide and does not impair the effects of the present invention, In addition to chlorine stabilizers, organic fungicides, pH adjusters, organic solvents and water, other components include, for example, an anionic copolymer such as a scale inhibitor, an antifoaming agent, polyacrylic acid, and ethylenediaminetetraacetic acid. Additive components such as chelating agents such as sodium salts, nonionic surfactants, and emulsion particles stabilized with higher alcohols may be included as necessary.

(Production method)
The one-component water treatment agent of the present invention can be produced by a method obtained as a uniform mixed solution of the above-described components. Specifically, at least a pH adjuster, a chlorine stabilizer, an inorganic chlorine agent, an organic solvent and an organic fungicide are added to water in this order, and the mixture is stirred and mixed at 40 ° C. or lower to adjust the pH to 2-6. Can be suitably obtained.
From the viewpoint of stably combining the combined chlorine type germicide and the organic germicide, it is preferable that the temperature at the time of liquid mixing is 40 ° C. or less, and stirring and mixing while cooling as necessary. . In addition, when the one-component water treatment agent contains components other than the above-described blending components, they can be added as appropriate, but in this case as well, care should be taken so that the temperature at the time of liquid mixing does not exceed 40 ° C. To do.
In addition, the pH adjustment of the one-pack type water treatment agent may be performed by adding hydrochloric acid or sodium hydroxide at the end after mixing the above-mentioned components.

(Applicable)
The one-component water treatment agent of the present invention can be applied to various water systems such as a paper pulp process water system, a cooling water system, and a reverse osmosis membrane treated water system. It can be suitably used as a slime control agent or preservative. For example, in a paper pulp process, a slime control agent such as white water or reused water, and a preservative for pulp slurry, starch slurry, coating solution, clay, etc. Suitable as an agent or the like.
The amount of the one-component water treatment agent used is appropriately adjusted according to the various water systems to be treated. However, in order to exert a sufficient effect, the concentration is usually 1 to 1000 mg / each with respect to each water system to be treated. L is preferably added continuously or intermittently.

  Hereinafter, the present invention will be described in more detail, but the present invention is not limited to the following examples.

[Preparation of water treatment agent]
Example 1
A one-component water treatment agent having the composition shown below was prepared as follows.
A pH adjuster, chlorine stabilizer, inorganic chlorine agent, organic solvent, and organic fungicide are added to water in this order, and the mixture is stirred and mixed while cooling to 40 ° C. or less, so that an effective concentration of 3% by mass is obtained. A one-pack type water treatment agent having a pH of 4.0 containing a chlorine component (inorganic chlorine agent) and an organic disinfectant having a concentration of 9% by mass was obtained.
<Composition composition>
・ Water (23.9% by mass)
-PH adjuster: 2.6% by mass of citric acid, 0.9% by mass of disodium hydrogen phosphate
(Finally, adjust to pH 4.0 with sodium hydroxide)
Chlorine stabilizer: 5.6% by mass of sulfamic acid
・ Inorganic chlorine agent: 25% by mass of aqueous solution containing 12% by mass of sodium hypochlorite
Organic solvent: 30% by mass of diethylene glycol
・ Organic fungicide: DBNE 75 mass% containing diethylene glycol solution 12 mass%

(Comparative Example 1)
Of the blend composition of Example 1, a pH adjuster and an organic solvent were not added, and an anionic copolymer was a copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (monomer-containing molar ratio 98). : 2, mass average molecular weight (GPC method) 9500) was mixed so as to have a solid content concentration of 4% by mass, and other components were stirred and mixed in the same manner as in Example 1. The mixture was adjusted to pH 4.0 with sodium hydroxide to obtain a water treatment agent containing an effective chlorine component (inorganic chlorine agent) having a concentration of 3% by mass and an organic disinfectant having a concentration of 9% by mass.

(Comparative Example 2)
A diethylene glycol solution containing 15% by mass of DBNE, which is an organic fungicide, was used as a water treatment agent.

(Comparative Example 3)
50% by mass of an aqueous solution containing 12% by mass of sodium hypochlorite as an inorganic chlorine agent, 18% by mass of sulfamic acid as a chlorine stabilizer, and 34% by mass of water were mixed with stirring. The mixed solution was adjusted to pH 13 or higher with sodium hydroxide to obtain a water treatment agent containing an effective chlorine component (inorganic chlorine agent) having a concentration of 6% by mass.

[Test 1] Storage stability evaluation Each water treatment agent prepared in Example 1 and Comparative Example 1 was stored in a constant temperature bath at a set temperature of 40 ° C., and DBNE and a combined chlorine type disinfectant (sodium chlorosulfamate). The residual change of the water treatment was measured over time, and the storage stability of the water treatment agent was evaluated. The residual amount of sodium chlorosulfamate was determined as the ratio of the residual chlorine concentration to the initial (immediately after preparation) bound chlorine (residual chlorine) concentration.
DBNE was measured with a high performance liquid chromatograph (“Agilent 1260”, manufactured by Agilent Technologies). The residual chlorine concentration was measured with a residual chlorine meter (“Pocket Colorimeter (registered trademark) II”, manufactured by Hack Co.).
The test results are shown in Table 1 below.

Even when the water-treated product of Example 1 was stored at 40 ° C. for 1 month, no change was confirmed by visual observation. Further, as can be seen from the results shown in Table 1, it was recognized that the residual amounts of DBNE and sodium chlorosulfamate were both kept high.
On the other hand, the water treatment agent of Comparative Example 1 was cloudy immediately after preparation. In addition, the concentrations of DBNE and sodium chlorosulfamate both decreased immediately after preparation, and decreased to less than half after two weeks.
From this, it can be said that the water-treated product of the present invention is excellent in storage stability because the combined chlorine-type fungicide and the organic fungicide are stably integrated into one agent.

[Test 2] Evaluation of antiseptic performance For the starch slurry having a solid content concentration of 21% (mass / volume), pH 6.9, and initial bacterial count 1.7 × 10 ⁵ CFU / mL obtained from Sakai Factory, Using each water treatment agent prepared in the comparative example, it was added at an addition concentration shown in Table 2 below. The same test was also performed when the water-treated products of Comparative Examples 2 and 3 were mixed at the time of addition and used in combination (two-component combination). In addition, the addition density | concentration in Table 2 is a value based on content of DBNE and sodium chlorosulfamate at the time of preparation of each water treatment product.
After standing at 30 ° C. for 2 hours and 1 day, pour it into a standard agar medium and incubate at 30 ° C. for 48 hours to measure the number of bacterial colonies (the number of bacteria), thereby evaluating the antiseptic performance. went. It can be said that the more the number of bacteria is reduced, the better the antiseptic performance.
In addition, the water treatment agent of Example 1 was used after 1 month from the preparation, and the water treatment agent of Comparative Example 1 was used after 2 weeks from the preparation. The water-treated products of Comparative Examples 2 and 3 were used immediately after preparation.
The test results are shown in Table 2 below. The case where no water treatment agent was added is also shown in Table 2 as a blank.

As can be seen from the results shown in Table 2, the water treatment agent of Example 1 has the same degree of antiseptic effect as the case of only the organic fungicide (DBNE) in which the addition concentration of DBNE is twice (Comparative Example 2). Moreover, it was recognized that the preservative effect superior to the case (comparative example 3) of only a combined chlorine type fungicide (sodium chlorosulfamate) was shown.
As shown in Test 1, the water-treated product of Comparative Example 1 is inferior in storage stability. Even when the addition concentrations of DBNE and sodium chlorosulfamate are the same as in Example 1, antiseptic performance is achieved. It was inferior.
Moreover, in Example 1, since the antiseptic effect almost equivalent to the case of two-component combination is obtained, even if it is a single agent, it has excellent storage stability and antiseptic performance, and is excellent. It can be said that the protective performance can be demonstrated.

Claims (3)

An inorganic chlorine agent containing at least one selected from hypochlorous acid and salts thereof , a sulfamic acid, a sulfamic acid derivative, and a chlorine stabilizer containing at least one selected from these salts , 2,2-dibromo- An organic fungicide containing at least one selected from 2-nitroethanol (DBNE) and 2-bromo-2-nitro-1,3-propanediol (BNP) , a pH adjuster, glycols, glycol ethers, esters, and include as a blending component an organic solvent and water containing at least one selected from alcohols, less than pH 3 or 5, one-WTA. pH adjustment agent comprises a strong acid, strong base, those with pH buffering capacity with a mixture of a weak acid and its conjugate base, or, those with pH buffering capacity in the mixture of weak base and its conjugate acid, claim 1 One-component water treatment agent according to 1. A method for producing a one-component water treatment agent according to claim 1 or 2 , wherein at least a pH adjuster, a chlorine stabilizer, an inorganic chlorine agent, an organic solvent and an organic fungicide are added to water. A method for producing a one-component water treatment agent, which is added in order and stirred and mixed at 40 ° C. or less to obtain a one-component water treatment agent having a pH of 3 or more and less than 5 .