JP2002193707A - Multi-function type water-treating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multi-function type water treating agent which is applied to water systems causing slime troubles, scale troubles and corrosion troubles. SOLUTION: This water-treating agent is characterized by containing a halogenated aliphatic nitroalcohol, one or more isothiazolone complexes, a carboxylic acid-based low molecular weight polymer, an azole compound and ethylene carbonate as active ingredients.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a water treatment agent. More specifically, the present invention relates to a multifunctional water treatment agent applied to an aqueous system in which slime, scale, and corrosion disorders occur.

[0002]

2. Description of the Related Art In recent years, with the development of the chemical industry and other industries, a large amount of industrial water has become necessary. As a source of industrial water, seawater, lake water, swamp water, river water, and the like are used in addition to industrial tap water. Various microorganisms grow in these industrial waters, and many of these microorganisms continue to proliferate further depending on the water quality and environment in which they exist, and cause various obstacles.

[0003] For example, when used as cooling water, microorganisms living in the water proliferate and form on the walls of irrigation facilities to form slime, which causes a decrease in heat exchange rate and poor running water. Failure occurs. In particular, in the case of open circulation using an open-type cooling tower, etc., in circulating use of water, circulating water is forcibly aerated in a part of the system, comes into contact with air, and is exposed to sunlight, causing bacteria and bacteria. The growth of aerobic microorganisms such as algae is promoted. Similar obstacles also occur in air-conditioning systems such as buildings and factories, and in cooling water systems provided with small cooling towers in cooling and heating facilities.

In general water systems, especially cooling water systems, in addition to slime damage, dissolved oxygen and chlorine ions in water,
Corrosion damage due to dissolved salts such as sulfate ions and accumulation of calcium ions and the like in water cause scale disturbances such as calcium carbonate and calcium sulfate, and calcium phosphate accompanying the use of polymerized phosphate-based anticorrosives.
In particular, with the recent high-concentration operation of the cooling water system, these obstacles have become more serious.

Conventionally, a slime treating agent, an anticorrosive, and a scale inhibitor have generally been individually added to water in order to effectively exert their effects. However, such a method is extremely complicated for a manager to operate, and a drug capable of treating various obstacles of water with one agent has been desired.

Under these circumstances, a mixture of a halogenated aliphatic nitro alcohol and an isothiazolone complex compound as a slime treating agent, an azole compound as an anticorrosive for copper, and a carboxylic acid type low molecular weight polymer as a scale inhibitor are mixed. An open water-based obstacle preventive agent comprising an agent has been proposed and put into practical use as a multifunctional water treatment agent. This composition has a synergistic effect in terms of the effect of suppressing the generation of microorganisms and the formation of slime, as compared with a case where a halogenated aliphatic nitro alcohol or an isothiazolone complex compound is blended alone.

However, when a halogenated aliphatic nitro alcohol and an isothiazolone complex compound are used as a slime-treating agent and an azole compound or a carboxylic acid-based low molecular weight polymer is added thereto, a viscous precipitate is generated at an early stage. ing. In order to prevent this, polyhydric alcohols, ketones, a technique of compounding an organic solvent such as an aromatic organic solvent as a stabilizer is known, but when a mixture containing these organic solvents is added to a cooling water system, There is a drawback that a large amount of foaming occurs, and the generated foam scatters around, or in some cases, the circulation pump entrains the foam and runs idle. In addition, when an organic solvent such as polyhydric alcohol is used as a stabilizer, it may become a nutrient source for microorganisms, and there have been restrictions on the method of use such as shortening a chemical injection interval to prevent this.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the prior art and to provide a multifunctional water treatment agent capable of exhibiting a stable effect.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies on the composition of a multifunctional water treatment agent. As a result, by adding ethylene carbonate as a stabilizer, foaming that occurs when added to a cooling water system is performed. It has been found that it is possible to avoid the occurrence of precipitates during storage for a long period of time, and arrived at the present invention. Further, as a secondary effect, it has been found that it is possible to prevent the growth of microorganisms which is observed when polyhydric alcohols are used as a stabilizer. That is, the present invention relates to a halogenated aliphatic nitro alcohol represented by the general formula (1), at least one kind of an isothiazolone complex compound represented by the general formula (2), a carboxylic acid-based low molecular weight polymer, an azole compound, and ethylene carbonate. And a water treatment agent characterized by containing as an active ingredient.

[0010]

Embedded image (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a lower alkyl group or a hydroxy lower alkyl group, R ² represents a hydrogen atom or a lower alkyl group, and X represents a halogen atom.)

[0011]

Embedded image (Wherein Y represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, R represents a hydrogen atom or a halogen atom, R ′ represents a hydrogen atom or a halogen atom, and R and R ′ are M may represent a cation atom or a group selected from the group consisting of alkaline earth metals, heavy metals and amines;
Z represents an anion atom or group that forms a compound with a cation M that has sufficient solubility to form a complex compound. A represents an integer of 1 or 2, and n represents an integer in which the anion Z satisfies the valence of the cation M. )

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION As the halogenated aliphatic nitro alcohol represented by the general formula (1) in the present invention, 2
-Chloro-2-nitroethanol, 1-chloro-1-nitropropanol-2, 3-chloro-3-nitrobutanol-2, 2-chloro-2-nitrobutanediol (1,3), 1-chloro-1 -Nitrobutanol-2,
2-chloro-2-nitrobutanol, 2-chloro-2-
Nitropentanol-3, 2,2-dichloro-2-nitroethanol, 2-chloro-2-bromo-2-nitroethanol, 3-chloro-3-nitro-pentanediol (2,4), 4-chloro-4 -Nitrohexanol-
3,2-bromo-2-nitroethanol, 2-bromo-
2-nitropropanol, 2-bromo-2-nitropropanediol (1,3), 3-bromo-3-nitropentanediol (2,4), 2,2-dibromo-2-nitroethanol, 4-bromo- 4-nitrohexanol-
3,2-fluoro-2-nitroethanol, 2-fluoro-2-nitrobutanediol (1,3), 3-iodo-3-nitrobutanol-2, 2-fluoro-2-chloro-2-nitroethanol, 2-iodo-2-bromo-
2-nitroethanol and the like.

Among these compounds, 2-bromo-2-nitropropanediol (1,3) (hereinafter referred to as bronopol) or 2,2-dibromo- It is preferable to use 2-nitroethanol (hereinafter referred to as DBNE).

The isothiazolone complex represented by the general formula (2) in the present invention includes 2-methyl-3-isothiazolone, 2-ethyl-3-isothiazolone, 2-octyl-4-chloro-3-isothiazolone, Benzyl-4,5-dichloro-3-isothiazolone, 2-allyl-3-isothiazolone, 2-propynyl-3-isothiazolone, 1,2-benzothiazolone, 5-chloro-2-
Methyl-4-isothiazolin-3-one, 2-methyl-
Zinc chloride such as 4-isothiazolin-3-one, zinc iodide, zinc sulfate, zinc acetate, copper chloride, copper bromide, copper nitrate, nickel chloride, calcium chloride, magnesium chloride, iron chloride, manganese chloride, sodium chloride, Complex compounds such as barium chloride, ammonium chloride, and other amine chlorides may be mentioned.

Among the above, particularly preferred isothiazolone complex compounds include 5-chloro-2-methyl-4-isothiazolin-3-onecalcium (II) chloride and 5-chloro-2-methyl-4-isothiazolin-3-one.
Chloro-2-methyl-4-isothiazolin-3-one magnesium (II) chloride.

The carboxylic acid-based low molecular weight polymer used in the present invention includes poly (sodium methacrylate),
Copolymers of acrylic acid and other monomers such as (meth) acrylic acid-acrylamide copolymer, maleic anhydride and other copolymers such as polymaleic anhydride and maleic anhydride-isobutylene copolymer, and Is an acrylic acid-maleic anhydride copolymer or the like.

Further, a carboxylic acid polymer containing phosphinic acid or its sodium salt represented by the following general formula (3), a phosphinocarboxylic acid copolymer represented by the following general formula (4), bis ( Poly-2-carboxyethyl) phosphinic acid or their sodium salts can also be used.

[0018]

Embedded image (Where M represents H or Na)

[0019]

Embedded image (In the formula, M represents a hydrogen atom or an alkali metal atom, and X and Y each represent the following formula.)

[0020]

Embedded image Or

[0021]

Embedded image (Wherein M ′ has the same meaning as M, n + m + n ′ + m ′ = 16,
However, n + m = 0 may be set. ).

These carboxylic acid polymers generally have a molecular weight in the range of 500 to 50,000.
Note that carboxylic acid-based polymers that are particularly preferable as the admixture are polymaleic anhydride and bis (poly-2-carboxyethyl) phosphinic acid.

The azole compound of the present invention includes benzotriazole, O-tolyltriazole, m-tolyltriazole, p-tolyltriazole, 5-ethylbenzotriazole, 5-n-propylbenzotriazole, 5-isobutylbenzotriazole, -Methylbenzotriazole, 5-chlorobenzotriazole, 4
-Nitrobenzotriazole, 5-methoxybenzotriazole, 5-hydroxybenzotriazole or 1-
(Substituted aminomethyl) -tolyltriazole is preferred. Of these, benzotriazole is preferred because it is easily available as a commercial product. In order to obtain the mixture of the present invention, the compounds can be easily prepared by blending the respective compounds in a desired ratio, adjusting the pH as necessary, or appropriately diluting with water.

The mixture according to the present invention is usually obtained in a liquid form,
The compounding amount of the compound to be compounded is in principle used within the range used for each conventional purpose, but the preferable compounding ratio is 1 to 20% by weight of bronopol, 0.1 to 1.0% of the isothiazolone complex compound. 5% by weight, 5 to 20% by weight of a carboxylic acid type low molecular weight polymer, 0.5 to 0.5% of benzotriazole
5% by weight and 5 to 20% by weight of ethylene carbonate.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

[0026]

EXAMPLES Example 1 Each of the following liquid-state agents of the present invention and comparative samples were prepared, and changes in appearance when stored at 50 ° C. corresponding to acceleration conditions were visually observed. Table 1 shows the test results. Invention Agent 1 Bronopol 5 parts by weight 5-Chloro-2-methyl-4-isothiazolin-3-one magnesium (II) chloride 1 part by weight Polymaleic anhydride 9 parts by weight Bis (poly-2-carboxyethyl) phosphinic acid 3 Parts by weight Benzotriazole 2 parts by weight Ethylene carbonate 8 parts by weight Water 72 parts by weight Total 100 parts by weight Inventive agent 2 DBNE 5 parts by weight 5-chloro-2-methyl-4-isothiazolin-3-one calcium (II) chloride 1 part by weight Parts polymaleic anhydride 9 parts by weight bis (poly-2-carboxyethyl) phosphinic acid 3 parts by weight benzotriazole 2 parts by weight ethylene carbonate 8 parts by weight water 72 parts by weight Total 100 parts by weight

Comparative Example 1 In the same manner as in Example 1, the storage stability was tested when no stabilizer was added to the composition and when a solvent other than ethylene carbonate was added. The results are shown in Table 1. Comparative Sample 1 Bronopol 5 parts by weight 5-chloro-2-methyl-4-isothiazolin-3-one magnesium (II) chloride 1 part by weight Polymaleic anhydride 9 parts by weight Bis (poly-2-carboxyethyl) phosphinic acid 3 parts by weight Parts benzotriazole 2 parts by weight water 80 parts by weight Total 100 parts by weight Comparative sample 2 Bronopol 5 parts by weight 5-chloro-2-methyl-4-isothiazolin-3-one magnesium (II) chloride 1 part by weight Polymaleic anhydride 9 parts by weight Parts bis (poly-2-carboxyethyl) phosphinic acid 3 parts by weight benzotriazole 2 parts by weight diethylene glycol 8 parts by weight water 72 parts by weight Total 100 parts by weight

[0028]

[Table 1]

Example 2 500 ml of tap water was placed in a 1 L pressure bottle, and the same inventive agent and comparative sample as in Example 1 and Comparative Example 1 were each added at 500 mg / L.
After adding a considerable amount, the height of bubbles generated when air was blown in at a flow rate of 1 L / min using a pump was measured. Table 2 shows the test results.

[0030]

[Table 2]

Example 3 The same inventive agent and comparative sample as in Example 1 were prepared and tested in a model plant having an open circulation cooling water system. The model plant has a water volume of 1 m ³ and a circulating water volume of 4 m ³ / hr, and has a heat exchanger (made of SUS304, heat transfer area of 0,3 m) in the system.
707 m ² ), and the outlet temperature was adjusted to 50 ° C. In addition, a bypass is provided in the system to adjust the return temperature of the cooling tower to 37
３８38 ° C., and the water supply temperature was adjusted to 30 ° C. Industrial water was used as makeup water for the model plant. The experiment was performed for 20 days for each test, and the concentration multiple of the cooling water was set to 5. Evaluation of the medicinal effect was conducted by measuring the height of bubbles generated in the lower tank of the cooling tower and the number of general bacteria in the cooling water every 5 days. Table 3 shows the test results.

[0032]

[Table 3]

[0033]

EFFECTS OF THE INVENTION The multifunctional water treatment agent of the present invention reduces the occurrence of precipitating during storage and the bubbling phenomenon at the time of use when added to a cooling water system as seen in conventional multifunctional water treatment agents. Can be avoided. Further, it does not become a nutrient source for the growth of microorganisms, and there is no restriction on the method of adding the drug.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H011 AA02 BA01 BA04 BA06 BB04 BB10 BC06 BC09 BC17 BC18 BC19 DA12 DD01 DF03 DH02

Claims (3)

[Claims] 1. A halogenated aliphatic nitro alcohol represented by the general formula (1), at least one isothiazolone complex compound represented by the general formula (2), a carboxylic acid-based low molecular weight polymer, and an azole compound And a water treatment agent comprising ethylene carbonate as an active ingredient. Embedded image (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a lower alkyl group or a hydroxy lower alkyl group, R ² represents a hydrogen atom or a lower alkyl group, and X represents a halogen atom.) (Wherein Y represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, R represents a hydrogen atom or a halogen atom, R ′ represents a hydrogen atom or a halogen atom, and R and R ′ are M may represent a cation atom or a group selected from the group consisting of alkaline earth metals, heavy metals and amines;
Z represents an anion atom or group that forms a compound with a cation M that has sufficient solubility to form a complex compound. A represents an integer of 1 or 2, and n represents an integer in which the anion Z satisfies the valence of the cation M. ) 2. The halogenated aliphatic nitro alcohol represented by the general formula (1) is 2-bromo-2-nitropropane-1,3-diol or 2,2-dibromo-2-nitroethanol. The water treatment agent according to 1. 3. The water treatment according to claim 1, wherein at least one of the isothiazolone complex compounds represented by the general formula (2) is a metal salt complex of 5-chloro-2-methyl-4-isothiazolin-3-one. Agent.