JP4748773B2 - Disinfectant algicide having ability to prevent discoloration and discoloration prevention method - Google Patents

Description

The present invention relates to a bactericidal algicidal agent having a discoloration preventing effect and a discoloration preventing method using the same.
More specifically, papermaking process water and pulp slurry in paper and pulp mills, various industrial cooling water and process water, washing water, coating color, cutting oil, latex, synthetic resin emulsion, starch slurry, calcium carbonate slurry, fiber oil agent The present invention relates to a bactericidal algicide and a method for preventing discoloration that are useful for preventing damage caused by microorganisms such as the above.

  In recent years, various obstacles caused by slimes of various industrial waters have occurred, causing various adverse effects. Slime is a viscous mass to mud that is mainly produced by the growth of microorganisms. For example, when this slime is generated in a heat exchanger or piping of a cooling water system in a factory, it reduces cooling efficiency or This may cause troubles that block the piping. In addition, when slime is generated in the papermaking process water and pulp slurry of a paper / pulp factory, it may be peeled off and mixed into the paper / pulp, causing paper breakage, and causing spots and coloring in the paper and pulp products themselves. , Leading to product quality degradation. Various microorganism control agents have been developed so far to prevent slime damage caused by these microorganisms. 2,2'-methylenebis (4-chlorophenol) (hereinafter referred to as MBCP) has long been known as a bactericidal agent, and has been widely improved. For example, an MBCP blended with ethylenediamine (Patent Document 1) and a blend of glycols or amines (Patent Document 2) have been proposed. The benzophenones used in the present invention, such as 2,4-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone, and 2,2 ′, 4,4′-tetrahydroxybenzophenone, reduce the skin irritation of isothiazolone compounds. It is known as a compound.

Japanese Examined Patent Publication No. 45-26114 Japanese Patent Laid-Open No. 3-60799 JP-A-11-180806

  Thus, MBCP is known as a bactericidal agent and an algicidal agent, and an improved preparation thereof has been proposed. However, when the MBCP preparation is added to an industrial water system or the like, the active ingredient concentration is several mg / 1 to several. Even at a low concentration of 10 mg / l, the added aqueous system may turn brown over time. This causes deterioration of the quality of the water system and gives anxiety to workers and users that metal corrosion has occurred. And this discoloration phenomenon tends to be accelerated especially under sunlight or ultraviolet irradiation conditions.

  The present invention is intended to solve these problems, and provides a bactericidal algicidal agent having an excellent bactericidal and algicidal effect while preventing discoloration of the target water system for bactericidal and algae treatment to which MBCP has been added. is there. Furthermore, this invention provides the discoloration prevention method of the sterilization algae processing target water system which added MBCP.

  Briefly, the present invention relates to a bactericidal algicidal agent having an anti-discoloration effect, characterized by containing MBCP and specific benzophenones, and a discoloration preventing method using the same.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research, and as a result of using specific benzophenones in MBCP, the effect of preventing discoloration of the target water system for sterilization by MBCP is effective. Based on this finding, the present invention was completed.

That is, the present invention
(1) and MBCP, under following general formula (1)

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and each represents hydrogen, a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms), one kind of benzophenones Or bactericidal algicidal agent having anti-discoloration effect, characterized by containing two or more types ,
( 2 ) The benzophenone is a compound selected from 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone and 2,4,4′-trihydroxybenzophenone according to item (1 ) Bactericidal algicide,
( 3 ) The bactericidal algicidal agent according to (1) or (2) , comprising MBCP and benzophenones at a mass ratio of 1: 0.01 to 1: 0.5,
( 4 ) The bactericidal algicidal agent according to any one of (1) to ( 3 ), which contains at least one of water, an organic solvent, a chelating agent, a scale inhibitor, and a corrosion inhibitor.
( 5 ) MBCP and the benzophenone represented by the general formula (I) described in the item (1) with respect to the water system subject to sterilization and algae treatment: A method for preventing discoloration of the water system to be treated, characterized by being used in a proportion.

  According to the present invention, it is possible to prevent discoloration of an aqueous system to which a bactericidal algicidal agent containing MBCP is added, and to effectively kill algae and cyanobacteria, particularly including Legionella bacteria. The present invention has an excellent sterilizing effect against various bacteria, and also has a merit in terms of equipment that is not corrosive to metals.

Hereinafter, the present invention will be specifically described.
The bactericidal algicidal agent having the effect of preventing discoloration of the present invention contains MBCP and benzophenones, and MBCP is dissolved in a solvent as it is, or mixed with sodium hydroxide, potassium hydroxide or the like and a solvent. In addition, it can be formulated as an MBCP alkali metal salt.
As the benzophenones of the present invention, it is preferable to use the compound represented by the general formula (I).

  Specific examples of benzophenones include 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,2 ′, 4,4′- Examples thereof include tetrahydroxybenzophenone and 2,3,4,4′-tetrahydroxybenzophenone. These benzophenones may be used alone or in combination of two or more.

  Even if this benzophenone is not previously blended with MBCP and formulated as a bactericidal algicide, discoloration can also be prevented by adding a benzophenone to a bactericidal algae treatment target water system to which MBCP has been added. That is, according to the present invention, MBCP and benzophenones are separately formulated and used, and an effect of preventing discoloration can be obtained by forming a state in which MBCP and benzophenones are simultaneously present in an aqueous system.

The bactericidal algicidal agent of the present invention preferably contains MBCP and benzophenones at a mass ratio of 1: 0.01 to 0.5. When the proportion of benzophenones is lower than the above range, a sufficient discoloration preventing effect cannot be obtained. Conversely, when the proportion of benzophenones is higher than the above range, the discoloration preventing effect can be obtained, but the cost is low. It becomes high and is not preferable in terms of economy.
The method of using the bactericidal algicidal agent of the present invention is not particularly limited, and MBCP and benzophenones are preliminarily mixed with the bactericidal algicidal agent in a predetermined ratio with respect to the water system subject to the bactericidal algicidal treatment. It may be added to the water system to be treated, or added separately so that the mass ratio is 1: 0.01 to 1: 0.5 in the system.

  When formulating the bactericidal algicidal agent of the present invention using a solvent, water or the following organic solvent can be applied as the solvent. For example, (1) glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, etc. (2) glycol ethers include diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, etc. (3) As amides, dimethylformamide, dimethylacetamide, N-methylpropionamide, 2-pyrrolidone, N-methyl Pyrrolidone, etc. (4) Monomethyl as amines Amine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, propylamine, can be given dipropylamine, diisopropylamine, butylamine, 3-aminopropyl methyl ether. These solvents may be used alone or in combination of two or more.

  Moreover, a chelating agent, a scale inhibitor, and a corrosion inhibitor can be mix | blended with the bactericidal algicide of this invention. Examples of chelating agents include ethylenediaminetetraacetic acid, alkali metal salts thereof, citric acid, and the like. As the scale inhibitor, conventionally known scale inhibitors can be used, and examples thereof include acrylic acid-based polymers and maleic acid-based polymers. As the corrosion inhibitor, conventionally known rust inhibitors can be used. For example, tolyltriazole, benzotriazole, methylbenzotriazole, 2-phosphonobutane-1,2,4-tricarboxylic acid, and a sodium salt thereof, hydroxy Examples thereof include ethylidene diphosphonic acid and its sodium salt.

  Next, the present invention will be described with reference to formulation examples, but the present invention is not limited to this formulation example. In the following formulation examples, “part” means “part by mass”.

Formulation Example 1
MBCP (10 parts), sodium hydroxide (3 parts), 4-hydroxybenzophenone (1 part), diethylene glycol (39 parts) and water (47 parts) were mixed and stirred to obtain a bactericidal algicidal agent.
Formulation Example 2
MBCP 10 parts, sodium hydroxide 3 parts, 4-hydroxybenzophenone
0.5 parts, 0.5 part of 4,4′-dihydroxybenzophenone, 39 parts of diethylene glycol and 47 parts of water were mixed and stirred to obtain a bactericidal algicidal agent.
Formulation Example 3
MBCP 5 parts, sodium hydroxide 2 parts, 4,4'-dihydroxybenzophenone 0.5 part, sodium polymaleate 10 parts, benzotriazole 1.5 parts, diethylene glycol 10 parts, water 71 parts Got.

Comparative Example 1
MBCP (10 parts), sodium hydroxide (3 parts), diethylene glycol (39 parts) and water (48 parts) were mixed and stirred to obtain a comparative drug.
Comparative Example 2
MBCP 10 parts, sodium hydroxide 3 parts, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole (ultraviolet absorber) 1 part, diethylene glycol 39 parts, water A comparative drug was obtained by mixing and stirring 47 parts.

Next, the usefulness as a bactericidal algicidal agent of the present invention will be described with reference to test examples.
Test Example 1 Discoloration test by UV-A irradiation of diluted fungicidal algicide (1)
In a 100 ml polypropylene container, 100 ml of a drug dilution solution (MBCP concentration of 100 ppm) obtained by diluting the bactericidal algicide obtained according to Formulation Examples 1 and 2 and Comparative Examples 1 and 2 with tap water was placed. Placed under a lamp (15W, 2) and irradiated at room temperature. After 2 weeks of irradiation, changes in the color of the diluted solution were observed. The appearance was determined according to the following criteria. The results are shown in Table 1.

Criteria-: No discoloration.
±: Slightly discolored. If diluted further 10 times with water, the discoloration is hardly noticed.
+: Slightly discolored.
++: Very discoloration.

  From Table 1, it can be seen that the discoloration prevention effect can be obtained even when tested at a concentration about 10 times higher than the concentration of MBCP used as an actual bactericidal algicidal agent. Further, as shown in Comparative Example 2, even if a benzotriazole-based ultraviolet absorber is used, the color change of the diluted solution cannot be suppressed.

Test Example 2 Discoloration test of bactericidal algicidal solution by UV-A irradiation (2)
First, Formulation A (MBCP 20 parts, sodium hydroxide 6 parts, water 74 parts) containing MBCP or 4,4′-dihydroxybenzophenone having the following composition, and Formulation B (4,4′-dihydroxybenzophenone 0.2 Part, 99.8 parts diethylene glycol).
In a 100 ml polypropylene container, 0.05 g of this preparation A, 0.05 g to 2.5 g of preparation B, and 100 g of tap water were added to prepare a diluted solution. The container was allowed to stand at room temperature for 2 weeks under a black light blue fluorescent lamp (15 W, 2 tubes), and the change in color tone was observed. The results are shown in Table 2. The symbols in the table are the same as in Test Example 1.

  As shown in Table 2, the effect of preventing discoloration is observed when the ratio of MBCP to benzophenone is in the range of 1: 0.01 to 1: 0.5.

Test Example 3 Discoloration Prevention Test in Cooling Tower The bactericidal algicide obtained according to Formulation Example 2 was continuously added at a concentration of 200 mg / l for 30 days to make-up water in a cooling tower of 30 refrigeration tons installed outdoors. As a result, even when used for 30 days in a cooling tower where sunlight hits, the cooling water was hardly colored. On the other hand, when the bactericidal algicide containing water in place of 4,4′-dihydroxybenzophenone in the above bactericidal algicide was continuously added to the same cooling tower make-up water at a concentration of 200 mg / l and continued for 30 days, The water was colored brown.

Test Example 4 Bactericidal effect against Legionella (1) Preparation of test bacterial solution:
Legionella [Legionella 11pneumophila ATCC 33153] cultured in B-CYEα agar medium at 35 ° C. for 48 hours is suspended in sterilized distilled water so that the number of bacteria per ml is 10 ^6. Prepare a test bacterial solution.
(2) Test operation:
Prepare a 2000, 1000, 500 mg / l drug dilution of the bactericidal algicide obtained according to Formulation Example 3 with sterile distilled water. Add 1 ml of these drug dilutions to 8 ml of HEPES buffer (pH 8.5) to prepare a test solution. Moreover, it operates similarly about the bactericidal algicide of the comparative example 1, and prepares a test liquid. In addition, 9 ml of HEPES buffer (pH 8.5) is used as a test solution to which no drug is added.
Add 1 ml of the test bacterial solution to the test solution, shake at 30 ° C., and measure the number of viable bacteria initially, 3 hours later and 24 hours later. (Uses B-CYEα agar medium)
The results are shown in Table 3.

  From Table 3, it can be seen that the bactericidal algicidal agent of the present invention exhibits an excellent bactericidal effect against Legionella pneumophila.

Claims (5)

2,2'-methylenebis (the 4-chlorophenol), under following general formula (I):

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent hydrogen, a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms)
A fungicidal algicidal agent having anti-discoloration effect, characterized in that it comprises one or more benzophenones represented by the formula: Benzophenones, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, microbicidal and algicidal of claim 1 Symbol placement is selected from 4,4'-dihydroxybenzophenone and 2,4,4'. The bactericidal algicidal agent according to claim 1 or 2 , comprising 2,2'-methylenebis (4-chlorophenol) and benzophenones in a mass ratio of 1: 0.01 to 1: 0.5. The bactericidal algicidal agent according to any one of claims 1 to 3 , comprising at least one of water, an organic solvent, a chelating agent, a scale inhibitor, and a corrosion inhibitor. Against sterilization algicidal process target water system, and 2,2'-methylenebis (4-chlorophenol), under following general formula (I):

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent hydrogen, a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms)
The method for preventing discoloration of the water system to be treated is characterized in that it is used in a ratio of 1: 0.01 to 1: 0.5 (mass ratio) .