JPH11222405A - Antimicrobial composition for industrial use and antimicrobial treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having powerful antimicrobial and bacteriostatic activities and effective for a wide range of microorganisms by including three specified compounds. SOLUTION: This composition is obtained by including (A) a halocyanoacetamide compound of formula I (X is a halogen; Y is H or a halogen; R1 is H or a lower alkyl) (e.g. 2,2-dibromo-3-nitrilopropionamide), (B) 0.01-10 pts.wt. preferably 0.5-5 pts.wt. halogenated aliphatic nitroalcohol derivative of formula II [R2 is a halogen or a (hydroxy)alkyl] (e.g. 2-bromo-2- nitropropane-1,3-diol) per pt.wt. of the component A and (C) 0.01-10 pts.wt. preferably 0.5-1 pt.wt. halogenated acetic acid ester derivative of formula III (R3 is an alkylene or an alkenylene) [e.g. 1,4-bis(bromoacetoxy)-2-butene] per pt.wt. the sum of the components A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pulp and paper industry for preventing the adhesion of slime derived from microorganisms such as bacteria and fungi in the papermaking process, and for coating paper, latex and starch slurry. An antibacterial composition for preventing industrial water-based compositions made based on water such as coating colors, washing water, cooling water, adhesives, metalworking oils, etc. from undergoing spoilage, discoloration, and deterioration in physical properties due to microbial contamination. And antimicrobial methods.

[0002]

2. Description of the Related Art In the papermaking process in the pulp and paper industry, a large amount of water is used to produce paper, and various organic substances necessary for producing paper are dispersed and dissolved in the water. Therefore, it is likely to be a nutrient source for microorganisms such as bacteria and fungi. During the papermaking process, microorganisms such as bacteria and fungi proliferate based on these nutrient sources, produce slimey metabolites, take in papermaking materials such as pulp and filler that are dispersed in the papermaking process, Slime is formed on the wall or flow box inside the stagnant chest. The formed slime is
It gradually increases and eventually comes off, is made into paper together with papermaking raw materials such as pulp, and appears as foreign matter on the paper, resulting in quality deterioration. Recently, to make paper at a very high speed,
In the worst case, the paper will be cut off, causing a drop in productivity.

[0003] In addition, industrial water-based compositions prepared based on water, such as paints, latex, and starch slurries, also become spoiled by being contaminated by bacteria,
Occurrence of odor, deterioration of physical properties such as decrease in viscosity, fluctuation of pH, and the like are caused, and fungus (filamentous fungi) propagates, thereby causing clogging, coloring, and foreign matter mixing of the strainer.

[0004] Various agents have been used as antibacterial agents to prevent the generation of slime due to microbial factors in the papermaking process. The same applies to antibacterial agents for the purpose of preventing spoilage of various aqueous compositions. For example, in the papermaking process, 2,2-dibromo-
In addition to 3-nitrilopropionamide, 4,5-dichloro-1,2-dithiol-3-one, methylenebisthiocyanate having excellent bacteriostatic power, 1,4-bis (bromoacetoxy) -2-butene or 1,2 -Bis (bromoacetoxy) ethane and the like are often used. To prevent spoilage of the aqueous composition, 5-chloro-2-methyl-4-isothiazolin-3-one, 1,2-, which has excellent bacteriostatic activity and excellent stability in the aqueous composition due to its preservative property. Benzisothiazolin-3-one, 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitropropane-1,
3-diol and the like are often used.

However, the long-term continuous use of a single drug is
Antibacterial agents using various combinations of two or three components have been used in the past because they are likely to cause the emergence of resistant bacteria.
For example, in the combination of two components,
4,5-Dichloro-1,2-dithiol- at 66
Combination of 3-one and 5-chloro-2-methyl-4-isothiazolin-3-one, 2,2-dibromo-3-nitrilopropionamide and 4,5-dichloro-1,2- A large number of combinations of dithiol-3-one are disclosed. Combinations of the three components include 2,2-dibromo-3-nitrilopropionamide, 4,5-dichloro-1,2-dithiole-3-one and 5-chloro-2-one described in JP-A-7-187920.
A combination of methyl-4-isothiazolin-3-one,
2,2-dibromo-3- as described in JP-A-7-25708
A combination of nitrilopropionamide, methylenebisthiocyanate, and 2,2-dibromo-2-nitroethanol is disclosed. These combinations have good potency in papermaking processes and aqueous compositions where a single agent has been used for a long time, but with two components,
Drugs in combination of components have become common as a means of controlling microorganisms, and even in combination formulations, resistant bacteria due to long-term use have begun to appear, so a drug effective at a low concentration with further sterilization and bacteriostatic efficacy is desired. ing.

[0006]

SUMMARY OF THE INVENTION In order to meet the above demands, the present invention is effective against a wide range of microorganisms having a strong bactericidal or bacteriostatic power, which was insufficient with conventional combinations. In providing various drugs.

[0007]

Means for Solving the Problems The present inventor has confirmed the efficacy of combinations of various components in order to solve the problems, and as a result of intensive studies, it has been found that (A) a halocyanoacetamide compound and (B) a halogen Aliphatic nitro alcohol derivatives and (C) halogenated acetate derivatives 3
It has been found that an industrial antibacterial composition containing various kinds of active ingredients is a very excellent antibacterial composition having good bactericidal and bacteriostatic properties even at a low concentration. That is, the present invention provides (A) the following general formula: (Wherein X represents a halogen atom, Y represents a hydrogen atom or a halogen atom, and R ₁ represents a hydrogen atom or a lower alkyl group), (B) a general formula shown below. (Wherein X represents a halogen atom and R ₂ represents a halogen atom or an alkyl group or a hydroxyalkyl group), and a halogenated aliphatic nitro alcohol derivative represented by the following formula: (Wherein X represents a halogen atom and R ₃ represents an alkylene group or an alkenylene group). An industrial antibacterial composition comprising a halogenated acetate derivative represented by the following formula: Is an antibacterial method in which 1 to 20,000 ppm is added to papermaking process white water or an industrial water-based composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the present invention has a general formula (Wherein X represents a halogen atom, Y represents a hydrogen atom or a halogen atom, and R ₁ represents a hydrogen atom or a lower alkyl group), for example, 2-chloro-3-nitrilopropion Amide, 2-
Bromo-3-nitrilopropionamide, 2,2-dichloro-3-nitrilopropionamide, 2,2-dibromo-3-nitrilopropionamide and the like are included. These may be used alone or in combination of two or more.

The halogenated aliphatic nitro alcohol derivative which is the component (B) of the present invention has a general formula Wherein X represents a halogen atom, R ₂ represents a halogen atom or an alkyl group or a hydroxyalkyl group, and a halogenated aliphatic nitro alcohol derivative represented by the formula:
For example, 2-bromo-2-nitropropane-1,3-diol or 2,2-dibromo-2-nitro-1-ethanol is included. These may be used alone,
Two or more types may be combined.

The component (C) of the present invention includes (C) a general formula (Wherein X represents a halogen atom and R ₃ represents an alkylene group or an alkenylene group), and a halogenated acetate derivative represented by, for example, 1,4-bis (bromoacetoxy) -2-butene, 2-bis (bromoacetoxy) ethane, 1,4-bis (chloroacetoxy) -2
-Butene and the like.

(A) The halocyanoacetamide compound is relatively excellent in bactericidal activity, (B) the halogenated aliphatic nitro alcohol derivative is relatively excellent in bacteriostatic effect, and (C) the halogenated acetate derivative is relatively bacteriostatic. Since the effects are excellent and the effects of the respective active ingredients are different, the effect cannot be expected if one or two of the three components of the present invention are extremely low in compounding amount. Parts by weight of component (B) is 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight.
When the total amount of the component (A) and the component (B) is 1 part by weight, the content of the component (C) is 0.01 to 10 parts by weight, preferably 0.5 to 1 part by weight. Is desirable. This content ratio is also desirable from the viewpoint of the synergistic effect of the effects obtained by mixing the respective active ingredients.

As an antibacterial method, an antibacterial composition containing the above three kinds of active ingredients may be added, or the above three kinds of active ingredients may be separately added. The amount added is 1 to 20000 ppm in the papermaking process white water or industrial water-based composition.
It is preferred to add.

The method of adding the active ingredient of the present invention to the aqueous composition during the papermaking process or to the aqueous composition may be either separately or in the form of a formulated mixture. The solvent, surfactant and the like used in the formulation are not particularly limited. However, since the chemicals to be added such as water in the papermaking process and aqueous compositions that cause the growth of microorganisms are mainly composed of water, the solvent is preferably relatively hydrophilic.

Examples of the solvent include glycol solvents such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, and hexylene glycol, and glycol ether solvents such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. And propylene carbonate. These may be used alone or in combination of two or more.
It is sufficient if there is an added amount capable of dissolving the seed.

As the surfactant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, a zwitterionic surfactant and the like can be used.

[0016]

EXAMPLES Next, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.
All the compounding ratios shown in the following table are% by weight. Further, the antimicrobial compositions of the respective examples were prepared by ordinary stirring at room temperature at the indicated ratios of the respective components shown in the respective examples.

Examples 1 to 6 The antibacterial agent compositions shown in Table 1 were prepared, and their performance was examined in Test Example 1, Test Example 2, Test Example 3, and Test Example 4. The indication of the active ingredient in the table is represented by the following abbreviations.

2,2-dibromo-3-nitrilopropionamide: DBNPA (component A) 2,2-dibromo-2-nitro-1-ethanol:
DBNE (component B) 1,4-bis (bromoacetoxy) -2-butene:
BBAB (C component)

[0019]

[Table 1]

Comparative Examples 1 to 4 The antibacterial agent compositions shown in Table 2 were prepared, and their performances were examined in Test Examples 1, 2, and 3.

[0021]

[Table 2]

Test Example 1 Evaluation of bactericidal activity against white water in the papermaking process “Test method” The following target samples to which the preparations of Examples and Comparative Examples were added at a predetermined concentration were cultured, and the time-dependent change in the number of bacteria was measured using a modified Waxman agar plate pour method (sterile water , And a fixed amount thereof is taken in a sterile petri dish, and a dissolved denatured Waxman agar medium is injected, and the mixture is solidified after being pulverized. The number of colonies formed after culturing in a thermostat chamber at 30 ° C for 2 days is counted. Was measured. Target sample: papermaking process white water, fine papermaking, pH 6.9, viable cell count 2.0 × 10 ⁷ CFU / ml “Test result” 30 minutes and 60 minutes after adding each preparation, Table 3 shows the difference between the bacterial value of the sample without the drug and the bacterial value of the sample with the preparation. Difference in increase / decrease value: Logarithmic value of bacterial count of drug-free sample after predetermined time-Addition to drug product
The larger the logarithmic value of the number of bacteria in the added sample, the greater the bactericidal effect. [Consideration] As shown in Table 3, the difference between the increase / decrease value of the preparations of the single active ingredients in Comparative Examples 1 to 3 and the increase / decrease value of the preparations of the two active ingredients in Comparative Examples 4 to 6 was observed. The difference between the increase and decrease of the preparations of the three active ingredients is significantly large, and the preparation of the three kinds of the active ingredients is more remarkable for the white water in the paper making process than the preparation of the single or two kinds of the active ingredients. It was confirmed that the bactericidal bactericide exhibited a high sterilizing power.

[0023]

[Table 3]

Test Example 2. Evaluation of bacteriostatic activity against white water in the papermaking process "Test method" After adding the specified concentrations of the preparations of Examples and Comparative Examples to the following target samples aseptically filtered, adding 1% of a 10-fold concentration of modified Waxman liquid medium, Was directly added for inoculation at 1%. The bacteriostatic power was measured by a microbial growth curve in which the change in turbidity by the turbidimetry was recorded with time. Target samples: papermaking process white water, fine papermaking, pH 6.9, viable cell count 2.0 × 10 ⁷ CFU / ml “Test result” Rise time of microbial growth curve of drug-free sample and microorganism of sample with each drug product Table 4 shows the difference from the rise time of the growth curve. Difference: rise time of each drug product-added sample- drug-free test
The greater the value of the difference between the rise times of the ingredients, the greater the bacteriostatic efficacy. [Discussion] As shown in Table 4, a preparation of a single active ingredient of Comparative Examples 1 to 3,
In comparison with the difference in the rise time between the preparations of the two active ingredients of Comparative Examples 4 to 6 and the drug-free sample, 3 to 3 of Examples 1 to 3
The difference between the rise times of the preparations of the various active ingredients shows a clearly large value, and the preparation of the three kinds of the active ingredients has a remarkable static resistance to white water in the papermaking process as compared with the preparation of the single kind or the mixture of the two kinds. It was confirmed that it exhibited bacterial activity.

[0025]

[Table 4]

Test Example 3 Preservative evaluation of SBR latex "Test method" 30 g of SBR latex (pH 7.9) was dispensed into a sterilized polypropylene bottle, a predetermined amount of a drug was added thereto, and the SBR latex (precipitated:
3.0 × 10 ⁷ ) was inoculated at 1%. This was cultured at 30 ° C. in a closed and stationary condition, and the viable cell count over time was measured by TGC agar plate pour method to determine the preservative effect. After the viable cell count, 1% of the spoiled product was inoculated weekly. "Test results" Judgment was made according to the following criteria.
It was shown to. [Discussion] As shown in Table 5, the evaluation results on the 28th day of the preparations of the single active ingredients of Comparative Examples 1 to 3 and the preparations of the two active ingredients of Comparative Examples 4 to 6 were +++ to +++. On the other hand, the evaluation results of the three types of active ingredients in Examples 1 to 3 are-to +
In comparison with the preparation of the active ingredient alone or a mixture of two kinds,
It was confirmed that the seed mixture preparation exhibited a remarkable antiseptic effect on SBR latex.

[0027]

[Table 5]

[0028]

As described above, when the present invention is applied, a strong bactericidal power, a long-lasting bacteriostatic power, and a long-term antiseptic effect, which were insufficient with the conventional single or combination of two kinds, are combined. It is possible to provide an antimicrobial composition or an antimicrobial method having the same.

Claims (4)

[Claims] (A) General formula (Wherein X is a halogen atom, Y is a hydrogen atom or a halogen atom, and R ₁ is a hydrogen atom or a lower alkyl group), (B) a general formula (Wherein X represents a halogen atom, R ₂ represents a halogen atom or an alkyl group or a hydroxyalkyl group) and a halogenated aliphatic nitro alcohol derivative represented by the following formula: (Wherein X represents a halogen atom and R ₃ represents an alkylene group or an alkenylene group). An industrial antibacterial composition comprising a halogenated acetate derivative represented by the following formula: 2. Component (A) is used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 1 part by weight of component (A). When the total amount is 1 part by weight, component (C) is 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight.
The industrial antibacterial composition according to claim 1, comprising 5 to 1 part by weight. 3. Component (A) is 2,2-dibromo-3-nitrilopropionamide and component (B) is 2-bromo-2-
Nitropropane-1,3-diol or 2,2-dibromo-2-nitro-1-ethanol, wherein component (C) is 1,4
-Bis (bromoacetoxy) -2-butene or 1,2-
The industrial antibacterial composition according to claim 1, which is bis (bromoacetoxy) ethane. 4. An antibacterial method comprising adding the industrial antibacterial composition according to claim 1 to a papermaking process white water or an industrial aqueous composition in an amount of 1 to 20,000 ppm.