JPH10298006A - Sterilization composition for industry and sterilization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having a strong sterilizing potency or bacteriostatic and fungistatic potencies and effective for a wide range of microorganisms by including a halocyanoacetamide compound, a halogenated acetate ester derivative, and a specific compound. SOLUTION: This composition comprises (A) a halocyanoacetamide compound of formula I (X is a halogen; Y is H, a halogen; R is H, a lower alkyl) (e.g. 2,2-dibromo-3-nitrilopropionamide), (B) a halogenated acetate ester derivative of formula II (Z is a halogen; A is an alkylene, an alkenylene) [e.g. 1,4-bis(bromoacetoxy)-2-butene], and (C) 4,5-dichloro-1,2-dithiol-3-one preferably in a weight ratio of 1:(0.1-10):(0.01-10). The composition is added to white water in a paper-making process, an aqueous composition for industry, etc., at a dose of 1-20000 ppm as the separated ingredients or as a formulated mixture.

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,
No. 66,4,5-Dichloro-1,2-dithiol-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one,
Many publications disclose a combination of 2,2-dibromo-3-nitrilopropionamide and 4,5-dichloro-1,2-dithiol-3-one in JP-A-1. The combination of the three components includes 2,2-dibromo-3-nitrilopropionamide, 4,5-dichloro-1,2-dithiol-3-one and 5-chloro-2-methyl described in JP-A-7-187920. -4-isothiazoline-3-
Combinations of 2,2-dibromo-3-nitrilopropionamide, methylenebisthiocyanate, and 2,2-dibromo-2- in JP-A-7-25708.
A combination of nitroethanol and the like are disclosed.
While these combinations have good efficacy in papermaking processes and aqueous compositions where a single agent has been used for a long time, two- and three-component agents have become commonplace as a means of controlling microorganisms. , Even in combination formulations, resistant bacteria due to long-term use have begun to appear,
There is a need for a drug that is effective at a low concentration with further bactericidal and bacteriostatic efficacy.

[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, as a result, it has been found that a halogenated acetoamide compound, a halogenated acetic acid ester derivative and An industrial antibacterial composition characterized by containing three kinds of active ingredients, 5,5-dichloro-1,2-dithiol-3-one, is excellent in having good bactericidal activity and bacteriostatic activity even at a low concentration. Antibacterial composition. 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 represents a hydrogen atom or a lower alkyl group) and (B) a compound represented by the following general formula: (Wherein Z represents a halogen, A represents an alkylene group or an alkenylene group) and (C) 4,5-dichloro-1,2-dithiol-
An industrial antibacterial composition characterized by containing 3-one, and an antibacterial method characterized by adding 1 to 20,000 ppm of these three active ingredients to papermaking process white water or an industrial aqueous composition. is there.

BEST MODE FOR CARRYING OUT THE INVENTION

The halocyanoacetamide compound as the component (A) of the present invention includes, for example, 2-chloro-3-
Nitrilopropionamide, 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 acetic acid ester derivatives which are component (B) of the present invention include, for example, 1,4-bis (bromoacetoxy) -2-butene, 1,2-bis (bromoacetoxy) ethane and 1,4-bis (bromoacetoxy) ethane. Bis (chloroacetoxy)
-2-butene and the like.

(A) The halogenated acetoamide compound is relatively excellent in bactericidal activity, (B) the halogenated acetate derivative is relatively excellent in bacteriostatic activity, and (C) 4,5-dichloro-1,2-dithiol- Since 3-one has relatively excellent bactericidal efficacy and the effect of each active ingredient is different, the effect cannot be expected if the amount of one or two of the three components of the present invention is extremely low. Component (B) 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), and the total amount of component (A) and component (B) is 1 part by weight. Parts (C) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 0.5 part by weight. This content ratio is also desirable from the viewpoint of the synergistic effect of the effects obtained by mixing the respective active ingredients.

The method of adding the active ingredient of the present invention to the aqueous composition during the papermaking step or to the aqueous composition may be either separately or in the form of a mixture. An excessive amount has an adverse effect on physical properties, appearance, quality, cost, and the like.

The solvent, surfactant and the like used in the preparation 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 singly or in combination of two or more kinds, as long as there is an added amount capable of dissolving three kinds of active ingredients.

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

[0015]

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) 1,4-bis (bromoacetoxy) -2-butene: B
BAB (Component B) 4,5-dichloro-1,2-dithiol-3-one: D
CDT (C component)

[0018]

[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.

[0020]

[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 examined by denaturation with modified waxman agar plate. Method (Dilute the sample with sterile water, take a certain amount of this in a sterile petri dish, inject the dissolved denatured Waxman agar medium, allow to pour, and solidify. The number is counted.). Target sample: papermaking process white water, high quality paper making, pH of a certain paper company
7.4, viable cell count 9.6 × 10 ⁶ CFU / ml “Test result” The bacterial value was measured 30 minutes and 60 minutes after the addition of each formulation, and the bacterial value of the drug-free sample and the formulation added Table 3 shows the difference between the increase and decrease in the bacterial value of the sample. Difference in increase / decrease value: The larger the logarithmic value of the number of bacteria of the sample without drug after a predetermined time−the value of the logarithm of the number of bacteria of the sample added with the pharmaceutical product, the larger the bactericidal effect. As shown in Table 3, as compared with the increase / decrease value difference 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, The difference in the increase / decrease value 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 bactericidal activity against white water in the papermaking process as compared with the preparation of the single kind or the mixture of the two kinds. Was confirmed.

[0022]

[Table 3]

Test Example 2 Evaluation of Bacteriostatic Activity against White Water in the Paper Making Process "Test Method" The following preparations were subjected to aseptic filtration of the preparations of Examples and Comparative Examples to a predetermined concentration, and then a 10-fold concentration of a modified waxman liquid medium was added. 1% was added, and 1% of the target sample was added as it was for inoculation. The bacteriostatic power was measured by a microbial growth curve in which the change in turbidity by the turbidimetry was recorded with time. Target sample: papermaking process white water, high quality paper making, pH of a certain paper company
7.2, viable cell count 8.9 × 10 ⁶ CFU / ml “Test results” Table 4 shows the difference between the rise time of the microbial growth curve of the sample without the drug and the rise time of the microbial growth curve of the sample with each preparation added. It was shown to. 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. As shown in Table 4, compared with the difference between the rise times of the preparations of the single active ingredients of Comparative Examples 1 to 3 and the drug-free sample of the preparations of the two active ingredients of Comparative Examples 4 to 6, Example 1
The difference between the rise times of the preparations of the three active ingredients of No. 3 shows a clearly large value. It was confirmed that it exhibited remarkable bacteriostatic power.

[0024]

[Table 4]

Test Example 3 Antiseptic Evaluation of Starch Slurry "Test Method" 10% of Cationized Tapioca Starch
A slurry (pH 6.2) was prepared, 30 g was dispensed into a sterilized polypropylene bottle, a predetermined amount of a drug was added, and then a starch slurry that had been spoiled in advance (the number of bacteria: 3.2 × 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" The test results were determined according to the following criteria, and the test results are shown in Table 5. 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 +++. Example 1 in contrast to +
The evaluation results of the three kinds of active ingredients of ~ 3 are + ~ ++, and the preparations of the three kinds of the active ingredients show a remarkable antiseptic effect on the starch slurry as compared with the preparations of the single kind or the mixture of the two kinds respectively. It was confirmed that.

[0026]

[Table 5]

[0027]

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] (1) General formula (A) (Wherein X is a halogen atom, Y is a hydrogen atom or a halogen atom, and R is a hydrogen atom or a lower alkyl group), (B) a general formula (Wherein Z represents a halogen, A represents an alkylene group or an alkenylene group) and (C) 4,5-dichloro-1,2-dithiol-
An industrial antibacterial composition comprising 3-one. 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 from 0.5 to 0.5 parts by weight. 3. Component (A) is 2,2-dibromo-3-nitrilopropionamide, and component (B) is 1,4-bis (bromoacetoxy) -2-butene or 1,2-bis (bromoacetoxy). The industrial antibacterial composition according to claim 1, which is ethane. 4. An industrial antibacterial composition according to claim 1, which is added to the papermaking process white water or industrial aqueous composition in an amount of 1 to 20,000 ppm.
An antimicrobial method characterized by being added.