JP2000169309A - Industrial antimicrobial composition and antimicrobial method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an industrial antimicrobial agent composition having powerful sterilizing activity, bacteriostatic power and antiseptic effect which are insufficient in a conventional combination when controlling microorganisms in a paper making process and in an aqueous composition and to provide an antimicrobial method. SOLUTION: This composition comprises (A) a halogenated hydantoin of the general formula (X and Y are the same or different halogen atoms; R1 and R2 are the same or different hydrogen atoms or alkyl groups) and (B) one or more kinds selected from the group consisting of methylenebisthiocyanate, 1,2-bis(bromoacetoxy)-ethane, 1,4-bis(bromoacetoxy)-2-butene, 4,5- dichloro-1,2-dithiol-3-one and 4,5-dichloro-n-octylisothiazolin-3-one as active ingredients.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND 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 paper making process, or for the coating of paints,
Prevents water-based industrial water-based compositions such as latex, starch slurry, paper coating colors, wash water, cooling water, adhesives, metalworking oils, etc. from undergoing decay, discoloration, and property deterioration due to microbial contamination The present invention relates to an antibacterial composition for industrial use and an antibacterial method.

[0002]

2. Description of the Related Art In the pulp and paper industry, a large amount of water is used in the paper making process. Since various organic substances are dispersed and dissolved in the water, microorganisms such as bacteria and fungi use these organic substances as a nutrient source. It is in a condition that is easy to breed. The grown microorganisms produce mucus metabolites, so pulp,
The papermaking raw materials dispersed during the papermaking process, such as fillers, are taken in, and slime is formed on the walls and flow boxes in chests where water flows. The formed slime gradually increases, and eventually comes off, is incorporated into paper together with papermaking raw materials such as pulp, and appears as foreign matter on paper, resulting in quality deterioration. Further, in the recent papermaking process, paper is formed at a considerably high speed. In the worst case, the paper is cut and the productivity is reduced. In addition, water-based industrial aqueous compositions such as coated paper, latex, and starch slurries also deteriorate when contaminated with these bacteria, causing odors, lowering viscosity, causing pH fluctuations, and causing fungi. Propagation of (filamentous fungi) causes strainer clogging and coloring.

[0003] Various antibacterial agents have been used to prevent the degradation by the microorganisms. For example, to prevent the generation of slime in the papermaking process, 4,5-dichloro-1,2-dithiol-3, including 2,2-dibromo-3-nitrilopropionamide (DBNPA), which has a strong bactericidal activity.
-One (DCDT), 4,5-dichloro-n-octylisothiazolin-3-one (DCOIT), 5-chloro-2-methyl-4-isothiazolin-3-one (Cl-
MIT), 1-bromo-3-chloro-5,5-dimethylhydantoin (BCDMH) and methylenebisthiocyanate (MBTC), 1,
2-bis (bromoacetoxy) ethane (BBAE) and 1,4-bis (bromoacetoxy) -2-butene (B
BAB) and the like, and as a preservative for preventing the deterioration of various aqueous compositions, 1,2-benzisothiazolin-3-one (excellent in bacteriostatic power and stability in the aqueous composition) BIT), 2,2-dibromo-2-nitroethanol (DBNE), 2-bromo-2-nitropropane-1,3-diol (BNP) and 2-bromo-
2-bromomethylglutaronitrile (BBMG), sodium omadine (NaPT) and hexahydro-
1,3,5-tris (2-hydroxyethyl) -s-triazine (glotan) and the like have been effectively used.

[0004] On the other hand, when these antibacterial agents are used alone and for a long period of time, resistant bacteria are likely to appear, and a method of using two or more of these agents in combination has conventionally been used. For example, a combination of 1-bromo-3-chloro-5,5-dimethylhydantoin with a water-soluble isothiazoline compound in JP-A-4-59707 and a halogenated hydantoin with 2,2-dibromo-3-in JP-A-10-101511 Combination with nitrilopropionamide, and further described in JP-A-7-187920, 2,2-dibromo-3-nitrilopropionamide, 4,5-dichloro-1,2-dithiol-3-one and 5-chloro-2-methyl -4-isothiazoline-3-
An ON combination and the like are disclosed. While these combinations have shown good efficacy against microbes in papermaking processes and aqueous compositions where single agents have been used for a long time, on the other hand, the combination of these multiple components has also resulted in a new long-term use. Since resistant bacteria have begun to emerge, it has been desired to develop an antibacterial agent that is effective at a low concentration with further sterilization and bacteriostatic power.

[0005]

SUMMARY OF THE INVENTION The present invention provides a synergistic effect on a wide range of microorganisms having a strong bactericidal or bacteriostatic power which cannot be achieved by the conventional combination in order to meet the above demands. It is intended to provide an antibacterial agent having the following.

[0006]

The present inventors have conducted intensive studies on the synergistic effect of various combinations of antibacterial components in order to solve this problem. As a result, among the various halogenated hydantoins, 1-bromo-3 was obtained. -Chloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin and 1,3-dichloro-5,5-dimethylhydantoin are particularly excellent in bactericidal activity and stability. Among the antibacterial agents to be combined, in particular, methylenebisthiocyanate (MBTC), 1,2
-Bis (bromoacetoxy) ethane, 1,4-bis (bromoacetoxy) -2-butene (BBAB), 4,5-
Dichloro-1,2-dithiol-3-one (DCDT)
And 4,5-dichloro-n-octylisothiazolin-3-one (DCOIT), which is a very excellent industrial antibacterial composition having good bactericidal and bacteriostatic properties against white water in the papermaking process even at a low concentration. And completed the present invention.

That is, the present invention relates to (A) Wherein X and Y represent the same or different halogen atoms, and R ₁ and R ₂ represent the same or different hydrogen atoms or alkyl groups, and (B) methylenebisthiocyanate, , 2
-Bis (bromoacetoxy) ethane, 1,4-bis (bromoacetoxy) -2-butene, 4,5-dichloro-
Industrial use, characterized by containing one or more selected from the group consisting of 1,2-dithiol-3-one and 4,5-dichloro-n-octylisothiazolin-3-one as an active ingredient. An antimicrobial composition.

Further, an antibacterial method comprising adding an industrial antibacterial composition having these two active ingredients to white water or an aqueous industrial composition in a papermaking process at a ratio of 1 to 10000 ppm.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION 1-bromo-3-chloro-5,5-dimethylhydantoin, which is the component (A) of the present invention,
1,3-Dibromo-5,5-dimethylhydantoin and 1,3-dichloro-5,5-dimethylhydantoin are antibacterial agents having particularly excellent bactericidal activity. On the other hand, methylenebisthiocyanate, 1,1 2-Bis (bromoacetoxy) ethane and 1,4-bis (bromoacetoxy) -2-butene are bacteriostatically acting fungicides and have different synergistic properties, so that a large synergistic effect is obtained. In addition, 4,5-dichloro-1,2-dithiol-3-one and 4,5-dichloro-n-octylisothiazolin-3-one are sterilized similarly to 1-bromo-3-chloro-5,5-dimethylhydantoin. Although these antibacterial agents act chemically, the spectrum of the target microorganisms differs from each other, so that a large synergistic effect can be obtained at an appropriate mixing ratio. However, if the amount of one of the two components is extremely low, the synergistic effect cannot be expected. Therefore, the ratio of the component (B) to 1 part by weight of the component (A) is 0.01 to 100 parts by weight, A ratio of 0.05 to 20 parts by weight is desirable.

As an antibacterial method using this industrial antibacterial composition, the antibacterial composition having the above two kinds of active ingredients is added to a paper-making process or an aqueous composition at a ratio of 1 to 10000 ppm. The method of addition is such that the above-mentioned two active ingredients are simultaneously or separately separately, for a total of 1 to 10,000.
You may add so that it may be in the range of ppm. Addition amount is 1
If it is less than ppm, a bactericidal effect cannot be expected and
If it exceeds 00 ppm, the added drug may remain in the paper as the product or in the wastewater from the process, and this is not preferred in terms of the cost of the drug.

It is desirable that the industrial antimicrobial composition be in a liquid form from the viewpoint of handling, but it may be used as a powder or tablet depending on the intended use. The solvent used in the formulation is not particularly limited, and solvents that dissolve the active ingredient such as halogenated hydantoin, for example, hydrophilic ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, hexylene Use glycol-based solvents such as glycol, glycol ether-based solvents such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether, nitrogen-containing solvents such as dimethylformamide and dimethylacetamide, and other oil-soluble solvents such as propylene carbonate and isophorone. can do. These may be used alone or in combination of two or more as necessary. As the surfactant, a nonionic surfactant, an anionic surfactant, a zwitterionic surfactant, or the like can be used, but the use of a nonionic surfactant is appropriate from the viewpoint of formulation stability. Other additives such as stabilizers can be used as needed.

[0012]

Next, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.
The compounding ratios shown in the table below are all by weight. In addition, the antibacterial agent composition of each Example and the comparative example was prepared by mixing and dissolving each component shown in the table at normal temperature.

Examples 1 to 8 Antibacterial compositions shown in Table 1 were prepared, and their performance was evaluated by Test Examples 1 to 3.

Comparative Examples 1 to 5 The antibacterial agent compositions shown in Table 1 were prepared, and their performances were evaluated by Test Examples 1 to 3.

[0015]

[Table 1]

(Note) * 1: 1-bromo-3-chloro-5,5-dimethylhydantoin (BCDMH: manufactured by Great Lakes Chemical Co.) * 2: Methylenebisthiocyanate (Rohm & Co.)
* 3: 1,2-bis (bromoacetoxy) -ethane (B
* 4: 4,5-Dichloro-1,2-dithiol-3-one (Microvan 86 20% ethylene glycol monomethyl ether liquid, manufactured by Yoshitomi Pharmaceutical Co., Ltd.) * 5: 4,5-Dichloro- n-octylisothiazolin-3-one (RH-287 25% ROHM &
* 6: Dimethylacetamide (DMAC)

(Test Example 1) Evaluation of bactericidal activity against white water in papermaking process "Test method" After adding 25 or 50 ppm of the antibacterial agent compositions obtained in Examples and Comparative Examples as a total concentration of active ingredients to the following target samples. After culturing for 30 minutes, the bacterial count of this sample was measured by a denatured waxman agar plate pour method. That is, a certain amount of the cultured sample solution is placed in a sterile petri dish,
The dissolved denatured Waxman agar medium was injected, pulverized and solidified. After culturing the solid in a constant temperature room at 30 ° C. for 2 days, the formed colonies were counted. Target sample: O paper company papermaking process white water, fine papermaking, pH 7.0 Viable bacteria count: 2.0 × 10 ⁷ CFU / ml “Test results” The test results are shown in Table 2 as the difference between increase and decrease values. Increase / decrease value difference: Shown by [number of colonies of antimicrobial-free sample (logarithmic value)-number of colonies of antimicrobial-added sample (logarithmic value)]. As shown in Table 2, the increase / decrease value difference between the two kinds of the antibacterial agents of Examples 1 to 8 was 1.8 to 2.9, and the one kind of the antibacterial agents of Comparative Examples 1 to 5 was The difference between the increase and decrease of the composition is clearly larger than 0.5 to 1.6, and it is confirmed that the antibacterial agent composition of the two kinds shows remarkable bactericidal activity against white water in the papermaking process. Was done.

[0018]

[Table 2]

(Test Example 2) Evaluation of Bacteriostatic Activity against White Water in the Paper Making Process "Test Method" The antibacterial agent compositions obtained in Examples and Comparative Examples were aseptically filtered from the following target samples, and the total concentration of the active ingredients was 5%. Alternatively, after adding 10 ppm, 1% of a 10-fold concentration modified Waxman liquid medium was added, and a target sample was added at 1% for inoculation. The rise time by turbidimetry was measured by a microbial growth curve which records the turbidity of the sample solution at 30 ° C. over time. Target sample: O paper company papermaking process white water, fine papermaking, pH 7.0 Viable bacteria count: 2.0 × 10 ⁷ CFU / ml “Test results” The test results are shown in Table 3 as differences in rise time. Rise time difference: [Rise time of sample with antimicrobial agent added-Rise time of sample with no antimicrobial agent added] The larger the time difference value, the greater the bacteriostatic power. [Consideration] As shown in Table 3, the difference between the rise times of the two types of antibacterial agent compositions of Examples 1 to 8 was 15 to 25.
In the comparative examples 1 to 5, the difference between the rise times of the active ingredients of one kind of the antibacterial agent compositions of 7 to 12 is clearly larger than that of the antibacterial agent compositions. On the other hand, it was confirmed that the bacteriostatic activity was remarkable.

[0020]

[Table 3]

[0021]

As described above, halogenated hydantoins such as 1-bromo-3-chloro-5,5-dimethylhydantoin, methylenebisthiocyanate, 1,2-bis (bromoacetoxy) -ethane, 1,4 -Bis (bromoacetoxy) -2-butene, 4,5-dichloro-1,
2-dithiol-3-one and 4,5-dichloro-n
Combination of a second component selected from the group consisting of octylisothiazolin-3-one, an industrial antibacterial agent composition and an antibacterial agent having both strong bactericidal activity and long-lasting bacteriostatic activity in a papermaking process. A method can be provided.

Claims (4)

[Claims] (1) General formula (A) (Wherein X and Y represent the same or different halogen atoms, and R ₁ and R ₂ represent the same or different hydrogen atoms or alkyl groups) and (B) methylenebisthiocyanate, 2-bis (bromoacetoxy) -ethane, 1,4-bis (bromoacetoxy) -2-butene, 4,5-dichloro-1,
An industrial antibacterial composition comprising as an active ingredient one or more selected from the group consisting of 2-dithiol-3-one and 4,5-dichlorooctylisothiazolin-3-one. Wherein component (A), X = Br, Y = Cl and R ₁ = R ₂ = represented by CH ₃ 1-bromo-3-chloro-5,5-dimethylhydantoin, X = Y = 1,3-dibromo-5 represented by Br and R ₁ ＲR ₂ ＣＨCH ₃
5-dimethylhydantoin or X = Y = Cl and R
₁ = R ₂ = 1,3- dichloro-5,5 represented by CH ₃
The industrial antimicrobial composition according to claim 1, which is any one of -dimethylhydantoin. 3. The ratio of component (B) to 0.01 to 100 parts by weight, especially 0.05 to 1 part by weight of component (A).
The industrial antibacterial composition according to claim 1, wherein the amount is from 20 to 20 parts by weight. 4. The industrial antibacterial agent composition according to claim 1,
Papermaking process 1 to 10,000 in white water or industrial water-based composition
An antibacterial method characterized by being added at a ratio of ppm.