JP2000063212A - Industrial antimicrobial agent composition and antimicrobial method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having strong germicidal power or strong bacteriostatic power, effective against a wide range of microorganisms and useful for prevention, etc., of the occurrence of slimes in a papermaking process in a paper pulp industrial field by including a specific halocyanoacetamide compound, a specified halogenated fatty acid ester-based compound, etc. SOLUTION: This composition is obtained by including three ingredients of (A) a halocyanoacetamide compound represented by formula I (X is a halogen; Y is H or a halogen; R is H or an alkyl) (preferably 2,2-dibromo-3- nitrilopropionamide, etc.), (B) a halogenated fatty acid ester-based compound represented by formula II (R is an alkylene or an alkenylene) [preferably 1,2-bis(bromoacetoxy)-2-ethane, etc.], and (C) 2-bromo-2-bromomethylglutaronitrile. The amounts of the contained ingredients are preferably 0.01-10 pts.wt., more preferably 0.1-1 pt.wt. each of the ingredients B and C based on 1 pt.wt. of the ingredient A.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to preventing adhesion of slime derived from microorganisms such as bacteria and fungi during the papermaking process in the field of paper and pulp industry, or to paint, latex, starch slurry liquid, paper. Antibacterial agent composition for preventing water-based industrial water-based compositions such as coating colors, cleaning water, cooling water, adhesives, metalworking oils, etc. from being decomposed, discolored, or deteriorated in physical properties due to microbial contamination. And an antibacterial method.

[0002]

2. Description of the Related Art In the pulp and paper industry, a large amount of water is required in the papermaking process, and various organic substances are dispersed and dissolved in it, so microorganisms such as bacteria and fungi feed various organic substances as nutrient sources. To breed as. Since this produces a mucous metabolite, it takes in the papermaking raw materials dispersed during the papermaking process, such as pulp and filler, and forms slime on the wall surface and the flow box in the chest where the water flow stagnates. The slime thus formed gradually increases, and eventually it separates and is made into paper together with a papermaking raw material such as pulp, and appears as foreign matter on the paper, resulting in deterioration in quality. Further, recently, since paper is made at a considerably high speed, in the worst case, it may cause a paper break and cause a decrease in productivity.

Also, water-based industrial water-based compositions such as coating liquids, latexes, and starch slurry liquids rot due to contamination with these bacteria,
It causes physical properties such as odor generation, viscosity decrease and pH change, and fungal (filamentous fungus) breeding causes clogging of strainers, coloring, contamination of foreign substances and the like.

Therefore, various antibacterial agents have been used so far in order to prevent deterioration due to microbial factors.
For example, to prevent slime generation in the papermaking process, 2,2-dibromo-3-nitrilopropionamide (DBNPA), 4,5-dichloro-1, which has a very strong bactericidal activity, is used.
2-dithiol-3-one (DCDT) and methylenebisthiocyanate (MBT) with excellent bacteriostatic activity (growth inhibitory activity)
C), 1,2-bis (bromoacetoxy) ethane (BB
AE) and 1,4-bis (bromoacetoxy) -2-
Butene (BBAB) and the like are used, and as a preservative for the purpose of preventing deterioration of various water-based compositions, 5-chloro-2, which has excellent bacteriostatic activity and stability in water-based compositions, is used.
-Methyl-4-isothiazolin-3-one (Cl-MI
T), 1,2-benzisothiazolin-3-one (BI
T), 2,2-dibromo-2-nitroethanol (DB
NE), 2-bromo-2-nitropropane-1,3-diol (BNP) and 2-bromo-2-bromomethylglutaronitrile (BBMG, 1,2-dibromo-2,
4-dicyanobutane) and the like are used.

On the other hand, when these antibacterial agents are used alone and for a long period of time, resistant bacteria are likely to appear. Therefore, conventionally, a method of using these agents in combination with two or three kinds has been taken. For example, in the combination of two components, the combination of 2,2-dibromo-3-nitrilopropionamide and 4,5-dichloro-1,2-dithiole-3-one in Japanese Patent Publication No. 1-20121 is disclosed in Japanese Examined Patent Publication No. 2,2-dibromo-3-nitrilopropionamide at -65642 and 5-chloro-2-methyl-4-
Many disclosures have been made such as combinations with isothiazolin-3-one. A combination of three components is disclosed in Japanese Patent Laid-Open No. 8-
2,2-Dibromo-3-nitrilopropionamide in 198714, 1,4-bis (bromoacetoxy)
A combination of 2-butene and 5-chloro-2-methyl-4-isothiazolin-3-one, JP-A-8-198715.
2,2-dibromo-3-nitrilopropionamide, a combination of 1,4-bis (bromoacetoxy) -2-butene and methylenebisthiocyanate, and the like are disclosed. These combinations have shown good efficacy against microorganisms in papermaking processes and aqueous compositions where a single agent has been used for a long time, while
Since new resistant bacteria have begun to appear due to long-term use due to the combination of the components and the three components, it is desired to develop an effective antibacterial agent at a low concentration with further sterilization and bacteriostatic activity.

[0006]

In order to meet the above-mentioned demands, the present invention is effective against a wide range of microorganisms having strong bactericidal power or bacteriostatic power which was insufficient in the conventional combination. To provide a new antibacterial agent.

[0007]

As a result of intensive studies on various combinations of antibacterial components in order to solve this problem, the present inventors have found that halocyanoacetamide compounds and halogenated fatty acid ester compounds are effective components. Compounds and 3- of 2-bromo-2-bromomethylglutaronitrile
Industrial antibacterial agent composition containing the component as an active ingredient is a very excellent antibacterial agent composition having good bactericidal activity against white water in papermaking process even at low concentration, bacteriostatic activity and antiseptic effect against industrial aqueous system composition. Then, they have completed the present invention.

That is, the present invention provides (A) the general formula (Wherein X represents a halogen atom, Y represents a hydrogen atom or a halogen atom, and R represents a hydrogen atom or an alkyl group), and (B) the general formula (Wherein X represents a halogen atom, R represents an alkylene or alkenylene group) and a halogenated fatty acid ester compound and (C) 2-bromo-2-bromomethylglutaronitrile. An industrial antibacterial agent composition characterized by:

In addition, an industrial antibacterial agent composition containing these three kinds of active ingredients is added to the white water in the papermaking process or the industrial aqueous composition at a ratio of 1 to 20000 ppm simultaneously or separately, thereby providing an antibacterial method. is there.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the halocyanoacetamide compound which is the component (A) of the present invention include 2-chloro-3-nitrilopropionamide, 2-bromo-3-nitrilopropionamide and 2,2-dichloro. -3-Nitrilopropionamide, 2,2-dibromo-3-nitrilopropionamide, and the like are included, but 2,2-dibromo-3-nitrilopropionamide (DBNPA), which is particularly excellent in bactericidal efficacy, is preferable.

Examples of the halogenated fatty acid ester compound as the component (B) of the present invention include 1,2-bis (chloroacetoxy) -2-ethane, 1,2-bis (bromoacetoxy) -2-ethane, and , 3-bis (bromoacetoxy) -2-propane, 1,4-bis (bromoacetoxy) -2-butene, etc. are included, but 1,2-bis (bromoacetoxy) -2 having particularly excellent bacteriostatic effect is included. -Ethane and 1,4-bis (bromoacetoxy) -2-butene are preferred.

The halocyanoacetamide compound of the present invention has excellent bactericidal activity, and the halogenated fatty acid ester compound and 2-bromo-2-bromomethylglutaronitrile have the general characteristics of excellent bacteriostatic activity. Since the spectrum of the microorganisms to be used is different, a total synergistic effect can be obtained with an appropriate blending ratio. However, if the compounding amount of one or two of the three kinds of components is extremely low, the synergistic effect cannot be expected. Therefore, the ratio of the three components is 1 part by weight of the component (A), and the ratio of the components (B) and The content of the component (C) is 0.01 to 10 parts by weight, preferably 0.1 to 1 part by weight.

As an antibacterial method using this antibacterial composition, the antibacterial composition containing the above-mentioned three kinds of active ingredients may be added in the range of 1 to 20,000 ppm during the papermaking process or to the aqueous composition, or The above three active ingredients may be added separately so that the total amount is in the range of 1 to 20000 ppm.

The solvent and other components used in formulating the antibacterial composition are not particularly limited, but water to be added as a chemical agent such as water in the papermaking process in which microorganisms grow and an aqueous composition is mainly water. Therefore, the solvent is relatively hydrophilic, for example, glycol solvents such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, hexylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether. A glycol ether solvent such as butyl ether or propylene carbonate is desirable. These are used singly or in combination of two or more kinds, and addition amounts necessary to dissolve three kinds of active ingredients are required.

As the surface active agent, nonionic surface active agents, anionic surface active agents, amphoteric surface active agents and the like can be used, but nonionic surface active agents such as polyoxyethylene nonyl phenyl ether are used because of formulation stability. Surfactants are suitable. Other additives such as stabilizers can be used if necessary.

[0016]

EXAMPLES Next, the present invention will be explained with reference to examples and comparative examples, but the present invention is not limited to these.
Further, the compounding ratios shown in the table below are all weight%. The antibacterial agent compositions of Examples and Comparative Examples were prepared by mixing and dissolving the components shown in the table at room temperature.

Examples 1 to 6 The antibacterial agent compositions shown in Table 1 were prepared, and the performance was evaluated by Test Examples 1 to 3.

[0018]

[Table 1]

(Note) (* 1) 2,2-dibromo-3-nitrilopropionamide (manufactured by DBNPA Rohm and Haas) (* 2) 1,2-bis (bromoacetoxy) -2-ethane (BBAE) (* 3) 1,4-bis (bromoacetoxy) -2-butene (BBAB manufactured by Ichikawa Gosei) (* 4) 2-bromo-2-bromomethylglutaronitrile (Tektamer38 Calgon Co.) Made)

Comparative Examples 1 to 9 The antibacterial agent compositions shown in Table 2 were prepared, and the performance was evaluated by Test Examples 1 to 3.

[0021]

[Table 2]

(Test Example 1) Papermaking process Evaluation of bactericidal activity against white water "Test method" The antibacterial agent compositions obtained in Examples and Comparative Examples were used as the total amount of the active ingredients of 25 or 5 in the following target samples.
After adding 0 ppm, the cells were cultured for 30 minutes or 60 minutes, and the number of bacteria in this sample was measured by the modified Waxman agar plate pour method. That is, a fixed amount of the cultured sample liquid is taken in a sterile petri dish, and the dissolved denatured Waxman agar medium is injected,
After pouring, the mixture was solidified and cultured in a thermostatic chamber at 30 ° C. for 2 days, and the number of formed colonies was counted. Target sample: S Papermaking company papermaking process White water, fine papermaking, pH
7.1 Viable cell count: 2.3 × 10 ⁷ CFU / ml “Test result” The test results are shown in Table 3 as the difference in increase / decrease value. Increase / decrease difference: [Number of colonies of antimicrobial-free sample (logarithmic value)
-The number of colonies of antibacterial agent-added samples (logarithmic value)], and the larger the increase / decrease value difference is, the larger the bactericidal efficacy is. The difference in increase / decrease value between the two antibacterial agent compositions is 0.7 to 3.0, whereas the difference in increase or decrease value between the three antibacterial agent compositions of the active ingredients of Examples 1 to 6 is 3.5 to 3.0. > 6.0, which is a clearly large value, and it was confirmed that the three kinds of antibacterial agent compositions exhibited remarkable bactericidal activity against white water in the papermaking process.

[0023]

[Table 3]

(Test Example 2) Papermaking process Evaluation of bacteriostatic power against white water "Test method" The following target samples were subjected to aseptic filtration, and the antibacterial composition obtained in Examples and Comparative Examples was used as the total concentration of the active ingredients of 5 Alternatively, after adding 10 ppm, 1% of a 10-fold concentrated denatured Waxman liquid medium was added, and the target sample was added 1% for inoculation. The rise time by the turbidimetric method was measured by a microbial growth curve in which the turbidity of the sample solution at 30 ° C. was recorded with time. Target sample: S Papermaking company papermaking process White water, fine papermaking, pH
7.1 Viable cell count: 2.3 × 10 ⁷ CFU / ml “Test result” The test results are shown in Table 4 as the difference in the rise time. Difference in rise time: [Rise time of antibacterial agent-added sample-rise time of antibacterial agent-free sample], and the larger the time difference value, the greater the bacteriostatic force. [Discussion] As shown in Table 4, the difference in the rise time of the antibacterial agent compositions of the active ingredients 1-2 of Comparative Examples 1-9 was 6-14.
In comparison with the above, the difference in the rise time of the antibacterial agent compositions of the three active ingredients of Examples 1 to 6 is clearly large at 17 to 26, and the antibacterial agent compositions of the three kinds are It was confirmed that the papermaking process shows remarkable bacteriostatic activity against white water.

[0025]

[Table 4]

(Test Example 3) Evaluation of antiseptic effect on starch slurry "Test method" 10% of cationized tapioca starch from Company T
After making 30 g of each as a slurry liquid (pH 6.3) and adding a predetermined amount of the antibacterial agent composition to a sterile polypropylene bottle,
Pre-rotted starch slurry (bacteria number: 4.5
× 10 ⁷ ) was inoculated with 1%. This was cultivated under a closed static condition at 30 ° C., and the viable cell count was measured with time by the TGC agar plate pour method. After measuring the viable cell count, the spoiled product was inoculated with 1% every week. "Test result" The measurement result of the viable cell count was expressed based on the following criteria, and the results are shown in Table 5. −: Less than 10 ² +: 10 ² or more and less than 10 ⁴ ++: 10 ⁴ or more and less than 10 ⁶ +++: 10 ⁶ or more but less than 10 ⁷ ++++: 10 ⁷ or more “Consideration” As shown in Table 5. The evaluation results on the 21st day of the antibacterial compositions of the active ingredients 1 and 2 of Comparative Examples 1 to 9 are ++ to ++.
In contrast, the evaluation results of the three active ingredients of Examples 1 to 6 are − to +, and the antibacterial composition containing the three active ingredients shows a remarkable antiseptic effect on starch slurries. Was confirmed.

[0027]

[Table 5]

[0028]

As described above, by combining the three components of the conventional halocyanoacetamide-based compound, halogenated fatty acid ester-based compound and 2-bromo-2-bromomethylglutaronitrile, the strength of the papermaking process can be improved. It is possible to provide an antibacterial agent composition and an antibacterial method which have excellent bactericidal activity, bacteriostatic activity for a long time, and long-term antiseptic effect in an aqueous composition.

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Claims (4)

[Claims] 1. A general formula (A) (Wherein X represents a halogen atom, Y represents a hydrogen atom or a halogen atom, and R represents a hydrogen atom or an alkyl group), and (B) the general formula (Wherein X represents a halogen atom, R represents an alkylene or alkenylene group) and a halogenated fatty acid ester compound and (C) 2-bromo-2-bromomethylglutaronitrile. An industrial antibacterial agent composition comprising: 2. Component (A) comprises X = Br, Y = Br and R
= 2,2-dibromo-3-nitrilopropionamide represented by ═H, component (B) is X═Br and R═CH ₂ C
Represented by H ₂ 1,2-bis (bromoacetoxy) ethane or X = Br and R = 1,4-bis represented by CH ₂ CH = CHCH ₂ claims a (bromoacetoxy) -2-butene 1. The industrial antibacterial agent composition described in 1. 3. Component (B) and component (C) are each 0.01 to 10 parts by weight, preferably 0.1 to 1 part by weight, relative to 1 part by weight of component (A). The antibacterial agent composition for industrial use according to 1. 4. The industrial antibacterial agent composition according to claim 1,
Papermaking process 1 to 20,000 for white water or industrial water-based composition
An antibacterial method characterized by being added simultaneously or separately in a proportion of ppm.