JP2000063210A - 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 isothiazoline-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) an isothiazoline-based compound represented by formula II (X and Y are each H or a halogen) (preferably 4,5-dichloro-2-n- octyl-4-isothiazolin-3-one, 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.

In addition, water-based industrial water-based compositions such as coated paper, latex, and starch slurry liquids also 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 (M, which has excellent bacteriostatic activity (bacterial growth inhibitory activity)
BTC), 1,2-bis (bromoacetoxy) ethane (BBAE) and 1,4-bis (bromoacetoxy)
2-Butene (BBAB) and the like are used, and as a preservative for the purpose of preventing the deterioration of various water-based compositions, 5-chloro-which has excellent bacteriostatic activity and stability in water-based compositions. 2-Methyl-4-isothiazolin-3-one (Cl
-MIT), 1,2-benzisothiazolin-3-one (BIT), 2,2-dibromo-2-nitroethanol (DBNE), 2-bromo-2-nitropropane-1,
3-diol (BNP) and 2-bromo-2-bromomethylglutaronitrile (BBMG, 1,2-dibromo-2,4-dicyanobutane) 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, 2,2-dibromo-3-nitrilopropionamide and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT) in Japanese Patent Publication No. 6-21043 are used. 2,2-dibromo-3-nitrilopropionamide and 5-chloro-2-methyl-4-isothiazoline-3 in JP-B-6-65642
-Many disclosures such as combinations with ON. As the combination of three components, a combination of 2,2-dibromo-3-nitrilopropionamide, methylenebisthiocyanate and 2,2-dibromo-2-nitroethanol in JP-A-7-25708, and JP-A-7-187920 can be used. 2,2-dibromo-3-nitrilopropionamide, 4,5-dichloro-1,2-dithiol-3-one and 5-chloro-2-methyl-4-isothiazolin-3-in
A combination of ON is disclosed. These combinations show good efficacy against microorganisms in the papermaking process and water-based compositions where a single agent has been used for a long period of time, but on the other hand, the combination of these two or three components has a long-term effect. Since new resistant bacteria have begun to appear due to use, 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]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on various combinations of antibacterial components in order to solve this problem. As a result, halocyanoacetamide compounds, isothiazoline compounds and 2 -Antimicrobial composition for industrial use containing 3 components of bromo-2-bromomethylglutaronitrile as an active ingredient has good bactericidal activity against white water in the papermaking process, bacteriostatic activity and antiseptic activity against industrial aqueous compositions even at low concentrations. The present invention has been completed by discovering that it is a very excellent antibacterial agent composition having both of the following.

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 hydrogen atom or a halogen atom, R represents a hydrogen atom or an alkyl group), and an isothiazoline-based compound and (C) 2-bromo-2-bromomethylglutaronitrile. This is an industrial antibacterial agent composition.

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 having excellent bactericidal effect is particularly desirable.

The isothiazoline compound as the component (B) of the present invention includes 2-methyl-4-isothiazoline-
3-one (MIT), 2-ethyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-
3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, 5-chloro-2-t-octyl-4.
-Isothiazolin-3-one, 4,5-dichloro-2-
2-Methyl-4-isothiazolin-3-one (MIT) and 5-chloro-2-methyl-, which have particularly excellent bactericidal and bacteriostatic effects, are included, including n-octyl-4-isothiazolin-3-one. A mixture with 4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is preferred.

The halocyanoacetamide compounds of the present invention have excellent bactericidal activity, the isothiazoline compounds have bacteriostatic activity as well as bactericidal activity, while 2-bromo-2-bromomethylglutaronitrile has excellent bacteriostatic activity. In addition to the general characteristics, the spectra of the target microorganisms are different, so that a comprehensive 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 ratio of the component (C) is 0.01 to 1 respectively.
A content ratio of 0 parts by weight, preferably 0.1 to 1 parts by weight is desirable.

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 in Test Examples 1 to 3.

[0018]

[Table 1]

(Note) (* 1) 2,2-dibromo-3-nitrilopropionamide (manufactured by DBNPA Rohm and Haas) (* 2) 2-methyl-4-isothiazolin-3-one and 5-chloro Mixture with 2-methyl-4-isothiazolin-3-one (ZONEN F11% ethylene glycol solution manufactured by Ichikawa Gosei Kagaku) (* 3) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one ON (RH-287 25% phenylxylylethane solution manufactured by Rohm and Haas Co., Ltd.) (* 4) 2-bromo-2-bromomethylglutaronitrile (Tektamer38 manufactured by Calgon Co., Ltd.)

(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 composition obtained in Examples and Comparative Examples was added to the following target samples in an amount of 25 or 50 ppm as a total concentration of active ingredient, and then 30 Minutes or 60 minutes,
The bacterial count of this sample was measured by the modified Waxman agar plate pour method. That is, an aliquot of the cultured sample solution was placed in a sterile petri dish, dissolved denatured Waxman agar medium was injected, and the mixture was poured and solidified. After culturing for 2 days in a thermostatic chamber at 30 ° C, the number of formed colonies was determined. I 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)
-Number of colonies of antibacterial agent-added sample (logarithmic value)], and the greater the difference in increase / decrease value, the greater the bactericidal effect. "Discussion" As shown in Table 3, the difference in increase / decrease value of the antibacterial agent compositions of the active ingredients 1 to 2 of Comparative Examples 1 to 9 is 0.5 to 3.1, as compared with Example 1. The difference in increase / decrease in the antibacterial agent composition of the three active ingredients of 3 to 6 is 3.4 to> 6.0, which is clearly large, and the antibacterial agent composition of the three kinds of mixture is against white water in the papermaking process. It was confirmed that they showed remarkable bactericidal activity.

[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.
Compared with the above, the difference 18 to 25 in the rise time of the antibacterial agent compositions of the three active ingredients of Examples 1 to 6 shows a clearly large value, and the antibacterial agent compositions of the three kinds are papermaking. It was confirmed that it showed remarkable bacteriostatic activity against white water in the process.

[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, the halocyanoacetamide compound, the isothiazoline compound and 2-bromo-
By combining three components of 2-bromomethylglutaronitrile, an antibacterial composition having strong bactericidal power in papermaking process, bacteriostatic power for a long time, and long-term antiseptic effect in an aqueous composition It is possible to provide a product and an antibacterial method.

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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 (X and Y in the formula are hydrogen atom or halogen atom, R
Represents a hydrogen atom or an alkyl group) and an isothiazoline-based compound represented by the formula (C) and (C) 2-bromo-2-bromomethylglutaronitrile. 2. Component (A) comprises X = Br, Y = Br and R
2,2-dibromo-3-nitrilopropionamide represented by ═H, the component (B) is X═H, Y═H, R═CH ₃
A mixture of 2-methyl-4-isothiazolin-3-one represented by and X-H, Y = Cl, and 5-chloro-2-methyl-4-isothiazolin-3-one represented by R = CH ₃ . Or X = Cl, Y = Cl, R = (CH ₂ ) ₇ C
4,5-dichloro -2-n-octyl represented by H ₃ -
The industrial antibacterial agent composition according to claim 1, which is 4-isothiazolin-3-one. 3. The ratio of the component (B) and the component (C) is 0.01 to 1 with respect to 1 part by weight of the component (A).
0 parts by weight, preferably 0.1 to 1 parts by weight.
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.