JP3172740B2 - Antimicrobial composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a novel antimicrobial composition, and more particularly, to an industrial antimicrobial composition having excellent antibacterial activity, which can be used at lower concentration and for a longer period of time than conventional products. It is about things.

[0002]

2. Description of the Related Art In a cooling water system of various plant plants, slime composed of bacteria, filamentous fungi, algae, etc. is generated in the system, and slime such as deterioration of thermal efficiency, blockage of water flow pipes, corrosion of pipe metal materials, and the like. It is known that disability often occurs. Also, in the paper pulp papermaking system, various additives such as cellulose and starch are used as a nutrient source, and slime mainly composed of bacteria, filamentous fungi, etc. is formed on the inner wall of the system, and such slime is generated from the wall surface. By peeling off, it is mixed as a foreign substance in the product, which causes undesirable situations such as lowering the product quality, causing paper breakage in the papermaking process, inhibiting continuous operation, and greatly reducing production efficiency. . Especially in the pulp and paper industry, starch, latex, casein, etc. are used in large quantities as additives, and all of these additives become nutrients for the propagation of microorganisms, so they are spoiled by microorganisms,
This is a major cause of product deterioration. In addition, microbial degradation of product quality and productivity in related fields such as water-based paints, emulsion paints, emulsion adhesives, metalworking oils, latex, starch paste liquids, and paper coating liquids that are rich in organic substances It is known that various obstacles such as the above occur. Conventionally, bacteria in such various industrial fields, fungi, yeast, against microbial disorders such as algae,
Because of its relatively simple and economical implementation, it has been treated with antimicrobial agents. Many industrial antibacterial agents used in such applications have been formulated and used as single products. However, when the antibacterial agent is used alone, there is a problem that bacteria resistant to the antibacterial agent are unavoidable, so that there is a problem that it is difficult to use the same antibacterial agent for a long period of time. In addition, for such resistant bacteria, measures to increase the applied concentration may be taken, but this causes toxicity problems, environmental pollution and economic problems. Under such circumstances, there has been a demand for the development of a drug that exhibits efficacy at lower concentrations and a drug that can be used for a longer period of time.

[0003]

SUMMARY OF THE INVENTION In accordance with the present invention, there is provided an industrial antibacterial agent having excellent antibacterial activity, which can be used for a long time at a lower concentration than conventional products. It is done for the purpose of.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to develop an industrial antibacterial agent having the above-mentioned preferable properties, and as a result, have combined a specific organic fungicide with a halogenated naphthyl ketone. As a result, the inventors have found that the object can be achieved, and have completed the present invention based on this finding. That is, the present invention relates to (A) bromomethyl-1-naphthyl ketone or bromomethyl-2-naphthyl ketone, and (B) 1,4-bis (bromoacetoxy) -2-butene, 2,2-dibromonitrilopropionamide, -Bromo-2-nitropropane-1,3-
Diol, methylenebisthiocyanate, 4,5-dichlorodithiolan-3-one, 5-chloro-2-methyl-
4-isothiazolin-3-one, 2-n-octyl-
4,5-dichloroisothiazolin-3-one and 1,2-
An antimicrobial composition comprising at least one organic fungicide selected from benzisothiazolones.

Hereinafter, the present invention will be described in detail. The bromomethylnaphthyl ketone of the component (A) in the composition of the present invention has the general formula

[0006]

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(Wherein R ¹ is a bromomethyl group)
Is bromomethylnaphthyl ketone represented by In the general formula [1], bromomethyl-1-naphthyl ketone is most preferably effective.

The compound represented by the general formula [1] includes bromomethyl-1-naphthyl ketone and bromomethyl-2-naphthyl ketone.

In the composition of the present invention, bromomethylnaphthyl ketone as the component (A) can be used alone or in combination of two or more. In the composition of the present invention,
As the component (B), at least one specific organic fungicide selected from organic halogen compounds having 3 or more carbon atoms and organic sulfur compounds is used.

The fungicides comprising the organic halogen compounds include 1,4-bis (bromoacetoxy) -2-butene, 2,2-dibromonitrilopropionamide,
Preferable examples include bromo-2-nitropropane-1,3-diol. On the other hand, as a bactericide comprising an organic sulfur compound, for example, methylene bisthiocyanate, a general formula

[0011]

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(X ¹ and X ² in the formula are each a hydrogen atom or a halogen atom, which may be the same or different, or form a ring with them. Good) and

[0013]

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(Wherein R ² represents a hydrogen atom, a methyl group or a cyclic or linear hydrocarbon group having 3 to 12 carbon atoms, X ³
And X ⁴ are each a hydrogen atom or a halogen atom, which may be the same, different from each other, or may form a ring with them. Are preferred.

A typical example of the compound represented by the general formula [2] is 4,5-dichlorodithiolan-3-
On can be mentioned. Representative examples of the compound represented by the general formula [3] include, for example, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n
-Octyl-4,5-dichloroisothiazolin-3-one, 1,2-benzisothiazolone and the like. In the composition of the present invention, one or more of these organic fungicides comprising the organic halogen compound and the organic sulfur compound as the component (B) are selected, and the above (A) is selected.
Used in combination with the halogenated naphthyl ketone component. The ratio of the component (A) to the component (B) depends on the application and is not particularly limited, but usually the weight ratio of the component (A) to the component (B) is from 1:20 to 20: 1. Each component is used in such a ratio.

The antibacterial composition of the present invention may contain other conventionally known industrial germicides as required, as long as the object of the present invention is not impaired. The formulation of the composition of the present invention is not particularly limited. For example, a liquid agent dissolved in a solvent, a flowable agent dispersed in water as particles, or a solid agent kneaded in a synthetic resin or the like or a solid agent impregnated in a carrier. It can be used as a mold and the like. When dissolved in a solvent to form a liquid, the solvent may be, for example, diethylene glycol monomethyl ether, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycols such as polyethylene glycol, and the like. Is dimethylformamide,
Dimethyl sulfoxide, water and the like. These solvents may be used alone or in combination of two or more.

The field of application of the composition of the present invention is not particularly limited as long as it can be applied to industrial antibacterial agents, and is generally used for slime control in cooling water systems and paper pulp mills, and for starch, casein and latex. ,
It is suitably used for antiseptic and mold-proofing of pigments, adhesives, paints, cutting oils, fibers, building materials, wood, leather, plastics and the like. The addition amount of the composition of the present invention is appropriately selected depending on the type of the object to which the composition is applied.However, when the object is usually a paper pulp papermaking system, that is, when used as a slime control agent, the addition amount of both components is usually The total amount is 1 to 100 μg
/ Ml, or 10 to 3,000 µg / ml when used in other fields.
As the addition method, both components may be added at a predetermined ratio, or a mixture of both components at a predetermined ratio in advance may be added.

[0018]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.

Examples 1 to 9 The antibacterial agent compositions shown in Table 1 were prepared, and their performance was examined in Test Examples 1 and 2.

[0020]

[Table 1]

(Note) KATHON 886: 5-chloro-2-methyl-4-isothiazolin-3-one (manufactured by Rohm and Haas)

Comparative Examples 1 to 10 The antibacterial compositions shown in Table 2 were prepared, and their performance was examined by Test Examples 1 and 2.

[0023]

[Table 2]

(Note) KATHON886: Same as the footnote in Table 1.

Test Example 1 Microorganism Growth Inhibition Test Using white water from a paper mill, the antimicrobial growth inhibitory effects of the various antimicrobial compositions prepared in Examples and Comparative Examples were compared.
After adjusting the pH to 5.5 by adding 10% by weight of bouillon liquid medium to white water, the antimicrobial composition of the example was added to 15 ppm, and the antimicrobial composition of the comparative example was added to 20 ppm.
The cells were cultured at ℃ using a biophoto recorder (manufactured by Toyo Sokki). The results are shown in Table 3 as the time at which turbidity starts to appear in each antimicrobial composition.

[0026]

[Table 3]

From Table 3, it can be seen that the antimicrobial composition of the present invention has a high effect of inhibiting the growth of microorganisms even though the addition temperature is lower than that of the comparative example, and the significance of the present invention was confirmed.

Test Example 2 Test for Possibility of Long-Term Use A preservative test of starch used in a paper mill was conducted by an abuse method. To a cationic starch slurry (20 wt%), 200 ppm of the antibacterial agent compositions of Examples and Comparative Examples, and 0.1 wt% of an activated sludge supernatant as a seed bacterium were added, and cultured at 30 ° C. An additional 0.1 wt% was added. At this time, the number of viable cells was measured on a bouillon agar medium immediately before the additional addition. In addition, an antimicrobial composition was added at an additional 200 ppm every two weeks, and the possibility of repeated use was examined. Table 4 shows the results.

[0029]

[Table 4]

(Note) Viable count of inoculum: 5.2 × 10 ⁷ CF
U / ml From Table 4, it was confirmed that the antibacterial agent composition of the present invention can be used for a long period of time.

[0031]

The antibacterial agent composition of the present invention is a combination of a halogenated naphthyl ketone and a bactericide comprising an organic halogen compound or an organic sulfur compound, and has a lower concentration than the use of each agent alone. In addition to being effective, it can be used for a longer period of time

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI A01N 43/80 102 A01N 43/80 102 47/48 47/48 (56) References JP-A-58-183606 (JP, A) JP-A-59-227805 (JP, A) JP-A-64-13001 (JP, A) JP-A-56-152402 (JP, A) JP-A-50-117933 (JP, A) (JP, U) U.S. Pat. No. 3,184,379 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 35/04 A01N 33/20 101 A01N 37/12 A01N 37/34 101 A01N 43 / 26 A01N 43/80 102 A01N 47/48 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] (1) bromomethyl-1-naphthyl ketone or bromomethyl-2-naphthyl ketone, and (B)
1,4-bis (bromoacetoxy) -2-butene, 2,2
-Dibromonitrilopropionamide, 2-bromo-2
-Nitropropane-1,3-diol, methylenebisthiocyanate, 4,5-dichlorodithiolan-3-one, 5-chloro-2-methyl-4-isothiazoline-3
An antibacterial composition comprising at least one organic fungicide selected from -one, 2-n-octyl-4,5-dichloroisothiazolin-3-one and 1,2-benzisothiazolone.