JPH04321604A - Antimicrobial agent composition - Google Patents

Abstract

PURPOSE:To obtain an industrial antimicrobial agent composition, composed of a halogenated naphthyl ketone and a specific organic germicide, having excellent antimicrobial activity, capable of exhibiting effects at a lower concentration than that in use of the single ingredients and usable for a long period. CONSTITUTION:An antimicrobial agent composition is obtained by using (A) a halogenated naphthyl ketone, preferably a compound expressed by formula I (R1 is 1-4C halogenoalkyl), especially bromomethyl-1-naphthyl ketone and (B) a germicide selected from (B1) >=3C organohalogen compounds, e.g. 1,4-bis(bromoacetoxy)-2-butene and (B2) organosulfur compounds, e.g. methylene bisthiocyanate, compounds expressed by formula II (X<1> and X<2> are H or halogen), e.g. 4,5-dichlorodithiolan-3-one and compounds expressed by formula III (R<2> is H, methyl or 3-12C hydrocarbon group; X<3> and X<4> are H or halogen), e.g. 1,2-benzisothiazolone in combination at (1:20)-(20:1) weight ratio of the ingredients (A):(B).

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention provides a novel antibacterial composition, more specifically, an industrial antibacterial composition that has excellent antibacterial activity and can be used for a long period of time at a lower concentration than conventional products. It is about things.

0002

[Prior Art] In the cooling water systems of various industrial plants, slime consisting of bacteria, filamentous fungi, algae, etc. is generated in the system, resulting in decreased thermal efficiency, blockage of water pipes, corrosion of metal materials of pipes, etc. It is known that failures often occur. In addition, in pulp and paper making systems, slime consisting mainly of microorganisms such as bacteria and filamentous fungi is formed on the inner wall surface of the system using various additives such as cellulose and starch as nutrients. Peeling can cause undesirable situations such as contamination as foreign matter in the product and deterioration of product quality, or inducing paper breakage in the papermaking process, hindering continuous operation, and significantly reducing production efficiency. . Particularly in the pulp and paper industry, large amounts of additives such as starch, latex, and casein are used, and these additives serve as nutritional sources for the growth of microorganisms, causing them to rot and cause product deterioration. This is a major cause. In addition, in related fields such as water-based paints rich in organic substances, emulsion paints, emulsion adhesives, metal processing oils, latex, starch pastes, and paper coating fluids, microorganisms can cause deterioration in product quality and productivity. It is known that various problems such as Conventionally, microbial disorders such as bacteria, filamentous fungi, yeast, and algae in various industrial fields have been treated with antibacterial agents because they are relatively simple and economical to implement. As industrial antibacterial agents used for such purposes, many compounds have been formulated and used as single products. However, when using a single antibacterial agent, bacteria that are resistant to the antibacterial agent inevitably appear, making it difficult to use the same antibacterial agent for a long period of time. In addition, measures may be taken to increase the applied concentration against such resistant bacteria, but in this case, problems of toxicity, environmental pollution, and economic efficiency arise. Under these circumstances, there has been a desire to develop drugs that are effective at lower concentrations and drugs that can be used for a longer period of time.

0003

[Problems to be Solved by the Invention] The present invention meets these needs and provides an industrial antibacterial agent that has excellent antibacterial activity, has a lower concentration than conventional products, and can be used for a long period of time. It was done for that purpose.

0004

[Means for Solving the Problems] As a result of intensive research to develop an industrial antibacterial agent having the above-mentioned favorable properties, the present inventors have combined a specific organic fungicide with a halogenated naphthyl ketone. The inventors have discovered that the object can be achieved by doing so, and have completed the present invention based on this knowledge. That is, the present invention provides an antibacterial composition comprising (A) a halogenated naphthyl ketone and (B) at least one organic fungicide selected from organic halogen compounds having 3 or more carbon atoms and organic sulfur compounds. It provides:

[0005] The present invention will be explained in detail below. The halogenated naphthyl ketone as the component (A) in the composition of the present invention is, for example, represented by the general formula

[0006]

[Chemical formula 1]

A halogenoalkyl naphthyl ketone represented by the formula (R1 in the formula is a halogenoalkyl group having 1 to 4 carbon atoms) is preferably used. R1 in the general formula [1] is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, or t-butyl group having at least one halogen atom. . The halogen atoms are preferably chlorine atoms and bromine atoms, and when two or more halogen atoms are present, they may be the same halogen atom or different halogen atoms. Furthermore, the number of carbon atoms is 2 to 4
In the case of the alkyl group, the halogen atom may be bonded to any carbon atom. In the general formula [1], halogenoalkyl-1-naphthylketone is most preferable in terms of effectiveness.

Examples of the compound represented by the general formula [1] include chloromethyl-1 or 2-naphthyl ketone,
Bromomethyl-1 or 2-naphthylketone, chloroethyl-1 or 2-naphthylketone, bromoethyl-1 or 2-naphthylketone, chloropropyl (n- or iso)
-1 or 2-naphthylketone, bromopropyl (n- or iso)-1 or 2-naphthylketone, chlorobutyl (
n-, iso, sec- or t-)-1 or 2-naphthyl ketone, bromobutyl (n-, iso, sec-, t-)
-1 or 2-naphthyl ketones and polyhalogenoalkyl-1 or 2-naphthyl ketones corresponding to these monohalogenoalkyl-1 or 2-naphthyl ketones, among which bromomethyl-1-naphthyl ketone is particularly preferred. is suitable.

In the composition of the present invention, one type of halogenated naphthyl ketone as the component (A) may be used, or two types may be used.
You may use combinations of more than one species. In the composition of the present invention, at least one organic fungicide selected from organic halogen compounds having 3 or more carbon atoms and organic sulfur compounds is used as component (B).

[0010] Examples of the fungicide comprising the organic halogen compound include 1,4-bis(bromoacetoxy)-2-
butene, 2,2-dibromonitrilopropionamide,
Preferable examples include 2-bromo-2-nitropropane-1,3-diol. On the other hand, as a disinfectant consisting of an organic sulfur compound, for example, methylene bisthiocyanate, the general formula

[0011]

[Chemical 2]

(X1 and X2 in the formula are each a hydrogen atom or a halogen atom, and they may be the same or different from each other, or they may form a ring. )as well as

[0013]

[C3]

(R2 in the formula is a hydrogen atom, a methyl group, or a cyclic or linear hydrocarbon group having 3 to 12 carbon atoms, X3
and X4 are each a hydrogen atom or a halogen atom, and they may be the same, different from each other, or they may form a ring)
Preferable examples include compounds represented by:

A representative example of the compound represented by the general formula [2] is 4,5-dichlorodithiolan-3-one. Also, general formula [3]
Representative examples of compounds represented by include, for example, 5-
chloro-2-methyl-4-isothiazolin-3-one,
2-n-octyl-4,5-dichloroisothiazoline-
Examples include 3-one, 1,2-benzisothiazolone, and the like. In the composition of the present invention, these (B
One or more types of organic fungicides consisting of organic halogen compounds and organic sulfur compounds as component () are selected and used in combination with the halogenated naphthyl ketone as component (A). The usage ratio of component (A) and component (B) varies depending on the use and is not particularly limited, but usually (
The weight ratio of component A) and component (B) is 1:20 to 20
Each component is used in a ratio of 1:1.

[0016] The antibacterial composition of the present invention may contain other conventionally known industrial fungicides as desired, as long as the object of the present invention is not impaired. There are no particular restrictions on the formulation form of the composition of the present invention; for example, it may be a liquid solution dissolved in a solvent, a flowable agent dispersed in water as particles, a solid agent kneaded into a synthetic resin, or a solid agent impregnated into a carrier. It can be used as a molding agent, etc. When dissolved in a solvent to form a liquid agent, examples of the solvent include glycol ethers such as diethylene glycol monomethyl ether and ethylene glycol monomethyl ether, glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and polyethylene glycol; Examples include dimethylformamide, dimethyl sulfoxide, and water. 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 used as an industrial antibacterial agent, but it is generally used for slime control in cooling water systems and paper and pulp factories, and for starch, casein, and latex. ,
Suitable for use in preserving pigments, adhesives, paints, cutting oils, fibers, building materials, wood, leather, plastics, etc. The amount of the composition of the present invention to be added is appropriately selected depending on the type of object to which the composition is applied, but usually when the object is pulp and paper making, that is, when used as a slime control agent, both components are The total amount is 1 to 100μg/
ml, or when used in other fields, it is preferably selected so that it is 10 to 3,000 μg/ml. Further, as for the addition method, both components may be added in predetermined proportions, or a mixture of both components in predetermined proportions may be added.

[0018]

EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.

Examples 1 to 9 Antibacterial compositions shown in Table 1 were prepared, and their performance was investigated in Test Examples 1 and 2.

[0020]

[Table 1]

(Note) KATHON886: 5-chloro-2-methyl-4-isothiazolin-3-one (manufactured by Rohm and Haas)

Comparative Examples 1 to 10 Antibacterial compositions shown in Table 2 were prepared, and their performance was investigated in Test Examples 1 and 2.

[0023]

[Table 2]

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

Test Example 1 Microbial Growth Inhibition Test Using white water from a certain paper mill, the microbial growth inhibiting efficacy of various antibacterial compositions prepared in Examples and Comparative Examples was compared. Add 10 wt% of bouillon liquid medium to white water and adjust the pH to 5.
5, the antibacterial agent composition of the example had a concentration of 15 ppm.
The antibacterial agent composition of the comparative example was added at a concentration of 20 ppm, and the antibacterial agent composition of the comparative example was added to a biophoto recorder (manufactured by Toyo Sokki Co., Ltd.) at 30°C.
was cultured using. The results are shown in Table 3 as the time at which turbidity began to appear for each antibacterial composition.

[0026]

[Table 3]

Table 3 shows that the antibacterial agent composition of the present invention has a higher microbial growth inhibiting effect than that of the comparative example even though the addition temperature is lower, confirming the significance of the present invention.

Test Example 2 Potential test for long-term use A preservative test for starch used in paper mills was carried out using the abuse method. To the cationic starch slurry (20 wt%), 200 ppm of the antibacterial agent compositions of Examples and Comparative Examples and 0.1 wt% of activated sludge supernatant liquid were added as seed bacteria, and cultured at 30°C. An additional 0.1 wt% was added. At this time, the number of viable bacteria was measured on a bouillon agar medium immediately before additional addition. Also, apply 200pp of antibacterial composition every two weeks.
m was added to investigate the possibility of repeated use. The results are shown in Table 4.

[0029]

[Table 4]

(Note) Number of viable bacteria of seed culture: 5.2×107
CFU/ml Table 4 confirms that the antibacterial composition of the present invention can be used for a long period of time.

[0031]

Effects of the Invention The antibacterial agent composition of the present invention is a combination of a halogenated naphthyl ketone and a bactericide consisting of an organic halogen compound or an organic sulfur compound, and has a lower concentration than when each agent is used alone. It is effective and can be used for a longer period of time.

Claims (1)

[Claims] Claim 1: (A) a halogenated naphthyl ketone;
) An antibacterial agent composition comprising at least one organic fungicide selected from organic halogen compounds having 3 or more carbon atoms and organic sulfur compounds.