JPH0813726B2 - Industrial antibacterial agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a halogenated acetic acid ester represented by the general formula (I) and 4,5-dichloro-2- (2-) represented by the formula (II).
The present invention relates to a novel industrial antibacterial agent containing octylisothiazolin-3-one (hereinafter sometimes abbreviated as "DOIT") and utilizing the synergistic effect of both.

The antibacterial agent is suitably used for industrial water systems related to the pulp and paper industry and cooling water for various industries.

(Prior art and problems) Conventionally, in various water systems such as waste water from the papermaking process in the pulp and paper industry, circulating cooling water in various industrial fields, water-based paints and papers produced using industrial water For coating liquids, latex, printing paste, leather, etc.,
Microbes that are harmful to them are rapidly propagated, which causes a decrease in productivity and quality.

Especially in water systems in the pulp and paper industry, recently,
A slime is generated by the multiplication of filamentous fungi and yeasts, and a channel where the pulp slurry flows, especially a rough wall surface where the slurry contacts, a chest, a flow box, a transport pipe, and other places where the flow velocity of the pulp slurry becomes low and stagnates. At, slime is deposited. This slime is often detached, causing paper scraps and paper pulp product contamination, as well as causing various disorders due to microbial growth.

The occurrence of such a failure becomes a particularly serious problem when using a high-speed machine, resulting in a significant decrease in productivity and economic loss.

Furthermore, even in the circulating water system for cooling the metalworking fluid,
Microbes proliferate and hinder the cooling performance and emulsifying ability of processed oils, and also produce an offensive odor, deteriorating the working environment, and causing undesirable phenomena in public health.

Further, in the cooling water system, the growth of microorganisms and the production of slime may cause a decrease in heat transfer efficiency of the heat exchanger and a blockage of the flow path.

Other obstacles due to the reproduction of harmful microorganisms are water-based paints,
It is also found in industrial products such as paper coating fluids, polymer latex, paper pulp, glue, leather, and metalworking fluids.

By the way, as the chemicals for suppressing or controlling the generation of harmful microorganisms in the water system or the industrial products, for example, organic metal compounds, organic chlorine compounds, organic sulfur compounds, quaternary ammonium salt compounds have hitherto been used. Although such compounds have been used, these compounds are toxic to the human body, emit a foul odor and a strange odor, and cause undesirable phenomena such as firing. In addition, these control agent-containing water systems adversely affect fish and shellfish when they are thrown into general rivers or the sea, and cause environmental conservation problems.

(Object, Structure and Effect of the Invention) The present inventors have completed the present invention as a result of intensive studies to eliminate the above-mentioned drawbacks of industrial antibacterial agents.

 That is, the present invention is as follows.

The following general formula (In the formula, X represents halogen, R represents an alkylene group, and an alkenylene group.) And a halogenated acetic acid ester represented by the following formula: An industrial antibacterial agent characterized by containing 4,5-dichloro-2-octylisothiazolin-3-one represented by the formula (1) in a weight ratio of (1: 100) to (100: 1).

The halogenated acetic acid ester, which is one component in the present invention, is a compound known per se, and when it is used alone, the activity is significantly inferior to bacteria and yeasts, and the desired effect can be obtained even in filamentous fungi at low concentration. I can't.

Similarly, 4,5-dichloro-2-octylisothiazolin-3-one is a compound known per se, and by itself, a desired effect can be obtained at low concentrations on yeasts, bacteria and filamentous fungi. Absent.

The industrial antibacterial agent of the present invention exerts an extremely excellent antibacterial action that cannot be expected at all by the constituent component alone, and is a harmful microorganism, filamentous fungi, bacteria, yeast, etc.,
It has a wide range of application regardless of its type.

Hereinafter, the industrial antibacterial agent of the present invention will be described in detail.

Examples of the compound of the general formula (I) in the present invention include the following.

Compound (1) Compound (2) Compound (3) Compound (4) The above halogenated acetic acid ester is not limited to one type, and two or more types may be used in combination. The content weight ratio of the compound of general formula (I) and DOIT is (1: 100) to (1
00: 1), preferably (1:50) to (50: 1).

Too little of either will not achieve a satisfactory effect.

The industrial antibacterial agent of the present invention is basically produced by uniformly mixing the above two components.

Generally, it is used as an aqueous solution, a solvent solution, an emulsion dispersion, or the like.

Examples of the solvent that can be used here include alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents and the like. In addition, the industrial bactericide of the present invention may be used by supporting it on any carrier, and the use mode is not particularly limited, and various methods can be adopted.

The amount added when using an industrial antibacterial agent varies depending on the concentration of microorganisms, but generally 0.01 to 100 ppm in the case of water-based systems in the fields of the pulp and paper industry, and in the case of fields such as water-based paints, glues and leather. It is 1 to 500 ppm, and a good bactericidal effect can be obtained at this level.

To the industrial antibacterial agent of the present invention, a stabilizer, a surfactant and the like may be added within a range that does not impair the object of the present invention.

(Examples and Comparative Examples) Industrial antibacterial agents were produced by the following formulations. All parts in the examples are parts by weight.

Example 1 1,2-Bis- (bromoacetoxy) ethane 25 parts DOIT 5 parts Diethylene glycol monomethyl ether (solvent) 68 parts Lapizole B-80 (surfactant, NOF Corporation) 2 parts Example 2 1,4- Bis- (bromoacetoxy) butene 25 parts DOIT 5 parts Diethylene glycol monomethyl ether 68 parts Lapizole B-80 2 parts Comparative Example 1 1,2-bis- (bromoacetoxy) ethane 30 parts Diethylene glycol monomethyl ether 68 parts Lapizole B-80 2 parts Comparative Example 2 1,4-bis- (bromoacetoxy) butene 30 parts Diethylene glycol monomethyl ether 68 parts Lapizole B-80 2 parts Comparative Example 3 DOIT 30 parts Diethylene glycol monomethyl ether 68 parts Lapizole B-80 2 parts Comparative Example 4 2-octyl -4-Chloro-3-isothiazolone 30 parts Diethylene glycol monomethyi Luther 68 parts Lapizole B-80 2 parts Comparative Example 5 2-Benzyl-4,5-dichloro-3-isothiazolone 30
Part Diethylene glycol monomethyl ether 68 parts Lapizole B-80 2 parts (Effect test) Regarding the industrial antibacterial agents produced in the above Examples 1-2 and Comparative Examples 1-5, the microbial growth inhibitory concentration and slime were measured by the following test methods. The occurrence prevention effect and the antibacterial effect were examined (hereinafter,% means% by weight).

Test Example 1 [Microbial growth inhibitory concentration test] The composition of the medium used was peptone 0.1%, glucose 0.05%,
0.01% potassium phosphate and 0.005% magnesium sulfate
Is a mixed aqueous solution of. The test method is as follows. Suspend the following test bacteria in the prepared culture solution, put a certain amount of this in a clean test tube, and put an industrial antibacterial agent at a specified concentration of 5, 10, 20, 40, and 80 ppm in each tube. After the addition, shaking culture was performed at 32 ° C. twenty four
The degree of microbial growth was determined by the turbidity caused by the reproduction of the bacteria after a lapse of time. The one in which no growth of bacteria was observed was observed, and the concentration was defined as the complete growth inhibitory concentration of the microorganism.

 The results are shown in Table 1.

 The abbreviations of the test bacteria are as follows.

Test bacteria Pse: Pseudomonas aeruginosa Aa: Aerobactor aerogenes Bs: Bacillus subtillis Av: Alcaligenes viscosu An: Aspergillus niger G.sp: Geotrichum sp. As is clear from Table 1 above, the industrial antibacterial agent (Examples 1 and 2) of the present invention was 10 ppm against any of the test bacteria.
It can be seen that, while the effect is exhibited at the following low concentrations, the comparative example cannot uniformly obtain an effective effect on all the test bacteria.

Test Example 2 [Test for Prevention of Bacterial Proliferation and Slime Generation in Wastewater After Paper Making Process] In the paper making process of a paper mill, the industrial antibacterial agent produced in the above Examples 1 to 2 and Comparative Examples 1 to 5 was applied to a white water bit.
The number of microorganisms in white water was measured by adding the solution to the concentration in water of 20 ppm for 7 days over 2 hours and 3 times.

As a test method, a sample of white water was diluted with sterilized water, a certain amount of this was sampled in a petri dish, and dissolved Waxman agar medium was injected, mixed, and solidified into a flat plate. Microbial colonies generated after culturing in an incubator (32 ° C) for 2 days were measured with a colony counter. Also, measure the number of paper breaks during papermaking,
The bactericidal effect was confirmed.

From the results in Table 2 above, it can be seen that the industrial antibacterial agents of the present invention (Examples 1 and 2) have an excellent bacteriostatic effect.

Test Example 3 [Bacterial growth prevention test in a papermaking coating solution] To a starch-based coating solution having a pH of 9.0, a broth liquid medium and a previously spoiled coating solution were added and stirred, and the concentration was adjusted to 300 ppm as described above. The manufactured antibacterial agent was added.

After storing this in a thermostat at 32 ° C. for 5 days, the number of viable bacteria in each coating solution was measured. The results are shown in Table 3 below.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeru Kurose 4-11-2 Ginza, Chuo-ku, Tokyo Somer Co., Ltd. (56) References JP-A-54-44024 (JP, A) JP-A-60 -1102 (JP, A)

Claims (1)

[Claims] 1. The following general formula (Wherein, X represents halogen, R represents an alkylene group or an alkenylene group), and a halogenated acetic acid ester represented by the following formula: An industrial antibacterial agent characterized by containing 4,5-dichloro-2-octylisothiazolin-3-one represented by the formula (1) in a weight ratio of (1: 100) to (100: 1).