JPH07121846B2 - Industrial antibacterial agent - Google Patents

Description

The present invention relates to a halogenated aliphatic nitroalcohol represented by the general formula (I) and 4,5-dichloro-2-octylisothiazoline represented by the formula (II). -3-ON (hereinafter "DO
It is sometimes abbreviated as "IT") and utilizes a synergistic effect of the two.

This industrial antibacterial agent is an industrial water related to the pulp and paper industry,
It is preferably used for cooling water for various industries.

(Prior art and problems) Conventionally, wastewater from the papermaking process in the pulp and paper industry,
In various water systems such as circulating cooling water in various industrial fields, it is harmful to water-based paints, coating liquids for paper, latex, printing paste, leather, etc. made using industrial water. It is easy for various microorganisms to multiply and proliferate, which causes a decrease in productivity and quality.

In particular, in the water system in the pulp and paper industry, slime has recently been generated due to the multiplication of filamentous fungi and yeasts, and the channel in which the pulp slurry flows, especially the rough wall or chest where the slurry contacts, the flow box, the transport pipe, In addition, slime is deposited and formed in a place where the flow velocity of the pulp slurry becomes low and stagnates. 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.

Further, even in a circulating water system for cooling metalworking oil agents, microorganisms multiply and hinder the cooling performance and emulsifying properties of the oilworking agents, and a bad odor is generated, which worsens the working environment and is a phenomenon unfavorable to public health. Is caused.

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 propagation of harmful microorganisms are also found in industrial products such as water-based paints, paper coating fluids, polymer latex, paper pulp, glue, leather and metalworking fluids.

By the way, as the water system, or as a drug for suppressing or controlling the generation of harmful microorganisms in the industrial product,
So far, for example, organometallic compounds, organochlorine compounds,
Organic sulfur compounds, quaternary ammonium salt compounds, etc. have been used, but these compounds are toxic to the human body, and emit an offensive odor or offensive odor. Occurs. 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 (Wherein R ¹ and R ² are hydrogen atom, halogen atom, alkyl group, hydroxyalkyl group, and X is a halogen atom), and a halogenated aliphatic nitroalcohol represented by the following formula An industrial antibacterial agent characterized by containing 4,5-dichloro-2-octylisosiazolin-3-one represented by the formula (10) in a weight ratio of (10: 1) to (1:10).

The halogenated aliphatic nitroalcohol which is one component in the present invention is a compound known per se, and when it is used alone, it is extremely inferior in activity to filamentous fungi and yeasts, and is desirable in low concentration against bacteria. No effect.

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, by itself, exhibits extremely excellent antibacterial action that cannot be expected at all, and also against harmful fungi such as filamentous fungi, bacteria and yeasts,
It has a wide range of application regardless of its type.

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

2-chloro-2-nitroethanol, 1-chloro-1-
Nitropropanol- (2), 3-chloro-3-nitrobutanol- (2), 2-chloro-2-nitrobutanediol- (1.3), 1-chloro-1-nitrobutanol- (2), 2 -Chloro-2-nitrobutanol, 2-
Chloro-2-nitropentanol (3), 2.2-dichloro-2-nitroethanol, 2-chloro-2-bromo-2-nitroethanol, 3-chloro-3-pentanediol- (2.4), 4 -Chloro-4-nitrohexanol- (3), 2-bromo-2-nitroethanol, 2
-Bromo-2-nitropropanol- (3), 2-bromo-2-nitrobutanediol- (1.3), 3-bromo-3-nitropentanediol- (2.4), 2.2
-Dibromo-2-nitro-ethanol, 1.1-dibromo-1-nitro-propanol- (2), 4-bromo-
4-nitrohexanol- (3), 2-fluoro-2-
Nitroethanol, 2-fluoro-2-nitrobutanediol- (1.3), 3-iodo-3-nitrobutanol (2), 2-fluoro-2-chloro-2-nitroethanol, 2-iodo-2- Bromo-2-nitroethanol, 2-chloro-2-nitro-propanediol- (1
・ 3), 2-bromo-2-nitro-propanediol-
(1.3) and the like.

The halogenated aliphatic nitro alcohol is not limited to one type, and two or more types may be used in combination.

The above content ratio by weight with the compound of formula (I) (1:10) to (1
0: 1), preferably (1: 5) to (5: 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 addition amount 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, in the case of fields such as water-based paints, glues, and leather. 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) An industrial antibacterial agent was produced by the following formulation. All parts in the examples are parts by weight.

Example 1 2-Bromo-2-nitro-propanediol- (1,3) 1
0 part DOIT 10 parts Diethylene glycol monomethyl ether (solvent) 78 parts Solpol 900A (surfactant, manufactured by Toho Chemical Co., Ltd.) 2 parts Example 2 2,2-dibromo-2-nitroethanol 10 parts DOIT 10 parts diethylene glycol monomethyl ether 78 parts Solpol 900A 2 parts Example 3 1,1-dibromo-1-nitropropanol- (2) 10 parts DOIT 10 parts Diethylene glycol monomethyl ether 78 parts Solpol 900A 2 parts Example 4 2,2-dibromo-2-nitroethanol 15 parts DOIT 5 parts Diethylene glycol monomethyl ether 78 parts Solpol 900A 2 parts Comparative Example 1 2-Bromo-2-nitro-propanediol- (1,3) 2
0 part Diethylene glycol monomethyl ether 78 parts Solpol 900A 2 parts Comparative Example 2 2,2-dibromo-2-nitroethanol 20 parts Diethylene glycol monomethyl ether 78 parts Solpol 900A 2 parts Comparative Example 3 1,1-dibromo-1-nitropropanol- ( 2) 20 parts Diethylene glycol monomethyl ether 78 parts Solpol 900A 2 parts Comparative Example 4 DOIT 20 parts Diethylene glycol monomethyl ether 78 parts Solpol 900A 2 parts Comparative Example 5 2-Bromo-2-nitro-propanediol- (1,3) 1
0 parts 5-chloro-2-octylisothiazolin-3-one 10
Part Diethylene glycol monomethyl ether (solvent) 78 parts Solpol 900A (surfactant, manufactured by Toho Kagaku) 2 parts Comparative Example 6 2-Bromo-2-nitro-propanediol- (1,3) 1
0 part 4,5-dichloro-2-octylisothiazolin-3-one 10 parts Diethylene glycol monomethyl ether (solvent) 78 parts Solpol 900A (surfactant, manufactured by Toho Chemical Co., Ltd.) 2 parts (effect test) Examples 1 to 4 above And the industrial antibacterial agents produced in Comparative Examples 1 to 6 were examined for microbial growth inhibitory concentration, slime generation preventing effect, and preservative effect by the following test methods (hereinafter,% means% by weight).

Test Example 1 [Microbial growth inhibitory concentration test] The composition of the culture medium used is a mixed aqueous solution of peptone 0.1%, glucose 0.05%, potassium primary phosphate 0.01% and magnesium sulfate 0.005%. The test method is to suspend the following test bacteria in the adjusted culture solution, take a certain amount of this in a clean test tube,
A bacteriostatic agent having a specified concentration of 5, 10, 20, 40, and 80 ppm was added to the mixture, and the culture was carried out at 32 ° C. with shaking. The degree of microbial growth was determined by the turbidity caused by the reproduction of the bacteria after 24 hours. 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.

Sample bacteria Pse: Pseudomonas aeruginosa Aa: Aerobactor aerogenes Bs: Bacillus subtillis Av: Alcaligenes viscosus An: Aspergillus niger G.sp: Geotrichum sp. (Note 2) + indicates complete growth of the test bacteria.

As is clear from Table 1 above, the industrial antibacterial agents of the present invention (Examples 1 to 4) are effective against any of the test bacteria at a low concentration of 10 ppm or less. In the examples, it can be seen that it is not possible to obtain a uniformly 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 certain paper mill, the industrial antibacterial agents produced in Examples 1 to 4 and Comparative Examples 1 to 4 were used as white water bits. The number of microorganisms in the 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 white water sample was diluted with sterilized water, a certain amount of this was taken 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 coefficient device. Also, measure the number of paper breaks during papermaking,
The bactericidal effect was confirmed.

From the results shown in Table 2 above, it can be seen that the industrial antibacterial agents of the present invention (Examples 1 to 4) 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 industrial 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.

Front page continuation (72) Inventor Shigeru Kurose 4-11-2 Ginza, Chuo-ku, Tokyo Somer Co., Ltd. (56) Reference JP-A-53-118527 (JP, A) JP-A-62-10003 ( JP, A)

Claims (1)

[Claims] 1. The following general formula (Wherein R ¹ and R ² are hydrogen atom, halogen atom, alkyl group, hydroxyalkyl group, and X is a halogen atom), and a halogenated aliphatic nitroalcohol represented by the following formula An industrial antibacterial agent characterized by containing 4,5-dichloro-2-octylisothiazolin-3-one represented by the formula (4) in a weight ratio of (10: 1) to (1:10).