JPH01197411A - Antimicrobial agent - Google Patents

Abstract

PURPOSE:To obtain an antimicrobial agent suitable for the treatment of industrial water relating to paper and pulp industries and of cooling water for various industries, by using a halogenated aliphatic nitroalcohol and 4,5-dichloro-2- octylisothiazolin-3-one as active components. CONSTITUTION:The objective agent contains (A) a compound of formula I [R<1> and R<2> are H, halogen or (substituted) alkyl; X is halogen] having extremely poor activity against molds and yeasts and giving no required effect against bacteria at a low concentration. e.g., 2-chloro-2-nitroethanol and (B) the compound of formula II giving no required effect against yeats, bacteria and molds at a low concentration. The ratio A:B is 1:10-10:1, preferably 1:5-5:1. The concentration of the antimicrobial agent in the treating object is 0.01-100ppm in the field of paper and pulp industries and 1-500ppm in the field of water- base paint, paste, etc.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a halogenated aliphatic nitroalcohol represented by general formula (1) and 4,5-dichloro-2-octylisothiazoline represented by formula (II). The present invention relates to a novel antibacterial agent containing -3-one (hereinafter sometimes abbreviated as rDOITJ) and utilizing the synergistic effect of both.

This antibacterial agent is suitably used for industrial water related to the pulp and paper industry and cooling water for various industrial uses.

(Prior art and problems) Conventionally, wastewater from the papermaking process in the Gio pulp industry,
It is harmful to various water systems such as circulating cooling water in various industrial fields, as well as water-based paints, paper coating fluids, latex, printing pastes, leather, etc. that are made using industrial water. microorganisms are likely to multiply, which causes a decline in productivity and quality.

In particular, in water systems in the pulp and paper industry, slime has recently been generated due to the proliferation of filamentous fungi and yeasts, and slime has been generated in waterways where pulp slurry flows, especially in areas with rough walls that come in contact with slurry, chests, flow boxes, transport pipes, etc. In other places where the flow rate of the pulp slurry is low and stagnates, slime is formed. This slime often detaches, causing paper breakage and contamination of Gion valve products, as well as causing various problems due to the growth of microorganisms.

The occurrence of such failures becomes a particularly serious problem when high-speed machines are used, resulting in a significant decrease in productivity and economic loss.

Furthermore, in the circulating water system for cooling metal processing fluids, microorganisms multiply and multiply, impairing the cooling performance and emulsifying properties of processing fluids, and producing bad odors, deteriorating the working environment, which is an undesirable phenomenon in terms of public health. is causing the

In addition, in a cooling water system, when microorganisms multiply and slime is generated, it causes a decrease in heat transfer efficiency of a heat exchanger and blockage of flow paths.

Other problems caused by the growth of harmful microorganisms occur in industrial products such as water-based paints, paper coatings, polymer latex, paper pulp, glues, leather, and metalworking fluids.

By the way, the agents for suppressing or controlling the occurrence of harmful microorganisms in the water system or the industrial products include:
Until now, 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, emit bad odors and strange odors, and even cause undesirable phenomena such as firing. arise. In addition, when these pesticide-containing water systems are sprayed into rivers, oceans, etc., they have an adverse effect on fish and shellfish, causing problems in terms of environmental conservation.

(Object, structure, and effect of the invention) The present inventors have completed the present invention as a result of extensive research in order to eliminate the above-mentioned drawbacks of antibacterial agents.

That is, the present invention is as follows.

An aliphatic nitroalcohol represented by the following general formula (wherein R' and R2 are a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and X represents a halogen atom) and an aliphatic nitroalcohol represented by the following formula. and 4,5-dichloro-2-octylisothiazolin-3-one (10:1) to (1:10)
An antibacterial agent characterized in that it is contained in a weight ratio of .

The activity is significantly inferior to that of parent organisms, and the desired effect cannot be obtained even at low concentrations against bacteria.

At low concentrations, the desired effect cannot be obtained against species, bacteria, and filamentous fungi.

The antibacterial agent of the present invention exhibits an extremely excellent antibacterial effect that cannot be expected from the constituent components alone, and is effective against harmful microorganisms such as filamentous fungi, bacteria, and yeast, regardless of their types. Has a wide range of application.

As the compound of general formula (I) in the present invention, the following can be exemplified.

2-chloro-2-nitroethanol, l-chloro-1-
Nitropropanol-(2), 3-chloro-3-nitrobutanol-(2), 2-chloro-2-nitrobutanediol-(1・3), 1-chloro-1-nitrobutanol-(2), 2-chloro-2-nitrophtanol, 2-
Chloro-2-nitropenknol (3), 2,2-dichloro-2-nitroethanol, 2-chloro-2-bromo-2-nitroethanol, 3-chloro-3-pentanediolu (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-nitropencundiol-(2.4), 2.2
-dibromo-2-nitroethanol, 1,1-dibromo-1-nitro-propano-71/-(21,4-7'
Lomo-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) etc. can be mentioned.

The above-described halogenated aliphatic nitroalcohols are not limited to one type, and two or more types may be used in combination.

The content weight ratio of the compound of formula (1) and nenjin = -1 (
1:10) to (10:1), preferably (1:5) to
(5:1).

If either one is too small, a satisfactory effect cannot be achieved.

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

- For boat fishing, it can be used as an aqueous solution, solvent solution, emulsified dispersion, etc.

Examples of solvents that can be used here include alcohol solvents, ketone solvents, ether solvents, and hydrocarbon solvents. Further, the industrial disinfectant of the present invention may be used by being supported on any carrier, and there are no particular restrictions on the mode of use, and various methods can be adopted.

The amount of antibacterial agent added varies depending on the microbial concentration, but is 0.01 to 1100 pp for water systems in fields such as boat fishing and paper and pulp industry.

1 to 500 ppm for water-based paints, glues, leather, etc.
A good sterilizing effect can be obtained at this level.

There is no problem in adding stabilizers, surfactants, etc. to the antibacterial agent of the present invention as long as the purpose of the present invention is not impaired.

(Examples and Comparative Examples) Antibacterial agents were manufactured using the following formulation. All parts in the examples indicate parts by weight.

Example 1 2-Bromo-2-nitro-propane 10 parts Diol-(1,3) DOIT 10 parts Diethylene glycol monomethyl 78 parts Ether (solvent) Tsurpol 900A (surfactant, 2 parts manufactured by Toho Chemical Co., Ltd.) Example 2 2 .2-Dibromo-2-nitroeta 10 parts Nol DOIT 10 parts Diethylene glycol monomethyl 78 parts Ether Tsurpol 900A 2 parts Example 3 1.1-dibromo-1-nitropro 10 parts Panol (2) DOITIO part Diethylene glycol 7-methyl 78 parts Ether Tsurpol 900A 2 parts Example 4 2.2-Dibromo-2-nitroeta 15 parts Nol DOIT 5 parts Diethylene glycol 7-methyl 78 parts Ether Tsurpol 900A 2 parts Comparative Example 1 2-7'Romo-2-nitro-propane 20 Diol-(1,3) 78 parts Ether Tsurpol 900A 2 parts Comparative Example 2 2.2-dibromo-2-nitroeta 20 parts Nordiethylene glycol monomethyl 78 parts Ether Tsurpol 900A 2 parts Comparative Example 3 1.1 -Dibromo-1-nitropro 20 parts Panol-(2) Diethylene glycol monomethyl 78 parts Ether Tsurpol 900A 2 parts Comparative Example 4 DOIT 20 parts Diethylene glycol 78 parts Methyl 78 parts Ether Tsurpol 900A 2 parts (Efficacy test) Above Examples 1- 4 and Comparative Examples 1 to 4, the microbial growth inhibitory concentration, slime generation prevention effect, and antiseptic effect were investigated using the following test methods (hereinafter,
% indicates weight %. ).

Test Example 1 [Microbial Growth Inhibitory Concentration Test] The composition of the medium used was a mixed aqueous solution of 0.1% peptone, 0.05% glucose, 0.01% potassium phosphate, and 0.005% magnesium sulfate. The test method is to suspend the following test bacteria in the prepared culture solution, take a certain amount of this into a clean test tube, and add the antibacterial agent at the specified concentration of 5, 10, 20, 40, and 80 ppm to each tube. and cultured with shaking at 32°C.

The degree of growth of the microorganisms was determined based on the turbidity produced by the proliferation of the bacteria after 24 hours. The concentration that completely inhibits the growth of microorganisms was determined by observing when no microorganisms were observed to grow.

The results are shown in Table 1.

The bacterial name abbreviations of the test bacteria are as follows.

Test bacteria Pse: Pseudomonas aerugi
nosaA, a: Aerobacter a
erogenesB,s: Bacillus
5ubtillisA,v: Alcalig
enes viscosesA,n: Asp
ergillus nigerG, sp: Ge
otrichum sp.

Table 1 (Note 1) Values indicate the minimum concentration (ppm) that completely inhibits growth.

(Note 2) + indicates complete growth of the test bacteria.

As is clear from Table 1 above, the antibacterial agent of the present invention (Examples 1 to 4) is effective against all test bacteria at a low concentration of 10 ppm or less, whereas in the comparative example It can be seen that it is not possible to obtain a uniformly effective effect on all test bacteria.

Test Example 2 [Bacterial growth prevention and slime generation prevention test in wastewater after papermaking process] The antibacterial agents produced in Examples 1 to 4 and Comparative Examples 1 to 4 above were applied to white water bits for one day in the papermaking process of a certain papermaking factory. The solution was added three times for 2 hours for 7 days so that the water concentration was 20 ppm, and the number of microorganisms in the white water was measured.

The test method involved diluting a white water sample with sterilized water, taking a quantitative amount of this in a Petri dish, and pouring dissolved Waxman agar medium into it, mixing it, and solidifying it into a flat plate.

After culturing in a thermostatic chamber (32° C.) for 2 days, microbial colonies generated were measured using a colony counter. The number of paper breaks during papermaking was also measured to confirm the bactericidal effect.

Table 2 From the results in Table 2 above, the antibacterial agent of the present invention (Examples 1 to 4)
) was found to have an excellent effect of inhibiting bacterial growth.

Test Example 3 [Bacterial growth prevention test in papermaking coating fluid] pH
A bouillon liquid medium and a previously spoiled coating solution were added to a 10.0 starch-based coating solution, stirred, and the antibacterial agent produced above was added to the solution to a concentration of 300 ppm Ff.

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.

Table 3

Claims (1)

[Claims] The following general formula ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼... (I) (In the formula, R^1 and R^2 are hydrogen atoms, halogen atoms,
The alkyl group which may have a substituent, and X represents a halogen atom. ) and 4,5-cyclo-2-octylisothiazolin-3-one (10:1 ) to (1:10) by weight.