JPS60139601A - Antimicrobial agent - Google Patents

Abstract

PURPOSE:An antimicrobial agent showing improved antimicrobial action on harmful microorganisms even at low concentration by synergistic action, not causing decomposition, change in color, etc. during long-term storate, comprising a 3-halogeno-3-nitro-2,4-pentane diol and another compound as active ingredients. CONSTITUTION:A well-known 3-halogeno-3-nitro-2,4-pentanediol is blended with an isothiazolone complex compound shown by the formula [R<1> is H, or (substituted) monofunctional hydrocarbon group; R<2> and R<3> are H, or halogen; M is metal cation such as Zn, Cu, Ni, Mn, etc. or ammonium; x is anion forming complex compound; a is 1 or 2; b is integer wherein anion X satisfies valence of cation M] or an isothiazolone derivative complex compound such as 5-chloro-2- methyl-3-isothiazolone magnesium nitrate, etc., to give active ingredients. EFFECT:Having the same uniform antimicrobial action on various molds as that of initial stage even after storage.

Description

[Detailed description of the invention] □ The present invention provides a novel antibacterial agent.

Traditionally, industrial water has been used for water systems such as wastewater from the papermaking process in the papermaking industry and circulating cooling water in various industrial fields. In liquids, latex, printing pastes, leather, etc., harmful microorganisms tend to multiply, causing a decline in productivity and quality.

In particular, in water systems in the pulp and paper industry, slime is generated due to the multiplication and proliferation of bacteria, fungi, and yeasts, and even in waterways where pulp slurry flows, there are places where the slurry comes in contact with rough walls, chests, flow areas, transportation high points, etc. Slime adheres to and forms over time at the slurry contact areas where the flow rate of the lupus slurry decreases and stagnates, and this slime often separates and causes contamination of paper pieces and paper pulp products. In addition, various problems are occurring due to the proliferation of microorganisms.

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

In addition, microorganisms multiplied in the circulating water system for cooling metal processing fluids, inhibiting the cooling performance and emulsifying properties of processing fluids.
In addition, bad odors are generated, deteriorating the working environment and causing undesirable phenomena in terms of public health.

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

Therefore, as agents for suppressing or controlling the occurrence of harmful microorganisms in water systems or the above-mentioned industrial products,
Until now, for example, organometallic compounds, organochlorine compounds,
Organic sulfur compounds, quaternary ammonium salt compounds, etc. have been developed, but these compounds are toxic to the human body, emit bad odors, and even cause undesirable phenomena such as foaming. arise. In addition, when water systems containing pesticides are treated with these pesticides and exposed to rivers, oceans, etc., they have a negative impact on fish and shellfish, causing problems in terms of environmental conservation.

The present inventor has completed the present invention as a result of extensive research into antibacterial agents in order to eliminate the above-mentioned drawbacks.

That is, the present invention provides 3-halogeno-3-2-2.4-
-An antibacterial agent containing entanediol and an isothiazolone complex compound or an isothiazolone derivative complex compound as active ingredients.

Up to now, it has been proposed to use a rhodanated aliphatic alcohol compound containing 3-halogeno-3-nitro-2°4-bentanediol alone or in combination with isothiazolone or its derivatives (JP-A-48 -484
No. 65, 53. -118527) is composed of a halogenated aliphatic alcohol compound, filamentous fungi,
There is a problem that the activity against yeasts is insufficient (significantly inferior to that of the present invention), and the desired effect cannot be obtained against bacteria at low concentrations. When used alone, it is difficult to achieve a satisfactory antibacterial effect unless used at high concentrations. On the other hand, if you use both in combination, you can expect some effect even at a low concentration immediately after preparation, but on the other hand, over time, each component will decompose and the antibacterial effect will decrease significantly, which is a fatal problem. Blame the flaws.

On the other hand, an antibacterial agent comprising 2-bromo-2-nitro-1,3-propanediol and an isothiazolone complex compound or an isothiazolone derivative complex compound is also known (Japanese Patent Publication No. 58
-4682'). Although this product does indeed exhibit excellent antibacterial effects in the initial stage even at low concentrations, there is a problem in that it cannot achieve the same effect as the initial stage unless it is used at higher concentrations over time.

The antibacterial agent of the present invention exhibits an extremely excellent antibacterial effect against harmful microorganisms such as filamentous fungi, bacteria, yeast, etc., irrespective of the type thereof, which cannot be expected from the constituent components alone, and also has a long-term effect. Even during storage, it does not cause decomposition, discoloration, etc., but even after storage, it has the same antibacterial effect as the initial one against various bacteria. - Hereinafter, the antibacterial agent of the present invention will be explained in detail.

First, 3-halogeno-3-nitro-2,
As 4-bentanediol, for example, 3-chloro-3
- ditro 2,4-intanediol, 3-bromo 3
-Nitro-2,4-pentanediol can be mentioned, but in the present invention, 3-bromo-3-nitro-2,4-pentanediol is preferred.

Such 3-halogeno-3-nitro-2.4-intanediol is a known compound and can be synthesized by known methods.

The following is an inthiazolone complex compound or an inthiazolone derivative complex used in the present invention.

In the formula, R1 represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and includes alkyl groups such as methyl, ethyl, propyl, and octyl groups, and alkenyl groups such as vinyl and allyl groups. , an alkynyl group such as a gulonolgyl group, an a+7-al group such as a phenyl group, a tolyl group,
Examples include aralkyl groups such as 2-phenylethyl groups, and groups in which the hydrogen atoms of these groups are partially substituted with halogen atoms or other arbitrary organic groups.

Further, HM and R3 each represent a hydrogen atom or a halogen atom, and examples thereof include a chlorine atom, a bromine atom, an iodine atom, and the like. In addition, Bt and HM may be the same or different.

M is a metal cation or ammonium, and examples of the 6-cation include magnesium, copper, calcium, zinc, manganese, iron, and nickel.

Further, examples of the anion forming the complex compound represented by X include chloride salt, odor salt, trichloride salt, iodide salt, sulfate salt, nitrate salt, acetate salt and the like.

a is 1 or 2, b is an anion, and y is an integer such that X satisfies the cation MOi valence.

Examples of the isothiazolone complex compound or isothiazo,ron derivative complex compound represented by the above general formula include 5-
Chloro-2-methy2-3-inchazolone magnesium nitrate, 2? -Methyl-3-inchazolone magnesium nitrate, 4-! Coro-2-:! Cutyl, -3-inchazolone calcium (I[) chloride, etc. can be added.

When using the above-mentioned 3-hydrano-3-nitro-2-4-, ntandiol and inothiazolone complex compounds, they are not divided into only one type, but seven types. There is no need to say that the above may be used in combination.

The most preferred composition in the present invention is that one component is 3-bromo-3-nitro-2,4-47tanediol and the other component is 5-chloro-2-methyl-3-isothiazolone magnesium nitrate) or U5-chloro 2-methyl-3-inchazolone magnesium nitrate. , 3-20 mo 3-nitro 2. The blending ratio of bentanediol and isothiazolone complex compound is 1/10710/
1, preferably 115 to 5/1 (weight ratio). If either one is too small, a satisfactory effect cannot be achieved.

The antibacterial agent of the present invention is basically prepared by uniformly mixing the two components described above, but it is generally used as an aqueous solution, a solvent solution, an emulsified dispersion, etc. Ru.

Examples of solvents that can be used here include alcohol solvents, ketone solvents, ether solvents, and hydrocarbon solvents. Furthermore, the antibacterial agent 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 any method can be adopted.

The amount of this antibacterial agent added varies depending on the concentration of microorganisms, but is generally 0.01 to 1100 pp for water systems used in fields such as the paper industry.

In the field of water-based paints, leather, etc., good antibacterial effects are exhibited at about 1 to 500 ppm.

However, there is no problem in adding stabilizers, surfactants, etc. to the antibacterial agent of the present invention as long as they do not impede the purpose of the present invention.

Next, examples of the present invention and comparative examples will be given.

All parts in the examples indicate parts by weight.

Example 1 A fungicide was prepared by uniformly mixing the following components.

3-promo 3-nitro 2,4-intanediol (
(hereinafter abbreviated as BNPE) 20 parts 3:1 (weight ratio) mixture of 5-chloro-2-methyl-3-inchazolone magnesium nitrate and 2-methyl-3-inchazolone magnesium nitrate 5 parts diethylene glycol 75 parts Example 2 An antibacterial agent was prepared in the same manner as in Example 1 using the following ingredients.

BNPE 20 parts 2-octyl-4-chloro-3-inothiazolone calcium (n) chloride 5 parts diethylene glycol 7
5 parts Comparative Example 1 An antibacterial agent was prepared in the same manner as in Example 1 using the following ingredients.

B N P E 25 copies Diethylene glycol 75 parts Comparative example 2 An antibacterial agent was prepared in the same manner as in Example 1 using the following ingredients.

3=1 (weight ratio) mixture of 5-chloro-2-methyl-3-inchazolone magnesium (n) nitrate and 2-methyl-3-inchazolone magnesium (n) nitrate 10 parts diethylene glycol 90 parts Comparative Example 3 An antibacterial agent was prepared from the following ingredients in the same manner as in Example 1.

2-octyl-4-chloro-3-inchazolone calcium (n) chloride 10 parts diethylene glycol
90 parts Comparative Example 4 An antibacterial agent was prepared from the following ingredients in the same manner as in Example 1.

B N P E 20 parts 3:1 (weight ratio) mixture of 5-chloro-2-methyl-3-inchazolone and 2-methyl-3-isothiazolone 5 parts Noethylene glycoV 75 parts Comparative Example 5 From the following ingredients A fungicide was prepared in the same manner as in Example 1.

2-promo 3-ditro-1,3-pronobutyldiol 20 parts 2-octyl-4-chloro-3-isothiazotetralucium(II) chloride 5 parts diethylene glycol
75 parts Next, the antibacterial agents prepared in Examples 1 to 2 and Comparative Examples 1 to 5 above were subjected to the following test methods to determine their microbial starvation inhibiting concentration, slime generation prevention effect, preservative effect, stability, etc. I looked into it.

Test 1 Microbial growth inhibitory concentration test.

The composition of the medium used is peptone 0.1%, glucose 0.05
%, potassium monophosphate 0.01% and magnesium sulfate 0.005. % mixed aqueous solution. The test method is to suspend the following test bacteria in an adjusted culture solution, place a certain amount of this into a clean test tube, and add B, 10, 20, 40°8
Add antibacterial agents at the specified concentrations of 0 ppm and heat at 32°C.
9. Perform shaking culture at After 24 hours, the degree of growth of the microorganisms was determined based on the turbidity produced by the proliferation of the microorganisms. The concentration that completely inhibits the growth of the microorganisms was determined by observing when no microorganism growth was observed. The results are shown in Table 1.

The bacterial name abbreviations in the test tubes are as follows.

Test tube A, a: A@robact@r a@rog
@n@sB, s:Bacll/us subtll
limA, v:A1ca11g@nes viaco
sesA, n:Asp@rgill/usyamaerG
, mp: Geotrichum sp (Note) + indicates complete growth of the test tube.

As is clear from Table 1 above, the antibacterial agent of the present invention (Examples 1 and 2) had a concentration of 10 ppm in all test cylinders.
While the antibacterial agents shown below are effective at low concentrations, all of the antibacterial agents used in Comparative Examples 1 to 3 are not effective unless used at low concentrations, and Comparative Example 5 They are effective at low concentrations for certain types of test cylinders, but need to be used at high concentrations for other test cylinders.
It can be seen that a uniformly effective effect cannot be obtained for all test tubes.

Test 2 In the papermaking process of a certain paper factory, the nine antibacterial agents prepared in Examples 1 to 2 and Comparative Examples 1 to 3 above were poured into white water bits three times for 2 hours a day until the concentration in water was 20 ppm. The number of microorganisms in the white water was measured. The test method involved diluting a white water sample with sterilized water, placing a certain 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 antibacterial effect was also confirmed by measuring the number of paper breaks during papermaking.

Table 2 From Table 2 above, it can be seen that the antibacterial agents of the present invention (Examples 1 and 2) have an excellent effect of inhibiting bacterial growth.

Test 3 Bacterial growth prevention test in paper manufacturing coating solution Add bouillon liquid medium and pre-rotted coating solution to a starch-based coating solution with a pH of 10.0 and stir. Add the antibacterial solution prepared above to a concentration of 300 ppm. agent was added. After storing this in a thermostatic chamber 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 Test 4 Storage stability test of components constituting antibacterial agents 50- of each of the anti-bacterial agents prepared in Example 1 and Comparative Example 4 was added to an internal volume of 100-
These pins were placed in a 40°C incubator for 308'. The pins were then taken out and each component constituting the antibacterial agent was analyzed using a gas chromatography lamp equipped with FID to examine the decomposition rate immediately after preparation, and the results shown in Table 4 below were obtained. It was done.

Test 5 Growth inhibitory concentration test after storage for a certain period 50 d of each of the antibacterial agents prepared in Example 1 and Comparative Example 4 were placed separately in brown pins with an internal volume of 100'' and these bottles were placed in a thermostat at 40°C. The antibacterial agents were left to stand for 15 or 30 days.The growth-inhibiting concentrations of the antibacterial agents against various test bacteria were investigated, and the results shown in Table 5 below were obtained.

From Table 5 above, even after storage for 15 or 30 days, the product of the present invention has a growth-inhibiting effect on each test sample at a concentration similar to that immediately after preparation, whereas the product of the comparative example It can be seen that the antibacterial agent has a good growth inhibiting effect immediately after preparation, but after storage, the growth inhibiting effect cannot be obtained unless it is used in large quantities.

Patent applicant Somar Kogyo Co., Ltd. Representative Patent Attorney Tsuchii Department 3

Claims (4)

[Claims] (1) A fungicide characterized by containing 3-haloeth-3-nitro-2,4-be as an active ingredient. (2) 3-ha-gutu 3-nitro 2.4--1! The diol is 3-chloro-3-nitro-2,4-nipentanediol or 3-promo-3-ethro-2,4-
-'! The antibacterial agent according to claim 1, which is tantanediol. □ (3) The antibacterial agent according to claim 1, which is a compound represented by isothiazolone complex compound paternal isothiazo. In formula 1, R1 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R1 and R8 are the same or different hydrogen atoms or halogen atoms, M is a golden bird cation or tetraammonium, and X forms a complex compound. anion, a is 1 or 2
, b are integers such that the anion X satisfies the valence of the cation M. (4) The antibacterial agent according to claim 3, wherein the metal cation represented by M is selected from zinc, silk, nickel, calcium, 1gnesium, iron, or mangaka.