JPH10251106A - Stabilized agent for exterminating harmful microorganism - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject exterminating agent having a good stability and manifesting a sufficient antimicrobial and microbicidal activities when used by formulating a specific compound of a specified proportion to an aqueous solution containing an isothiazolone-based compound. SOLUTION: The objective compound is obtained by formulating (B) 0.05-0.9 pt.wt. 3-halogeno-3-nitro-2,4-pentanediol with (A) 100 pts.wt. aqueous solution or an aqueous dispersion containing (i) an isothiazolone-based compound and (ii) 3,3-dibromo-3-nitro-2-propanol. Preferably, the component (i) is at least one kind selected from an isothiazolone compound (e.g. 2-methyl-3-isothiazolone) and an isothiazolone complex compound (e.g. 5-chloro-2-methyl-3-isothiazolone magnesium nitrate), and the formulation weight ratio of the components (i) to (ii) is (10:1) to (1:10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel stabilized harmful microorganism-eliminating agent, and more particularly to a stabilized agent having improved stability of active ingredients and exhibiting a sufficient antibacterial and bactericidal action when used. It is related to harmful microorganisms.

[0002]

2. Description of the Related Art Conventionally, water systems in the pulp and paper industry, such as white water in the papermaking process and circulating cooling water in various industrial fields, water-based paints that require industrial water, coating solutions for paper, In the fields of latexes, polymer emulsions, printing pastes, adhesives, metalworking oils such as cutting oils, leather, wood, etc., harmful microorganisms are liable to multiply and proliferate, which causes a decrease in productivity and quality. Has become. Especially in the water system in the pulp and paper industry, bacteria,
Slime is generated by the propagation of filamentous fungi and yeasts, and slime is produced in waterways where pulp slurry flows, especially in rough walls, chests, flow boxes, transport pipes, and other places where the flow velocity of the pipe slurry is low and stagnant. Is remarkably adhered.

[0003] The slime is often desorbed, causing not only paper breakage and contamination of pulp and paper products, but also causes various obstacles due to propagation of microorganisms. The occurrence of such an obstacle becomes a major obstacle, particularly when a high-speed machine is used, and causes a significant decrease in productivity and economic loss.

In addition, the growth of microorganisms in a circulating water system for cooling such as a metalworking oil agent impairs cooling performance and emulsifying properties and generates an odor, which adversely affects the working environment.

[0005] In addition, obstacles caused by the propagation of harmful microorganisms are also observed in the production of industrial products such as water-based paints, coating solutions for paper, polymer latex, pulp for papermaking, glue, leather, wood, and metalworking oils. .

As an agent for suppressing or controlling the generation of harmful microorganisms in the water system or industrial product, for example, an isothiazolone complex compound or an isothiazolone derivative complex compound and dibromonitro alcohol in a weight ratio of 1:10 to 10: 1. Are known (JP-A-63-316702).

This product has a wide range of applications as a bactericidal / bactericidal agent in the above-mentioned water-based or industrial products, and exhibits excellent bactericidal / bactericidal action. However, there is a drawback that the antibacterial and bactericidal effects are not sufficiently exhibited during use.

[0008]

DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks of such a conventional drug containing an isothiazolone compound and dibromonitroalcohol, shows good stability, and has sufficient antibacterial properties at the time of use. The purpose of the present invention is to provide a harmful microorganism eradication agent capable of exhibiting a bactericidal action.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a harmful microorganism-eliminating agent having improved stability. As a result, an isothiazolone-based compound and 3,3-dibromo-3-nitro- It has been found that the purpose can be achieved by adding a specific compound at a predetermined ratio to an aqueous solution or aqueous dispersion containing 2-propanol, and based on this finding, the present invention has been completed. Reached.

That is, the present invention relates to (A) an isothiazolone compound and (B) 3,3-dibromo-3-nitro-
Aqueous solution or dispersion 1 containing 2-propanol
(C) 3-halogeno-3-nitro-2,4-pentanediol 0.05 as a stabilizing component per 100 parts by weight.
The present invention provides a stabilized harmful microbial eradication agent, characterized in that the composition contains up to 0.9 parts by weight.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The isothiazolone-based compound as the component (A) in the harmful microorganism-eliminating agent of the present invention is generally represented by the general formula:

Embedded image (In the formula, R ¹ is a hydrogen atom or a monovalent hydrocarbon group, R ² and R ³ are each a hydrogen atom or a halogen atom, and they may be the same or different.) An isothiazolone compound represented by the general formula

Embedded image (Wherein R ¹ , R ² and R ³ have the same meaning as described above;
Is a metal cation or ammonium, Y is an anion forming a complex compound, a is 1 or 2, and b is an integer satisfying the valency of the anion Y of the cation M). At least one is used.

In the above general formulas (I) and (II),
Examples of the monovalent hydrocarbon group of R ¹ include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; And a group in which a hydrogen atom of the above is partially substituted with a halogen atom or any other organic group. Further, as the halogen atom in R ² and R ³ , a chlorine atom and a bromine atom are preferably exemplified. R ² and R ³ may be the same or different from each other. In particular, those in which R ² is a hydrogen atom and R ³ is a chlorine atom have excellent antibacterial effects.

Further, examples of MY _b in formula (II), zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc acetate, copper chloride, copper bromide, copper nitrate, nickel chloride, calcium chloride , Magnesium chloride, magnesium nitrate, iron chloride, manganese chloride, sodium chloride, barium chloride, ammonium chloride and the like. Of these, magnesium nitrate and calcium chloride are preferred.

As the isothiazolone compound represented by the general formula (I), for example, 2-methyl-3-isothiazolone, 2-propyl-3-isothiazolone, 2-octyl-3-isothiazolone, 4-chloro-2-methyl -3-isothiazolone, 5-chloro-2-methyl-3-
Isothiazolone, 4-bromo-2-methyl-3-isothiazolone, 4,5-dichloro-2-methyl-3-isothiazolone, 4,5-dibromo-2-methyl-3-isothiazolone, 4,5-dichloro-2- Octyl-3-isothiazolone, 4,5-dibromo-2-octyl-3-isothiazolone and the like can be mentioned.

On the other hand, as the isothiazolone complex compound represented by the general formula (II), for example, the complex compounds of the above-mentioned isothiazolone compounds can be mentioned. Isothiazolone magnesium nitrate and 2-methyl-3-isothiazolone magnesium nitrate are advantageous because of their excellent antibacterial and bactericidal properties.

In the present invention, the isothiazolone compound of the component (A) may be used alone or in combination of two or more. When two or more kinds are used in combination, for example, 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone or 5
A mixture of 5-chloro-2-methyl-3-isothiazolone magnesium nitrate and 2-methyl-3-isothiazolone magnesium nitrate in a weight ratio of 5: 1 to 1: 1 is preferred because of its excellent bactericidal and fungicidal properties. .

In the harmful microorganism-eliminating agent of the present invention,
3,3-Dibromo-3-nitro-2-propanol used as the component (B) has the formula

Embedded image It is a compound represented by these.

In the present invention, the mixing ratio of the component (A) and the component (B) is preferably in the range of 10: 1 to 1:10 by weight. When the amount of the component (A) is larger than this range, the fungicidal activity against mold and bacteria may not be sufficiently exhibited, and when the amount of the component (A) is small, the effect of inhibiting the growth of mold and bacteria is sufficiently exhibited. Not done. In order to sufficiently exhibit bactericidal and antiproliferative effects against molds and bacteria, (A)
The mixing ratio of the component and the component (B) is particularly preferably in the range of 5: 1 to 1: 5.

The harmful microorganism-eliminating agent of the present invention comprises the above (A)
An aqueous medium or an aqueous dispersion containing the component and the component (B). As the aqueous medium used for preparing the aqueous solution or the aqueous dispersion, water may be used alone, or A mixture of water and a water-miscible organic solvent such as an alcohol solvent, an ether solvent, and an amide solvent may be used. Preferred examples of the water-miscible organic solvent include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-
Various known polyols and polyol ether-based liquid compounds such as pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and tripropylene glycol monomethyl ether, N, N-dimethylformamide, N , N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.

In the harmful microorganism-eliminating agent of the present invention, as the stabilizing component, component (C),

Embedded image It is necessary to compound 3-halogeno-3-nitro-2,4-pentanediol represented by the formula (X in the formula is a halogen atom). In addition, as the halogen atom represented by X in the general formula (IV), a chlorine atom and a bromine atom are preferable.

In the harmful microorganism-eliminating agent of the present invention, the component (C) is added in an amount of 0.1 part by weight to 100 parts by weight of an aqueous solution or an aqueous dispersion containing the components (A) and (B).
It is necessary to mix in the range of 0.5 to 0.9 parts by weight. If the amount is less than 0.05 part by weight, the desired stability cannot be obtained, and the object of the present invention cannot be sufficiently achieved.
If it exceeds 0.9 parts by weight, the effect of improving the stability is not seen for the amount, and it is rather economically disadvantageous. In consideration of stability and economy, the preferred amount of the component (C) is 100 parts by weight of the aqueous solution or the aqueous dispersion.
It is selected in the range of 0.1 to 0.5 parts by weight.

The harmful microorganism-eliminating agent of the present invention is basically prepared by adding the components (A), (B) and (C) to an aqueous medium and mixing them uniformly. The component (A), the component (B) and the component (C) may be individually added to an aqueous system to be used.

Further, an emulsifying dispersant, an antifoaming agent and the like can be added to the harmful microorganism-eliminating agent of the present invention as long as the object of the present invention is not impaired. Examples of the emulsifying dispersant include an anionic surfactant and a nonionic surfactant. The addition amount of the harmful microorganism-eliminating agent of the present invention varies depending on the microorganism concentration. However, in general, in the case of a water system in the field of the pulp and paper industry, an isothiazolone compound and 3,3-dibromo-3 are used. Based on the total amount of -nitro-2-propanol,
0.01 to 100 ppm, in the case of fields such as water-based paint, glue and leather, 1 to 500 ppm, and in the case of wood such as pulp chips, the range is 100 to 1000 ppm;
A good bactericidal effect can be obtained with such an amount.

[0024]

EFFECT OF THE INVENTION The stabilized harmful microbial eradication agent of the present invention uses 3-bromo-3-nitro-2,4-pentanediol as a stabilizing component, so that an isothiazolone-based compound as an active ingredient and 3,3-dibromo-3-
The decomposition of nitro-2-propanol can be significantly suppressed, and the stability is greatly enhanced. Therefore, storage and transportation thereof are also greatly facilitated.

[0025]

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

The residual ratio of the active ingredient was measured according to the following method. Specimen of harmful microorganisms at 40 ℃
A part of each sample is collected daily, and the residual concentrations of the isothiazolone compound and 3,3-dibromo-3-nitro-2-propanol are measured by liquid chromatography. To calculate the residual ratio. Residual rate (%): (Z ₁ / Z ₀ ) × 100 where Z ₀ is the initial concentration of isothiazolone compound or 3,3-dibromo-3-nitro-2-propanol, Z
₁ indicates the concentration of the isothiazolone compound or 3,3-dibromo-3-nitro-2-propanol after 10 or 30 days.

Example 1 5-Chloro-2-methyl-3-isothiazolone magnesium nitrate 3 parts by weight, 3,3-dibromo-3-nitro-2-propanol 1 part by weight, water 42 parts by weight, diethylene glycol monomethyl ether 50 Parts by weight, and 3-bromo-3-nitro-2,4
-0.5 parts by weight of pentanediol was added and mixed uniformly to prepare a harmful microorganisms-killing agent. Table 3 shows the residual ratio.

Example 2 26 parts by weight of Caisson WT manufactured by Rohm and Haas
1 part by weight of 3,3-dibromo-3-nitro-2-propanol, 19 parts by weight of water and 50 parts by weight of diethylene glycol monomethyl ether are uniformly mixed, and 3-bromo-3-nitro-2,4- 0.5 parts by weight of pentanediol was added and uniformly mixed to prepare a harmful microorganisms-killing agent. Table 3 shows the residual ratio.

Examples 3 to 5 Harmful microorganism elimination agents having the composition shown in Table 1 were prepared. Table 3 shows the residual ratio.

[0030]

[Table 1]

[Note] (A) Component-1: 5-chloro-2-methyl-3-isothiazolone magnesium nitrate (A) Component-2: Caisson W, manufactured by Rohm and Haas Company
T (mixture of 5-chloro-2-methyl-3-isothiazolone magnesium nitrate and 2-methyl-3-isothiazolone magnesium nitrate at a weight ratio of 3: 1; solids concentration 14.1% by weight (A) 3: 4,5-dichloro-3-isothiazolone magnesium nitrate (B) component: 3,3-dibromo-3-nitro-2-propanol (C) component: 3-bromo-3-nitro-2,4-pentane Diol DEGME: diethylene glycol monomethyl ether

Comparative Examples 1 to 5 A harmful microorganism-eliminating agent having the composition shown in Table 2 was prepared without blending 3-bromo-3-nitro-2,4-pentanediol. Table 3 shows the residual ratio.

[0033]

[Table 2]

[Note] The components (A) -1 to 3, components (B) and DEGME are the same as those in Table 1.

[0035]

[Table 3]

From these results, it can be seen that all of the harmful microorganism-eliminating agents of Examples of the present invention have higher stability than those of Comparative Examples.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A01N 33:20)

Claims (3)

[Claims] 1. A stabilizing component for 100 parts by weight of an aqueous solution or dispersion containing (A) an isothiazolone compound and (B) 3,3-dibromo-3-nitro-2-propanol, (3) A stabilized harmful microorganism-eliminating agent characterized by containing 0.05 to 0.9 parts by weight of 3-halogeno-3-nitro-2,4-pentanediol. 2. The stabilized harmful microorganism-eliminating agent according to claim 1, wherein the isothiazolone-based compound as the component (A) is at least one selected from isothiazolone compounds and isothiazolone complex compounds. 3. The stabilized harmful microorganism-eliminating agent according to claim 1, wherein the mixing ratio of the component (A) and the component (B) is 10: 1 to 1:10 by weight.