WO2000067578A1

WO2000067578A1 - Composite bactericidal compositions

Info

Publication number: WO2000067578A1
Application number: PCT/JP1999/005025
Authority: WO
Inventors: Ryoji Funatsu; Shinji Yoshizawa
Original assignee: Somar Corporation
Priority date: 1999-05-10
Filing date: 1999-09-14
Publication date: 2000-11-16
Also published as: JP2000319113A; JP4245097B2; AU5651299A

Abstract

Composite bactericidal compositions having a broad antibacterial spectrum, showing an excellent effect of inhibiting the proliferation of a number of microorganisms, sustaining this effect over a long time and little affecting the environment. These compositions are characterized by containing: (A) 2-methyl-3-isothiazolone optionally containing up to 0.8 % by weight of 5-chloro-2-methyl-3-isothiazolone; (B) 2-bromo-2-nitropropane-1,3-diol; and (C) 2,2-dibromo-3-nitrilopropionamide.

Description

Description Composite fungicide composition Technical field

INDUSTRIAL APPLICABILITY The present invention has a wide range of antibacterial spectrum as a synergistic effect of a combination of specific compounds, has a good effect of suppressing the growth of many microorganisms, has excellent sustainability of the effect, and has an environmental effect. O The technical background relates to a composite fungicide composition with little effect on

Conventionally, water systems in the pulp and paper industry, for example, various water systems such as white water in the papermaking process and circulating cooling water in various industries, water-based paints prepared using industrial water, paper coating solutions, In fields such as latexes, polymer emulsions, metal oils such as cutting oils, leather, print paste, adhesives, and wood, harmful microorganisms grow and thrive, causing a decline in productivity and quality. ing. Especially in the water system in the pulp and paper industry, slime is generated by the propagation of bacteria, filamentous fungi, and yeasts. In places where the flow velocity decreases and stagnation occurs, slime formation is remarkable.

This slime can fall off, cause paper breakage and contamination of pulp and paper products, cause various obstacles due to the propagation of microorganisms, and cause a significant decrease in productivity, especially when high-speed machines are used. Incurs economic losses.

In addition, the growth of microorganisms in the circulating water system for cooling such as metalworking oils may impair cooling performance and emulsifying properties, generate odors, and cause unfavorable phenomena in public health, such as worsening the working environment.

In addition, the propagation of harmful microorganisms can also damage industrial products such as water-based paints, paper coatings, latex, paper pulp, glue, leather, and wood. Especially in the case of latex, if no preservative is added, it will spoil in a short period of time, and not only will it smell putrefactive, but also If it is used as a paper coating agent, the resulting coated paper emits a foul odor, making it impossible to produce it as a product and causing a drop in productivity.

Until now, organometallic compounds, quaternary ammonium salts, and the like have been used as agents to suppress or prevent the generation of harmful microorganisms in these water systems and industrial products. In addition to being toxic to the human body, it emits offensive odors and unpleasant odors, and is accompanied by physical phenomena such as foaming that are not easy to handle.In addition, water containing these control agents is used for general rivers and seas. If released into water, it will have an adverse effect on aquatic organisms, and is a social problem in terms of environmental conservation.

Therefore, in order to avoid such a problem, a bactericide composition comprising a combination of an isothiazolone compound and a halocyanoacetamide compound (JP-A-61-83105, JP-A-62-70105). No. 301, JP-A-3-17674 and JP-A-5-210810), a bactericide comprising a combination of an isothiazolone compound and a halogenated aliphatic alcohol. Composition (Japanese Patent Publication No. 60-52421, Japanese Patent Application Laid-Open No. 60-84203), 2-bromo-2-nitropropane-1,3 as halogenated aliphatic nitro alcohol -A fungicide composition using a diol (Japanese Patent Application Laid-Open No. 52-118527), a fungicide composition comprising a combination of a halocyanoacetamide and a halogenated aliphatic nitro alcohol (Japanese Patent Application (Published by No. 60-231 163) and isothiazolone compounds and dissolve them To use an aqueous composition (for example, Japanese Patent Application Laid-Open No. HEI 4-93005) containing a water-based solvent for this purpose and a nitrobromo-based compound as a stabilizing component. However, all of them have a problem that the working environment is destroyed because the antibacterial spectrum is narrow and the composition is Ames-positive. Disclosure of the invention

Under such circumstances, the present invention has a wide range of antibacterial spectrum, exhibits a good growth-inhibiting effect on many microorganisms, and has a conventional amount of drug added to maintain antibacterial activity. The object of the present invention is to provide a composite fungicide composition which can be reduced to the same amount or less, has excellent effect persistence, and has little effect on the environment. The present inventors have developed a composite fungicide composition having a broad spectrum of antibacterial spectrum. As a result of extensive research, the combination of specific isothiazolone compounds, halogenated aliphatic nitrous alcohols and halocyanoacetamides has resulted in a wider range of harmful microorganisms than conventional industrial fungicides due to their synergistic effect. Effective against S. cerevisiae, inhibiting its reproduction, Ames-negative and free from environmental pollution, and containing 2,2-dibromo-3-ditripropionamide As a result, it was found that the undesired action of 5-chloro-2-methyl-3-isothiazolone which is present as an impurity was suppressed, and the present invention was completed based on this finding.

That is, the present invention relates to (A) 2-methyl-3-isothiazolone, (B) 2-bromo-2-nitropropane-1,3-diol and (C) 2,2-dibromo-3-di-triamine. An object of the present invention is to provide a composite fungicide composition containing propionamide. BEST MODE FOR CARRYING OUT THE INVENTION

In the composite fungicide composition of the present invention, (A) a component represented by the following formula:

2-methyl-3-isothiazolone represented by the formula: This 2-methyl-3-isothiazolone has the formula

5-methyl-2-methyl-3-isothiazolone represented by the following formula may be contained as an impurity, but is included in the present invention if the amount is less than 0.8% by weight. It may be. If the content of 5-chloro-2-methyl-3-isothiazolone is 0.8% by weight or more, there is a risk of inducing a mutation in the DNA of a microbial gene. In order to completely prevent DNA mutation, the content of the 5-chloro-2-methyl-3-isothiazolone is desirably 0.5% by weight or less.

In the composite fungicide composition of the present invention, the component (B) has the following formula:

B r

Bromo - - 2 - Two Toro propane - 2 represented by _{_{HO-CH 2 -C-CH 2}} -OH N0 2, 3 - diol is used. The component (B) is preferably used in a ratio of 0.5 to 10 times the weight of the component (A). (B) If the amount of the component is less than 0.5 times the weight, the rapid action of the drug is not sufficiently exerted, so that it is difficult to prevent the decay of microorganisms that have already been propagated. However, if it exceeds 10 times the weight, the sustained effect of the drug is reduced, and the long-term preservative effect on the target object is not sufficiently exhibited. Considering the fast-acting properties, anti-corruption properties and sustained effect of the drug, the more preferable amount of the component (B) is 1 to 5 times the weight of the component (A).

In the composite fungicide composition of the present invention, the component (C) has the following formula:

B r O

I II

N≡ C-C—— C NH

2,2-dibromo-3-di-tripropionamide represented by Br is used. The component (C) is preferably used in a ratio of 0.8 to 10 times the weight of the component (A). If the amount of this component (C) is less than 0.8 times the weight, as an impurity in the 2-methyl-3-isothiazolone of component (A), up to 0.8% by weight of 5-chloro-2-methyl-3-isothiazolone is contained. DNA-corrected paper due to impurities when mixed (Rule 91) When the weight exceeds 10 times, the decomposition of the component (C) is accelerated, and the desired effect is not sufficiently exerted at the time of use. Considering prevention of DNA mutation and prevention of degradation of the active ingredient, the more preferable amount of the component (C) is 1.5 to 10 times the weight of the component (A).

As described above, in the present invention, the combination of the component (A), the component (B) and the component (C;>) is effective for a wide range of harmful microorganisms for the first time and prevents DNA mutation. Can be.

The composite germicidal composition of the present invention is basically prepared by uniformly mixing the components (A), (B) and (C), but is generally a solvent solution or dispersion. It is used as a liquid.

Solvents that can be used here include alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, and the like.Propylene carbonate, ethylene carbonate, dimethyl glutarate, ethylene glycol diamine Even if a solvent such as acetate is used, a stable preparation can be obtained. Further, when used for latex, it is preferable to use a solvent such as ethylene daryl or diethylene glycol to prevent the occurrence of emulsion shock.

The amount of the complex fungicide composition of the present invention to be used varies depending on the concentration of microorganisms. Generally, in the case of water systems in the pulp and paper industry, the components (A), (B) and (C) It is about 1 to 50 Ppm based on the total amount of the components, and in the fields of latex, water-based paint, glue, leather and the like, it is about 20 to 400 ppm, and a good effect can be obtained in this range.

To the composite germicidal composition of the present invention, a stabilizer, a surfactant, and the like can be added as needed, as long as the object of the present invention is not impaired.

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

In addition, the symbol of the component used in each example means the following compound.

I T: 2-Methyl-3-isothiazolone (5-methyl-2-methyl-3

-Contains 0.5% by weight of isotizazolone)

BNP: 2-Bromo-2-nitropropane-1,3-diol D BNP A: 2,2-Dibromo-3-di-tripropionamide DBNE: 2,2-Dibromo-2-nitroethyl alcohol

D E G: Diethylene glycol

Examples 1 and 2, Comparative Examples 1-4

Each component was blended at the blending ratio shown in Table 1 to prepare a composite disinfectant composition solution. This composite bactericide composition solution was subjected to a bactericidal test according to the following method.

(1) Sterilization test

[Bactericidal effect on white water]

A sterilization test using chemicals was performed using white water from the papermaking process where slime troubles occurred frequently.

Each of the composite disinfectant composition solutions of Examples and Comparative Examples was added to white water so as to have the drug concentrations shown in Table 2 (concentrations as a total amount of components other than DEG and water), and allowed to stand for 15 minutes. 1 ml of this solution was mixed with a heated and dissolved waxman agar medium, solidified, and cultured at 32 ° C. The number of viable bacteria 48 hours later was measured and used as an indicator of the bactericidal effect of the drug. Table 2 shows the results.

[Long-term preservative effect on latex]

Each of the composite disinfectant composition solutions of Examples and Comparative Examples added to the SBR latex at the drug concentrations shown in Table 3 was left in a constant temperature room at 35 ° C. Then, the number of viable bacteria in the latex was measured after 1, 7, 14 and 21, and the long-term preservative effect of the drug was determined. In addition, in order to clarify the persistence of the preservative effect of the drug, the bacteria were re-inoculated and the cultivation was continued after counting the number of bacteria after 7 and 14. Table 3 shows the results.

(2) Ames test

The Ames test was performed using the complex disinfectant composition solution shown in Table 1, and a test was performed to determine whether or not mutations were observed in DNA. Table 2 shows the results. table 1

Table 2 Number of viable bacteria of Ames (PPm) per 1 m1 of drug concentration ο Test Example 1 20 10 ² > Negative Example 2 20 10 ² > Negative Comparative example 1 20 4.8 X 10 ⁶ Positive Comparative example 2 20 8.1 X 10 ⁵ Negative Comparative Example 3 20 1.3 10 ⁵ Negative Comparative Example 4 20 1.8 X 10 ⁴ Positive No addition 1.1 X 10 ⁷ Table 3

Industrial applicability

The combined fungicide composition of the present invention exhibits a synergistic effect that cannot be expected from a single component by combining three types of active ingredients, and is a mutagen to DNA. -Even if the black mouth -2-methyl-3-isothiazolone is contained up to 0.8% by weight of 2-methyl-3-isothiazolone, the effect as a mutagen is not exhibited. As a result, the range of microbes that can be sterilized is greatly expanded, and has an extremely broad spectrum of antibacterial properties.In addition, the growth of various microbes can be effectively suppressed over a long period of time, and environmental destruction can occur. It has the advantage of not having.

Accordingly, the composite disinfectant composition of the present invention is particularly useful for water systems in the pulp and paper industry, such as white water in the papermaking process, and various water systems such as circulating cooling water in various industries, water-based paints, and paper coatings. It is suitably used in the fields of metalworking oils, adhesives, leather, wood, etc., such as working fluids, latex, polymer emulsions, printing pastes, cutting oils, etc.

Claims

The scope of the claims

1 Contains (A) 2-methyl-3-isothiazolone, (B) 2-bromo-2-nitropropane-1,3-diol and (C) 2,2-dibromo-3-ditripropionamide A composite germicidal composition comprising:

2 The components (A), (B) and (C) are dissolved or dispersed, and the content ratio of the components (A) and (B) is 1: 0.5 to 1:10 by weight, 3. The composite fungicide composition according to claim 1, wherein the content ratio of the component (A) to the component (C) is 1: 0.8 to 1:10 by weight.