JPH03130204A - Industrial germicide and method for sterilization - Google Patents

Abstract

PURPOSE:To obtain a germicide, capable of exhibiting excellent effects at low temperatures or under neutral or alkaline conditions by using a specific isophthalonitrile derivative and a specified germicide such as methylenebis- thiocyanate in combination. CONSTITUTION:An industrial germicide, obtained by using an isophthalonitrile derivative selected from 5-chloro-2,4,6-trifluoroisophthalonitrile and 5-chloro-2,4- difluoro-6-methyoxyisophthalonitrile and at least one compound selected from germicides of methylenebis-thiocyanate, 2,2-dibromo-3-nitriliopropionamide and 2-bromo-2-nitro-1,3-diacetoxypropane in combination and most suitable as sheet forming process water, etc., in especially paper and pulp factories. The aforementioned germicide is capable of exhibiting synergistic action among the respective active ingredients and sterilization treatment can be carried out in a low concentration without deteriorating effects thereof even in a change of temperature or pH.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Use This invention relates to an industrial disinfectant and a disinfection method. For more details, see filtration process water in the paper and pulp industry, cooling water and cleaning water for various industries, heavy oil sludge, metal processing fluids,
The present invention relates to an industrial sterilizer and sterilization method useful for preserving and sterilizing textile oils, paints, paper coating fluids, latex, and adhesives.

(b) Conventional technology Slime caused by sterilization and fungi has traditionally been generated in cooling water systems in the papermaking process in the paper and pulp industry and in various lining industries, resulting in problems such as deterioration in the quality of manufactured products and reductions in production efficiency. It is known that there is.

In addition, many industrial products, such as heavy oil sludge, metal processing oils, textile oils, paints, various latexes, and glues, are subject to rot and contamination due to sterilization and fungi, staining the products and reducing their value.

Many disinfectants have been used to prevent damage caused by these microorganisms. In ancient times, organic mercury compounds and chlorinated phenolic compounds were used, but these drugs are highly toxic to the human body and seafood, and cause environmental pollution, so their use has been regulated, and recently, comparative Low toxicity organic nitrogen sulfur compounds, organic halogen compounds, and organic nitrogen sulfur compounds are widely used as industrial disinfectants.

Isophthalonitrile derivatives, methylene bisthiocyanate, 2,2-dibromo-3-
Nitrilopamide and 2-bromo-2-nitro-1,3-diacetoxypropane are each known as such relatively low toxicity fungicides.

Although the various low-toxicity disinfectants mentioned above have low toxicity, it is desirable to reduce their usage as much as possible from the viewpoints of pollution, environment, and reduction of sterilization cost.

Therefore, there is a need for a fungicide that exhibits a bactericidal effect for a longer period of time with as little amount as possible, and from this point of view, for example, 5-chloro-2,4,6-trifluoroisophthalonitrile, Research is being carried out to develop an effective bactericidal effect when used in combination with organic fungicides. Specifically, 5chloro-2,4,6-trifluoroisophthalonitrile and 2-bromo-2-nitro-1,
Synergistic agents have been proposed that are used in combination with specific aliphatic nitro alcohols such as 3-propanediol and 1,1-dibromo-1-nitro-2-propanol (Japanese Patent Application Laid-Open No.
4-61402).

(c) Problems to be solved by the invention However, the bactericidal efficacy of the above-mentioned conventional synergistic agents containing 5-chloro-2,4,6-trifluoroisophthalonitrile significantly decreases as the temperature decreases. Additionally, there was the problem that its bactericidal efficacy was low in neutral to alkaline aqueous systems. Also, 5-chloro-2
, 4-difluoro-6-medoxyisophthalonitrile encountered similar problems.

Therefore, for example, when assuming a system to be sterilized such as papermaking process water in a paper/pulp factory, an effective addition amount in summer (e.g., water temperature 40°C) will not be effective in winter (e.g., water temperature 17°C). It is not possible to obtain a bactericidal effect,
In addition, it is significantly sterilized in the so-called neutral papermaking process water and alkaline papermaking process water, which is targeted for white water with pH 7 to 8, at an effective addition amount for so-called acidic papermaking process water, which is targeted for white water with a pH of 3.5 to 6. This caused the inconvenience of reduced effectiveness.

The present invention was made under such circumstances, and it provides 5-chloro2.4.6-)lifluoroisophthalonitrile which can exhibit a strong bactericidal effect even in low-temperature environments and neutral to alkaline environments. Or, it is intended to develop a new combination drug containing 5-chloro-2,4-difluoro-6-medoxyisophthalonitrile.

(d) Means for solving the problem Thus, according to the present invention, 5-chloro-2,4,6-
trifluoroisophthalonitrile or 5-chloro-2,
An isophthalonitrile derivative selected from 4-difluoro-6-medquinisophthalonitrile, (a) methylenebisthiocyanate, (b) 2,2-dibucomo-3-ditonitrilovionamide, (C) 2- An industrial fungicide characterized by containing as an active ingredient at least one compound selected from the fungicide bromo-2-nitro-1,3-diacetoxypropane is available for $4.

The isophthalonitrile derivative used in this invention is 5-chloro-2,4,6-trifluoroisophthalonitrile or 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile, which is mixed may be used. Among these, 5-chloro-2,4
, 6-trifluoroisophthalonitrile is preferred.

This invention relates to 5-chloro-2,4,6-trifluoroisophthalonitrile and 5-chloro-2,4-difluoro-
Among many organic fungicides, (a) 'methylene bisthiocyanate, (b) 2,2-dibromo-3-nitrilopropionamide, or (C) 2- When bromo-2-nitro-1,3-diacetoxypropane is selected, a bactericidal agent with significantly improved bactericidal efficacy in low-temperature and neutral papermaking process water systems can be obtained compared to conventional combination agents. Otsu's decision based on the discovery of facts.

5-chloro-2,46, which is an essential component in this invention
-Trifluoroisophthalonitrile [hereinafter referred to as compound (1)
)] or ]5-chloro-2,4-nofur-6methoxyisophthalonitrile.
I)] is carried out by a known method, for example, a chemical industry magazine,
73.447 (1970) and JP-A-63-2275
Each can be obtained by the method disclosed in No. 02.

In addition, in this invention, the above compound (1) or (■)
Methylene bisthiocyanate (hereinafter referred to as ingredient) used in combination with
a)), 2,2-dibromo-3-nitrilopropionamide (hereinafter component (b)) and 2-bromo-2-nitro-1,3-diacetoxypropane (hereinafter component (C)).
)) are disinfectants described in, for example, Japanese Patent Publication No. 4G-23847, Japanese Patent Publication No. 42-10386, and Japanese Patent Application Laid-open No. 120603/1989, and commercially available products can be used as they are.

The bactericidal agent of the second invention exhibits an extremely synergistic bactericidal effect that cannot be expected from each of the nurturing ingredients individually, and is effective against harmful microorganisms such as bacteria, fungi, yeast, etc. It has a wide range of application regardless of the situation. Moreover, even when the temperature of the system to be sterilized decreases, its excellent sterilizing effect does not decrease, and it exhibits excellent sterilizing effect even at low temperatures.
It exhibits an effective bactericidal effect in neutral to alkaline environments such as aqueous systems in the neutral papermaking process.

In the fungicide of this invention, the compound (R or (II)
The blending ratio of compound (I) or (n) with component (a), (b), or (C) is adjusted so that the above synergistic bactericidal effect is efficiently expressed. The blending ratio of (a), (b) or (c) is l:10~
A ratio of 10:1 is suitable, and a ratio of 1:5 to 5:1 is preferred.

The fungicide of this invention comprises the above compound (1) Makoha (■)
It can be prepared by uniformly mixing the component (a), (b) or (c) as is, but generally an aqueous solution,
It is preferable to use it in the form of a solvent solution, emulsified dispersion, or the like.

Solvents that can be used here include alcoholic solvents such as methanol, ethanol, and isopropanol, acetone, and MEK1? Ketone solvents such as vilBK,
Ether solvents such as dibutyl cellosolve, diethyl calpitol, methyl cellosolve, ethyl cellosolve, methyl calpitol, ethyl carpitol, methyl acetate, ethyl acetate, 3-methoxybutyl acetate, 2-methoxyethyl acetate, 2-ethyne ethyl acetate Examples include ester solvents such as propylene carbonate, and hydrocarbon solvents such as xylene, diethylbenzene, naphtha, and kerosene.

Furthermore, the bactericidal agent of the present invention may be used by being supported on any carrier (for example, kaolin, clay, pennite, CMC, etc.), and there are no restrictions on its mode, and various formulation forms may be adopted. can. Stabilizers, surfactants, etc. may be added to the extent that they do not impede the effects of the present invention.

When using the disinfectant of this invention, the amount added will vary depending on the microbial a-density in the system to be sterilized, but generally in the case of water systems in fields such as the paper and pulp industry, the total a-density of the active ingredients is 0. .01-1100pp, water-based paint, glue,
In the case of fields such as metal processing oil, it is also 1 to 500.
ppm, thereby achieving the above-mentioned sterilizing effect.

However, the compound ([) or (■) used in this invention and the component (a), (b) or (c) may be added simultaneously or separately into the system to be sterilized, so that the The same bactericidal effect as above can be obtained by the interaction of each component. Therefore, the present invention provides for industrial sterilization target systems using 5-chloro-2゜4,6-trifluoroisophthalonitrile or 5-chloro-2,4-difluoro-6-medoxyisophthalonitrile. An isophthalonitrile derivative, (a) methylene bisthiocyanate, (
b) 2.2-dibromo-3-nitriloprobionamide, (C) at least one compound selected from the fungicide 2-bromo-2-nitro-1.3-diacetquinpropane at the same time. Alternatively, the present invention also provides an industrial sterilization method characterized in that sterilization is carried out by adding the components separately.

(E) Example An industrial fungicide of the present invention and a fungicide of a comparative example were prepared according to the following formulations. Note that all parts are by weight.

Example 1 5-chloro-2,4,6-1-lifluoroisophthalonitrile 10 parts methylene bisthiocyanate
10 parts propylene carbonate
80 parts Example 2 5-chloro-2,4,6-)lifluoroisophthalonitrile In2.2-dibromo-3-nitriloprobionamide 10 parts Propylene carbonate
80 parts Example 3 5-chloro-2,4,6-)lifluoroisophthalonitrile 10 parts 2-bromo-2-nitro-1,3-diacetoxypropane 10 parts propylene carbonate
80 parts Comparative Example 1 5-chloro-2,4,6-trifluoroisophthalonitrile 20 parts Propylene carbonate
80 parts Comparative Example 2 Methylene bisthionoanate
20 parts propylene carbonate
80 parts Comparative Example 3 2,2-dibromo-3-nitrilobipionamide
20 parts propylene carbonate
80 parts Comparative Example 4 2-bromo-2-nitro-1,3-diacetoquine propane 20 parts Propylene carbonate
80 parts Example 4 5-chloro-2,4-difluoro-6-nodoxyisophthalonitrile 10 parts Methylene bisthiocyanate
10 parts propylene carbonate
80 parts Example 5 5-chloro-2,4-diflufuro 6-methoxyisophthalonitrile IO part 2,2-dibromo-3-ditrilopionamide
10 parts propylene carbonate
80 parts Example 6 5-chloro-2,Il-difluoro-6-nodoquinisophthalonitrile 10 parts 2-bromo-2-nitro-1,3-diacetoxypropane 10 parts Propylenocarbonate
80 parts Comparative Example 5 20 parts of 5-chloro-2,4-difluoro-6-nodoxyisophthalonitrile 80 parts of propylene carbonate (Evaluation of bactericidal effect Ia5) Prepared in Examples 1 to 6 and Comparative Examples 1 to 5 above The bactericidal effect of the bactericidal agent was investigated using the following test method.

The above preparation was added to white water [pH 7.6, mainly Pseudomonas, Flavobacterium, Micrococcus, and Bacillus] collected from a high-quality paper machine (neutral paper making) at a certain paper factory to a predetermined concentration. After, 37℃, 27℃
1 and shaken at 17°C for 60 minutes, and the number of viable bacteria was determined.

The results are shown in Table 1. Note that the drug concentration indicates the concentration of each drug used.

Table 1 (Continued) Table 1 As is clear from the results in Table 1 above, according to the disinfectant of the example, although the amount of active ingredient was the same, the disinfectant'pH of the comparative example (the active ingredient was ), and a synergistic effect is clearly recognized. It can be seen that not only an excellent synergistic effect is observed, but also an excellent synergistic effect that is equivalent to that under a high temperature (37°C) at a low temperature (17°C). Further, when comparing the cases of compound (1) and (If), the case of compound (1) is more preferable.

And, this tendency is similar to that of 5-chloro-2,4,6-trifluoroisophthalonitrile or 5-chloro-2,
Component (a), (b) or (c) is added to 1 part by weight of 4-difluoro-6-nodoxyisophthalonitrile in an amount of
The ratio of 5 was particularly recognized in ancient times.

(f) Effects of the Invention According to the disinfectant and sterilization method of the present invention, a strong sterilization effect is exhibited in various systems to be sterilized based on the synergistic action of each active ingredient. Therefore, it becomes possible to carry out sterilization treatment using active ingredients with a lower agricultural content than in the past.

This excellent sterilization effect is not adversely affected by changes in the temperature or pH of the sterilization system, especially if the temperature of the sandy water changes or the pH changes depending on the type of white water used. Even if it changes, it will not actually decrease.

Therefore, the disinfectant and sterilization method of the present invention are effective in sterilizing various target systems, especially industrial water systems that experience temperature fluctuations such as paper-making water, and where various liquid water types are used. It is useful for sterilization treatment inside.

Claims (1)

[Scope of Claims] An isophthalonitrile derivative selected from 1,5-chloro-2,4,6-trifluoroisophthalonitrile or 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile; At least one fungicide selected from the following fungicides: (a) methylene bisthiocyanate, (b) 2,2-dibromo-3-nitrilopropionamide, and (c) 2-bromo-2-nitro-1,3-diacetoxypropane. An industrial fungicide characterized by containing a seed compound as an active ingredient. 2. Isophthalonitrile derivative is 5-chloro-2,4
, 6-trifluoroisophthalonitrile. Claim 1
disinfectant. 3. The disinfectant according to claim 1, wherein the system to be sterilized is papermaking process water in a paper/pulp factory. 4. For industrial sterilization target systems, 5-chloro-2,4,6
-trifluoroisophthalonitrile or 5-chloro-2
, 4-difluoro-6-methoxyisophthalonitrile, (a) methylene bisthiocyanate, (b) 2,2-dibromo-3-nitrilopropionamide, (c) 2-bromo- An industrial sterilization method characterized in that sterilization is carried out by simultaneously or separately adding at least one compound selected from 2-nitro-1,3-diacetoxypropane sterilizers. 5. Isophthalonitrile derivative is 5-chloro-2,
The sterilization method according to claim 4, wherein the sterilization method is 4,6-trifluoroisophthalonitrile. 6. The sterilization method according to claim 4, wherein the target system for industrial sterilization is papermaking process water in a paper/pulp factory. 7. Paper making process water is p
The sterilization method according to claim 6, having a liquid property of H7 to 8.