JP3009273B2 - Industrial fungicides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial disinfectant and a disinfecting method. More specifically, for the preservation and sterilization of papermaking process water in the paper and pulp industry, cooling water and washing water for various industries, heavy oil sludge, metalworking oils, fiber oils, paints, coating liquids for paper, latex and paste. The present invention relates to useful industrial germicides and sterilization methods.

[0002]

2. Description of the Related Art Conventionally, slime is generated by bacteria and fungi in papermaking processes in the paper and pulp industries and in cooling water systems in various industries, and there are obstacles such as deterioration of product quality and reduction of production efficiency. Are known. In addition, many industrial products such as heavy oil sludge, metalworking oils, fiber oils, paints, various latexes, sizing agents, etc., cause decay or contamination by bacteria or fungi, and contaminate the products to lower their value.

[0003] Many fungicides have been used to prevent these microbial disorders. In the past, organic mercury compounds and chlorinated phenol compounds were used, but these drugs are highly toxic to the human body and seafood,
The use has been regulated to cause environmental pollution. Recently, relatively low-toxic organic nitrogen sulfur compounds, organic halogen compounds and organic sulfur compounds have been widely used as industrial germicides (bactericidal control). Encyclopedia of fungicides, published in 61, published by the Japan Society of Antibacterial and Fungicide).

The active ingredient of the present invention, 5-chloro-
2,4,6-trifluoroisophthalonitrile and 5-
Chloro-2,4-difluoro-6-methoxyisophthalonitrile is known as one of such relatively less toxic fungicides. Although the above-mentioned various low-toxicity fungicides have low toxicity, it is desirable to reduce the amount of use as much as possible from the viewpoints of pollution, the environment, and the cost of sterilization treatment.

[0005] Accordingly, there is a need for a fungicide which exhibits a long-term disinfecting effect with a minimum amount of addition, and from this viewpoint, for example, 5-chloro-2,4,6-
Studies have been conducted on trifluoroisophthalonitrile to exhibit a synergistic germicidal effect in combination with other organic germicides. And specifically, 5-chloro-2,4,
6-trifluoroisophthalonitrile and 2-bromo-
There has been proposed a synergistic agent which is used in combination with specific aliphatic nitro alcohols such as 2-nitro-1,3-propanediol and 1,1-dibromo-1-nitro-2-propanol (Japanese Patent Application Laid-Open No. Sho 64). -61402).

[0006]

SUMMARY OF THE INVENTION The present inventors have found that α-chloro-benzaldoxime, a component of the present invention, has an effective bactericidal effect even in small amounts in industrial systems, especially in reducing industrial systems. Is found. But,
From the viewpoint of pollution, environmental aspects and reduction of sterilization treatment costs,
It was desired to reduce the amount used as much as possible.

Accordingly, the present inventors have proposed the above-mentioned α-chloro-
Benzaldoxime has 5-chloro- as a second component.
2,4,6-trifluoroisophthalonitrile or 5-
The addition of chloro-2,4-difluoro-6-methoxyisophthalonitrile exerts a similar effect at a fraction of the amount of drug used alone, which is more potent than the bactericidal effect of itself. A remarkable synergistic effect was found in practical use, and the present invention was completed.

[0008]

According to the present invention, (a) α-chloro-benzaldoxime and
(b) 5-chloro-2,4,6-industrial, characterized by containing a trifluoride Roy soft tallow nitrile or 5-chloro-2,4-difluoro-6-methoxy-isophthalonitrile as effective ingredient A fungicide is provided.

The active ingredient (a) of the present invention, α-chloro-benzaldoxime, has the following formula (I):

[0010]

Embedded image Which is known as a raw material (intermediate) for the synthesis of industrial germicides such as α-chloro-O-acylbenzaldoximes, α-chloro-chloro-benzaldoximes ( No. 50-15844 and No. 54-36647.
1-33171).

The active ingredient (b) of the present invention, 5-chloro-2,4,6-trifluoroisophthalonitrile or 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile, is known. Methods, for example, Chemical Industry Magazine, 73 , 447 (1970), and JP-A-63-227.
Each of them can be obtained by the method disclosed in No. 502.

According to the present invention, the above-mentioned active ingredient (a) is used, among many low-toxic organic fungicides, as 5-chloro-2,
It is based on the discovery that when used in combination with 4,6-trifluoroisophthalonitrile or 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile, an extremely excellent synergistic bactericidal effect is obtained. . The 5-chloro-2,4,6-trifluoroisophthalonitrile and 5-chloro-2,4-diflufur-6-methoxyisophthalonitrile used in combination are known organic fungicides, but the active ingredient There is no known example of using it in combination with (a) or a compound similar thereto.

The synergistic effect of the combination of the active ingredient (a) according to the present invention with 5-chloro-2,4,6-trifluoroisophthalonitrile or 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile. Is more preferable and more preferable ratio is 2% by weight.
0: 1 to 1:10 and 9: 1 to 1: 9. It is preferable that each active ingredient of the present invention is usually used in the form of a liquid preparation in a one-part preparation.

In the case of a one-pack preparation, a usual organic solvent or dispersant is used. In the case where the system to be disinfected is various water systems such as process water for the papermaking process or cooling water for factories, it is considered to be a liquid formulation using water or a hydrophilic organic solvent and a dispersant in consideration of the dissolution and dispersibility of the active ingredient. Is preferred. Examples of the hydrophilic organic solvent include amides such as dimethylformamide, glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol, methyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene. Glycol ethers such as glycol monomethyl ether, alcohols having up to 8 carbon atoms or methyl acetate,
Ethyl acetate, 3-methoxydibutyl acetate,
Esters such as 2-ethoxymethyl acetate, 2-ethoxyethyl acetate, and propylene carbonate are exemplified.

As the dispersant, a cationic surfactant,
Anionic surfactants, nonionic surfactants or amphoteric surfactants are suitable, and nonionic surfactants are preferred from the viewpoint of stability as a preparation. Examples of the nonionic surfactant include higher alcohol ethylene oxide adduct (ethylene oxide is hereinafter abbreviated as EO), alkylphenol (EO) adduct, fatty acid (EO) adduct, polyhydric alcohol fatty acid ester (EO) adduct,
Higher alkylamine (EO) adducts, fatty acid amide (EO) adducts, (EO) adducts of fats and oils, propylene oxide [P. O), (EO) copolymer,
Alkylamine (PO) (EO) copolymer adduct,
Fatty acid esters of glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, and alkylolamides. The mixing ratio of these preparations is such that the total amount of the fungicidal active ingredients (a) and (b) is 1 to 50 parts by weight, and the dispersant is at least 0.01 part by weight based on 1 part by weight of the active ingredient It is preferred that the balance be a hydrophilic organic solvent.

When the system to be sterilized is an oil system such as heavy oil sludge, cutting oil or oil paint, it is preferably a one-pack preparation using a hydrocarbon solvent such as kerosene, heavy oil or spindle oil. The various surfactants described above may be used. The amount of the bactericide of the present invention varies depending on the object to be sterilized. Particularly, when the bactericide is added to a process water system in a papermaking process or an industrial cooling water system, the concentration (bacteriostatic concentration) that suppresses the growth of microorganisms is Usually, the addition of about 0.05 to 20 mg / l as the total concentration of the active ingredient is sufficient. When used bactericidally, the purpose can be achieved at a total concentration of the active ingredient of 0.5 to 50 mg / l.

In the present invention, two active ingredients (a),
When (b) is added at the same time, it is convenient to use the same preparation as described above, but it is preferable to separate them separately from each other in terms of the long-term storage stability of the preparation, or they may be added separately. In such cases, they are used as separate preparations. Therefore, according to the present invention, there is further provided an industrial sterilization method characterized by adding the active ingredient (a) and the active ingredient (b) to the industrial sterilization target system.

Also in this case, it is convenient to make each preparation into a liquid preparation. For example, such a preparation can be prepared by adding the above-mentioned organic solvent or dispersant. Needless to say, each of the active ingredients of the present invention can be directly added separately to a target system for sterilization or bacteriostasis in which the active ingredients can be directly dissolved or dispersed. The active ingredients (a) and (b) of the present invention exert excellent synergistic effects in industrial sterilization target systems based on their synergistic effects. Accordingly, even when each of the active ingredients (a) and (b) is used at a concentration that cannot substantially exert a bactericidal effect alone, the intended bactericidal effect can be exhibited.

[0019]

[Examples] Formulation examples which are examples of the present invention are shown below. All parts in the examples are parts by weight. (Formulation Example 1) α-chloro-benzaldoxime 10 parts 5-chloro-2,4,6-trifluoroisophthalonitrile 10 parts Dimethyl succinate 80 parts (Formulation Example 2) α-chloro-benzaldoxime 10 parts 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile 10 parts Dimethyl succinate 80 parts (Comparative Preparation Example 1) α-chloro-benzaldoxime 20 parts Dimethyl succinate 80 parts (Comparative Preparation Example 2) 5 -Chloro-2,4,6-trifluoroisophthalonitrile 20 parts Dimethyl succinate 80 parts (Comparative Formulation Example 3) 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile 20 parts Dimethyl succinate 80 parts (test example 1) [synergistically by compounding ratios of the components effect confirmation test] certain paper mill newsprint papermaking machine white water (pH 5.1 collected from (acidic papermaking), SO ₃ ^2-27 ppm, Bacillus, Mikuroko' Scan genus Pseudomonas, Flavobacterium, the Alcaligenes spp mainly), was added 5ppm as the total amount of the various active ingredients and shaken for 30 minutes at 37 ° C.. Thereafter, the viable cell count was measured, and the initial cell count (7.5 × 10 ⁵ cells / m 2)
The sterilization rate for l) was determined. (Test results) Table 1 shows the test results.

[0020]

[Table 1] A: α-chloro-benzaldoxime B: 5-chloro-2,4,6-trifluoroisophthalonitrile C: 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile (Test Example 2) Newspaper making process of paper mill (acid paper making,
pH 4.5, SO ₃ ^2-70 ppm, Bacillus, Micrococcus spp, Pseudomonas, Flavobacterium, the Alcaligenes spp mainly), was added a predetermined amount of various formulation examples,
Immediately thereafter, the number of viable bacteria was measured. (Test results) Table 2 shows the test results.

[0021]

[Table 2]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-130204 (JP, A) JP-A-3-118304 (JP, A) JP-A 63-227502 (JP, A) JP-A 51- 125732 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 37/52 A01N 37/34

Claims (2)

(57) [Claims] (1) α-chloro-benzaldoxime and 5-
An industrial fungicide containing chloro-2,4,6-trifluoroisophthalonitrile or 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile as an active ingredient. 2. An α-chloro-benzaldoxime and 5-
Industrial use characterized by adding chloro-2,4,6-trifluoroisophthalonitrile or 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile simultaneously or separately to sterilize. Sterilization method.