JPH0373521B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an industrial bactericidal algicidal composition, and more particularly, it contains at least one dithiocarbamic acid heavy metal salt and a compound of the general formula (However, R represents hydrogen or a halogen atom.)
The present invention relates to an industrial bactericidal and algicidal composition containing 2-methylisothiazolin-3-one or its metal complex salt compound as an active ingredient. Many industrial bactericides and algaecides have been developed, and their uses include, for example, industrial water, papermaking white water,
Paints, ship bottom paints, cutting oils, polymer emulsions, etc. are used in a wide range of products, but there are limits to their effectiveness from the beginning and they may not be effective against some organisms. Expected effects may not be obtained due to the acquisition of resistance of organisms to chemicals, for example, in the case of industrial water, the heat exchange function may be reduced, or the generated potential difference may accelerate the corrosion of equipment, and in the case of paper manufacturing white water, the product may deteriorate. In addition to quality deterioration, problems such as paper breaks during the papermaking process impede continuous operation and cause a decline in production efficiency, causing great economic damage. Therefore, there is a strong desire to establish measures for controlling industrial pests that have stable, long-lasting effects and wide applicability. Given this current situation, and in order to monitor the evolution of pests, acquire resistance, and avoid it, it has been proposed to apply new drugs one after another.
There are natural limits in terms of the number and types of drugs and their performance, and the variety of industrial pests, as well as the possibility of simultaneous resistance to two or more drugs during use. This problem has not yet been solved for several reasons, such as the fact that organisms with this phenomenon can easily occur, and that it contains complex biological content that is difficult to elucidate. Therefore, the present inventors conducted repeated research to establish a method for controlling industrial pests that avoids the above-mentioned problems and can withstand a wide range of uses.As a result, the heavy metal salt of dithiocarbamic acid of the present invention and the general formula (However, R represents hydrogen or a halogen atom.)
The present inventors have discovered that a composition containing a 2-methylisothiazolin-3-one compound or a metal complex salt thereof as an active ingredient exhibits a stable and long-lasting pesticidal effect, and has completed the present invention. The dithiocarbamic acid heavy metal salt of the present invention is widely used as a fungicide in the field of agriculture and horticulture, and is known to exhibit excellent effects. And because it has low toxicity to humans and animals,
It is widely used industrially as a water treatment agent such as disinfectant, algaecide, and slime control agent, but although its effects are long-lasting, the effects are somewhat slow, and there are drawbacks in this respect. On the other hand, 2-methylisothiazolin-3-one compounds or their metal complex salt compounds are compounds with excellent bacteriostatic activity, and are reported in Japanese Patent Publication No. 53-23968 and Japanese Patent Publication No. 46-21240 to be effective against bacteria, algae, etc. It is known to have a wide range of activities and to be long-lasting. However, the effective concentration varies depending on the type of organism, and the long-lasting effect also varies depending on the type of organism.
The duration varies from several months to three months, and there is a problem with the stability of the effect. Furthermore, when used as described above, there are problems due to the occurrence of resistant organisms and changes in the types of organisms. The compositions of the invention are significantly potentiated and have improved persistence at low concentrations where the compounds of the invention alone do not exhibit activity. Specific examples of heavy metals in the dithiocarbamic acid of the present invention include manganese ethylenebisdithiocarbamate, zinc ethylenebisdithiocarbamate, zinc-coordinated manganese ethylenebisdithiocarbamate, zinc monomethyldithiocarbamate,
Examples include a mixed salt in which zinc dimethyldithiocarbamate and monomethyldithiocarbamic acid, dimethyldithiocarbamic acid, and/or ethylenebisdithiocarbamate are bonded via zinc. In addition, examples of the 2-methylisothiazolin-3-one compounds generally indicated above include 5-chloro-2-methylisothiazolin-3-one and 2-methylisothiazolin-3-one, and metal salts that can form metal complex salts with these include: Zinc chloride, calcium chloride, magnesium chloride,
Examples include magnesium nitrate, iron chloride, sodium chloride, copper nitrate, and zinc sulfate. The active ingredients of the present invention can be blended in any ratio as desired, preferably in the range of 1:50 to 1:0.02. The composition of the present invention may be used as it is, or may be used simultaneously with a commonly used carrier. For example, the form is aqueous solvent,
Emulsions, microcapsules, pastes, granules,
It can be used in any form such as a powder, and examples of carriers that can be used include water, organic solvents, and inorganic compounds. These active ingredients can also be used in combination with other active ingredients, such as fungicides, insecticides, algaecides, and herbicides.
Furthermore, it is also possible to add auxiliary agents, such as surfactants, emulsifiers, rust preventives, pigments, spreading agents, etc. Stabilizers may also be added to stabilize the active ingredient. Next, the present invention will be specifically explained with reference to the following examples. Example 1 The following were prepared as a drug of the present invention and a comparative drug. 1 5-chloro-2-methylisothiazoline-3
-one magnesium chloride and manganese ethylenebisdithiocarbamate in a 1:1 ratio2 5-chloro-2-methylisothiazoline-3
-1:1 ratio of magnesium chloride salt and zinc-coordinated manganese ethylenebisdithiocarbamate3 5-chloro-2-methylisothiazoline-3
-1:1 mixture of magnesium chloride salt and ethylenebisdithiocarbamic acid and/or dimethyldithiocarbamic acid bound via zinc 4 5-chloro-2-methylisothiazoline-3
-one magnesium chloride and zinc monomethyldiocarbamate in a 1:1 ratio 5 2-methylisothiazoline-3-one magnesium chloride and ethylenebisdithiocarbamate zinc in a 1:1 ratio 6 2-methylisothiazoline-3 -1:1 ratio of magnesium chloride salt and zinc-coordinated manganese ethylenebisdithiocarbamate 7 5-chloro-2-methylisothiazoline-3
-one magnesium nitrate and manganese ethylene bisdithiocarbamate in a ratio of 1:28 5-chloro-2-methylisothiazoline-3
-one magnesium nitrate and zinc dimethyldithiocarbamate in a ratio of 1:29 5-chloro-2-methylisothiazoline-3
-one magnesium chloride salt and 2-methylisothiazoline-3-one magnesium chloride salt (1:1) and manganese ethylenebisdithiocarbamate in a 2:1 ratio10 5-chloro-2-methylisothiazoline-3
-one magnesium chloride salt 11 2-methylisothiazoline-3-one magnesium chloride salt 12 Manganese ethylenebisdithiocarbamate 13 Example 2 of a hybrid salt in which ethylenebisdithiocarbamate and/or dimethyldithiocarbamate are bonded via zinc 10Algae liquid (Chlorellaspp,
complex mainly consisting of Scendesmusspp),
Urea was added thereto as a nitrogen source at a rate of 0.5 g/unit. Apply the drug at a predetermined concentration to this,
The growth of algae was investigated over time. The results are shown in the table below.

【table】

[Table] Example 3 The killing power of molds and bacteria that occur in industrial water and exhibit harmful effects was tested.
Added the active ingredient at the concentration of the test drug (5 ppm)
PotatoDextroseAgar flat medium was inoculated by spraying various suspensions (approximately 10 ⁶ Cells/ml) shown in the table below, cultured in an incubator at 25°C for 24 hours, and the presence or absence of growth of each was investigated.

【table】

[Table] Example 4 Aggregates adhering to the cooling water pipes of a factory were collected, and a certain amount of this was added to a culture solution (0.1% urea water), and then the present invention was added at the following concentration. The composition was added, stirred, and cultured at 20 to 30°C for 10 days for investigation.

【table】

Claims (1)

[Claims] 1 Manganese ethylene bisdithiocarbamate,
Zinc ethylenebisdithiocarbamate, zinc-coordinated manganese ethylenebisdithiocarbamate, zinc monomethyldithiocarbamate, zinc dimethyldithiocarbamate, and monomethyldithiocarbamate or dimethyldithiocarbamate and/or ethylenebisdithiocarbamate are bonded via zinc. at least one kind of dithiocarbamic acid heavy metal salt selected from mixed salts,
general formula (However, R represents hydrogen or a halogen atom.)
An industrial germicidal algae composition comprising 2-methylisothiazolin-3-one or a metal complex thereof as an active ingredient.