JPH062643B2 - Industrial fungicide - Google Patents

Description

TECHNICAL FIELD The present invention relates to an industrial fungicide. The industrial bactericide of the present invention is suitably used for industrial water related to the pulp and paper industry, cooling water for various industries, and the like.

(Prior art and problems) Conventionally, wastewater from the papermaking process in the pulp and paper industry,
In various water systems such as circulating cooling water in various industrial fields, it is harmful to water-based paints, coating liquids for paper, latex, printing paste, leather, etc. made using industrial water. It is easy for various microorganisms to multiply and proliferate, which causes a decrease in productivity and quality.

In particular, in the water system in the pulp and paper industry, slime has recently been generated due to the multiplication of filamentous fungi and yeasts, and the channel in which the pulp slurry flows, especially the rough wall or chest where the slurry contacts, the flow box, the transport pipe, In other places where the flow velocity of other pulp slurries becomes smaller and stagnant, slime adheres and forms. This slime is often detached, causing paper scraps and paper pulp product contamination, as well as causing various disorders due to microbial growth. The occurrence of such a failure becomes a particularly serious problem when using a high-speed machine, resulting in a significant decrease in productivity and economic loss.

Further, also in the circulating water system for cooling the metal working oil agent, microorganisms multiply and inhibit the cooling performance and emulsifying property of the working oil agent, and also a bad odor is generated, which deteriorates the working environment and is preferable from the viewpoint of public health. It causes a phenomenon that does not exist.

Further, in the cooling water system, the growth of microorganisms and the production of slime may cause a decrease in heat transfer efficiency of the heat exchanger and a blockage of the flow path.

Other obstacles due to the propagation of harmful microorganisms are also found in industrial products such as water-based paints, paper coating fluids, polymer latex, paper pulp, glue, leather and metalworking fluids.

By the way, as agents for suppressing or controlling the generation of harmful microorganisms in the above-mentioned water systems and industrial products, for example, organometallic compounds, organochlorine compounds, organosulfur compounds, quaternary ammonium salt compounds have hitherto been used. , Etc. have been used, but these compounds are toxic to the human body, give off a bad odor or an offensive odor, and cause undesirable phenomena such as foaming. In addition, these control agent-containing water systems adversely affect fish and shellfish when they are thrown into general rivers or the sea, and cause environmental conservation problems.

(Problem of the Invention) It is an object of the present invention to provide an industrial bactericide that solves the above problems found in the prior art.

(Means for Solving the Problems) The present inventors have completed the present invention as a result of intensive studies to solve the above problems.

That is, according to the present invention, the general formula (Wherein R ¹ and R ² are a hydrogen atom, a halogen atom, a lower alkyl group or a lower hydroxyalkyl group, and X is a halogen atom), and an aliphatic nitro alcohol represented by the formula: An industrial bactericide characterized by containing tribromoacetoxypropane represented by

Examples of the above-mentioned halogen atom include chlorine, bromine, iodine and fluorine.

Further, as the lower alkyl group, a methyl group, an ethyl group,
Examples of the lower hydroxyalkyl group such as propyl group include hydroxymethyl group and hydroxyethyl group.

The halogenated aliphatic nitroalcohol which is one component of the industrial germicide of the present invention is a compound known per se,
If it is used alone, its activity is markedly inferior to filamentous fungi and yeasts, and the desired effect cannot be obtained even at low concentrations against bacteria.

Similarly, tribromoacetoxypropane is also a known compound per se, and yeast alone, bacteria,
The desired effect cannot be obtained at low concentrations for filamentous fungi.

The industrial bactericidal agent of the present invention, by itself, exhibits extremely excellent bactericidal and antibacterial effects that cannot be expected at all, and it is a kind against harmful microorganisms such as filamentous fungi, bacteria, yeasts, etc. It has a wide range of application regardless of.

Examples of the compound of the general formula (I) in the present invention include the following.

2-chloro-2-nitroethanol, 1-chloro-1-nitropropanol- (2), 3-chloro-3-nitrobutanol- (2), 2-
Chloro-2-nitrobutanediol (1.3), 1-chloro-1-nitrobutanol- (2), 2-chloro-2-nitrobutanol, 2
-Chloro-2-nitropentanol (3), 2.2-dichloro-2-nitroethanol, 2-chloro-2-bromo-2-nitroethanol, 3-chloro-3-nitropentanediol- (2.4) , 4-chloro-4-nitrohexanol- (3), 2-bromo-2-nitroethanol, 2-bromo-2-nitropropanol (3), 2-bromo-2-nitrobutanediol (1.3), 3-Bromo-3-nitropentanediol- (2.4), 2.2-dibromo-2-nitro-ethanol, 1.1-dibromo-1-nitro-propanol (2), 4
-Bromo-4-nitrohexanol (3), 2-fluoro-2-nitroethanol, 2-fluoro-2-nitrobutanediol- (1
・ 3), 3-Iodo-3-nitrobutanol- (2), 2-fluoro-2
-Chloro-2-nitroethanol, 2-iodo-2-bromo-2-nitroethanol, 2-chloro-2-nitropropanediol
(1.3), 2-bromo-2-nitro-propanediol- (1.3) and the like.

The compounds of the general formulas (I) and (II) described above are not limited to one type each, and two or more types may be used in combination.

Further, the use ratio of the compound of the general formula (I) and the compound of the formula (II) is, by weight ratio, 1/100 to 100/1, preferably 1/50 to 50/1,
More preferably, it is 1/10 to 10/1.

The industrial bactericide of the present invention is basically produced by uniformly mixing the above two components. Generally, it is used as an aqueous solution, a solvent solution, an emulsion dispersion, or the like. Examples of the solvent that can be used here include alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents and the like. In addition, the bactericide of the present invention may be used by supporting it on any carrier, and the use mode is not particularly limited, and various methods can be adopted.

The amount of the disinfectant added when used depends on the concentration of microorganisms, but generally 0.01 to 100 ppm in the case of water systems in the fields of the pulp and paper industry, 1 to 1 in the case of water-based paints, glues, leather, etc. It is 500 ppm, and at this level a good bactericidal effect can be obtained.

It is acceptable to add a stabilizer, a surfactant, etc. to the industrial bactericide of the present invention within a range that does not impair the object of the present invention.

(Examples) Next, the present invention will be described in more detail with reference to Examples.
All parts shown below are parts by weight.

Example Various industrial bactericides having the following composition were prepared.

Product of the present invention [I] 2-Bromo-2-nitro-propanediol- (1,3) 10 parts Tribromoacetoxypropane 10 parts Diethylene glycol monomethyl ether 78 parts Rapisol B-80 (surfactant manufactured by NOF Corporation) 2 parts Inventive product [II] 2,2-dibromo-2-nitroethanol 10 parts Tribromoacetoxypropane 10 parts Diethylene glycol monomethyl ether 78 parts Rapisol B-80 2 parts Inventive product [III] 1,1-dibromo- 1-Nitropropanol (2) 10 parts Tribromoacetoxypropane 10 parts Diethylene glycol monomethyl ether 78 parts Lapizole / B-80 2 parts Inventive product [IV] 2,2-dibromo-2-nitroethanol 5 parts Tribromoacetoxypropane 15 Part Diethylene glycol monomethyl ether 78 parts Lapizole / B-80 2 parts Product of the present invention [V] 3-Bromo-3-nitropentane-2,4-diol 10 parts Trib Lomoacetoxypropane 15 parts Diethylene glycol monomethyl ether 78 parts Lapizole / B-80 2 parts Inventive product [VI] 2-Bromo-2-nitrobutane-1,3-diol 10 parts Tribromoacetoxypropane 15 parts Diethylene glycol monomethyl ether 78 parts Rapisol・ B-80 2 parts Inventive product [VII] 2-bromo-2-nitropropanol (3) 10 parts Tribromoacetoxypropane 15 parts Diethylene glycol monomethyl ether 78 parts Lapizole B-80 2 parts Comparative product [I] 2- Bromo-2-nitro-propanediol- (1,3) 20 parts Diethylene glycol monomethyl ether 78 parts Lapizole / B-80 2 parts Comparative product [II] 2,2-dibromo-2-nitroethanol 20 parts Diethylene glycol monomethyl ether 78 parts Lapizole / B-80 2 parts Comparative product [III] 1,1-dibromo-1-nitropropanol (2) 20 parts Diethylene glycol Lumonomethyl ether 78 parts Lapizole / B-80 2 parts Comparative product [IV] Tribromoacetoxypropane 20 parts Diethylene glycol monomethyl ether 78 parts Lapizole / B-80 2 parts Next, for each of the industrial fungicides mentioned above, Microbial growth inhibitory concentration, slime generation preventing effect, and antiseptic effect were examined by such test methods (hereinafter,% indicates weight%).

Test Example 1 [Microbial growth inhibitory concentration test] The composition of the culture medium used is a mixed aqueous solution of peptone 0.1%, glucose 0.05%, potassium primary phosphate 0.01% and magnesium sulfate 0.005%. The test method is to suspend the following test bacteria in the prepared culture solution, take a certain amount of this in a clean test tube,
A bactericide having a specified concentration of 5, 10, 20, 40, and 80 ppm was added thereto, and shake culture was performed at 32 ° C. The growth rate of the microorganism was determined by the turbidity generated by the propagation of the bacteria after 24 hours, and the concentration was defined as the complete growth inhibitory concentration of the microorganism.

The results are shown in Table 1.

The abbreviations of the test bacteria are as follows.

Test bacterium Pse: Pseudomonas aeruginosa A. a: Aerobactor aerogenes B. s: Bacillus subtillis A. v: Alcaligenes viscosus A. n: Aspergillus niger G. sp: Geotrichum sp. As is clear from Table 1 above, the industrial fungicides of the present invention (the products [I] to [VII] of the present invention) are effective against any of the test bacteria at a low concentration of 10 ppm or less. On the other hand, it can be seen that the comparative product cannot uniformly obtain effective effects on all the test bacteria.

Test Example 2 [Test for Prevention of Bacterial Proliferation and Slime Generation in Wastewater After Paper Making Process] In the paper making process of a certain paper mill, the product of the present invention [I] to
Add [VII] fungicide to white water bit for 2 hours a day, 3
It was added over 7 days so that the concentration in water was 20 ppm, and the number of microorganisms in white water was measured. The results are shown in Table 2.

As a test method, a sample of white water was diluted with sterilized water, a certain amount of this was sampled in a petri dish, and dissolved Waxman agar medium was injected, mixed, and solidified into a flat plate. Microbial colonies generated after culturing in an incubator (32 ° C) for 2 days were measured with a colony counter. Also, measure the number of paper breaks during papermaking,
The bactericidal effect was confirmed.

From the results in Table 2 above, it can be seen that the industrial bactericides of the present invention (the products [I] to [VII] of the present invention have an excellent bacteriostatic effect.

Test Example 3 [Bacterial growth prevention test in a papermaking coating solution] To a starch-based coating solution having a pH of 10.0, a broth liquid medium and a previously spoiled coating solution were added and stirred, and the concentration was adjusted to 300 ppm as described above. The manufactured industrial fungicide was added.

After storing this in a thermostat at 32 ° C. for 5 days, the number of viable bacteria in each coating solution was measured. The results are shown in Table 3 below.

Claims (1)

[Claims] 1. A general formula (Wherein, R ¹ and R ² represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower hydroxyalkyl group, and X represents a halogen atom), and an aliphatic nitro alcohol represented by the formula: An industrial bactericide characterized by containing tribromoacetoxypropane represented by: