JPH0780727B2 - Industrial fungicide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a dibromonitroalcohol compound represented by the general formula (I) and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide [ Hereinafter, the compound (II) will be abbreviated.], And a novel industrial bactericide utilizing the synergistic effect of the bactericidal effects of both compounds.
The industrial bactericide is preferably used in an industrial water system related to paper pulp production.

(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 addition, slime is deposited and formed in a place where the flow velocity of the pulp slurry becomes low and stagnates. This slime is often released, causing paper scraps and contamination of pulp and paper products, 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, even in a circulating water system for cooling metalworking oil agents, microorganisms multiply and hinder the cooling performance and emulsifying properties of the oilworking agents, and a bad odor is generated, which worsens the working environment and is a phenomenon unfavorable to public health. Is caused.

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 the chemicals for suppressing or controlling the generation of harmful microorganisms in the water system or the industrial products, for example, organic metal compounds, organic chlorine compounds, organic sulfur compounds, and quaternary ammonium have hitherto been used. Although salt compounds and the like have been used, these compounds are toxic to the human body, emit a foul odor and a strange odor, and cause undesirable phenomena such as foaming. In addition, these pesticide-containing water systems adversely affect fish and shellfish when they are thrown into a general river or the sea, which causes a problem in environmental protection.

(Object, Structure and Effect of the Invention) The present inventors have completed the present invention as a result of intensive studies to eliminate the above-mentioned defects of the antibacterial agent.

That is, the present invention has the general formula (Wherein R represents a hydrogen atom or an alkyl group), a dibromonitroalcohol compound represented by
The present invention provides an industrial bactericide characterized by containing 4,4-tetrachlorotetrahydrothiophene-1,1-dioxide.

The compound represented by the general formula (I) is a fungicide described in JP-B-40-8917, and the compound (II)
Is a fungicide described in US Pat. No. 2,957,887.

Each of these bactericides has an insufficient bactericidal effect, such as limited effects on certain types of microorganisms, and also lacks sustainability of effects, and is not yet satisfactory as an industrial bactericide.

The industrial bactericide of the present invention exerts an extremely excellent bactericidal effect which can not be expected at all by the individual constituent components, and is irrespective of the type against harmful microorganisms such as filamentous fungi, bacteria and yeasts. Has a wide range of applications.

Examples of the compound represented by the general formula (I) in the present invention include 2,2-dibromo-2-nitroethanol and 2,2-dibromo-2-nitro-1-methylethanol. These compounds are not limited to one kind when compounded, and two or more kinds may be used in combination.

The compounding ratio (weight) of the compound represented by the general formula (I) and the compound (II) is (1:10) to (10: 1), preferably (1 :).
5) to (5: 1). If either one is too small, a satisfactory effect cannot be obtained.

The industrial germicide of the present invention is basically prepared by uniformly mixing the above-mentioned two components, but it is generally used as an aqueous solution, a solvent solution, an emulsified 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 industrial 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 this industrial bactericide to be added varies depending on the concentration of microorganisms, but generally 0.01 to 100 ppm in the case of a water-based system in the field of the pulp and paper industry, a water-based paint, a paste,
In the case of leather and the like, it is 1 to 500 ppm, and a good bactericidal effect can be obtained at this level.

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 and Comparative Examples) Industrial fungicides were prepared according to the following formulations. All parts in the examples are parts by weight.

Example 1 2,2-Dibromo-2-nitro-1-methylethanol 10
Parts compound (II) 10 parts diethylene glycol monomethyl ether 75 parts SOLPOL 900A (manufactured by Toho Kagaku) 5 parts EXAMPLE 2 2,2-dibromo-2-nitroethanol 10 parts compound (II) 10 parts diethylene glycol monomethyl ether 75 parts SOLPOL 900A 5 parts Comparative Example 1 Compound (II) 20 parts Diethylene glycol monomethyl ether 75 parts Solpol 900A 5 parts Comparative Example 2 2,2-dibromo-2-nitroethanol 20 parts Diethylene glycol monomethyl ether 80 parts Comparative Example 3 2,2-dibromo-2 -Nitro-1-methyl ethanol 20
Part Diethylene glycol monomethyl ether 80 parts Comparative Example 4 2-Bromo-2-nitropropanediol 10 parts 3,3,4,4-Tetrachlorotetrahydrothiophene-1,1-
Dioxide 10 parts Diethylene glycol monomethyl ether 75 parts Sorpol 900-A 5 parts Comparative Example 5 2-chloro-2-nitropropanediol 10 parts 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-
Dioxide 10 parts Diethylene glycol monomethyl ether 75 parts Sorpol 900-A 5 parts (Effect test) With respect to the industrial bactericides prepared in Examples 1 to 2 and Comparative Examples 1 to 3, a slime generation preventing effect is obtained by the following method. And the antiseptic effect was investigated.

Test Example 1 [Test for Prevention of Bacterial Proliferation and Slime Generation in Wastewater after Paper Making Process] In a paper making process of a certain paper mill, the industrial bactericide prepared in Examples 1 to 2 and Comparative Examples 1 to 3 was applied to a white water bit. The number of microorganisms in white water was measured by adding the solution to the concentration in water of 20 ppm for 7 days over 2 hours and 3 times.

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 shown in Table 1 above, it can be seen that the industrial fungicides of the present invention (Examples 1 and 2) have an excellent bacteriostatic effect.

Test Example 2 [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 coating solution which has been spoiled in advance were added and stirred, and the concentration was adjusted to 300 ppm as described above. The prepared 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 2 below.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-175406 (JP, A) JP-B-40-8917 (JP, B1)

Claims (1)

[Claims] 1. A general formula (Wherein R represents a hydrogen atom or an alkyl group), a dibromonitroalcohol compound represented by
An industrial fungicide containing 4,4-tetrachlorotetrahydrothiophene-1,1-dioxide.