JPH10330205A - Industrial microbicide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an industrial microbicide exerting a less influence upon a human body and environment than any prior industrial microbicides and effecting an excellent microbicidal action upon microorganisms covering a wider range in an industrial field, by including a specific compound. SOLUTION: This objective microbicide is obtained by including at least one selected from the compounds shown by formula I (R1 is a lower alkyl, etc.; R2 is H, etc.; R3 is piperazyl, etc.; X1 and X2 are each H or a halogen), formula H or formula III(R4 is a lower alkyl or H; Y is oxygen or sulfur) or the salt of the at least one compound, (as respective exemplary compounds of formulas I to III, norfloxacin, enoxacin, ofloxacin, etc., are listed). The microbicide produces its effect when added to pulp slurry in paper manufacturing process, industrial water such as cooling water in metalworking process, and a variety of industrial goods such as an aqueous coating material, coating liquid for paper, polymer latex, paper pulp, adhesive paste, leather, metalworking oil in the ratio of 10000 to 0.01 mg/kg.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial germicide which is excellent in controlling slime in industrial water in the papermaking process, industrial raw materials such as emulsion paints, pastes, metalworking oils, fiber oils, and microbial control of industrial products. About.

[0002]

2. Description of the Related Art Conventionally, microorganisms harmful to industrial water are liable to proliferate, causing a decrease in productivity, quality and workability.

[0003] In particular, in the water system in the pulp and paper industry, slime is generated due to the proliferation of bacteria, filamentous fungi, and yeasts, and the pulp slurry flows through the water passages, especially in the places where the slurry comes into contact with rough walls, chests, flow boxes, and the like. ,
A large amount of slime easily adheres to a transport pipe or other place where the flow velocity of the pulp slurry is low and stagnates. This slime is often detached and re-incorporated into the pulp slurry to move to the papermaking process, causing paper breakage or product contamination, as well as causing various obstacles due to the propagation of microorganisms. The occurrence of such an obstacle becomes a serious problem, especially when a high-speed machine is used, and causes a significant decrease in productivity and economic loss.

[0004] For example, the propagation of microorganisms in a circulating water system for cooling such as a metal working process causes problems in metal working, such as impairing cooling performance and emulsifying properties, and generates a bad smell, thereby deteriorating the working environment. Cause undesirable phenomena in public health.

Further, the growth of harmful microorganisms is not only a problem in the various industrial processes as described above, but also in aqueous paints, paper coating liquids, polymer latex, paper pulp, sizing agents, leather, metal It is also found in industrial products such as processing oils and causes various obstacles such as quality deterioration and hygiene problems.

[0006] By the way, the chemicals for controlling the generation of harmful microorganisms in the industrial water system or industrial products include:
Heretofore, for example, organometallic compounds, organic chlorine compounds, organic sulfur compounds, quaternary ammonium salts, and the like have been used. However, they are toxic to the human body, emit odors and off-flavors, and further cause undesired phenomena such as foaming. In addition, if a water system containing these is discharged into a general river or sea, it will not only have an adverse effect on fish and shellfish, but will also cause environmental conservation problems.

[0007] Such a problem can be avoided, for example, by 2-bromo-2-nitropropanediol-
1,3 are known. However, this compound has a specific action and limits the types of microorganisms that can be sterilized, and the bactericidal effect is insufficient for water systems containing many types of microorganisms such as white water, and the effect is not long-lasting. It was not fully satisfactory as an industrial germicide.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an industrial germicide which has less effect on the human body and the environment than conventional industrial germicides and is effective against a wide range of microorganisms.

[0009]

SUMMARY OF THE INVENTION The present inventors have studied various compounds in order to achieve the above object, and as a result, they have been conventionally used as antibacterial agents in the medical field (therefore, their effects on the human body and the environment). The compound having the following general formula shows excellent bactericidal action (antimicrobial action) against a wide range of microorganisms in the industrial field, and is extremely effective as an industrial bactericide. I came to.

The industrial fungicide of the present invention has the following general formula I:
It is characterized by comprising at least one of the compounds having II and III, or a salt thereof.

[0011]

Embedded image

In the above formula, R1 to R4, X1 to X2, and Y are as follows. R1: lower alkyl group, cycloalkyl group, phenyl group, or a halide thereof R2: hydrogen group, amino group, or methyl group R3: piperazyl group, piperidyl group, pyrrolidinyl, methylpiperazyl group, dimethylpiperazyl group, aminopiperazyl group, A methylpiperidyl group, a dimethylpiperidyl group, an aminopiperidyl group, a methylpyrrolidyl group, a dimethylpyrrolidyl group, an aminopyrrolidyl group, or a halogen R4: a lower alkyl group, or hydrogen X1, X2: a hydrogen group, or a halogen group; X1 and X2 may be the same or different Y: oxygen or sulfur

In the compounds having the above general formulas I to III, the lower alkyl group for R1 has 1 to 4, preferably 2 to 3 carbon atoms. The cycloalkyl group particularly preferably has 3 carbon atoms, and may have a fluorine, phenyl group or methyl group added thereto.

The methylpiperazyl group of R3 is 3 or 4
-A methylpiperazyl group is preferred. The dimethylpiperazyl group is preferably a 3,5-dimethylpiperazyl group. The amino piperazyl group is preferably a 3 or 4-amino piperazyl group. The methyl piperidyl group is preferably a 3-methyl piperidyl group. The anomipiperidyl group is preferably a 4-aminopiperidyl group. The pyrrolidyl group is preferably a 1, 2 or 3-pyrrolidyl group. The aminopyrrolidyl group is
A 3-aminopyrrolidyl group is preferred.

The lower alkyl group of R4 is particularly preferably one having 1 carbon atom.

In the present invention, the compound having the above general formula may be a salt thereof. This salt includes compounds having the above general formula, inorganic acids such as hydrohalic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and hydrobromic acid, and halogen acids such as chloric acid; acetic acid, oxalic acid, gluconic acid, benzoic acid Carboxylic acids such as methanesulfonic acid, benzenesulfonic acid, sulfonic acids such as p-toluenesulfonic acid, lactic acid, tartaric acid, organic acids such as oxyacids such as citric acid, or alkali metals such as sodium and potassium Salts, amine salts such as diethanolamine, diethylenetriamine, isopropylamine, and morpholine, and compounds in various other forms.

Specific examples of the compound used as the industrial fungicide of the present invention include the following compounds.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

The industrial disinfectant of the present invention includes pulp slurry in the papermaking process, industrial water such as cooling water in the metalworking process, water-based paint, coating liquid for paper, polymer latex, pulp for papermaking, paste It exhibits its bactericidal effect by being added to various industrial products such as leather, leather and metalworking oils.

[0022] The amount of the fungicide of the present invention is 10,000 to 0.01 mg / k in these industrial waters and industrial products.
g, preferably 1000 to 0.1 mg / kg. If the addition amount is larger than this, the effect is saturated, so that not only is it economically disadvantageous, but also there is a concern that a large amount of addition may adversely affect the human body and the environment. On the other hand, if the amount is too small, a sufficient effect cannot be obtained.

The bactericide of the present invention may further contain, if necessary, additives such as a surfactant, a thickener and a filler, in addition to the above-mentioned compounds.

The bactericide of the present invention, if necessary, containing these additives can be used as a solution or dispersion using an appropriate solvent, or can be mixed with a water-soluble solid or fine powder. It can also be used as a powder or tablet.

The solvent is preferably water, but alcohols such as methanol and ethanol; ethylene glycol, propylene glycol, polyethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether. Glycols such as butyl ether;
Dimethyl sulfoxide, dimethylformamide, ethylene glycol diasate, diethylene glycol monoethyl ether acetate and the like can be used.

Examples of the water-soluble solids and fine powders used in the above-mentioned powders, granules and tablets include inorganic salts such as sodium chloride, anhydrous sodium sulfate and magnesium sulfate; high molecular weight polyethylene glycol; porous dextrin; Saccharides such as glucose and lactose; natural fibers such as cellulose powder, waste paper powder, pulp powder, fine fibers, bran, and bran; and the like. These may be mixed with the industrial germicide of the present invention in a kneader, a blender or the like and used as powders or granules, or may be used after tableting with a tableting machine.

[0027]

【Example】

[Examples of preparation of industrial disinfectants] Disinfectants having the compositions shown in Table 4 were prepared.

[0028]

(Parts by weight) Formulation Example 1 Norfloxacin 10 Surfactant ^{* 1} 3 Thickener ^{* 2} 0.5 Water 86.5 Formulation Example 2 Sparfloxacin acetate 10 Diethylene glycol monomethyl ether 20 Water 70 Formulation example Reference Signs List 3 Tosfloxacin tosylate 3 Ciprofloxacin hydrochloride 7 Water 90 Formulation example 4 Lomefloxacin hydrochloride 5 Enoxacin hydrochloride 5 Water 90 Formulation example 5 Difloxacin sodium salt 10 Ofloxacin sodium salt 10 Water 80 Formulation example 6 Floroxacin amine salt 15 Ethylene Glycol 10 Water 75 Formulation Example 7 Temafloxacin 5 Lufloxacin 10 Surfactant ^{* 1} 3 Thickener ^{* 2} 0.5 Water 81.5 Comparative Formulation Example 1 2-bromo-2-nitropropanediol-1,330 Water 70 * 1: Kao Corporation's product name "Dimor "Use * 2: xanthan gum (SanAkirasha trade name" KELZAN "use)

Example 1 [Measurement of Minimum Inhibitory Concentration of Microorganism] The bactericide of each preparation was diluted with sterilized water,
0, 330, 100, 70, 60, 50, 40, 30,
20, 10, 5, and 1 mg / kg were added to each petri dish and mixed with a bouillon agar medium to prepare a plate medium. The following A to D pre-cultured in advance on this plate medium
Were inoculated and allowed to stand at 33 ° C. for 48 hours, and then the minimum inhibitory concentrations for these microorganisms were measured. Table 5 shows the results.

Test microorganisms A: Escherichia coli B: Aerobacterium aerogenes C: Pseudomonas aeruginosa D: Bacillus subtilis

[0031]

[Table 5]

Example 2 (Sterilization test of paper pulp slurry) Circulating white water collected from a papermaking process in a paper mill was added to a Waxman liquid medium, and cultured at 30 ° C. with shaking for 1.5 hours. Microorganisms. 10m of each preparation example
The diluted test microorganism was inoculated into a waxman liquid medium added to a concentration of g / kg, and cultured with shaking at 33 ° C. for 48 hours, and the turbidity was measured. Table 6 shows the results.

[0033]

[Table 6]

Example 3 (Preservative test of starch slurry) Water was added to tapioca starch (manufactured by Nippon Shokuhin Kabushiki Kaisha) to prepare a slurry having a tapioca starch concentration of 20% by weight. / Kg and left at 30 ° C. The state of the rot was observed for 14 days. Table 7 shows the results.

[0035]

[Table 7]

[0036]

INDUSTRIAL APPLICABILITY The industrial bactericide of the present invention can effectively and sustainably control a wide range of microorganisms in industrial water and industrial products despite its low toxicity to the human body and the environment.

Claims (1)

[Claims] An industrial fungicide comprising at least one selected from compounds having the following general formulas I, II and III, or a salt thereof. Embedded image In the above formula, R1: a lower alkyl group, a cycloalkyl group, a phenyl group, or a halide thereof R2: a hydrogen group, an amino group, or a methyl group R3: a piperazyl group, a piperidyl group, a pyrrolidinyl, a methylpiperazyl group, a dimethylpiperazyl group R4: lower alkyl group, or hydrogen X1, X2: hydrogen group, or halogen, aminopiperazyl group, methylpiperidyl group, dimethylpiperidyl group, aminopiperidyl group, methylpyrrolidyl group, dimethylpyrrolidyl group, aminopyrrolidyl group, or halogen And X1 and X2 may be the same or different Y: oxygen or sulfur