JPH0825848B2 - Industrial sterilizer, antiseptic, algaecide - 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 bactericidal, antiseptic and algicidal agent. More specifically, it is effective as a papermaking process in the pulp and paper industry, cooling water for various industries, metal addition oils, fiber oils, water-based paints, paper coating solutions, latexes, preservatives such as sizing agents, and bactericides, And various water, industrial sterilization, antiseptic, which is useful for the prevention of damage by algae in the wastewater system,
Regarding algicides.

[0002]

2. Description of the Related Art It has been conventionally known that slime due to bacteria and fungi is generated in a papermaking process in the pulp and paper industry and in cooling water systems in various industries to cause loss such as deterioration of product quality and production efficiency. ing. Also, in many industrial products such as metalworking oils, fiber oils, water-based paints, paper coating liquid latexes, and paste solutions, spoilage by bacteria and contamination by fungi cause great damage. In addition, many obstacles occur in various uses and wastewater systems due to the generation of algae. Many fungicides and algaecides have been used to prevent damage by these microorganisms. In the old days, organic mercury compounds such as mercury ethyl phosphate and phenyl mercury acetate, and chlorinated phenol compounds such as pentachloro various phenols and trichlorophenol were used. However, these compounds are highly toxic, become a problem in terms of environmental safety, and their effects on the human body are clarified, and their use is being regulated.

Therefore, as a substitute drug, a cyclic nitrogen-sulfur compound, a bromine compound, a thiocyan compound, a quaternary ammonium salt compound or the like has been recently used alone or in a mixture thereof. It also has various drawbacks in use, for example, the drug effect is insufficient, the drug is irritating to the human body,
When it is used for a long period of time, it has the drawback that it tends to be resistant and it foams in the work environment, giving rise to adverse effects such as a bad odor.

The present inventors have conducted various studies to develop a drug effective as an industrial bactericidal / algicidal agent, and as a result, dichloroglyoxime is a good bactericidal / algicidal agent as a new bactericidal drug. I found and proposed that (Japanese Patent Application No. 3-21
385), and by further combining the dichloroglyoxime with an isothiazolone derivative or a complex compound of an isothiazolone derivative, it was found that the compound has further excellent bactericidal and algicidal actions (Japanese Patent Application No. 3-97955).

[0005]

DISCLOSURE OF THE INVENTION The present inventor further combined the above-mentioned dichloroglyoxime having a bactericidal and algicidal action with another bactericidal agent to obtain a further excellent bactericidal effect and algalicidal effect. As a result of various studies to find out the industrial sterilization, antiseptic, and algicidal agents, the present invention has been completed, and the present invention provides a novel industrial sterilizing, antiseptic, and algicidal agent.

[0006]

The gist of the present invention is represented by the general formula (1)

[0007]

[Chemical 11]

(Wherein X ₁ represents a hydrogen atom or a chlorine atom)
Glyxime represented by, and industrial sterilization containing at least one compound selected from the following compound group as an active ingredient,
It is an antiseptic and algaecide. Since the compound represented by the general formula (1) is produced as a mixture of a monochloro compound and a dichloro compound, it may be used as it is in a mixed state. The monochloro compound has almost no effect as compared with the dichloro compound. (A) Halogenated aliphatic nitro alcohol compound represented by the following formula

[0009]

[Chemical 12]

(Wherein X ₂ represents a halogen atom, R ₁ represents a hydrogen atom or a halogen atom, an alkyl group or a hydroxyalkyl group, R ₂ represents a hydrogen atom or an acetyl group, R ₃
Represents a hydrogen atom, an alkyl group, a hydroxyalkyl group or an acetoxyalkyl group. ) (B) 1,2-Benzisothiazol-3 (2H) -one

[0011]

[Chemical 13] (C) 2-Bromo-2- (bromomethyl) glutaronitrile

[0012]

Embedded image (D) Methylenebisthiocyanate

[0013]

[Chemical 15] (E) 4,5-Dichloro-3H-1,2-dithiol-
3-on

[0014]

Embedded image (F) 2,2-dibromo-2-cyanoacetamide

[0015]

[Chemical 17] (G) Mucobromic acid

[0016]

Embedded image (H) Halogenated acetic acid ester compound represented by the following formula

[0017]

[Chemical 19] (I) 3.3,4,4-tetrachlorotetrahydrothiophene-1,1 dioxide

[0018]

Embedded image

The drug of the present invention is usually used by being directly mixed and added to various target systems. At this time, the preparation can be made by dissolving the both in a suitable organic solvent and adding an interfacial lubricant, if necessary. Suitable organic solvents include ethylene glycol and diethylene glycol monomethyl ether type solvents. However, the above compounds may be separately added to the target system.

Although dichloroglyoxime has a strong bactericidal activity, it lacks inhibitory power and is poor in practical use when used alone. On the other hand, the above single compounds of the nine compound groups have a bactericidal activity but have a low bactericidal activity, or show no antibacterial activity against some bactericides, filaments, and algae, etc. Although it exhibits activity, it has various drawbacks such as extremely poor activity at low concentrations, and each of them alone has poor practicability. However, by using dichloroglyoxime and the above-mentioned single compounds of nine compounds each having a drawback, it is possible to control the growth of a wide range of microorganisms.

Industrial sterilization, antiseptic and algaecide agents of the present invention are used in papermaking and pulp manufacturing processes, industrial cooling water, cooling / cooling cooling water, lubricating oil for metalworking, aqueous emulsion,
In the process of manufacturing or processing paper, wood, plywood, paint, paste, pulp, fiber, etc., and capable of controlling fungi, bacteria, yeasts, algae, etc. that propagate on these finished products Is.

The main causative bacteria of microbial disorders such as industrial water, metalworking lubricating oil, aqueous emulsion, paper wood, paint and plywood are as follows. Alpergillus niga-penicillium funiculosum geothorium candidum cladosporium cladosporioides and other filamentous fungi, or enrobacta-aerogenes bacillus subtilis pseudomonas fluorescens flavobacterium aquatail acinet bacter calcoacetica or teus and other bacteria It is an algae such as Chlorella pyrenoidosa. The industrial bactericidal, antiseptic and algaecide agents according to the present invention act effectively on these fungi or algae and can completely suppress the generation of industrially harmful microorganisms with a small dose.

The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

[0024]

[Examples] Table 1 shows an example of compounding with a compound to be combined with the dichloroglyoxime of the present invention and a comparative example of the preparation of each compound alone.

[0025]

[Table 1]

In each preparation, diethylene glycol monomethyl ether was used as the solvent, and the surfactant TR-70 was used.
2 was added at 2% to formulate.

Experimental Example 1 The minimum inhibitory concentration (MIC) of the drugs shown in Table 1 was determined using Enterobacter-aerogenes bacteria separated from papermaking water (white water). As a test method, a diluted denatured Waxman medium (denatured Waxman medium: water = 4: 5) inoculated with Enterobacter-aerogenes bacteria at about 10 ⁶ cells / ml was placed in a 9 ml L-shaped culture tube to give a predetermined concentration (200 , 100, 50, 25, 12.5, 6.3,
3.1, 1.6, 0.8 ppm) was added to the diluted drug solution (1 ml) and the mixture was mixed with a mono-shaker at 30 ° C. for 24 hours.
It was judged by the presence or absence of growth of the bacteria after the time culture. Table 2 shows the results.

[0028]

[Table 2]

All of the drugs combined with dichloroglyoxime of Examples 1 to 8 are drugs having an inhibitory effect, but when combined with dichloroglyoxime, the MIC was lower than that of single use (Comparative Examples 11 to 18). The growth of bacteria can be suppressed with a smaller amount.

Experimental Example 2 The minimum bactericidal concentration (MBC) of the drug shown in Table 1 was determined using the Enterobacter aerogenes. As a test method, physiological saline was inoculated to about 10 ⁶ Enterobacter-aerogenes bacteria / ml in a 9 ml L-shaped culture tube, and given a predetermined concentration (200, 100, 50, 25, 1).
2.5, 6.3, 3.1, 1.6, 0.8 ppm) was added to the diluted drug solution (1 ml), and the viable cell count after culturing for 1 hour on a mono-shaker at 30 ° C. Conventional method (SPC method)
The concentration sterilized by 99.9% was measured. The results are shown in Table 3.

[0031]

[Table 3]

The agents of Examples 1 to 8 showed lower MBC than those of any of the comparative examples used alone, synergistically enhancing the bactericidal activity, and the results of Table 2 together with the excellent controllability and bactericidal activity were excellent. It is a drug with antibacterial activity.

Experimental Example 3 In the same manner as in Experimental Example 2, the minimum bactericidal concentration (MB) of the drug shown in Table 1 was used using Enterobacter aerogenes.
C) was determined. The results are shown in Fig. 1. As is clear from FIG. 1, the concentration of MBC is much lower than that when it is used alone, and a synergistic improvement in bactericidal activity is observed.

Experimental Example 4 Suppression test (MI) using white water of the paper manufacturing company A producing paper for the base paper and white water of paper manufacturing company B producing the newspaper.
C) was performed. As a method, white water and a modified Waxman medium mixed solution (white water: denatured Waxman medium = 5: 4) 9
Predetermined concentration in ml (200, 100, 50, 25, 1,
2.5, 6.3, 3.1, 1.6, 0.8 ppm) of the drug solution diluted to 1 ml was added and the bacterial growth after culturing for 24 hours on a mono-shaker at 30 ° C It was judged by the presence or absence of. The results are shown in Table 4.

[0035]

[Table 4]

Although the chemicals of Examples 1 to 8 combined with dichloroglyoxime have an inhibitory effect on white water of a paper manufacturing company, they are used alone when combined with dichloroglyoxime (Comparative Examples 11 to 11). Compared to 18), it shows a lower MIC and can suppress the growth of bacteria with a smaller amount used.

Experimental Example 5 A sterilization test was carried out using white water produced by a paper manufacturing company A that manufactures a coat base paper and a paper manufacturing company B that manufactures a newspaper. As a method, a certain amount (drug 2
0 ppm), and the number of viable cells after mono-shaking culture at 30 ° C. for 1 hour is measured by a conventional method (SPC method) and compared with a drug-free product. The results are shown in Table 5.

[0038]

[Table 5]

The agents of Examples 1 to 10 have higher bactericidal action than those of the comparative examples used alone, and synergistically enhance the bactericidal activity.
Along with the results of Table 3 and FIG. 1, it is a drug having an excellent bactericidal effect.

Experimental Example 6 A fixed amount (100 ppm) of the chemicals shown in Table 1 was added to an emulsion type cutting oil commercially available and stirred uniformly. This was diluted 10 times with industrial water and emulsified, and the resulting mixture was put in an Erlenmeyer flask equipped with a screw thread and put in a rotary shaker at 30 ° C. to wait for the progress of rotting. Daily standard (SP
The preservative efficacy was determined by measuring the viable cell count according to method C). The results are shown in Table 6.

[0041]

[Table 6]

The agents of Examples 1 to 8 could be preserved longer than those of the comparative examples alone.

Experimental Example 7 A culture of cyanobacteria separated from a cooling water system is diluted 100 times with cooling water and 9 ml is dispensed into an L-shaped culture tube. On the other hand, the drugs shown in Table 1 were used at various concentrations (200, 10
0, 50, 25, 12.5, 6.3, 3.1, 1.6,
0.8 ppm) and cultivated under mono-shaking at 30 ° C. under irradiation of light to measure turbidity on a daily basis. The effective concentration is the concentration at which no increase in turbidity is observed after one week. And
The results are shown in Table 7.

[0044]

[Table 7]

The agents of Examples 1 to 8 were suppressed at a lower concentration than any of the comparative examples used alone, and a synergistic inhibitory effect was observed.

Experimental Example 8 An aqueous slurry containing 10% of oxidized starch was prepared, and a starch slurry which had already spoiled was added, and the mixture was dispensed into an Erlenmeyer flask equipped with a screw while uniformly stirring. Add the chemicals shown in Table 1 to a constant amount (100 ppm) and roll at 30 ° C.
Put in a Tally shaker and incubate. The viable cell count of each sample is measured daily by a conventional method (SPC method) to determine the antiseptic effect. Table 8 shows the results.

[0047]

[Table 8]

Experimental Example 9 In the same manner as in Experimental Example 3, the standard strain Escherichia
The minimum bactericidal concentration (MBC) for the combined drugs represented in Table 9 was determined using E. coli JCM1649. The results are shown in Table 10.

[0049]

[Table 9]

[0050]

[Table 10]

As is clear from Table 10, the composition shown in Table 9 of the present invention shows that the minimum bactericidal concentration (MBC) is much lower than that of the single use by varying the ratio of the active ingredients, and synergistically. Improvement of bactericidal power was recognized.

[0052]

INDUSTRIAL APPLICABILITY As described above, the present invention controls the growth of a wide range of microorganisms by using dichloroglyoxime in combination with nine kinds of compounds having bactericidal and algicidal effects which are not used alone. And was able to be an excellent industrial sterilizer, antiseptic and algaecide.

[Brief description of drawings]

FIG. 1 shows the minimum bactericidal concentration (M) of the combination example of Example 9, Comparative Examples 19 and 21 against Enterobacter aerogenes.
FIG.

FIG. 2 is a diagram showing the minimum bactericidal concentration (MBC) of the compounding examples of Example 10, Comparative Examples 20 and 21 against Enterobacter aerogenes.

[Explanation of symbols]

 The vertical axis represents MBC.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location A01N 43:26 37:12 43:80 47:48) (56) Reference JP-A-62-195309 (JP, A) JP-A-5-70306 (JP, A)

Claims (1)

[Claims] 1. A general formula (1): (In the formula, X ₁ represents a hydrogen atom or a chlorine atom) and an industrial bactericidal agent, an antiseptic agent, and an algicidal agent containing at least one compound selected from the following compound groups as an active ingredient (a) Halogenated aliphatic nitro alcohol compound represented by the formula: (In the formula, X ₂ represents a halogen atom, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group or a hydroxyalkyl group,
R ₂ represents a hydrogen atom or an acetyl group, R ₃ represents a hydrogen atom,
An alkyl group, a hydroxyalkyl group or an acetoxyalkyl group is shown. ) (B) 1,2-benzisothiazol-3 (2H) -one (C) 2-Bromo-2- (bromomethyl) glutaronitrile embedded image (D) Methylenebisthiocyanate embedded image (E) 4,5-Dichloro-3H-1,2-dithiol-
3-on (F) 2,2-dibromo-2-cyanoacetamide embedded image (G) Mucobromic acid (H) Halogenated acetic acid ester compound represented by the following formula: (I) 3.3,4,4-tetrachlorotetrahydrothiophene-1,1 dioxide