JPH08151303A - Industrial fungicide composition - Google Patents

Abstract

(57) [Summary] [Structure] (A) Industrial fungicide, and (B) 10 to 10 carbon atoms.
An industrial fungicide composition comprising a combination of 30 saturated or unsaturated fatty acids and at least one selected from fats and oils containing these as an acid component. [Effect] Due to the synergistic effect, excellent antibacterial activity is exhibited, the amount of the industrial bactericide used can be reduced, and the use cost can be reduced.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel industrial bactericidal composition, and more specifically, it is excellent in its synergistic effect by combining a conventional industrial bactericidal agent with higher saturated or unsaturated fatty acids and oils and fats. The present invention relates to an industrial bactericide composition that exhibits antibacterial activity and can reduce the amount of bactericide used.

[0002]

2. Description of the Related Art In a cooling water system of various factory plants, slime composed of bacteria, filamentous fungi, algae, etc. is generated in the system, which causes a decrease in thermal efficiency, clogging of water passage pipes, corrosion of pipe metal materials, and other slimes. It is known that disorders often occur.

Further, in the paper pulp papermaking system, slime mainly composed of bacteria and filamentous fungi is formed on the inner wall surface of the system by using various additives such as cellulose and starch as nutrient sources. Is peeled from the wall surface, it is mixed as foreign matter in the product, which lowers the product quality and induces paper breakage in the paper making process to obstruct continuous operation, resulting in a significant decrease in production efficiency. Be invited. Particularly in the pulp and paper industry, a large amount of starch, latex, casein, etc. are used as additives, and since all of these additive substances serve as a nutrient source for microbial propagation, they are decomposed by microorganisms and deteriorate the product. It is a big cause.

In addition, water-based paints rich in organic substances,
Emulsion paint, emulsion adhesive, metalworking oil,
In related fields such as latex, starch paste solution and paper coating solution, it is known that various obstacles such as deterioration of product quality and productivity due to microorganisms occur.

Heretofore, with respect to microbial disorders such as bacteria, filamentous fungi, yeasts and algae in various industrial fields,
Since it is relatively simple to carry out and economical, it is treated with an industrial fungicide.

In general, when an industrial bactericidal agent is used, it is desirable from the economical and safety point of view that it has excellent antibacterial activity and requires only a small amount of it. BACKGROUND ART Industrial bactericide compositions have been developed in which two or more kinds of agents are combined and synergistic effects thereof enhance antibacterial activity.

[0007] By the way, higher fatty acids are known to show antibacterial activity against certain microorganisms [[B
iosci. Biotech. Biochem. "Fifth
Volume 7, pp. 2194-2195 (1993)],
It is not known to use the higher fatty acids in combination with a usual industrial bactericide to enhance the antibacterial activity of the industrial bactericide.

[0008]

The present invention is based on the combination of certain compounds with conventional industrial fungicides.
The purpose of the present invention is to provide an industrial fungicide composition capable of enhancing antibacterial activity by the synergistic effect and reducing the amount of the fungicide used.

[0009]

Means for Solving the Problems As a result of intensive studies to develop an industrial antibacterial composition having excellent antibacterial properties, the present inventors have found that an industrial antibacterial agent and saturated or unsaturated higher fatty acids and It was found that an unexpected synergistic effect is exhibited when used in combination with fats and oils containing it as a component, and the present invention has been completed based on this finding.

That is, the present invention provides at least one selected from (A) industrial fungicides, (B) saturated or unsaturated fatty acids having 10 to 30 carbon atoms, and fats and oils containing these as an acid component. An industrial fungicide composition comprising a combination with a seed is provided.

In the composition of the present invention, the type of the industrial bactericide used as the component (A) is not particularly limited, and various conventionally known industrial bactericides can be used. Preferable examples include cyanoacetamide compounds, halonitro compounds, isothiazolone compounds and the like. Here, examples of the halocyanoacetamide compound include 2,2-dibromo-
3-Nitrilopropionamide, 2-chloro-3-nitrilopropionamide, 2-bromo-3-nitrilopropionamide, 2,2-dichloro-3-nitrilopropionamide, N-methyl-2,2-dibromo-3- Examples of the halonitro compound include 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitropropane-1,3-diol, β-bromo-β-nitrostyrene, and 2-nitrobromopropionamide. -Bromo-2-nitro-1,3-diacetoxypropane, 5-bromo-5-nitro-1,3-dioxane and the like can be mentioned. Further, as an inchazolone compound, for example, 4-
Isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-4-isothiazolin-3-one, 2- n-octyl-4-isothiazolin-3-one, 2-n-decyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4
-Isothiazolin-3-one and the like. Further, other industrial fungicides include, for example, 4,5-dichloro-1,2-dithiol-3-one, methylenebisthiocyanate, bis (1,4-bromoacetoxy)-
2-butene, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and the like can be mentioned.

These industrial bactericides may be used alone or in combination of two or more kinds. In the composition of the present invention, as the component (B), saturated or unsaturated fatty acids having 10 to 30 carbon atoms, and fats and oils containing these as an acid component are used. By combining the component (B) with the industrial bactericide of the component (A), the synergistic effect improves the antibacterial activity, and the amount of the industrial bactericide used is 1 /
It can be reduced to about 2 to 1/5.

Examples of the saturated fatty acid having 10 to 30 carbon atoms include lauric acid, myristic acid, palmitic acid,
Examples include stearic acid, arachidic acid, behenic acid, and the like. As unsaturated fatty acids having 10 to 30 carbon atoms, oleic acid (cis-9-octadecenoic acid), linoleic acid (9,12-octadecadienoic acid), α-linolenic acid (9,12,15- Octadecatrienoic acid), γ-
Examples thereof include linolenic acid (6,9,12-octadecatrienoic acid). Further, a saturated or unsaturated fatty acid containing a hydroxyl group can also be used, and examples thereof include 12-hydroxystearic acid and ricinoleic acid (12-hydroxy-9-octadecenoic acid). Examples of oils and fats containing these fatty acids as acid components include linseed oil and castor oil. Among these, especially α-linolenic acid, γ-
Linolenic acid, linoleic acid, oleic acid, myristic acid,
Lauric acid, linseed oil and castor oil are preferred.

The fatty acids and oils and fats as the component (B) may be used alone or in combination of two or more kinds. In the composition of the present invention, the mixing ratio of the component (A) and the component (B) is usually selected in the range of 5: 1 to 1: 5, preferably 2: 1 to 2: 5. If this usage ratio deviates from the above range, the synergistic effect will not be sufficiently exhibited, and the object of the present invention will not be sufficiently achieved.

In the industrial germicidal composition of the present invention, the above-mentioned components (A) and (B) may be uniformly mixed in advance and added to the object to be treated, or the components (A) and (B). ) Components may be separately added to the object to be treated. When the component (A) and the component (B) are uniformly mixed, it is usually preferable to dissolve each component in a solvent to prepare a uniform solution for use.

Examples of the solvent that can be used here include alcohol-based solvents, ketone-based solvents, ether-based solvents, hydrocarbon-based solvents, among others, triol-based solvents such as glycerin and trimethylolpropane,
Glycol-based solvents such as alkylene glycol, dialkylene glycol and dialkylene glycol monoalkyl ether are preferred, and glycerin, trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether or dipropylene glycol are particularly preferred. Further, propylene carbonate, ethylene carbonate, γ-butyrolactone, N-methylpyrrolidone, tetrahydrofurfuryl alcohol and the like may be used. These solvents may be used alone or in combination of two or more.

Also, when the component (A) and the component (B) are added separately, it is advantageous to use the solvent and use each component in the form of a solution. The application field of the composition of the present invention may be a field to which an industrial bactericide can be applied, and is not particularly limited, but generally for slime control in a cooling water system or a pulp and paper plant,
Preservatives such as starch and casein, latex, pigments,
It is preferably used for preserving products such as adhesives, paints and leathers, and further for preserving metal working oils.

The amount of the industrial bactericidal composition used varies depending on the concentration of microorganisms, but generally in the case of water systems in the fields such as the pulp and paper industry, the component (A) is 0.1 to 0.1%.
The range of 100 ppm and 1 to 100 ppm of the component (B) is preferable, and in the case of fields such as water-based paints, glues and leathers,
(A) component 1 to 500 ppm and (B) component 10 to 50
The range of 0 ppm is preferred.

[0019]

The industrial bactericidal composition of the present invention is a combination of an industrial bactericidal agent with higher saturated or unsaturated fatty acids and fats and oils, and exerts an excellent antibacterial activity by its synergistic effect. The amount of the industrial bactericide used is about 1/2 to 1/5 as compared with the case where it is used alone, which is economically advantageous.

[0020]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

In each table, "aE + b" means the viable cell count a × 10 ^b cells / ml.

Example 1 Antibacterial activity against E. coli (1) Combination with 2,2-dibromo-3-nitrilopropionamide E. coli (E. c) cultured in Waxman liquid medium
oli, DH-5) is diluted 100 times with sterile distilled water,
Add γ-linolenic acid solution in dimethyl sulfoxide to γ
-Linolenic acid was added so that the final concentration was 50 ppm, and at the same time, a predetermined amount of 2,2-dibromo-3-nitrilopropionamide was added, and the change in the viable cell count over time was determined by the agar plate method. For comparison, the viable cell count was also obtained in the case where γ-linolenic acid was not added and only 2,2-dibromo-3-nitrilopropionamide was added. In this case, dimethyl sulfoxide and 2,2-dibromo-3-nitrilopropionamide were added. The results are shown in Table 1.

[0023]

[Table 1]

As can be seen from Table 1, when only γ-linolenic acid was added without using a bactericide, no growth inhibitory effect on E. coli was observed. However, when used in combination with a germicide, in the concentration range of 10 ppm or more,
It was observed that the viable cell count of Escherichia coli was reduced to 1/10 or less, and it was confirmed that the antibacterial activity was significantly improved by the synergistic effect.

In addition, bactericide 1 containing γ-linolenic acid
It was confirmed that the number of viable bacteria in the 0 ppm test group and the fungicide-only 40 ppm test group had almost the same results.
It was confirmed that by adding linolenic acid, a bactericidal effect at a level that was conventionally required to have a concentration of 40 ppm can be achieved at a concentration of about 10 ppm.

(2) Combination with Caisson WT In the above (1), Cason WT (trade name, manufactured by Rohm and Haas Co.) was used in place of 2,2-dibromo-3-nitrilopropionamide. , (1). The results are shown in Table 2. The composition of Caisson WT is 5-chloro-2-methyl-4-isothiazolin-3-one 10.1% by weight, 2-methyl-4-isothiazolin-3-one 3.8% by weight and other (magnesium chloride , Magnesium nitrate, water) 8
It is 6.1% by weight.

[0027]

[Table 2]

As can be seen from Table 2, when γ-linolenic acid was added in the high-concentration range of the bactericide, it was confirmed that the antibacterial activity was improved by the synergistic action.

(3) Combination with 2,2-dibromo-2-nitroethanol In the above (1), instead of 2,2-dibromo-3-nitrilopropionamide, 2,2-dibromo-2-
The same procedure as in (1) was performed except that nitroethanol was used. The results are shown in Table 3.

[0030]

[Table 3]

As can be seen from Table 3, when γ-linolenic acid was added in the high concentration region of the bactericide, the effect of improving the antibacterial activity by the synergistic effect was confirmed.

(4) Combination with mixed preparation A In the above (1), instead of 2,2-dibromo-3-nitrilopropionamide, Caisson WT (Rohm) is used.
The same procedure as (1) was performed except that a mixed preparation A (manufactured by Anders Co., Ltd.) and 2,2-dibromo-2-nitro-ethanol was used (weight ratio 1: 2). The results are shown in Table 4.

[0033]

[Table 4]

As can be seen from Table 4, the efficacy of the mixed preparation A in which a plurality of commonly used bactericidal components are combined against Escherichia coli by the addition of γ-linolenic acid is 1 It appeared that the viable cell count decreased to / 10 or less, and the effectiveness of the addition of γ-linolenic acid was confirmed.

(5) Combination with mixed preparation B In the above (1), 2,2-dibromo-3-nitrilopropionamide is used instead of 2,2-dibromo-3-
The same procedure as in (1) was performed except that a mixed preparation B of nitrilopropionamide and 2,2-dibromo-2-nitro-ethanol (weight ratio 20: 9) was used. The results are shown in Table 5.
Shown in

[0036]

[Table 5]

As can be seen from Table 5, the efficacy of the mixed preparation B in which a plurality of commonly used bactericidal components are combined against Escherichia coli by the addition of γ-linolenic acid is 1 It appeared that the viable cell count decreased to / 10 or less, and the effectiveness of the addition of γ-linolenic acid was confirmed.

Example 2 B. subtilis
(1) Combination with 2,2-dibromo-3-nitrilopropionamide Bacillus subtilis (Bs) cultured in Waxman liquid medium
ubtilis) is diluted 100 times with sterile distilled water, and a solution of γ-linolenic acid in dimethyl sulfoxide is diluted with γ-
Linolenic acid was added so that the final concentration was 50 ppm, and at the same time, a predetermined amount of 2,2-dibromo-3-nitrilopropionamide was added, and the change in the viable cell count with time was determined by the agar plate method. For comparison, the viable cell count was also obtained in the case where γ-linolenic acid was not added and only 2,2-dibromo-3-nitrilopropionamide was added. In this case, dimethyl sulfoxide and 2,2-dibromo-3-nitrilopropionamide were added. The results are shown in Table 6.

[0039]

[Table 6]

As can be seen from Table 6, the efficacy of 2,2-dibromo-3-nitrilopropionamide against Bacillus subtilis by addition of γ-linolenic acid showed that the viable cell count was reduced to 1/10 or less in almost all test groups. The effect of adding γ-linolenic acid was confirmed.

(2) Combination with Caisson WT In the above (1), Cason WT (trade name, manufactured by Rohm and Haas Co., Ltd.) was used in place of 2,2-dibromo-3-nitrilopropionamide. , (1). The results are shown in Table 7.

[0042]

[Table 7]

As can be seen from Table 7, the efficacy of caisson WT against Bacillus subtilis by the addition of γ-linolenic acid appears in the form of a decrease in the viable cell count of 1/10 or less in the test zone in which viable cells can be confirmed. , The effectiveness of γ-linolenic acid addition was confirmed.

(3) Combination with 2,2-dibromo-2-nitroethanol In the above (1), instead of 2,2-dibromo-3-nitrilopropionamide, 2,2-dibromo-2-
The same procedure as in (1) was performed except that nitroethanol was used. Table 8 shows the results.

[0045]

[Table 8]

As can be seen from Table 8, the efficacy of 2,2-dibromo-2-nitroethanol against Bacillus subtilis by the addition of γ-linolenic acid is 1/10 or less in the test group in which almost all viable bacteria can be confirmed. It appeared in the form of a decrease in the viable cell count, and the effectiveness of the addition of γ-linolenic acid was confirmed.

Example 3 (1) Antibacterial activity against Escherichia coli E. coli (E.c.) cultured in Waxman liquid medium
oli, DH-5) is diluted 100 times with sterile distilled water,
Dimethylsulfoxide solution of various fatty acids or fats and oils was added to this so that the final concentration of various fatty acids or fats and oils would be 50 ppm, and at the same time, a predetermined amount of 2,2-dibromo-3-nitrilopropionamide was added, and the viable bacteria were added over time. The transition of the number was obtained by the agar plate method. For comparison, the viable cell count was also obtained in the case of adding only 2,2-dibromo-3-nitrilopropionamide without adding fatty acid or fat. In this case, dimethyl sulfoxide and 2,
2-Dibromo-3-nitrilopropionamide was added. The results are shown in Tables 9 and 10.

[0048]

[Table 9]

[0049]

[Table 10]

(2) Antibacterial activity against B. subtilis In the above (1), B. subtilis (B.s.
ubtilis) was used, and the same procedure as in (1) was performed. The results are shown in Tables 11 and 12.

[0051]

[Table 11]

[0052]

[Table 12]

As can be seen from Tables 9 to 12, the fatty acid and the acid component thereof were compared with the changes in the viable cell count showing the efficacy of 2,2-dibromo-3-nitrilopropionamide when no fatty acid was added. The effect of enhancing the bactericidal effect was exhibited by adding the fats and oils contained as. That is, in the experimental system using Escherichia coli, the viable cell count shows a transition at a level of about 1/10 or less due to the addition of fatty acids in a wide range.

Further, a more remarkable effect was observed in the experimental system using Bacillus subtilis. When 2,2-dibromo-3-nitrilopropionamide was used alone at a concentration of 5 ppm, viable bacteria were observed 15 minutes after the addition of the drug, whereas fatty acids (myristic acid, oleic acid, lauric acid, linoleic acid, linoleic acid) were observed. When the acid) was added, no viable bacteria were observed at that concentration. Also, after adding the same chemicals, 1
Observed bactericide concentration of viable bacteria after 5 minutes is 1.25
It was from ppm. Therefore, in consideration of obtaining the same drug efficacy, 2,2-dibromo-3-nitrilopropionamide, which had conventionally required a concentration of 5 ppm, was potentiated by the addition of fatty acids, resulting in 1.25 p
It has been proved that the effect is exhibited at the use of about pm and it is possible to greatly reduce the cost.

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Claims (4)

[Claims] 1. An (A) industrial fungicide, and (B) a carbon number of 1.
At least 1 selected from 0 to 30 saturated or unsaturated fatty acids and fats and oils containing these as an acid component
An industrial fungicide composition consisting of a combination with a seed. 2. The industrial fungicide composition according to claim 1, wherein the industrial fungicide of component (A) is at least one selected from halocyanoacetamide compounds, halonitro compounds and isothiazolone compounds. 3. The component (B) is at least one selected from α-linolenic acid, γ-linolenic acid, linoleic acid, oleic acid, myristic acid, lauric acid, linseed oil and castor oil. The industrial fungicide composition according to 1 or 2. 4. The industrial bactericidal composition according to claim 1, 2 or 3, wherein the weight ratio of the component (A) to the component (B) is 5: 1 to 1: 5.