JP3194687B2 - Industrial fungicides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel industrial bactericide which can be suitably used in various industrial fields such as water systems such as the pulp and paper industry. More specifically, the present invention relates to a novel industrial bactericide which exhibits an excellent killing action and a growth inhibiting action against bacteria and fungi and has good storage stability.

[0002]

2. Description of the Related Art Conventionally, in addition to water systems in the pulp and paper industry, for example, various water systems such as white water in the papermaking process and circulating cooling water in various industrial fields, water-based paints and papers prepared using industrial water. In the fields of coating fluids, latex, polymer emulsions, printing pastes, adhesives, metalworking oils such as cutting oils, leather, wood, etc., microorganisms such as mold and bacteria harmful to them are liable to multiply. This causes a decrease in productivity and quality. Especially, in the water system in the pulp and paper industry, slime is generated by the proliferation of bacteria, filamentous fungi, and yeasts. Slime adheres and is formed in a place where the flow velocity of the pipe slurry becomes small and stagnates.

[0003] The slime is often detached, causing not only paper breakage and contamination of paper pipe products, but also various obstacles due to the propagation of microorganisms.

[0004] The occurrence of such an obstacle causes a remarkable decrease in productivity and economical loss particularly when operating on a high-speed machine.

[0005] In addition, the propagation of microorganisms in the circulating water system for cooling metal working oils and the like causes phenomena unfavorable to public health, such as impairing the cooling performance and emulsifying properties, and generating a bad odor and deteriorating the working environment. cause.

[0006] In addition to such obstacles caused by the propagation of harmful microorganisms, there are other problems such as water-based paints, paper coating liquids, latex, polymer emulsions, printing pastes, adhesives, and metal working oils such as cutting oils. It is also found in consumer products.

[0007] By the way, in order to suppress or prevent the generation of harmful microorganisms in the water system or the industrial product, organic metal compounds, organic chlorine compounds, organic sulfur compounds, quaternary ammonium salts and the like have hitherto been used. Although used, these compounds are toxic to the human body, emit odors and off-flavors, and cause undesirable phenomena such as foaming. In addition, when these pesticide-containing water systems are dumped into general rivers, seas, and the like, they adversely affect fish and shellfish and cause environmental conservation problems.

In order to avoid such a problem, it has been proposed to use a bactericide obtained by dissolving a cyanoacetamide compound and methylenebisthiocyanate in a solvent such as ethylene glycol or polyethylene glycol (Japanese Patent Application Laid-Open (JP-A) No. 2002-287, 1988). In this methylene bisthiocyanate, contamination of impurities in the production process cannot be avoided, and part of the methylene bisthiocyanate changes during storage to produce other substances. Bisthiocyanate inevitably contains impurities. When this methylenebisthiocyanate is dissolved in a solvent in combination with a cyanoacetamide compound, some of the impurities contained in the methylenebisthiocyanate promote the decomposition of the cyanoacetamide compound, so that the bactericide has a storage stability. It is inevitable that the concentration of cyanoacetamide compound will decrease over time, and if the drug is stored for a long period of time, especially when the drug is stored under high temperature conditions such as in the summer, the drug will deteriorate and the bactericidal effect will decrease. There are drawbacks such as discoloration of the drug.

[0009]

DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks associated with a bactericide comprising a combination of a cyanoacetamide compound and methylenebisthiocyanate, is excellent in killing bacteria and fungi and suppressing growth, and is storage-stable. The object of the present invention is to provide an industrial bactericide having good properties.

[0010]

The present inventors have made intensive studies on stabilizing an industrial bactericide containing a combination of a cyanoacetamide compound and methylenebisthiocyanate, and as a result, have obtained an oxidizing agent. It has been found that the purpose can be achieved by adding an inorganic salt, and based on this finding, the present invention has been completed.

That is, the present invention relates to the following (A):

Embedded image (Wherein X is a halogen atom, Y is a hydrogen atom or a halogen atom, R ¹ and R ² are each a hydrogen atom or a lower alkyl group, and they may be the same or different. ), (B) methylene bisthiocyanate, and (C) an oxidizable inorganic salt.

In the industrial fungicide of the present invention, the cyanoacetamide compound represented by the general formula (I) used as the component (A) is represented by X in the general formula (I).
And a halogen atom of Y is preferably a chlorine atom and a bromine atom, respectively.

Examples of the lower alkyl group for R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. R ¹ and R ² may be the same or different.

Therefore, examples of the cyanoacetamide compound of the component (A) include 2-chloro-3-nitrilopropionamide, N-methyl-2-chloro-3-nitrilopropionamide, N, N-dimethyl-2- Chloro-
3-nitrilopropionamide, 2,2-dichloro-3
-Nitrilopropionamide, N-methyl-2,2-dichloro-3-nitrilopropionamide, N, N-dimethyl-2,2-dichloro-3-nitrilopropionamide, 2-bromo-3-nitrilopropionamide, N -
Methyl-2-bromo-3-nitrilopropionamide,
N, N-dimethyl-2-bromo-3-nitrilopropionamide, 2,2-dibromo-3-nitrilopropionamide, N-methyl-2,2-dibromo-3-nitrilopropionamide, N, N-dimethyl- 2,2-dibromo-3-nitrilopropionamide and the like can be mentioned. These may be used alone or in combination of two or more. Among these, 2,2-dibromo-3-nitrilopropionamide is particularly preferred because of its excellent bactericidal properties.

In the fungicide of the present invention, the oxidizing inorganic salt of the component (C) further added to the methylene bisthiocyanate of the components (A) and (B) is, for example, sodium peroxide. , Potassium bromate, sodium bromate, potassium chlorate, sodium chlorate, magnesium nitrate, calcium nitrate, sodium nitrate, ammonium nitrate and the like. They are,
It is used for improving the storage stability of the bactericide, and ammonium nitrate, potassium nitrate and sodium nitrate are particularly preferred in that they exhibit excellent effects. These may be used alone or in combination of two or more.

In the fungicide of the present invention, the mixing ratio of the components (A) and (B) is the same as that of the conventional industrial fungicide, and is 10: 1 to 1:10 by weight. Preferably, it is selected in the range of 10: 1 to 1: 5. If the amount of the component (A) is too small, the bactericidal activity against bacteria decreases. On the other hand, if the amount of the component (B) is too small, the bactericidal activity against mold decreases and the inhibitory effect on bacterial growth decreases.

The content of the component (C) in the present invention depends on the component (B), and is usually selected within the range of 100: 0.1 to 100: 100 by weight of the component (B) and the component (C). It is. If the amount of the component (C) is smaller than this, the effect of improving storage stability is not sufficiently exhibited.
As the amount of the component increases, the performance as a bactericide decreases. From the viewpoint of the balance between the effect of improving the storage stability and the performance as a bactericide, the particularly preferable content ratio of the component (C) is in the range of 25 to 75 with respect to the component (B) 100.

The bactericide of the present invention contains the above-mentioned components (A), (B) and (C) as active ingredients, and it is advantageous that the preparation is dissolved in an organic solvent. is there.

The organic solvent used at this time is the above-mentioned (A)
Any component can be used as long as it can dissolve the components, component (B) and component (C), and is appropriately selected from alcohols, ketones, ethers, hydrocarbons, alkylene carbonates and the like. Examples of preferred organic solvents include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, and trimethylolpropane; polyalkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, and diethylene glycol monobutyl ether. And alkyl ethers thereof, cyclic ethers such as tetrahydrofuran and tetrahydropyran, alkylene carbonates such as ethylene carbonate and propylene carbonate, lactones such as γ-butyrolactone, and lactams such as N-methylpyrrolidone. However, an alkylene carbonate, particularly propylene carbonate, is preferred because it exhibits a particularly excellent stabilizing effect. These solvents may be used alone or in combination of two or more. In particular, a mixed solvent system of propylene carbonate and an organic solvent which easily dissolves the component (C) and is compatible with propylene carbonate, for example, diethylene glycol, is preferable. In this case, the mixing ratio of propylene carbonate and diethylene glycol is 100: 10 to 1
0: 100, preferably 100: 15 to 100: 1
00 range.

The bactericide of the present invention may be used by being supported on any carrier, and there is no particular limitation on the mode of use, and various methods can be adopted.

The amount of the fungicide to be added at the time of use varies depending on the concentration of microorganisms. In general, in the case of a water system in fields such as the pulp and paper industry, the components (A) and (B) are used.
1 to 100 pp based on the total amount of component and component (C)
m, 10 to 50 in the case of water-based paint, glue, leather, etc.
0 ppm, and a good bactericidal effect can be obtained in this range.

Water or a surfactant may be added to the fungicide of the present invention, if desired, as long as the object of the present invention is not impaired.

[0023]

The industrial bactericide of the present invention is a combination of a cyanoacetamide compound and methylenebisthiocyanate and an inorganic salt having an oxidizing property. The decomposition of the cyanoacetamide compound is remarkably suppressed. And extremely high stability. Therefore, it can be advantageously stored and transported, particularly under high temperature conditions.

The industrial bactericide of the present invention is excellent in killing effect of bacteria and mold and suppressing growth of germs and especially in water systems in the pulp and paper industry, such as white water in paper making process and circulating cooling water in various industrial fields. In addition to various water systems, water-based paints prepared using industrial water, coating liquids for paper, latex, polymer emulsions, printing pastes, adhesives, metalworking oils such as cutting oils, and fields such as leather. It can be suitably used.

[0025]

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

Examples 1 to 3 2,2-dibromo-3-nitrilopropionamide 10
Parts by weight, 5 parts by weight of methylenebisthiocyanate and 2 parts by weight of various nitrates shown in Table 1 were added to a mixed solvent of 70 parts by weight of propylene carbonate and 13 parts by weight of diethylene glycol to make the total amount 100 parts by weight. An industrial fungicide was prepared by stirring. The ratio between methylene bisthiocyanate (component B) and nitrate (component C) in these examples was 100: 40 by weight. The composition of the industrial fungicide thus obtained is shown in Table 1.
Shown in

Example 4 An industrial fungicide was prepared in the same manner as in Example 1 except that the amount of ammonium nitrate was changed to 0.1 part by weight and the amount of diethylene glycol was changed to 14.9 parts by weight. The ratio between methylene bisthiocyanate (component B) and ammonium nitrate (component C) in this example was 100: 2 by weight. Table 1 shows the composition of the industrial germicide thus obtained.

Examples 5 and 6 An industrial disinfectant was prepared in the same manner as in Example 1 except that the amounts of propylene carbonate and diethylene glycol in the mixed solvent in Example 1 were changed as shown in Table 1. In these examples, the ratio between methylene bisthiocyanate (component B) and ammonium nitrate (component C)
The weight ratio was 100: 40. Table 1 shows the composition of the industrial germicide thus obtained.

Example 7 2,2-Dibromo-3-nitrilopropionamide 30
Parts by weight, 10 parts by weight of methylenebisthiocyanate and 5 parts by weight of ammonium nitrate were mixed with 3 parts of propylene carbonate.
An industrial disinfectant was prepared by adding a mixed solvent consisting of 0 parts by weight and 25 parts by weight of diethylene glycol and mixing well. The weight ratio of methylene bisthiocyanate (component B) to ammonium nitrate (component C) in this example was 100: 50. Table 1 shows the composition of the industrial germicide thus obtained.

[0030]

[Table 1]

Example 8 The amount of ammonium nitrate in Example 1 was 0.2 parts by weight, and only propylene carbonate was used as a solvent.
An industrial fungicide was prepared in the same manner as in Example 1 except that 8 parts by weight was used. The ratio between methylene bisthiocyanate (component B) and ammonium nitrate (component C) in this example was 100: 4. Table 2 shows the composition of the industrial germicide thus obtained.

Examples 9 to 13 Industrial disinfectants were prepared in the same manner as in Example 1 except that the amount of ammonium nitrate in Example 1 was changed to 5 parts by weight and the solvent was changed to a mixed solvent shown in Table 2. In these examples, the ratio between methylene bisthiocyanate (component B) and ammonium nitrate (component C) was 100: 100 by weight.
Met. Table 2 shows the composition of the industrial germicide thus obtained.

[0033]

[Table 2]

Comparative Examples 1-4 2,2-Dibromo-3-nitrilopropionamide 10
Parts by weight and 5 parts by weight of methylene bisthiocyanate were added to 85 parts by weight of a mixed solvent having the composition shown in Table 3, and mixed well to prepare an industrial disinfectant containing no nitrate. Table 3 shows the composition of the industrial germicide thus obtained.

[0035]

[Table 3]

Test Example 10 g of the industrial disinfectant obtained in each of the examples and comparative examples was taken and stored in a 55 ° C. constant temperature room. Immediately thereafter, 10 g, 20 days, and 30 days later, 2 g of each sample was collected, and the residual concentration of the cyanoacetamide compound was measured using liquid chromatography. The results are shown in Table 4 as the residual ratio. The residual ratio was determined according to the following equation. Residual rate (%) = M ² / M ¹ × 100 where M ¹ is the initial concentration of the cyanoacetamide compound,
M ² is the concentration after storage of cyanoacetamide compounds.

[0037]

[Table 4]

As is apparent from this table, the addition of an oxidizing inorganic salt significantly improves the stability of the cyanoacetamide compound over time. This effect is achieved by using propylene carbonate or a mixed solvent thereof with diethylene glycol as a solvent. This is particularly noticeable when used. Even when the solvent containing propylene carbonate is used, when the inorganic salt having oxidizing property is not added, the stability over time is low.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ identification code FI A01N 59:06) A01N 59:06) (58) Investigated field (Int.Cl. ⁷ , DB name) A01N 47/48 A01N 37 / 34 A01N 59/00 CA (STN)

Claims (6)

(57) [Claims] (A) General formula (1) (Wherein X is a halogen atom, Y is a hydrogen atom or a halogen atom, R ¹ and R ² are each a hydrogen atom or a lower alkyl group, and they may be the same or different. An industrial fungicide comprising a cyanoacetamide compound represented by the formula (1), (B) methylenebisthiocyanate and (C) an oxidizable inorganic salt. 2. The industrial fungicide according to claim 1, wherein the content ratio of the component (B) to the component (C) is in the range of 100: 0.1 to 100: 100 by weight. 3. The industrial fungicide according to claim 1, wherein the component (C) is a nitrate. 4. The industrial disinfectant according to claim 1, wherein the components (A), (B) and (C) are dissolved or dispersed in an organic solvent. 5. The industrial fungicide according to claim 4, wherein the organic solvent is an alkylene carbonate or a mixture thereof with another organic solvent. 6. The industrial fungicide according to claim 5, wherein the other organic solvent is a polyalkylene glycol or an alkyl ether thereof.