JPH0812507A - Industrial microbicide - Google Patents

Abstract

PURPOSE:To provide a new industrial microbicide by using an alpha- chlorobenzaldoxime acetate derivative known as an industrial microbicide in combination with 3,3,4,4tetrachlorotetrahydrothiophene-1,1-dioxide and a halocyanoacetamide compound. CONSTITUTION:This industrial microbicide is produced by using an alpha- chlorobenzaldoxime acetate derivative of formula I ((n) is 0-2) in combination with 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and a halocyanoacetamide compound of formula II (R<1> is H, a halogen or an alkyl; R<2> is H or an alkyl; X is a halogen). The agent may be further incorporated with a halogenated acetic acid ester of formula III (Y is a halogen; L is an alkylene or an alkenylene). The industrial microbicide has remarkably expanded treatment range of microorganisms and extremely broad antimicrobial spectrum. It has excellent bactericidal and fungicidal effects, proliferation suppressing effect on bacteria and fungi and high stability.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention can greatly expand the range of microorganisms that can be sterilized, has an extremely broad antibacterial spectrum, and has excellent bactericidal and fungicidal effects as well as an effect of suppressing the growth of bacteria and mold. Exhibits a unique synergistic effect of being excellent and high in stability, and is especially useful for water systems in the pulp and paper industry, such as various water systems such as white water in the papermaking process and circulating cooling water in various industrial fields, as well as industrial water. A new industry suitable for use in the fields of water-based paints prepared by using, coating liquids for paper, latexes, polymer emulsions, printing pastes, adhesives, metalworking fluids such as cutting oils, and leather. The present invention relates to a disinfectant.

[0002]

2. Description of the Related Art Conventionally, in the fields described above,
Microbes harmful to them are easily propagated, which causes a decrease in productivity and quality. Especially in the water system in the pulp and paper industry, slime is generated by the multiplication of bacteria, filamentous fungi, and yeasts, and the channel in which the pulp slurry flows, especially the rough wall surface where the slurry contacts, chests, flow boxes, transport pipes, etc. Slime is deposited and formed in a place where the flow velocity of the pipe slurry becomes small and stagnates. This slime is often detached, causing scraps of paper and contamination of paper pipe products, as well as causing various damages due to the growth of microorganisms. The occurrence of such a trouble becomes a serious problem especially when using a high-speed machine, resulting in a significant decrease in productivity and an economic loss.
Further, for example, the proliferation of microorganisms in a circulating water system for cooling such as a metalworking oil agent causes a phenomenon which is not preferable in public health, such as impairing the cooling performance and emulsifying property, or generating a bad odor and deteriorating the working environment. In addition, other obstacles due to the proliferation of harmful microorganisms include water-based paints, paper coating solutions, polymer latex, paper pulp, glue, leather,
Also found in industrial products such as metalworking fluids.

By the way, as the agents for suppressing or controlling the generation of harmful microorganisms in the water system or the industrial products, for example, organometallic compounds, organochlorine compounds, organosulfur compounds, quaternary ammonium salts have been used so far. , Etc. have been used, but these compounds are toxic to the human body, give off a bad odor or an offensive odor, and cause undesirable phenomena such as foaming. In addition, these pesticide-containing water systems, when thrown into general rivers or the sea, have an adverse effect on fish and shellfish and cause environmental conservation problems.

As a means for avoiding such a problem, for example, a composition comprising an α-chlorobenzaldoxime acetate derivative and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (special (Kaisho 62-294602), 2,2-dibromo-3-
Composition consisting of nitrilopropionamide and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (US Pat. No. 3,928,198), α-chlorobenzaldoxime acetate and halo. A composition comprising a cyanoacetamide compound (Japanese Patent Publication No. 57-54482), a composition containing α-chlorobenzaldoxime acetate and a halogenated acetic acid ester (Japanese Patent Publication No. 5801), and a halocyanoacetamide compound And a halogenated acetic acid ester (Japanese Patent Publication No. 57-54481) are known. However, each of these has a limited range of microorganisms that can be sterilized and cannot obtain a broad antibacterial spectrum, so the applicable range is limited, and it is not always satisfactory as an industrial bactericide.

[0005]

Under the circumstances, the present invention can greatly expand the range of microorganisms that can be sterilized.
Having an extremely broad antibacterial spectrum, and exhibiting excellent bactericidal and fungicidal effects, and having an excellent effect of suppressing the growth of various microorganisms, and also made to provide a highly stable industrial bactericide Is.

[0006]

The inventors of the present invention have conducted various studies to develop industrial fungicides having a wide range of application, and as a result, α-chlorobenzaldo, which has been used as a conventional industrial fungicide, has been obtained. For oxime acetate derivatives, 3,
3,4,4-Tetrachlorotetrahydrothiophene-
It has been found that the object can be achieved by combining 1,1-dioxide with a halocyanoacetamide compound and optionally a halogenated acetic acid ester, and the present invention has been completed based on this finding.

That is, the present invention provides (A) general formula (I)

[Chemical 6] Α-chlorobenzaldoxime acetate derivative represented by the formula (n is an integer of 0 to 2), (B) 3,
3,4,4-Tetrachlorotetrahydrothiophene-
1,1-dioxide, (C) general formula (II)

[Chemical 7] (Wherein R ¹ is a hydrogen atom, a halogen atom or a lower alkyl group, R ² is a hydrogen atom or a lower alkyl group, and X is a halogen atom) and optionally a general formula (D) (III)

Embedded image The present invention provides an industrial bactericide characterized by containing a halogenated acetic acid ester represented by the formula (Y is a halogen and L is an alkylene group or an alkenylene group).

Examples of the α-chlorobenzaldoxime acetate derivative of the general formula (I) used as the component (A) of the present invention include, for example, α-chlorobenzaldoxime acetate and α-chloro-4-chlorobenzaldoxime acetate. , Α-chloro-2,4-dichlorobenzaldoxime acetate and the like.

3,3 used as the component (B) of the present invention
4,4-tetrachlorotetrahydrothiophene-1,1
-Dioxide has the chemical formula

[Chemical 9] Is represented by

In the bactericide of the present invention, the mixing ratio of the component (A) and the component (B) is in the range of 1: 5 to 10: 1, more preferably 1: 3 to 8: 1. It is preferable that the compound (1) has a particularly excellent synergistic effect. If the component (A) is too small, the bactericidal activity against yeasts, bacteria and filamentous fungi will decrease, and if it is too large, the growth inhibitory activity against yeasts, bacteria and filamentous fungi will decrease. If the amount of component (B) is too small, the growth inhibitory power against yeasts, bacteria and filamentous fungi will decrease, and if it is too large, the bactericidal power against yeasts, bacteria and filamentous fungi will decrease.

The halocyanoacetamide compound used as the component (C) of the present invention is represented by the above general formula (II), and the halogen atom of R ^{1 in} the formula is, for example, Cl, Br or the like. Examples of the lower alkyl group include a methyl group and an ethyl group, and examples of the lower alkyl group of R ² include a methyl group and an ethyl group. Examples of the halogen atom of X include Cl,
Br and the like can be mentioned. As the component (C), 2,2-dibromo-3-nitrilopropionamide, in which R ¹ and X are both Br, is preferable because of its excellent bactericidal property, and other 2-chloro-3-nitrilopropionamide, 2-Bromo-3-nitrilopropionamide, 2,2-dichloro-3-nitrilopropionamide, N-methyl-2,2-dibromo-3-nitrilopropionamide and the like can be mentioned. These may be used alone or in combination of two or more.

In the disinfectant of the present invention, the mixing ratio of the component (C) is 1 with respect to the total amount of the components (A) and (B).
0-800% by weight, more preferably 20-400% by weight
It is preferable to set it in the range of since a particularly excellent synergistic effect can be obtained. If the blending ratio is too small, the bactericidal activity against bacteria is reduced, and if it is too large, the bactericidal activity against mold is reduced.

In the bactericide of the present invention, in addition to the components (A), (B) and (C), the halogenated acetic acid ester of the general formula (III) is optionally used as the component (D). It can be mixed. This general formula (I
Examples of the halogen atom of Y in II) include Cl, B
r and the like, and as the alkylene group of L,
Examples thereof include an ethylene group, a propylene group, a trimethylene group, a butylene group, a pentamethylene group, and a hexamethylene group, and examples of the alkenylene group include a propenylene group, a butenylene group, and a hexenylene group. As the component (D), X is Br and L is -C.
Bisbromoacetoxybutene- _{2 in which} H ₂ —CH═CH—CH ₂ — has a large synergistic effect and is preferred. Other,
Examples of the component (D) include 1,2-bisbromoacetoxyethane, 1,2-bisbromoacetoxypropane,
1,2-bischloroacetoxyethane and the like can be mentioned. These may be used alone or in combination of two or more.

When the component (D) is blended in the disinfectant of the present invention, the blending ratio is 10 to 600% by weight based on the total amount of the components (A), (B) and (C). ,
More preferably, the range of 30 to 400% by weight is preferable because a particularly excellent synergistic effect can be obtained. If this blending ratio is too small, the bactericidal activity against bacteria and yeasts deteriorates, and the bactericidal activity against filamentous fungi decreases, and if it is too large, the bactericidal activity against yeasts and filamentous fungi, growth inhibition The power decreases.

The bactericidal agent of the present invention basically comprises the above-mentioned three components (A), (B) and (C) or four components obtained by adding the component (D) optionally used thereto to a uniform composition. It is prepared by mixing, but it is generally used as a solvent solution. Examples of the solvent that can be used here include alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents and the like, among which glycerin,
Triol-based solvents such as trimethylolpropane, alkylene glycols, dialkylene glycols, glycol-based solvents such as dialkylene glycol monoalkyl ethers are preferred, and especially glycerin, trimethylolpropane, ethylene glycol, propylene glycol,
Diethylene glycol, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether or dipropylene glycol are 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.

The bactericide of the present invention may be used by supporting it on any carrier, and there are no particular restrictions on the mode of use, and various methods can be employed.

The amount of the bactericide added when it is 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 components (A), (B) and (C) are used. 1 to 50 ppm based on the total amount of the components, 20 to 400 ppm in the case of the field of water-based paints, glues, leathers, etc. In addition, in the case of a four-component fungicide further added with the component (D), the total amount of the four components is Based on this, in the case of water systems in the fields of the pulp and paper industry, etc.
In the case of leather and the like, it is 25 to 300 ppm, and a good bactericidal effect can be obtained in this range. In the fungicide of the present invention,
It does not matter at all to add a stabilizer, a surfactant and the like within a range that does not impair the object of the present invention, and the surfactant has an effect of increasing the solubility.

[0018]

The bactericide of the present invention comprises three components of α-chlorobenzaldoxime acetate derivative, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and a specific halocyanoacetamide compound. And by combining it with the optional halogenated acetic acid ester in addition to the four components, there is a unique synergistic effect that cannot be achieved with these individual components, and which cannot be expected from them. Since the range can be greatly expanded, it has an extremely broad antibacterial spectrum, exhibits excellent bactericidal and fungicidal effects, has an excellent effect of suppressing the growth of various microorganisms, and has a high stability Water systems in the pulp and paper industry,
For example, in addition to various water systems such as white water in the papermaking process and circulating cooling water in various industrial fields, water-based paints, paper coating liquids, latexes, polymer emulsions, printing pastes, metal working oils such as cutting oils, and adhesives. It is suitable for use in fields such as leather and leather.

[0019]

EXAMPLES Next, further details will be described with reference to Examples and Comparative Examples. In addition, the part in an example shows a weight part. Examples 1 to 40, Comparative Examples 1 to 6 A fungicide composed of the compositions having the respective composition components and blending amounts (shown in parts by weight) shown in Table 1 and Table 2 was prepared.

[0020]

[Table 1]

[0021]

[Table 2]

* 1 to * 6 in these tables have the following meanings. * 1: α-chlorobenzaldoxime acetate * 2: 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide * 3: 2,2-dibromo-3-nitrilopropionamide * 4: bisbromo Acetoxybutene * 5: Diethylene glycol monomethyl ether * 6: Diethylene glycol

Reference Example The bactericides obtained in the respective examples and comparative examples were subjected to the following tests. (1) Bacterial growth prevention test and slime generation prevention test in white water in the papermaking process In the papermaking process of a papermaking factory, one bactericide is added to the white water bit.
Concentration in water is 20pp for 2 hours and 3 times a day
was added for 7 days to measure the number of microorganisms in white water. 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. The number of paper breaks was also measured during papermaking to confirm the effect of preventing slime generation. The results are shown in Tables 3 and 4.

(2) Bacterial Growth Prevention Test in Papermaking Coating Solution A broth liquid medium and a coating solution which has been spoiled in advance were added to a starch-based coating solution for papermaking, stirred, and sterilized to have a concentration of 300 ppm. The agent 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 Tables 3 and 4.

(3) Stability test Each antibacterial agent sample was stored in a thermostatic chamber at 40 ° C., a part of each sample was collected daily, and by liquid chromatography,
The residual concentrations of the component (A) and / or the component (B) and / or the component (C) were measured, and their residual rates are shown in Tables 5 and 6. The residual rate was calculated by the following formula. Residual rate (%) = (X ′ / X) × 100 (X in the formula represents the content of each component at the time of formulation, X ′ represents the content of each component after 30 days)

(4) Antibacterial spectrum test A certain amount of various microorganisms shown in Table 7 was taken, diluted with a fixed amount of sterilized water, and this fixed amount was put into a test tube. Concentration of components is 0.5ppm, 1pp
m, 2ppm, 4ppm, 8ppm to add,
After contacting for 60 minutes in an incubator (32 ° C.), a fixed amount of this was taken into a petri dish, and the dissolved Waxman agar medium was poured into the dish and mixed to solidify into a flat plate. In the incubator (32
The microbial colonies generated after culturing for 2 days at (° C.) Were visually compared with blanks (without addition of chemicals), and the minimum bactericidal concentration of microorganisms was determined according to the generation status of the microbial colonies. A list of the resulting antibacterial activity is shown in Tables 7 to 10.

[0027]

[Table 3]

[0028]

[Table 4]

[0029]

[Table 5]

[0030]

[Table 6]

[0031]

[Table 7]

[0032]

[Table 8]

[0033]

[Table 9]

[0034]

[Table 10]

From these results, the bactericides of the respective Examples of the present invention have excellent fungal growth-preventing action and slime-preventing action in white water of a papermaking plant as compared with those of Comparative Examples. It can be seen that the coating solution has an excellent antibacterial effect, has an extremely broad antibacterial spectrum, and is as stable as the two-component system.

Claims (5)

[Claims] 1. (A) General formula: Α-chlorobenzaldoxime acetate derivative represented by the formula (n is an integer of 0 to 2), (B) 3,
3,4,4-Tetrachlorotetrahydrothiophene-
1,1-dioxide and (C) general formula: (Wherein R ¹ is a hydrogen atom, a halogen atom or a lower alkyl group, R ² is a hydrogen atom or a lower alkyl group, and X is a halogen atom), and a halocyanoacetamide compound is contained. Industrial fungicide. 2. (A) General formula: Α-chlorobenzaldoxime acetate derivative represented by the formula (n is an integer of 0 to 2), (B) 3,
3,4,4-Tetrachlorotetrahydrothiophene-
1,1-dioxide, (C) general formula: (Wherein R ¹ is a hydrogen atom, a halogen atom or a lower alkyl group, R ² is a hydrogen atom or a lower alkyl group, and X is a halogen atom), and (D) the general formula: 5] An industrial bactericide characterized by containing a halogenated acetic acid ester represented by the formula (Y is halogen and L is alkylene group or alkenylene group). 3. The compounding ratio of the component (A) and the component (B) is in the range of 1: 5 to 10: 1 on a weight basis.
The industrial fungicide described. 4. The industrial sterilization according to claim 1, 2 or 3, wherein the content of the component (C) is in the range of 10 to 800% by weight based on the total amount of the components (A) and (B). Agent. 5. The blending amount of component (D) is 10 to 600 with respect to the total amount of component (A), component (B) and component (C).
The industrial bactericide according to claim 2, 3 or 4, which is in the range of weight%.