JPH0372601B2 - - Google Patents

Description

[Detailed description of the invention]

(a) Purpose of the Invention (Field of Industrial Application) The present invention relates to an industrial disinfectant, and particularly to an industrial disinfectant that prevents various industrial materials and products from deteriorating due to various fungi such as mold. (Prior art) Many damages such as rot and contamination caused by microorganisms, especially fungi such as mold, are not only caused by diseases of humans and animals, damage to food and agricultural products, but also damage caused by many industrial products, such as It also extends to paper pulp products, paints, building materials, adhesives, cutting oils, textile oils, and various latexes. Conventionally, many disinfectants have been used to prevent damage caused by these microorganisms. for example,
Inorganic or organic compounds of heavy metals such as mercury, tin, and copper have been widely used because of their strong bactericidal properties. However, the above-mentioned metal compounds are avoided because of their toxicity to human stock or environmental pollution due to mixing with wastewater, and in recent years, non-metallic disinfectants have been widely used. (Problems to be Solved by the Invention) Many of these non-metallic disinfectants are limited to the type of bacteria, or exhibit an instantaneous bactericidal effect when added to an aqueous system. However, there were problems in that it was easily hydrolyzed and lacked long-lasting antibacterial activity. For example, benzimidazole compounds, which are considered to be the best non-metallic fungicides, are completely ineffective against molds such as Alternaria and Mucor at practical concentrations (100 to 500 ppm). The problem is that you can't hope for it. In addition, in order to solve this problem, Japanese Patent Publication No. 58-39124 discloses a composite agent of a benzimidazole compound and tetrachloroisophthalonitrile, but since the addition concentration is high, further improvement is required. There are still issues that need to be addressed. One of the active ingredients of the present invention, diiodomethyl-p-tolylsulfone, is expressed by the following formula (): JP-A-50-46833, JP-A-56
In JP-A-63902, JP-A-56-113706, JP-B-Sho 57-16082, etc., it is disclosed as a synergistic antifungal agent when used in combination with other compounds. However, in both cases, problems remain that need to be further improved, such as the toxicity of the compounds used in combination. This invention was made in view of the above circumstances, and is based on diiodomethyl, which is known as a preservative and antifungal agent.
By using p-tolylsulfone and 2-methoxycarbonylaminobenzimidazole, which is one of the benzimidazole compounds mentioned above, in combination, it can be expected to be effective against most target objects.
The present invention has been completed by discovering an industrially significant synergistic effect that is stronger than the bactericidal action of each agent alone, or in other words, exhibits the same effect with a fraction of the amount of each agent when used alone. It came to this. Also, especially
Compared to the invention of Japanese Patent Publication No. 58-39124 (a composite agent of a benzimidazole compound and tetrachloroisophthalonitrile), which is known as the agent that exhibits the best effect as a composite agent of benzimidazole compounds. The present invention was developed after confirming that the composite agent of the present invention exhibits the same or higher bactericidal activity at a concentration of 1/3 or less. (b) Structure of the invention Thus, according to this invention, diiodomethyl-
There is provided an industrial fungicide characterized by containing p-tolylsulfone and 2-methoxycarbonylaminobenzimidazole as active ingredients. The toxicity of diiodomethyl-p-tolylsulfone represented by the formula (), which is one of the active ingredients of this invention, is as _follows :
The acute toxicity LD ₅₀ value for rats is 10,000 mg/Kg, which is 9,400 mg/Kg, indicating low toxicity with no skin irritation, no inhalation toxicity, and only slight eye toxicity. The other active ingredient, 2-methoxycarbonylaminobenzimidazole, has the following formula (): The acute toxicity _LD50 value for rats is expressed as
It has low toxicity of over 7000mg/Kg. As described above, the industrial fungicide of the present invention can be used in combination with those with a low LD ₅₀ value as described above, and the amount added can be reduced due to their synergistic effect, so there is no risk of residual toxicity or pollution. , can be used very safely. The ratio of diiodomethyl-p-tolylsulfone of the above formula () to 2-methoxycarbonylaminobenzimidazole of the formula () is preferably 9:1 to 1:9 by weight;
In particular, a ratio of 2:1 to 1:5 is preferred from the viewpoint of synergistic effects. Each of the above-mentioned compounds is usually used in the form of a direct mixture that is added to various target systems. The target systems of the present invention include general industrial products such as paper pulp products, paints, building materials, adhesives, cutting oils, textile oils, various latexes, wood and bamboo products, and leather. Furthermore, depending on the purpose of use, the industrial disinfectant of the present invention may be dispersed in a suitable carrier or mixed with a suitable solid carrier, and if necessary, may be further added with known dispersants, suspending agents, spreading agents, penetrating agents, etc. Wetting agents, wetting agents, sticky agents, stabilizers, etc. are added to produce wettable powders, powders, granules, fine granules,
It may be used in the form of tablets, pastes, suspensions, sprays, etc., and may also be used in combination with other bactericidal agents, insecticides, deterioration inhibitors, etc. The liquid carrier used in the industrial disinfectant of the present invention may be any liquid as long as it does not react with the active ingredient, such as water, methyl alcohol, ethyl alcohol, glycol, alcohols such as glycerin, acetone, and methyl ethyl ketone. Ketones, aliphatic hydrocarbons such as hexane and liquid paraffin, aromatic hydrocarbons such as benzene and xylene, halogenated hydrocarbons such as carbon tetrachloride and chloroform, acid amides,
Examples include esters and nitriles, and these may be used alone or in combination of two or more. Examples of solid carriers include kaolin bentonite, clays such as acid clay, talcs such as talcum powder and waxite powder, diatomaceous earth, silica anhydride, silicas such as mica powder, alumina, sulfur powder, activated carbon, etc. These may be used alone or in combination of two or more. Further, as the dispersant, cationic surfactants, anionic surfactants, nonionic surfactants, or amphoteric surfactants are suitable, and nonionic surfactants are preferred from the viewpoint of stability as a formulation. Examples of the nonionic surfactant include higher alcohol-ethylene oxide (E/O) adducts, alkylphenol E/O adducts, fatty acid E/O adducts, polyhydric alcohol fatty acid ester E/O adducts, and alkyl amines. E/O adducts, fatty acid amide E/O adducts, E/O adducts of fats and oils,
Propylene oxide (P・O)・E・O copolymer, alkylamine P・O・E・O copolymer adduct, fatty acid ester of glycerin, fatty acid ester of pentaerythritol, fatty acid ester of sorbitate and sorbitan, sucrose fatty acid esters, alkyl ethers of polyhydric alcohols, alkylolamides, and the like. Among these, higher alcohol E/O adduct, alkylphenol E/O adduct, polyhydric alcohol fatty acid ester E/O adduct, fatty acid amide E/O adduct, P/
O・E・O copolymers, alkyl ethers of polyhydric alcohols, alkylamine P・O・E・O copolymer adducts, and alkylolamides, or a combination of two or more of these are preferred, and alkylamines P・O・E/O copolymer adducts (e.g., N,
Particularly preferred is the use of nonionic surfactants of the N, N', N'-polyoxypropylene/polyoxyethylene diamine, etc.) or alkylolamide type. In some cases (for example, when stability of the preparation is not a problem), a cationic, anionic or amphoteric surfactant may be used. The industrial fungicide of this invention exhibits a remarkable synergistic effect against contamination, deterioration, and even putrefaction caused by molds, so it can be used as a fungicide and preservative for various industrial materials and products. Useful. Note that the above two active ingredients of this invention may be added separately to the target system and used in combination depending on the case. Accordingly, from another perspective, this invention provides diiodomethyl-p-tolylsulfone. and 2-methoxycarbonylaminobenzimidazole in combination such that the ratio of the former to the latter is 9:1 to 1:9 by weight. This invention will be explained in detail below with reference to Test Examples and Examples, but the invention is not limited thereby. Test Example 1 (Synergistic effect against Aspergillus niger) Dispense the liquid medium of Aspergillus niger into 10 ml sterile test tubes, and add the drug to each concentration.
Using Asperigillus niger as a test bacterium, prepare a 10ml spore suspension by suspending 1ase from a slant culture medium, add 0.1ml of this to the above test tubes, and
Static culture is carried out at ℃ for 6 days. Thereafter, the presence or absence of bacterial growth was visually observed, and the amount of each drug added at which no bacterial growth was observed was measured. The Kull method [(1961
Applied Microbiology No. 9, pp. 538-541.
(see F. C. Kull et al.), i.e. the formula []
If the value is less than 1, there is a synergistic effect,
If the value is 1, there is an additive effect, and if the value is greater than 1, there is an antagonistic effect.] Accordingly, the first
Shown in the table. Q _A /Q _a +Q _B /Q _b [] However, Q _a ; Minimum inhibitory concentration of Compound A alone
(mg/) Q _b ; Minimum growth-inhibiting concentration of compound B alone
(mg/) Q _A ; Concentration of compound A in the inhibitory concentration of the composite agent (mg/) Q _B ; Concentration of compound B in the inhibitory concentration of the composite agent (mg/)

[Consideration]

As is clear from the test results, it can be seen that by combining Compound A and Compound B, a synergistic effect is exhibited at each ratio. Especially A:B
It can be seen that a remarkable synergistic effect is exhibited at a ratio of 67:33 to 17:83 (2:1 to 1:5). Especially in the ratio of 29:71, compound A,
It can be seen that mold growth is inhibited by combining Compound A at a concentration of 0.4 mg/1/20, which is the growth-inhibiting concentration of B alone, and Compound B at a concentration of 1/8. The total amount added is approximately 1/1 of that of compounds A and B alone.
It can be seen that mold growth can be inhibited at an amount of 6 and a remarkable synergistic effect is exerted. Test Example 2 [Two types of mixed bacteria (Trichoderma T-1+
Synergistic effect against Fusarium moniriforme.] Two types of mixed bacteria (Trichoderma T-1 + Fusarium
The synergistic effect of Compound A and Compound B was tested using M. moniriforme as a test bacterium. The results are shown in Table 2. Note that Compounds A and B are the same as those used in Test Example 1.

[Consideration]

As is clear from the test results, by combining Compound A and Compound B at a weight ratio of 9:1 to 1:9, the growth inhibitory concentration is lowered by one rank, indicating that a synergistic effect is exhibited. Test example 3 A certain paper company's UKP pulp sheet was disintegrated, and 2
% slurry is prepared. Pour the 150ml into a 200ml Erlenmeyer flask and cover the mouth with aluminum foil.
Sterilization was performed at 120°C and 1 atm for 15 minutes. After cooling at room temperature,
Immediately after adding each drug at a predetermined concentration, 1.5 ml of a spore suspension of 9 types of mixed bacteria was added, and the mixture was shaken for 1 hour. Thereafter, it is suctioned through a glass filter (7 cm in diameter) to obtain a pulp sheet. This was punched out to a diameter of 4 cm and placed on an inorganic salt medium poured into a shear dish.27
Incubate at ℃ and visually observe the presence or absence of mold. The results are shown in Table 3. The nine types of mixed bacteria used as test bacteria are a mixture of the following nine types of bacteria that are representative of harmful molds. 1 Aspergillus niger 2 Penicillium eitrinum 3 Trichoderma T-1 4 Rhizopus stolonifer 5 Cladosporium cladosporioides 6 Chaetomium globosum 7 Mucor hiemalis 8 Alternaria sp. 9 Fusarium moniriforme Compounds A and B are the same as the compounds used in Test Example 1.

[Consideration]

As is clear from the test results (see Test Nos. 2 to 7), for example, Test No. 8 as shown in
There was no mold growth even after several days, indicating that a so-called synergistic effect was being exerted. Also, test no.
As shown in 8 and 9, a composite agent of Compound B and tetrachloroisophthalonitrile, which is well known to be effective as an industrial fungicide (Japanese Patent Publication No. 58
-39124) requires an additive concentration of 2 to 3 times that of the composite agent of the present invention in order to prevent mold growth, demonstrating the usefulness of the present invention. Test Example 4 Paper (Toyo Paper No. 26) is punched out into a circle with a diameter of 4 cm, and 0.7 ml of the drug diluted to each concentration is soaked into it.The inorganic salt medium is poured into a shear dish and hardened.Similar to the test bacteria in Test Example 3. Add 0.1 ml of the spore suspension of the 9 types of mixed bacteria so that it is uniform. The paper is placed on top of the paper and incubated at 27°C, and the presence or absence of mold growth is observed with the naked eye. The results are shown in Table 4. -, +, in the table
, has the same meaning as shown in Table 3. Moreover, compounds A and B are the same as the compounds used in Test Example 1.

[Consideration]

As is clear from the test results, with Compound A alone and Compound B alone, mold growth was observed after 8 days even when 50 mg/kg was added as shown in Test Nos. 3 and 5; It can be seen that when used in combination (combined use), a remarkable synergistic effect was exerted, with no mold growth even after 8 days when 5 mg/g was added, as shown in Test Nos. 6 and 8. In addition, in the composite agent of Compound B and tetrachloroisophthalonitrile shown in Test Nos. 10 and 11 (invention of Japanese Patent Publication No. 58-39124), even if 180 mg/g was added.
Although mold growth was observed after 10 days, as shown in Test Nos. 7 and 9, in the composite agent of the present invention, mold growth was observed after 10 days with the addition of 50 mg/less than 1/3.
There was no mold growth after 12 days, demonstrating the usefulness of this invention compared to conventional products. Example 1 Using the JIS Z-2911 paint mold resistance test method, the effects of various emulsion paints on molds (Alternaria sp,
Trichoderma sp, Aspergillus sp, Penicillium
sp) The results obtained for the test bacteria are shown in Table 5.
As the emulsion paint, vinyl acetate emulsion paint and acrylic resin emulsion paint were used.

[Table] Example 2 A precursor material was sprinkled with various concentrations of chemicals, sealed in a plastic bag, and stored at 30°C. The results are shown in Table 6. Compounds A and B are the same as those used in Test Example 1.

[Table] The table shows the degree of mold growth -, +,...
indicates the following meaning.

[Table] Example 3 50 parts of a test chemical and 50 parts of a 2% polyvinyl alcohol aqueous solution were mixed and kneaded well to form a paste. This paste was diluted 50 times with water and added to pulp at a kraft pulp manufacturing plant, Chiest. This pulp (hydration rate approximately 50%) was punched into 4 cm diameter pieces, poured with an inorganic salt medium, and placed in a hardened shear dish.
0.1ml of mixed spore suspension of Penicillium sp, Penicillium sp)
was evenly sprinkled onto a pulp sheet, incubated at 27°C, and observed for mold growth over time. The test results are shown in Table 7. Compounds A and B are the same as those used in Test Example 1, and in the table, -, +, and , which indicate the degree of mold growth, have the meanings given in Example 2.

[Table] means the composite agent.
Example 4 Red pine sapwood (length 5 cm x width 5 cm x thickness 1
cm) for 30 seconds and air dry. This test side was placed on a potato dextrose agar medium, sprinkled with 0.5 ml of mold spore suspension, and cultured at 27°C for 3 weeks. Bacteria isolated from this tree (Hilminthosporium sp, Trichoderma sp,) were used as test bacteria. The test results are shown in Table 8. Compound A, B
is the same as the compound used in Test Example 1, and the comparative preparation is a composite agent of 2,4,5,6-tetrachloroisophthalonitrile and Compound B in a weight ratio of 2:1. . Further, in the table, the expressions -, ±, +, indicating the degree of mold propagation represent the meanings shown in Example 2.

[Table] (c) Effects of the invention As is clear from the above, the industrial fungicide of this invention has an effect that cannot be expected from the effect when each active ingredient is used alone, especially against fungi. Since it exhibits a synergistic effect and both of the two active ingredients have low toxicity, it is an excellent product that is very useful industrially.

Claims (1)

[Claims] 1. diiodomethyl-p-tolylsulfone and 2-
An industrial fungicide characterized by containing methoxycarbonylaminobenzimidazole as an active ingredient in a weight ratio of 9:1 to 1:9. 2 diiodomethyl-p-tolylsulfone and 2-
The industrial fungicide according to claim 1, wherein the weight ratio with methoxycarbonylaminobenzimidazole is from 2:1 to 1:5.