JPH07247201A - Germicidal and fungicidal composition - Google Patents

Abstract

PURPOSE:To obtain a germicidal and fungicidal composition, hardly coloring various industrial raw materials or industrial products, etc., and capable of simultaneously controlling various microorganisms in a low dose by using a diiodomethyl p-tolyl sulfone and a specific phenol compound in combination. CONSTITUTION:This germicidal and antifungal composition is obtained by using diiodomethyl p-tolyl sulfone and a phenol compound expressed by the formula (R<1> and R<2> each is H or methyl) in combination. The blending ratio thereof is preferably 0.01-100 pts.wt. compound expressed by the formula based on 1 pt.wt. diiodomethyl p-tolyl sulfone. For example, 2,2-(4'-hydroxyphenyl) propane, 4,4'-dihydroxydiphenylmethane, 2,4'-dihydroxydiphenylmethane and 2,2'-dihydroxydiphenylmethane are cited as the compound expressed by the formula. The composition is capable of manifesting excellent synergistic effects on various microorganisms and molds and providing remarkable effects in a low dose or concentration. Since both of the respective compounds constituting the composition have low toxicity to humans and livestock, the composition is safe.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to diiodomethyl-p-
Tolyl sulfone and general formula (1)

[Chemical 2] (In the formula, R ¹ and R ² represent hydrogen or a methyl group, and may be the same or different from each other.) A bactericidal and fungicidal composition containing a phenol compound as an active ingredient.
The composition of the present invention is useful, for example, as a germicidal fungicide for various industrial raw materials or industrial products.

[0002]

2. Description of the Related Art Conventionally, various industrial raw materials or industrial products such as paints, pastes, woods, leathers, fibers, plastics and pulps have been sterilized in order to prevent the deterioration of the products or the change of appearance due to microorganisms. It is widely practiced to add fungicides. Since these industrial raw materials or industrial products often come into direct contact with the human body, the additives used above not only have a high bactericidal and fungicidal effect, but are highly safe for humans and animals, and A compound that does not cause problems such as pollution is required.

It is generally known that iodine-based germicidal fungicides are highly safe and have a broad antibacterial spectrum. Among them, diiodomethyl-p-tolylsulfone is a known compound having particularly high safety and having high activity as a germicidal fungicide and an algicidal agent. Diiodomethyl-
p-Tolyl sulfone is a yellow to tan powder solid. Also, its toxicity is small, and acute toxicity LD
₅₀ is orally 10000 mg / kg (rat), 9400 mg / kg
It is a (mouse) and does not cause skin irritation and mutagenicity on humans. Further, it is a compound having a very excellent effect of widely inhibiting the growth of fungi.

This diiodomethyl-p-tolylsulfone has a very high bactericidal effect on some bacteria, for example, methicillin-resistant Staphylococcus aureus (MRSA), but is sufficient for all bacteria. It does not have a bactericidal effect. Therefore, when using this and adding it to industrial raw materials or industrial products as a bactericidal fungicide,
It must be used as a mixture with other compounds having a high bactericidal effect.

[0005] Further, an iodo-based germicidal fungicide such as diiodomethyl-p-tolylsulfone may give a yellow color to the industrial products when it is added, although it is weak. In some cases, the use of diiodomethyl-p-tolylsulfone is limited, as coloring can reduce the value of the product or can be cosmetically problematic. Therefore, when diiodomethyl-p-tolylsulfone is used as a germicidal fungicide, it is desired to be mixed with a compound having not only a germicidal fungicidal effect but also an effect of suppressing coloring. However, among the compounds that have hitherto been used as germicidal fungicides, no compound satisfying the condition of having the effect of suppressing the coloration by diiodomethyl-p-tolylsulfone has been found.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fungicidal and fungicidal composition having excellent properties, overcoming the above-mentioned conventional drawbacks. That is, it is less likely to color various industrial raw materials or industrial products, and at the same time, a wide variety of fungi that cause pollution and deterioration can be obtained.
Moreover, it is an object to provide a bactericidal and fungicidal composition which is controlled with a lower dose and is highly safe.

[0007]

In order to achieve the above object, the inventors of the present invention have conducted an earnest search for a compound having a fungicidal and fungicidal effect that can be used together with diiodomethyl-p-tolylsulfone. In the process, paying attention to the phenol compound represented by the general formula (1) (chemical formula 2),
Further research continued, when the compound and diiodomethyl-p-tolylsulfone were used in a mixture, the activity of each of them was not hindered, and when they were used alone due to a synergistic effect. It was found that it showed higher activity than that of More surprisingly, it was also found that the slight coloring phenomenon that has been conventionally observed when using diiodomethyl-p-tolylsulfone is suppressed by using a mixture of the above-mentioned phenol compounds, and the present invention It came to completion.

That is, the present invention relates to diiodomethyl-p
-Tolyl sulfone and general formula (1)

[Chemical 3] (In the formula, R ¹ and R ² represent hydrogen or a methyl group, and may be the same or different from each other.) A bactericidal and fungicidal composition containing as an active ingredient a compound represented by the formula .

The present invention will be described in detail below. In the present invention, specific compounds represented by the general formula (1) (formula 3) include, for example, 2,2- (4′-hydroxyphenyl)
Propane, 4,4'-dihydroxydiphenylmethane, 2,
4'-dihydroxydiphenylmethane and 2,2'-dihydroxydiphenylmethane can be mentioned. These are generally very safe, for example, the oral toxicity LD ₅₀ of 4,4′-dihydroxydiphenylmethane is 4950 mg / kg (rat).

The mixing ratio of the two active ingredients in the fungicidal fungicide of the present invention is 0.01 to 0.01 parts by weight of the compound represented by the general formula (1) (formula 3) per 1 part by weight of diiodomethyl-p-tolylsulfone. 100 parts by weight, more preferably 0.1 to 10 parts by weight. Although the effect can be seen even if this is out of the range of 0.01 to 100 parts by weight, generally, the synergistic effect thereof becomes gradually smaller.

When the fungicidal and fungicidal composition of the present invention is used, it is possible to directly use a mixture of two active ingredients, but diiodomethyl-p-tolyl can be used in order to efficiently bring out each effect. The sulfone and the compound represented by the general formula (1) (formula 3) may be supported on an appropriate carrier or added with an appropriate compounding agent to prepare various dosage forms depending on the purpose of use. preferable. For example,
The composition of the present invention can be used in the form of oil, emulsion, paste, powder, wettable powder, flowable agent, and aerosol.

Further, the composition of the present invention is mixed with a paint, kneaded into a synthetic resin sheet, blended with latex and kneaded with a packing agent such as carpet to exert a sustained release effect, and impregnated with fibers. , Or attached with an adhesive, and the like.

Examples of carriers that can be used in the germicidal and fungicidal composition of the present invention include kaolin, bentonite, acid clay, talc, diatomaceous earth, silica sand, mica, inert solid carriers such as white carbon, water, methanol, ethanol, Ethylene glycol, propylene glycol, acetone,
Liquid carrier such as methyl ethyl ketone, ethyl ether, n-hexane, white kerosene, toluene, xylene, cyclohexane, dimethylformamide, N-methyl-2-pyrrolidinone, ethyl acetate, phthalates, dimethyl sulfoxide, nitrogen gas, dimethyl ether, propane Examples thereof include gas carriers such as gas and butane gas, and they are not limited to these and can be used in a wide range. These may be used alone or in combination of two or more.

The compounding agent used in the germicidal and fungicidal composition of the present invention includes, for example, emulsifiers and dispersants such as soaps, sulfuric acid esters of higher alcohols, alkylsulfonic acids, alkylallylsulfonic acids, and Examples thereof include quaternary ammonium salts, oxyalkylamines, fatty acid esters, polyalkylene oxide-based or anhydrosorbitol-based surfactants, and the like. Further, instead of these surfactants or as an auxiliary agent thereof, gelatin, starch, alginic acid, agar, carboxymethyl cellulose, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, xanthan gum, high molecular anionic heteropolysaccharide, vegetable oil, bentonite, etc. However, the present invention is not limited to these and can be used in a wide range. These may be used alone or in combination of two or more.

The content ratios of the two active ingredients in the fungicidal and fungicidal composition of the present invention differ depending on the purpose of use or dosage form. Further, when using the composition of the present invention,
The dosage forms and the like listed above as examples may be added as they are, or a solvent, a diluent, a bulking agent, or the like may be added at an appropriate time and diluted before addition.

[0016]

[Examples] The composition of the present invention is described below according to formulation examples, and
The action of the composition of the present invention will be described in detail with reference to test examples. These are only specific examples, and the present invention is not limited to these. In the following, "part""%""ppm"
Are all on a weight basis, and the abbreviations of compounds A to E respectively represent the following compounds. Compound A: Diiodomethyl-p-tolylsulfone Compound B: 2,2- (4'-hydroxyphenyl) propane Compound C: 4,4'-dihydroxydiphenylmethane Compound D: 2,4'- Dihydroxydiphenylmethane Compound E ・ ・ ・ 2,2'-dihydroxydiphenylmethane

Formulation Example 1 After dissolving 1 part of compound A and 1 part of compound C in 15 parts of xylene and 5 parts of dimethylformamide, 78 parts of white kerosene were mixed and dissolved to prepare an oil solution.

Formulation Example 2 After dissolving 5 parts of compound A and 5 parts of compound C in 15 parts of xylene and 15 parts of dimethylformamide, 10 parts of a mixture of polyoxyethylene alkylphenyl ether and alkylallyl sulfonate was added, and further white It was dissolved with 65 parts of kerosene to prepare an emulsion.

Formulation Example 3 15 parts of compound A, 15 parts of compound B, 50 parts of diatomaceous earth, 10 parts of a mixture of polyoxyethylene alkylphenyl ether and alkylallyl sulfonate, and 10 parts of white carbon are uniformly mixed and ground to be hydrated. The agent was adjusted.

Formulation Example 4 15 parts of compound A, 15 parts of compound C, 50 parts of diatomaceous earth, 10 parts of a mixture of polyoxyethylene alkylphenyl ether and alkylallyl sulfonate, and 10 parts of white carbon are uniformly mixed and ground to hydrate. The agent was adjusted.

Formulation Example 5 15 parts of compound A, 15 parts of compound E, 50 parts of diatomaceous earth, 10 parts of a mixture of polyoxyethylene alkylphenyl ether and alkylallyl sulfonate, and 10 parts of white carbon are uniformly mixed and ground to hydrate. The agent was adjusted.

Formulation Example 6 15 parts of compound A, 15 parts of compound D, 50 parts of diatomaceous earth, 10 parts of a mixture of polyoxyethylene alkylphenyl ether and alkylallyl sulfonate, and 10 parts of white carbon are uniformly mixed and ground to hydrate. The agent was adjusted.

Formulation Example 7 20 parts of compound A, 20 parts of compound D, 1 part of polyoxyethylene alkylphenyl ether, and 39 parts of water are uniformly mixed.
After grinding, a mixture of 0.2 parts of xanthan gum and 19.8 parts of water was added to this to prepare a flowable agent.

Test Example 1 (Efficacy test against fungi) A reagent solution is dissolved in 3 parts of dimethylformamide, and a sterilized 0.075% agar solution at 50 ° C. is used to prepare a 500 ppm aqueous solution of drug agar. This 500 ppm aqueous solution of drug agar is diluted with a sterilized 50 ° C. potato dextrose agar medium (pH = 6.0) and immediately dispensed and solidified in a petri dish having a diameter of 9 cm to prepare a drug-containing agar medium having a predetermined concentration. A spore suspension of the test bacterium, which has been previously cultured in a slant medium, is streaked with a platinum loop on the drug-treated medium. This was cultured at 28 ° C. for 10 days, and the presence or absence of growth of each bacterium was examined to determine the minimum growth inhibitory concentration (ppm) in the medium required to inhibit the growth of the bacterium. The results are shown in Table 1.

[0025]

[Table 1] From Table 1, the composition of the present invention comprising diiodomethyl-p-tolylsulfone and the compound represented by the general formula (1) (Chemical Formula 3) was compared with Comparative Examples 1 and 2 prepared by using each of them alone. However, a synergistic bactericidal effect is clearly observed, and it can be seen that the growth of bacteria can be effectively inhibited at an extremely low concentration.

Test Example 2 (Bacterial Efficacy Test) A reagent solution is dissolved in 3 parts of dimethylformamide, and a sterilized 0.075% agar solution at 50 ° C. is used to prepare a 500 ppm aqueous drug agar solution. This 500 ppm aqueous solution of drug agar is diluted with a sterilized 50 ° C. broth agar medium and immediately dispensed and solidified into a petri dish having a diameter of 9 cm to prepare a drug-containing agar medium having a predetermined concentration. The test bacterium, which has been previously cultivated in the slant medium, is streaked on the drug treatment medium with a platinum loop. This was cultured at 37 ° C. for 10 days, and the presence or absence of growth of each bacterium was examined to determine the minimum growth inhibitory concentration (ppm) in the medium required to inhibit the growth of the bacterium. The results are shown in Table 2.

[0027]

[Table 2] From Table 2, the composition of the present invention comprising diiodomethyl-p-tolyl sulfone and the compound represented by the general formula (1) (Chemical Formula 3) is compared with Comparative Examples 3 and 4 prepared by using each of them alone. However, a synergistic bactericidal effect is clearly observed, and it can be seen that the growth of bacteria can be effectively inhibited at an extremely low concentration.

Test Example 3 (Test for Preventing Coloring Effect) Any one of the ones prepared in Formulation Examples 3 to 6 was added to an acrylic emulsion paint so as to have a concentration of 2% by weight, and each of them was added. After coating on a straight plate (7 cm x 15 cm) and air-drying at room temperature for 7 days, it was irradiated with ultraviolet rays for 1 week continuously with an ultraviolet fade meter to observe how the color of the coating film changed. In Comparative Example 5, the compound A alone contained 3000 ppm in the acrylic emulsion paint.
Was added in the same manner as above to perform the same procedure. The results are shown in Table 3.

[0029]

[Table 3] Conventionally, iodo-based germicidal fungicides such as diiodomethyl-p-tolylsulfone have been sometimes weakly colored when added and used in industrial products. However, it can be seen from Table 3 that the use of the composition of the present invention can suppress the coloration of products and the like due to diiodomethyl-p-tolylsulfone.

[0030]

As is clear from the above description, diiodomethyl-p-tolyl sulfone and the compound represented by the general formula (1)
The composition of the present invention comprising the compound represented by the formula (1) exhibits an excellent synergistic effect against various bacteria and fungi, and an excellent effect can be obtained at a low dose or a low concentration. Furthermore, when added to various industrial raw materials or industrial products, it is possible to suppress coloring due to the use of diiodomethyl-p-tolylsulfone. Further, since each of the compounds constituting the composition of the present invention has low toxicity to humans and animals, they can be safely used as various industrial raw materials or industrial products.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshinori Tanaka 1900, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] 1. Diiodomethyl-p-tolyl sulfone and the compound represented by the general formula (1) (In the formula, R ¹ and R ² represent hydrogen or a methyl group and may be the same or different from each other.) A bactericidal and fungicidal composition containing as an active ingredient a compound. 2. Diiodomethyl-p-tolyl sulfone 1
A compound represented by the general formula (1) (chemical formula 1) with respect to parts by weight.
The bactericidal and fungicidal composition according to claim 1, which is contained in an amount of 0.01 to 100 parts by weight.