JP3489981B2 - Antiseptic and fungicide - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an emulsion paint, an oil paint, an electrodeposition paint, an organic adhesive, a pigment, a clay,
To prevent deterioration of various industrial raw materials and products such as ink, cutting oil, wood, leather, textiles, and white water during paper production by bacteria, yeast, filamentous fungi, algae, and various industrial raw materials The present invention relates to a novel antiseptic and fungicide for preventing environmental pollution by microorganisms such as product storage areas, product manufacturing floors, walls, and ceilings.

[0002]

2. Description of the Prior Art One of the active ingredients of the present invention, 3-iodo-2-propargylbutylcarbamate (hereinafter referred to as "compound A"), diiodomethyl-p-tolylsulfone (hereinafter referred to as "compound B"), 3, 4 , 4'-trichlorocarbanilide (hereinafter referred to as "compound C"), 2, 4,
4'-trichloro-2'-hydroxydiphenyl ether (hereinafter referred to as "Compound D"), 2- (4-thiazolyl) benzimidazole (hereinafter referred to as "Compound E"),
Methyl-2-benzimidazole carbamate (hereinafter referred to as "Compound F") is known as an antifungal agent ("Encyclopedia of Antibacterial and Antifungal Agents", Japanese Society of Antibacterial and Antifungal Agents,
Published August 22, 1986).

Further, those containing a mixture of compound B and compound E as an active ingredient or those containing it as an active ingredient are disclosed in JP-A No. 7-18812 and JP-B No. 53-182.
No. 1 (Industrial antifungal composition), JP-A-59-212
No. 678 (polyester polyurethane elastic yarn having antibacterial properties), JP-A-57-141467, JP-A-57-141468 (coating composition for temporary protection having mold resistance), JP-A-SHO No. 56-62857 (antifungal coating composition).

Further, Japanese Patent Publication No. 2-40754 discloses that
Described is an aluminum product with an antibacterial / mildew-proof composite coating, which is obtained by treating the surface of aluminum with a mixture of compound D and compound E.

[0005]

In order to protect industrial raw materials and products from deterioration due to bacteria, yeast, mold, etc., it is necessary to prevent the generation of various microorganisms nonselectively and eradicated. However, the antiseptic and fungicides that have been used so far are restricted in their use because they are highly toxic to humans and animals, and the effects are weakened when the amount used is small, or the residual effects over a long period of time are poor. In addition, there are few conventional drugs that sufficiently exhibit both the antiseptic effect and the antifungal effect. Compound A, Compound B, Compound C, Compound D used in the present invention,
Both compound E and compound F have such drawbacks and their use alone is not always satisfactory.

Therefore, there is a demand for the development of a novel antiseptic and fungicide which can prevent the generation of various microorganisms that deteriorate the industrial raw materials and products with a small amount of drug instead of the conventional agents for a long period of time.

[0007]

DISCLOSURE OF THE INVENTION In order to develop a new antiseptic and fungicide which meets the above-mentioned needs, the present inventors have conducted extensive tests on various compounds and conducted extensive studies. As a result, a mixed agent of one kind selected from the compound A or the compound B and one kind selected from the compound C or the compound D or a salt thereof represented by the chemical structural formulas described later, or a mixed agent of the two kinds. And compound E or a salt thereof or compound F
Alternatively, it has been found that by using a mixture of three kinds with one kind selected from its salt, it is useful as an antiseptic and fungicide for various industrial raw materials and products.

Therefore, the gist of the first aspect of the present invention is to select, as an active ingredient, one selected from 3-iodo-2-propargylbutylcarbamate or diiodomethyl-p-tolylsulfone and 3,4,4 '. -Trichlorocarbanilide or 2,4,4'-trichloro-2 '
-Hydroxydiphenyl ether or a salt thereof, and one component selected from the group consisting of two components,
In antiseptic and antifungal agents.

The gist of the second aspect of the present invention is to use, as an active ingredient, one selected from 3-iodo-2-propargylbutylcarbamate or diiodomethyl-p-tolylsulfone and 3,4,4 '. -Trichlorocarbanilide or two components of 2,4,4'-trichloro-2'-hydroxydiphenyl ether or a salt thereof and 2- (4-thiazolyl) benzimidazole or a salt thereof or methyl -2-A benzimidazole carbamate or one kind selected from salts thereof and three kinds of components as an active ingredient are contained in the antiseptic and fungicide.

The chemical structural formulas of the active ingredients of the antiseptic and fungicide of the present invention are shown below.

Compound A 3-Iodo-2-propargyl butyl carbamate

[Chemical 1]

Compound B Diiodomethyl-p-tolylsulfone

[Chemical 2]

Compound C 3,4,4'-trichlorocarbanilide

[Chemical 3]

Compound D 2,4,4'-trichloro-2
´-Hydroxydiphenyl ether

[Chemical 4] Examples of the salt of compound D include sodium salt, potassium salt, calcium salt and the like.

Compound E 2- (4-thiazolyl) benzimidazole

[Chemical 5] Examples of the salt of compound E include lactate and dodecylbenzene sulfonate.

Compound F Methyl-2-benzimidazole carbamate

[Chemical 6] Examples of the salt of compound F include lactate and dodecylbenzene sulfonate.

The antiseptic / antifungal agent of the present invention, that is, a mixture of two components consisting of any one of compound A or compound B and any one of compound C or compound D,
Alternatively, a mixture of three components in which compound E or a salt thereof, or compound F or a salt thereof is used in combination with the mixture of two components is used in various industrial applications, as will be apparent from the test examples described below. It acts synergistically as an antiseptic and fungicide to prevent microbial deterioration of raw materials and products.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Formulation and Use of Antiseptic and Antifungal Agent The antiseptic and antifungal agent of the present invention can be obtained by the following method. That is, 2 or 3 types of active ingredients of the present invention and suitable carriers and auxiliaries such as surfactants, binders, stabilizers and the like are mixed, and powders, wettable powders, emulsions, solutions,
Formulations such as flowable agents (sol agents) and granules may be used.

The content of the active ingredient of the present invention in these preparations is 1 in the case of powders, wettable powders, emulsions, liquids, flowables and granules, as the total amount of 2 kinds or 3 kinds of ingredients. To 100% (same as below by weight%). In the case of 100%, it means that the two kinds of active ingredients can be used as they are as a powder or the like.
In the case of two kinds of components, the mixing ratio of compound A or compound B and compound C or compound D is 1 for compound A or compound B.
The amount of compound C or compound D is 0.01 to 10 parts, preferably 0.2 to 5 parts, and particularly preferably 1 part with respect to parts (parts by weight, the same applies hereinafter).

In the case of three kinds of components, the mixing ratio of compound A or compound B and compound C or compound D and compound E or compound F is 1 part by weight of compound A or compound B (part by weight, the same applies hereinafter). , Compound C or compound D and compound E or compound F are 0.01 to 10 parts, preferably 0.2 to 5 parts, and particularly preferably 1 part.

The carrier that can be used in the above may be either solid or liquid as long as it is commonly used for antiseptic and antifungal agents, and is not limited to a particular carrier. For example, as a solid carrier, mineral powder (kaolin, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, phosphorus, lime, white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc.), vegetable powder ( Soybean flour, wheat flour, wood flour,
Starch, crystalline cellulose, etc.), alumina, silicates, sugar polymers, highly dispersible silicic acid, waxes and the like.

As the liquid carrier, water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, chloro) are used. Benzene, cumene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, dichloromethane, chloroethylene, trichlorofluoromethane, dichlorodifluoromethane, etc.), ethers (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran, etc.) , Ketones (acetone, methyl ethyl ketone, cyclohexane, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate) Dioctyl phthalate, amyl acetate, etc.), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2- Propanol, etc.), amines (ethylamine, dimethylamine, trimethylamine, isobutylamine, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), industrial gasoline (petroleum ether, solvent naphtha, etc.), petroleum Fractions (paraffins, kerosene, gas oil, etc.) are included.

Further, in the preparation of powders, emulsions, wettable powders, sol agents (flowable agents), granules and the like, a surfactant is used for the purpose of emulsification, dispersion, solubilization, wetting, foaming, spreading and the like. used. Examples of such a surfactant include those shown below, but the surfactant is not limited to the following examples.

Nonionic type (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc.)

Anionic type (alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfonate, etc.)

Cationic type [alkylamine salt, (laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride), etc.]

Amphoteric type [carboxylic acid (betaine type), sulfate ester, etc.]

In addition to these, polyvinyl alcohol (PVA) and carboxymethyl cellulose (CM
Various auxiliary agents such as C), gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate, etc. can be used. Further, if necessary, an appropriate amount of a stabilizer such as an antioxidant and an ultraviolet absorber can be added.

Further, the antiseptic / antifungal agent of the present invention can be used by mixing with various other industrial antiseptic / antifungal agents and various agricultural bactericides.

Although some examples will be given below, the mixing ratio of the active ingredient, auxiliary components and other addition amounts are not limited to the following examples.

Example 1 (Flowable Agent) 15 parts of compound A, 15 parts of compound C, 2 parts of polyoxyethylene nonylphenyl ether, 2 parts of carboxymethylcellulose and 76 parts of water were put into a ball mill and ground and mixed for 12 hours. , To obtain a flowable agent containing 30% of the active ingredient.

Example 2 (flowable agent) 10 parts of compound A, 10 parts of compound C, compound E 10
Part, polyoxyethylene nonyl phenyl ether 2
Parts, 2 parts of carboxymethylcellulose and 76 parts of water are put into a ball mill and ground and mixed for 12 hours to obtain a flowable agent containing 30% of the active ingredient.

Example 3 (Wettable powder) 15 parts of compound A, 15 parts of compound C, 0.5 part of polyoxyethylene nonylphenyl ether, 7 parts of lauryl sulfate, 25 parts of white carbon and 57.5 parts of clay were mixed and ground. Thus, a wettable powder containing 30% of the active ingredient is obtained.

Example 4 (Wettable powder) 10 parts of compound A, 10 parts of compound C, compound E 10
Parts, polyoxyethylene nonyl phenyl ether 0.5
Part, lauryl sulphate 7 parts, white carbon
25 parts and 57.5 parts of clay are mixed and ground to obtain a wettable powder containing 30% of the active ingredient.

Example 5 (Emulsion) 1.5 parts of Compound A, 1.5 parts of Compound C, 53 parts of dimethyl sulfoxide, 40 parts of methyl isobutyl ketone.
And 5 parts of Solpol 900A (trade name of emulsifier manufactured by Toho Chemical Industry Co., Ltd.) are mixed and dissolved to obtain an emulsion containing 3% of the active ingredient.

Example 6 (Emulsion) 1 part of compound A, 1 part of compound C, 1 part of compound E, 53 parts of dimethyl sulfoxide, 40 parts of methyl isobutyl ketone and SOLPOL 900A (manufactured by Toho Chemical Industry Co., Ltd.) 5 parts (trade name) are mixed and dissolved to obtain an emulsion containing 3% of the active ingredient.

Further, by substituting the other active ingredients of the present invention for the compounds A, C and E in the above examples, the desired antiseptic and fungicide can be obtained.

The antiseptic / antifungal agent of the present invention is used as follows. That is, various preparations prepared according to the above-mentioned examples are used as they are, or diluted with water or a suitable organic solvent (1) added to various industrial raw materials or during a manufacturing process or to a product. , (2) Method of coating or spraying on the surface of various industrial raw materials and products, (3)
A method of immersing various industrial raw materials and products in a diluting solution of the industrial antiseptic and fungicide of the present invention, (4) manufacturing of various industrial raw materials and products, ceilings, walls, floors, working machines, mushrooms at storage locations Such as the method of applying or spraying on the wall, floor, ceiling, etc. of the cultivation room, etc., (5) various industrial raw materials, the method of applying or spraying on the packaging surface of products, etc. It can be used by various methods depending on the method of using the antiseptic and fungicide, but is not limited to a specific method.

[0039]

Use of the antiseptic and fungicide of the present invention brings about the following effects.

First of all, the drug of the present invention non-selectively and eradicates the development of various microorganisms such as bacteria, yeast and filamentous fungi. Therefore, it can be widely used as an industrial antiseptic and fungicide. Second, it shows a strong antiseptic and antifungal effect even with a small dose. Thirdly, a strong antiseptic and antifungal effect can be exerted for a long time even with a small dose. The effect is exerted as a synergistic effect as compared with the effect of each single agent. Fourth, there are few problems such as human toxicity. Fifth,
It can be used by various methods such as spraying, coating, mixing with industrial raw materials and products, but any method will adversely affect the industrial raw materials and products or the floors, walls, etc. of these manufacturing sites and storage areas. There is no such thing.

Since the antiseptic / antifungal agent of the present invention has the above-mentioned characteristics, various antibacterial / antifungal agents for industrial use, such as various industrial raw materials and products, and their manufacturing sites and storage locations, are exemplified below. Can be widely used as, but is not limited to only the examples.

(1) During the manufacturing process of the water-based or oil-based coating,
Prevents spoilage problems caused by growth of bacteria, filamentous fungi, yeasts, etc. during storage and use, and prevents contamination of filamentous fungi on painted surfaces after painting.

(2) Casein, polyvinyl alcohol,
Bacteria such as starch or other adhesives or glues, filamentous fungi,
Prevents spoilage due to yeast growth and contamination of filamentous fungi on the coated surface.

(3) Preventing deterioration of quality due to growth of bacteria, filamentous fungi, yeast, etc. during storage of papermaking raw materials such as wet pulp and chips.

(4) Prevention of contamination and deterioration of quality of processed products and materials such as wood, plywood, bamboo and leather due to growth of bacteria, filamentous fungi and yeast.

(5) Prevention of contamination and deterioration of quality of natural fibers, synthetic fibers and their blended products, materials, etc. due to growth of filamentous fungi.

(6) Prevention of quality deterioration damage due to growth of bacteria, filamentous fungi, and yeast on synthetic emulsion or emulsion wax

(7) Prevention of quality deterioration damage due to growth of bacteria, filamentous fungi, and yeast in surfactants, preparations used, and the like.

(8) Prevention of quality deterioration damage due to growth of bacteria, filamentous fungi and yeast in hydraulic fluids and the like.

(9) Prevention of deterioration of quality due to growth of bacteria, filamentous fungi, yeast in plastics and rubber, or antibacterial.

(10) Control of slime disorders caused by bacteria, filamentous fungi, yeasts and algae during the papermaking process.

(11) Manufacture of various industrial raw materials and products,
Prevents environmental pollution from bacteria, filamentous fungi, and yeast on ceilings, floors, walls, etc. where processing and storage are performed.

Next, test examples are shown to show the usefulness as the antiseptic / antifungal agent of the present invention.

In Test Examples 1 to 5, the antiseptic / antifungal agent of the present invention exhibits the same antiseptic / antifungal effect even if one of the active ingredients, Compound E and Compound F, is replaced with its salt.

Test Example 1 Fungus resistance test of emulsion coating The test method was according to the method of JIS Z 2911. That is, a flowable prepared according to Example 1 or 2 was added to a vinyl acetate emulsion white paint so as to have a predetermined concentration, and the mixture was stirred and mixed with a homogenizer for 30 seconds to prepare a paint. 1 in diameter for the resulting coating liquid
A 2.5 cm size filter paper (Toyo Filter Paper No. 2) is dipped in the sample to uniformly apply it, and then air dried at room temperature for 48 hours.
In this case, the thickness of the coating film is uniform, and the weight of the paint attached to the filter paper is 90 to 110% of the weight of the filter paper. This filter paper was used as a circular test piece with a diameter of 3 cm, and a beaker with a capacity of 200 ml was prepared for each test piece. 200 ml of water was added to it and kept at 20 ° C, and the test piece was immersed in it for 18 hours. Then, the test piece is taken out and hung at room temperature for 2 hours, and further dried (80 to 8
Hang in 5 ℃). Two hours later, the test piece was taken out and the agar medium in a Petri dish (composition: glucose 40 g, peptone 10 g, agar 25 g, and purified water 1000 ml).
The mixture was applied to the center of the culture surface of Aspergillus niger, Penicillium funiculosum, Cladosporium cladsporioides, Gliocladium virens, and Aureobasidium pullulans mixed spore suspension and sprayed evenly on the medium surface and the test piece. Inoculate.

The Petri dish was covered with a lid and cultured in an incubator at 28 ± 2 ° C., and 3 days, 7 days and 14 days thereafter, the mold growth state on the test piece was examined according to the following criteria.

The drugs in the control group were prepared and tested according to Example 1. The results are shown in Tables 1 and 2.

[0058]

[0059]

[Table 1]

[0060]

[Table 2]

Test Example 2 Field Test of Emulsion Paint A predetermined amount of a flowable agent prepared according to Example 1 or 2 is added to a vinyl acetate emulsion white paint and mixed sufficiently to obtain a paint liquid. This coating solution was applied to a concrete wall surface, and after 3 months, 6 months, and 12 months, the generation of mold and bacteria was investigated according to the following criteria.

The drugs in the control group were prepared and tested according to Example 1 or 2. The results are shown in Tables 3 to 4.

[0063]

[0064]

[Table 3]

[0065]

[Table 4]

Test Example 3 Mold resistance test of starch paste 15 parts of tapioca starch and 85 parts of an aqueous solution prepared by adding a wettable powder prepared according to Example 3 or Example 4 to a predetermined concentration were added to a flask having a volume of 200 ml. put in,
Stir to 70 ° C., then slowly cool to prepare starch paste. Put it in a beaker with a capacity of 200 ml, and mix the fungal mixed spore liquid (Aspergillus niger, Penicillium citrinum, Cladosporium cladosporioides, Ketomium globosum).
1 ml is sprayed. Cover the beaker with aluminum foil and incubate in a thermo-hygrostat having a temperature of 28 ± 2 ° C. and a humidity of 95 to 99%. The degree of mold resistance was evaluated every one week based on the same criteria as in Test Example 1.

The drugs in the control group were prepared and tested according to Example 3 or 4. The results are shown in Tables 5-6.

[0068]

[Table 5]

[0069]

[Table 6]

Test Example 4 Preservative effect test of casein 88 parts of an aqueous solution prepared by adding 10 parts of casein and a wettable powder prepared according to Example 3 or 4 to a predetermined concentration and 2 parts of ammonia water in a volume of 200 ml. The mixture is placed in a flask of, the temperature is adjusted to 80 ° C. with stirring, and then the casein solution is prepared while gradually cooling. 200 it
Place in a beaker with a capacity of ml and add 0.1 ml of the deteriorated casein. Cover the beaker with aluminum foil and incubate in a thermostat at a temperature of 30 ° C. After 10 days and 20 days, 1 ml of the casein solution was taken out and measured by the agar plate dilution method.

The drugs in the control group were prepared and tested according to Example 3 or 4. The results are shown in Tables 7-8.

[0072]

[Table 7]

[0073]

[Table 8]

Test Example 5 Floor preservative and antifungal effect test The emulsion prepared according to Example 5 or 6 was diluted with water to a predetermined concentration, and then 100 ml / m on the floor surface.
Two days after spraying, one day, two days, and three days later, the bacteria were collected by a stamp agar and then cultured on an agar plate, and the presence or absence of the bacteria was examined according to the following criteria.

The drugs in the control group were prepared and tested according to Example 5 or Example 6. The results are shown in Tables 9 to 10.

Survey criteria -No outbreak of bacteria is observed. + Occurrence of bacteria is recognized.

[0077]

[Table 9]

[0078]

[Table 10]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI A01N 47/30 A01N 47/30 C (56) References JP-A-50-46833 (JP, A) JP-A-61-97204 ( JP, A) JP 61-118303 (JP, A) JP 7-17812 (JP, A) JP 7-41409 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. As an active ingredient, 3-iodo-2-propargylbutyl carbamate or diiodomethyl-p-
Two kinds of components, one kind selected from tolyl sulfone and one kind selected from 3,4,4'-trichlorocarbanilide or 2,4,4'-trichloro-2'-hydroxydiphenyl ether or a salt thereof. An antiseptic and antifungal agent, which comprises: 2. As an active ingredient, 3-iodo-2-propargyl butyl carbamate or diiodomethyl-p-
Two kinds of components, one kind selected from tolyl sulfone and one kind selected from 3,4,4'-trichlorocarbanilide or 2,4,4'-trichloro-2'-hydroxydiphenyl ether or a salt thereof. And 2- (4-thiazolyl) benzimidazole or a salt thereof or methyl-
An antiseptic and antifungal agent, which comprises, as an active ingredient, three kinds of components, one selected from 2-benzimidazole carbamate or a salt thereof.