JPH0113684B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD OF THE INVENTION The present invention relates to non-medical fungicides for agricultural and industrial use. Namely, for agricultural purposes, rice blast, rice sesame leaf blight, rice white leaf blight, rice Bakanae disease, pear black spot, grape late rot, tomato leaf mold, kidney bean sclerotium, cucumber vine split disease, New agricultural fungicides and emulsion paints, oil-based paints, electrodeposition paints, organic adhesives, pastes, clays, etc. for controlling Chinese cabbage soft rot, cucumber powdery mildew, etc.
A new product to prevent various industrial raw materials and products, such as ink, cutting oil, grinding oil, wood, leather, textiles, hydraulic oil, and white water used in paper manufacturing, from deteriorating due to bacteria, yeast, filamentous fungi, etc. The present invention relates to non-medical disinfectants, including industrial preservatives and fungicides. Conventional technology Formula: (In the formula, X' represents a potassium atom, an ammonium group, or a quaternized organic nitrogen group, and the organic nitrogen group may form a heterocycle containing a nitrogen atom.)
A tetraphenylboron compound represented by the above formula, specifically a tetraphenylboron compound of the above formula in which X' is a potassium atom, an ammonium group, an alkyl- or phenyl-substituted ammonium group, or a pyridinium group, is used as an antifouling agent for underwater antifouling paints. It is known that the triphenylboron pyridinium compound is useful as a component as described in Japanese Patent Publication No. 54-1571, and it is disclosed in U.S. Pat. No. 3,211,679 that the triphenylboron pyridinium compound is useful as an underwater antifouling agent. There is. Furthermore, in Japanese Patent Application Laid-open No. 155185/1985, the formula: (In the formula, R ₁ represents a hydrogen atom, a halogen atom, or a lower alkyl group, R ₂ represents a halogen atom, a lower alkyl group, or a lower alkenyl group,
It is disclosed that a tetraarylboron-ammonium complex represented by R ₃ represents a heterocyclic amine is useful as an industrial preservative and fungicide. Problems to be Solved by the Invention In order to protect agricultural crops, industrial raw materials, and products from microbial deterioration caused by bacteria, yeast, filamentous fungi, etc., the occurrence of various microorganisms must be eradicated. However, many of the non-medical fungicides that have been used so far are highly toxic to humans and animals, and their use is regulated, their effectiveness becomes weak when used in small amounts, or they lack long-term residual effects. In addition, there are few drugs that have been used to date that sufficiently exhibit both antiseptic and antifungal effects, or even if they are effective against filamentous fungi, there are very few that are highly effective against bacteria. In this respect, it is still not fully satisfactory. Under these circumstances, the present inventors have developed a drug that can quickly and eradicate mold fungi, bacteria, etc., and can also provide residual efficacy, and is particularly useful for controlling bacteria. The object of the present invention is to provide a drug that is highly effective and can be widely used both as an agricultural fungicide and as an industrial preservative and fungicide for various industrial raw materials and products. Means and Effects for Solving the Problems In order to develop a new non-medical disinfectant that meets the above-mentioned needs, the present inventors subjected a wide range of new and known compounds to various tests and examined their physiological activities. did. As a result, the formula: (wherein,
quinolinium group or N-methylpyrrolidonium group) has low toxicity;
It can control pathogenic fungi by directly spraying on various agricultural crops or coating seeds, and can also prevent microbial deterioration by adding, mixing, retaining, or adhering to various industrial materials, manufacturing processes, and products. It has been found that this method is particularly effective in preventing deterioration or damage caused by bacteria, which have been difficult to control in the industrial field, and can solve various problems caused by these bacteria. Therefore, the present invention provides as an active ingredient the formula ()
The present invention provides a non-medical disinfectant containing at least one compound of the following. Hereinafter, the active ingredient compound, formulation method, and usage method of the fungicide of the present invention will be specifically explained. (Active Ingredient Compounds) Representative examples of active ingredient compounds represented by formula () that are effective for the purpose of the present invention are shown in Table 1.

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[Table] The tetraphenyl boron compound represented by the formula () is described in Analytical Chemistry, Vol. 17, p. 1548 (1968
(1969), Vol. 18, pp. 81 and 264 (1969), or according to the method described therein. For example, pyridinium
tetraphenylborate

A production example of [Formula] is shown below. Pyridinium tetraphenylborate (compound
Production of No. 8) In a 500ml four-necked flask, a reflux condenser, a thermometer,
Install a nitrogen introduction pipe and a stirrer. This flask is charged with 7.3 g (0.3 mol) of magnesium in pieces and 15 ml of tetrahydrofuran, heated to 60°C while introducing nitrogen gas from the nitrogen inlet tube, and 2 g of chlorobenzene is added dropwise to activate the magnesium. . Next, 23.9g of chlorobenzene was added from the dropping funnel.
(total 25.9 g, 0.23 mol) in tetrahydrofuran 255
ml solution was added dropwise. Reaction temperature is 55-60
It was maintained at ℃. After the dropwise addition was completed, the mixture was heated under reflux for 30 minutes. The thus produced Grignard reagent of phenylmagnesium chloride was cooled to room temperature, and then 15.7 g (0.05 mol) of trihexylborate was added dropwise from the dropping funnel over 15 minutes at room temperature. The reaction temperature rose to 50°C. After the dropwise addition was completed, the mixture was heated under reflux for 2 hours. Return this to room temperature,
20g (0.19mol) of anhydrous carbonated soda and 100ml of distilled water
was added dropwise at 40 to 50°C. After dropping, stir for 30 minutes, then add 80 ml of benzene, stir well, and separate into organic and aqueous layers. Separate the organic layer, and for the aqueous layer, add 100 ml of tetrahydrofuran, mix well, let stand, and separate. It liquefied. The tetrahydrofuran layer was combined with the previous organic layer, and the solvent was distilled off using an evaporator. Distillation was stopped when white crystals began to appear. 200 ml of methanol was added to this to dissolve it. In this way, sodium tetraphenylborate was produced. Pyridine hydrochloride 5.8g (0.05g) in a 500ml beaker
mol), and added 100 ml of distilled water to dissolve it.
When the methanol solution of sodium tetraphenylborate was added to the mixture while stirring, a fine white powder was produced. After addition, stir for 30 minutes to complete the reaction, filter out the white crystals formed,
Wash with 50 ml of distilled water x 2 and vacuum dry to obtain 18.5 g of pyridinium tetraphenylborate (yield 92.6).
%) was obtained. Melting point 220-222℃. (Formulation method) The non-medical bactericide of the present invention can be obtained by the following method. That is, the active ingredient compound of the present invention is blended with appropriate carriers and auxiliary agents, such as surfactants, binders, stabilizers, etc.
It may be formulated into wettable powders, emulsions, liquids, sol preparations (flowable preparations), etc. by conventional methods. The active ingredient content of the invention in these formulations is
For wettable powders, emulsions, liquids, and sol formulations, 1 to 90%
(wt%: same below). As carriers that can be used, any solid or liquid carrier commonly used for non-medical disinfectants can be used, and the carrier is not limited to any particular carrier.
For example, solid carriers include mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite,
Gypsum, calcium carbonate, apatite, white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc.), vegetable powder (soybean flour, wheat flour, wood flour, tobacco flour, starch, crystalline cellulose, etc.), alumina, silicates,
Examples include sugar polymers, highly dispersed silicic acid, and waxes. Liquid carriers include water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (benzene,
Toluene, xylene, ethylbenzene, chlorobenzene, cumene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride,
dichloromethane, chlorethylene, trichlorofluoromethane, dichlorodifluoromethane, etc.),
Ethers (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc.), nitriles ( acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.) ), industrial gasoline (petroleum ether, solvent naphtha, etc.) and petroleum fractions (paraffins, kerosene, light oil, etc.). In addition, emulsions, hydrating agents, sol agents (flowable agents),
Surfactants (or emulsifiers) are used for purposes such as emulsification, dispersion, solubilization, wetting, foaming, lubrication, and spreading. Examples of such surfactants include those shown below, but of course the surfactants are not limited to these 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 sulfates, arylsulfonates, etc.) Cationic type [alkylamines (laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzyl ammonium chloride, etc.)], amphoteric type [carboxylic acids (betaine type), sulfuric esters, etc. ] In addition to these, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC),
Various adjuvants such as gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate, gum tragacanth, etc. can be used. Further, if necessary, a suitable amount of stabilizers such as antioxidants and ultraviolet absorbers can be added. Furthermore, the non-medical fungicide of the present invention can be used in combination with various other agricultural fungicides and various industrial preservatives and fungicides. Examples Some examples are listed below, but the blending ratio of active ingredients, auxiliary ingredients and their addition amounts are not limited to the following examples. In the examples, all parts represent parts by weight. Example 1 Flowable agent 20 parts of Compound No. (8), 2 parts of lauryl sulfate, 2 parts of xanthan gum, 1 part of hydroxypropyl cellulose, and 75 parts of distilled water were charged into a ball mill and pulverized and mixed for 12 hours to make it effective. A flowable agent containing 20% of the ingredients is obtained. Example 2 Wettable powder 20 parts of Compound No. (7), 7 parts of lauryl sulfate, and 73 parts of talc are uniformly mixed and ground to obtain a wettable powder containing 20% of the active ingredient. Example 3 Emulsion 5 parts of compound No. (4), 50 parts of dimethylformamide, 40 parts of methyl isobutyl ketone, and 5 parts of Solpol 800A (trade name of an emulsifier manufactured by Toho Chemical Industry Co., Ltd.) were mixed and dissolved to prepare the active ingredient. An emulsion containing 5% is obtained. Example 4 Powder 3 parts of compound No. (14), silicic anhydride fine powder
0.5 parts, calcium stearate 0.5 parts, clay 50
part and 46 parts of talc are uniformly mixed and ground to obtain the active ingredient 3.
Obtain a powder containing %. (How to use) The non-medical disinfectant of the present invention is used as follows. That is, a method of spraying, spraying, or coating various agricultural products or seeds with various formulations prepared according to the above examples, either as they are or diluted with water or an appropriate organic solvent;
A method of adding or applying the fungicide to various industrial raw materials or during the manufacturing process or to products, a method of applying or spraying on the surface of various industrial raw materials or products, and a method of adding or spraying the disinfectant of the present invention to various industrial raw materials or products. It can be used in various ways, such as by immersing it in a disinfectant, and is not limited to any particular method. Effects of the Invention When the non-medical disinfectant of the present invention is used, the following effects are brought about. First, since the drug of the present invention has a broad antibacterial spectrum, it non-selectively and completely inhibits the development of various microorganisms such as bacteria, yeast, and filamentous fungi. Therefore, it can be widely used as a non-medical disinfectant. Second, when used on various agricultural crops and seed rice, it does not cause any phytotoxicity. Thirdly, it exhibits strong antiseptic and antifungal effects even when used in small doses. Fourthly, high antiseptic and antifungal effects can be exerted over a long period of time even when a small amount of the drug is used. Fifth, there are no problems with toxicity to humans or animals. Sixth, the drug of the present invention can be used in various ways such as spraying, spraying, coating, and mixing on various agricultural crops, seeds, and industrial raw materials and products; It does not have any adverse effect on raw materials or products. Since the non-medical fungicide of the present invention has the above-mentioned characteristics, it can be widely used as a fungicide and preservative for various agricultural products, seeds, and various industrial raw materials and products, as illustrated below. can be used. (1) Controls blast disease, sesame leaf blight, and kanae disease that occur during the rice cultivation process (2) Controls black spot disease that occurs during the pear cultivation process (3) Late rot that occurs during the grape cultivation process Controlling diseases (4) Controlling leaf mold that occurs during tomato cultivation (5) Controlling sclerotium disease that occurs during kidney bean cultivation (6) Powdery mildew that occurs during cucumber cultivation,
Controlling vine splitting disease (7) Controlling soft rot that occurs during the Chinese cabbage cultivation process (8) Preventing slime damage caused mainly by bacteria, filamentous fungi, and algae during the papermaking process (9) During the manufacturing process of water-based or oil-based paints , Prevention of spoilage problems due to the growth of bacteria, filamentous fungi, yeast, etc. during storage and use, and contamination problems due to the growth of filamentous fungi on the painted surface after painting (10) Coating adhesives made of casein, polyvinyl alcohol, starch, etc. or prevention of rotting problems due to the growth of bacteria, yeast, filamentous fungi, etc. on pastes, etc., and contamination problems due to the growth of filamentous fungi on coated adhesive surfaces (11) Preventing filamentous problems during storage of papermaking raw materials such as wet pulp and chips Prevention of quality deterioration caused by the growth of fungi, yeast, and bacteria (12) Prevention of contamination and quality deterioration caused by the growth of filamentous fungi on processed products and materials such as wood, plywood, bamboo, and leather (13) Natural fibers, Prevention of contamination and quality deterioration caused by the growth of filamentous fungi on synthetic fibers, their blended products, and materials (14) Prevention of quality deterioration caused by the growth of yeast, bacteria, and filamentous fungi in synthetic emulsions or emulsion tuxes, etc. (15) Preventing quality deterioration caused by the growth of yeast, bacteria, and filamentous fungi in concrete admixtures, etc. (16) Preventing quality deterioration caused by the growth of yeast, bacteria, and filamentous fungi in hydraulic fluids, etc. (17) Plastics, rubber, etc. Prevention of quality deterioration due to growth of yeast, bacteria, and filamentous fungi Next, various test examples will be shown to demonstrate the usefulness of the non-medical disinfectant of the present invention. Test Example 1 Antibacterial activity test Dissolve the test compound in acetone and add 1 ml of it to 20 ml of culture medium (for filamentous fungi, use potato decoction agar (PH
5.8) and mixed with bouillon agar (PH7.0) for bacteria to prepare a drug-containing medium at a predetermined concentration. A spore suspension of the test bacteria that had been previously cultured on a slant medium (7 days at 28°C for filamentous fungi, 2 days at 30°C for bacteria) was streaked onto the drug-containing medium using a platinum loop. In the case of filamentous fungi
After culturing at 24°C for 72 hours, and for bacteria at 30°C for 48 hours, the presence or absence of growth of each bacteria was investigated. The growth inhibitory concentration (ppm)] was determined.The results are shown in Table 2.

[Table] Test Example 2 Rice blast control effect test Example 2 was applied to third leaf stage seedlings of paddy rice (variety: Asahi) grown in clay pots with a diameter of 9 cm in a greenhouse.
A chemical solution of a predetermined concentration of a hydrating powder prepared according to the method was sprayed. Thereafter, it was kept under moist room conditions (humidity 95-100%, temperature 24-25°C) overnight, and a spore suspension of rice blast fungus was inoculated by spraying one day after spraying. Five days after inoculation, the number of rice blast lesions per third leaf was investigated.
The control value (%) was calculated using the following formula. In addition, chemical damage to rice was investigated using the following indicators. The test was conducted twice at one concentration, and the average control value was determined. The results are shown in Table 3. Comparative drugs are O,
This is a commercially available fungicide (general name: IBP emulsion) containing O-diisopropyl and S-benzyl phosphorothiolate. The investigation indicators for drug damage are also used in the following test examples. Control value (%) = (1 - number of blast lesions in the sprayed area / number of blast lesions in the non-sprayed area) x 100 Investigation index for chemical damage 3: Very 2: Many 1: Only 0: None

[Table] Test Example 3 Rice Sesame Leaf Blight Control Effect Test Example 2 was applied to 4th leaf stage seedlings of paddy rice (variety Asahi) grown in clay pots with a diameter of 9 cm in a greenhouse.
A predetermined concentration chemical solution of a hydrating powder prepared according to the method was sprayed, and one day later, a conidial suspension of the rice sesame leaf blight fungus was spray-inoculated. Five days after inoculation, the number of rice sesame leaf blight lesions per fourth leaf was investigated, and the control value (%) and chemical damage to rice were investigated in the same manner as in Test Example 2. The test was conducted twice at one concentration, and the average control value was calculated. The results are shown in Table 4. In the table, the comparative drug is 3-(3,5-dichlorophenyl)-N-isopropyl-2,4-
It is a commercially available fungicide (generic name: Iprodione) containing dioxoimidazolidine-1-carboxamide.

[Table] Test Example 4 Sclerotinia blight control effect test Prepared according to Example 1 on second true leaf stage green beans (variety Taisho Kintoki) cultivated in clay pots with a diameter of 9 cm in a greenhouse. 10 ml of a predetermined concentration solution of the flowable agent was sprayed per pot. One day later, a piece of agar containing bacteria was inoculated into the center of each single leaf of the second true leaf by punching out the tip of a bacterial colony of common bean sclerotium fungus, which had been previously cultured on a potato decoction agar medium at 20℃ for 2 days, with a 5 mm cork borer. did. The specimens were then stored in a humid room at 20°C for 3 days to induce disease development. In the investigation, the length of green bean sclerotium lesions in each treatment plot was measured using calipers, and the control value (%) was calculated using the following formula. In addition, drug damage to green beans was investigated using the same criteria as in Test Example 2. Control value (%) = (1 - bean sclerotide lesion length in sprayed area / kidney bean sclerotide lesion length in non-sprayed area) x 100 The test was conducted in duplicate at one concentration, and the average control value was calculated. did. The results are shown in Table 5.
The comparative drug is N-3,5-dichlorophenyl)
It is a commercially available fungicide (generic name: procymidone) containing 1,2-dimethyl cyclopropane-1,2-dicarboximide.

[Table] Test Example 5 Seed disinfection effect test against rice baka-nae disease A hydrating agent prepared according to Example 2 using 10 g of naturally infected paddy (variety Reimei) placed in a sarannet bag and the same amount of paddy. 50ml of a diluted solution of the specified concentration of
It was placed in a beaker and sterilized by immersion at 15°C for 24 hours. Thereafter, the rice seeds were soaked in ion-exchanged water at 15°C for 5 days. The soaked rice seeds were germinated at 30°C for 24 hours and sown in black volcanic ash soil (fertilizer amount: 4.5 g of ammonium sulfate, 6 g of lime superphosphate, and 1.5 g of potassium chloride) in a plant vat (30 cm x 30 cm x 10 cm). After sowing, seedlings were raised in a glass room. 26 days after sowing (four-leaf stage), rice seedlings were pulled out and the number of infected rice seedlings (elongated length and diseased and dead seedlings) was determined by visual observation.
Seed disinfection rate (%) and phytotoxicity were determined using the following formula.
The test was conducted at one concentration twice, and the average seed disinfection rate was calculated. The results are shown in Table 6. In the table, the comparative drug is a commercially available fungicide containing methyl 1-(n-butylcarbamoyl)-2-benzimidazolecarbamate (generic name Benomyl).
It is. Seed disinfection rate (%) = (1 - Rate of diseased rice seedlings in treated area / Rate of diseased rice seedlings in untreated area) x 100

[Table] Test Example 6 Powdery mildew control effect test on cucumber Powdery mildew control effect According to Example 1, the first leaf stage seedlings of cucumber (cultivar: Sagami Hanshiro) were cultivated in clay pots with a diameter of 9 cm in a greenhouse. 10 ml of the prepared flowable agent at a predetermined concentration was sprayed, and after being left overnight, a suspension of powdery mildew spores was sprayed and inoculated. The lesion area ratio (%) was investigated 10 days after inoculation, and the control value (%) was calculated using the following formula.
was calculated. Furthermore, chemical damage to cucumbers was investigated using the same criteria as in Test Example 2. The result is the 7th
As shown in the table. The comparative drug in the table is a commercially available liquid preparation (generic name: dimethylmol) containing 6-methylquinoxaline-2,3-dithiocarbonate. Control value (%) = (1 - percentage of lesion area in sprayed area/ percentage of lesion area in non-sprayed area) x 100

[Table] Test Example 7 Mold resistance test of emulsion paint The test method was conducted according to the method of JIS Z-2911. That is, a test agent prepared according to Example 2 is added to a vinyl acetate emulsion white paint to a predetermined concentration, and the mixture is stirred and mixed with a homogenizer for 30 seconds to prepare a paint liquid. A piece of paper (Toyo Paper No. 2) with a diameter of 12 cm is dipped in the resulting paint solution, and the sample is evenly applied to it, and then air-dried for 48 hours in a room at a temperature of about 20°C and a humidity of about 75%. In this case, the thickness of the coating film is uniform and the weight is equal to the weight of the paper.
Adjust to 90-110%. This paper is used as a circular test piece with a diameter of 3 cm, and each test piece
Prepare one 200ml beaker and add 200ml of water to it.
ml and kept at about 20℃, soak the test piece in it for 18 hours, then take out the test piece and hang it indoors for 2 hours, and then hang it in a dryer (80-85℃). After 2 hours, the specimen was removed and placed on an agar plate (4% glucose, 1% peptone, agar) in a Petri dish.
2.5%) in the center of the culture surface, and 2%
Test bacteria [Aspergillus niger] were cultured separately on potato decoction agar medium with grape sugar added
ATCC9642, Penicillium funiculosum
FERM S-6, Cladosporium Cladosporioides FERM S-8, Aureobasidium pullulans FERM S-10, Gliocladium virens FERM S-10] mixed spore suspension (5 types of bacteria) Spread 1 ml of a mixture of equal amounts of single spore suspension on the surface of the medium and the test piece.
Inoculate by spraying. Cover the Petri dish and keep it at 28±2℃.
After 3 days, 5 days, 7 days, and 14 days, the growth state of mold on the test piece was investigated according to the following criteria. The results are shown in Table 8. In the table, the comparative drug (A) is a commercially available drug (emulsion) containing parachlorometaxylenol, and the comparative drug (B) is a commercially available drug (emulsion) containing bistributyltin oxide.

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【table】 %,
Comparative drug (B) Bitributyltin oxide 20%
Test Example 8 Mold resistance field test of emulsion paint A predetermined amount of the flowable test chemical prepared according to Example 1 is added to a vinyl acetate emulsion white paint and thoroughly mixed to form a paint liquid. This paint solution was applied to a concrete wall surface, and mold growth was investigated according to the following criteria 3 months, 6 months, 12 months, 18 months, and 24 months later. At the same time, we investigated the deterioration of the paint solution stored in tin cans due to mold growth. (Survey criteria) 3 No mold growth 2 Mold growth is observed on a portion of the coated surface, and the area does not exceed one-third of the total area 1 Mold growth is observed on the entire surface, and the area does not exceed the total area The test results, which covered more than one-third of the cases, are shown in Table 9.

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[Table] Test Example 9 Wood fungicide efficacy test This test was conducted in accordance with the method for testing the effectiveness of wood fungicides described in the Japan Wood Preservation Association Standard No. 2 (1979 edition). That is, an emulsion prepared according to Example 3 was diluted with xylene so that the active ingredient reached a predetermined concentration, and a piece of wood (2.5 cm in size) was added to the emulsion.
A piece of pine wood measuring 2.5 cm x 0.5 cm was immersed in a solution containing 20% potato juice and 2% glucose (hereinafter referred to as PD medium) for 3 minutes to absorb the nutrient solution and heated to 60°C.
(We use two types: one that has been dried in the water, and one that is not immersed in a PD medium and does not absorb the nutrient solution)
soak to absorb the drug. This piece of wood was air-dried for two days and used as a test specimen. Place this test specimen in a Petri dish and use JIS-Z-2911
Test solution cultured on potato decoction agar medium specified in (Aspergillus niger ATCC9642,
Brush 1 ml of a mixed spore solution (a mixture of 5 single spore suspensions in equal amounts) of Penicillium funiculosum ATCC9644, Rhizopus stronifer IF06354, Aureobasidium pullulans IF06353, Gliocladium virens ATCC9643) onto the test specimen. Apply it using. Cover the Petri dish and culture at a temperature of 26±2°C and a humidity of 70-80%. The investigation was conducted after 3 days, 7 days, 14 days, 21 days, and 28 days of culture, and the mold growth status of the specimens was investigated according to the following criteria. The results are shown in Table 10. Investigation criteria 3: No mold growth is observed on the test specimen. 2: Mold growth is observed only around the test piece. 1: Mold growth is observed on one-third or less of the area of the upper surface of the test piece. 0: Mold growth is observed on one-third or more of the area of the upper surface of the test piece. Comparative drug C is a commercially available fungicide containing 2% 2,4-thiazolylbenzimidazole, 4% 1,2-benzisothiazolin-3-one, and 1% diiodomethyl paratolylsulfone as active ingredients. It is.

[Table] Test Example 10 Mold resistance test of starch paste Water to which 150 parts of tapioca starch and a hydrating agent prepared according to Example 2 were added to a predetermined concentration.
Pour 85 parts into a 200ml flask and stir while stirring.
The starch paste is prepared by heating to 70°C and then gradually cooling. Place it in a Petri dish with a diameter of 9 cm. Add the mixed spore suspension (Aspergillus niger) into it.
ATCC6275 Penicillium citrinum
ATCC9849, Rhizopus nigricans SN32,
Spray inoculate 1 ml each of Cladosporium herbalum IAMF517 and Chaetomium gloposum ATCC6205). The cells were cultured in a constant temperature chamber at a temperature of ±28° C. and a humidity of 95 to 99%, and the degree of mold resistance was evaluated every week using the same criteria as in Test Example 7. As a comparison agent, a commercially available organic nitrogen sulfur fungicide was prepared in the same manner as the agent in Example 1 and tested. The results are shown in Table 11.

[Table] Next, a preservative effect test example is shown for the non-medical disinfectant of the present invention. Test Example 11 Preservative effect test of casein solution 10.0 parts of casein and 88 parts of water to which a hydrating agent prepared according to Example 2 was added to a predetermined concentration and 2 parts of ammonia water were placed in a 200 ml flask and stirred. Heat to 80°C, then gradually cool to obtain a casein solution. This casein solution was placed in a beaker, covered with aluminum foil, and stored in a thermostat at 30°C. After 3, 7, 14, and 20 days, 1 ml of the casein solution was taken out, and the increase in the number of bacteria was measured by the agar dilution method. The results are shown in Table 12.

[Table] Test Example 12 Preservative effect test on glue The drug of Example 1 was added uniformly to 3% carboxymethyl cellulose (hereinafter referred to as CMC) glue and 10% potato starch glue so that the active ingredient was at a predetermined concentration. After mixing, the mixture was placed in a synthetic resin cup, covered with aluminum foil, and stored in a constant temperature chamber (30°C). The investigation was conducted after 7 and 14 days of storage by streak culture (37
℃ for 48 hours), and the status of bacterial development was investigated according to the following criteria. The results are shown in Tables 13 and 14. Investigation criteria + Glue where bacteria were generated - Glue where bacteria were not generated

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Claims (1)

[Claims] 1. As an active ingredient, the formula: (wherein,
A non-medical disinfectant comprising at least one compound represented by a quinolinium group or an N-methylpyrrolidonium group.