JPH0225887B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to bis(dimethylthiocarbamoyl)
The present invention relates to an industrial preservative and fungicide containing a mixture of disulfide (TMTD) and 2,4,5,6-tetrachloroisophthalonitrile (TPN) as an active ingredient. The objects of the present invention are emulsion paints, oil-based paints, electrodeposition paints, organic adhesives, pastes,
To prevent various industrial raw materials and products such as clay, ink, cutting oil, grinding oil, leather, textile and white water during paper manufacturing from being contaminated by bacteria, yeast, filamentous fungi, actinomycetes and a wide variety of other substances and further deterioration. To provide a preservative and fungicide. Conventionally, organic mercury-based compounds, organic tin-based compounds, pentachlorophenol (PCP), deirdrin, formalin, and the like have been used as preservatives and fungicides in the industrial field described above. However, the use of these drugs has come to be considered undesirable from the viewpoint of toxicity to humans and livestock and environmental hygiene. Therefore, in place of these drugs, highly safe and effective drugs such as bacteria, yeast, filamentous fungi, actinomycetes,
It is desired to develop a new preservative and fungicide that is non-selective and destructive to mold. In order to develop a new antiseptic and fungicidal agent that meets these demands, the present inventors tested many agents and conducted extensive studies. As a result, we found that when a mixture of TMTD and TPN is added to industrial raw materials or products such as emulsion paints and organic adhesives, it has the following excellent anti-corrosion and anti-mold effects. In other words, when these two compounds are used in combination, the disadvantages of using each compound alone are canceled out, and the advantage is that it exhibits a non-selective and eradicative antiseptic and antifungal effect against various fungi. They discovered a unique characteristic. Such a preservative and fungicidal effect is developed with a remarkable synergistic control effect that even those skilled in the art would not have expected from the effects when TMTD and TPN are used alone. In order to efficiently exhibit the excellent antiseptic and antifungal effect as described above when carrying out the present invention,
TMTD and TPN can be formulated into emulsions, flowables (sols), wettable powders, liquids, etc. according to conventional methods and used in the same way as general preservatives and fungicides, but are limited to special uses. Never. In this case, the mixing ratio of TMTD and TPN is preferably 1 part (weight part) of TMTD to 0.1 to 10 parts of TPN, more preferably 3 parts of TMTD to TPN.
1 part, and in this case the highest synergistic effect is expressed. In addition, it is preferable to change the mixing ratio as appropriate depending on the object of antiseptic and mold prevention. Furthermore, the preservative and fungicide of the present invention can be mixed or used in combination with other known industrial preservative and fungicides. These known preservatives and fungicides include, for example, zinc diethyldiocarbamate, 2-(4
-thiazolyl)-benzimidazole, methylbenzimidazole carbamate, parachloro-metaxylenol, bis(2-pyridylthio-1-
oxide), but the present invention is not limited to these examples. The preservative and fungicide of the present invention can also be used in combination with or in combination with an insecticidal compound for the purpose of preservative, fungicidal, insecticidal or insect repellent purposes. Next, some examples of the present invention will be shown. In addition, all parts in the examples indicate parts by weight. Example 1 Emulsion TMTD 4.5 parts, TPN 1.5 parts, Solpol 800A
(trade name of emulsifier manufactured by Toho Chemical Industries, Ltd.), 46 parts of xylene, and 46 parts of methyl cellosolve were mixed and dissolved to obtain an emulsion. Example 2 Flowable agent 30 parts of TMTD, 10 parts of TPN (both compounds and particle sizes are 10μ or less), 2 parts of lauryl sulfate, 2 parts of sodium alkylnaphthalene sulfonate, 1 part of hydroxypropyl cellulose, and 55 parts of water. were mixed uniformly to obtain a flowable agent. Example 3 Wettable powder 30 parts of TMTD, 10 parts of TPN, 5 parts of Nurex powder (trade name of a surfactant manufactured by NOF Corporation) and 55 parts of clay were crushed and mixed uniformly to form a wettable powder. I got it. Next, test examples of the present invention will be shown. Test Example 1 Antibacterial activity test 1 ml of a chemical solution diluted with sterile water and a medium cooled to 50℃ [Potato decoction agar (PH5.8) is used for filamentous fungi, and bouillon agar (PH7.8) is used for bacteria. 0)
[Using] 9 ml of the drug was mixed in a 9 cm diameter sterilized glassware to prepare an agar plate containing a drug solution of a predetermined concentration.
Cultivate in advance on a slant medium (for filamentous fungi, incubate at 28℃ for 7 days)
A spore suspension of the test bacteria that has been incubated at 30°C for 2 days) is inoculated onto the drug-containing medium using a platinum loop. After culturing filamentous fungi at 28°C for 72 hours and bacteria at 30°C for 48 hours, the presence or absence of growth of each fungus was investigated to determine the minimum drug concentration in the medium required to completely inhibit the growth of the fungi ( The minimum inhibitory concentration for bacterial growth (ppm) was determined. The results are shown in Table 1, and it was clearly observed that the mixture of TMTD and TPN had a synergistic bactericidal effect.

【table】

[Table] Test Example 2 Mold resistance test of emulsion paint The test method was conducted according to the method of JISZ-2911.
Specifically, a test agent prepared according to Example 1 was added to a vinyl acetate emulsion white paint at a predetermined concentration, and the mixture was stirred and mixed with a homogenizer for 30 seconds to prepare a paint liquid. The resulting paint liquid has a diameter of 12
cm size filter paper (Toyo Roshi Co., Ltd. filter paper No.
2), and after applying the sample evenly, it was air-dried for 48 hours indoors at a temperature of about 20° C. and a humidity of about 75%. In this case, the coating film was adjusted to have a uniform thickness and a weight of 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 one beaker with a capacity of 200 ml was prepared for each test piece.
Add 200ml of water to it and keep it 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 put it in a dryer (80℃
85℃). After 2 hours, the test pieces were taken out, stuck on the center of the culture surface of an agar plate (4% glucose, 1% peptone, 2.5% agar) in a Petri dish, and cultured separately on potato decoction agar medium supplemented with 2% glucose. Test bacteria (Aspergillus niger ATCC9642, Penicillium luteum
A mixed spore suspension (equal amounts of single spore suspensions of three types of bacteria) of ATCC9644 and Trichoderma T-1ATCC9645 was sprayed and inoculated evenly onto the surface of the medium and the test piece. . Cover the Petri dish and culture in a thermostat at 28 ± 2°C, and after 3 days,
After 5 and 7 days, the state of mold growth on the test piece was investigated according to the following criteria. The results are shown in Table 2. In addition, comparative drug A in the table is a commercially available drug (emulsion) containing tributyltin oxide, comparative drug B is a commercially available drug containing methylbenzimidazole carbamate, and comparative drug C is a commercially available drug containing 3 parts of TPN and ethylene. 3 parts of thiuram monosulfide, and comparative drug D is the comparative drug.
Comparative drug E was an emulsion prepared according to Example 1, using 3 parts of B and 3 parts of ethylenethiuram monosulfide as active ingredients, and Comparative drug E containing 3 parts of TMTD and 3 parts of thiophanate methyl as active ingredients. The display standards for mold resistance are as follows. Growth status of mycelia No mycelial growth is observed on the inoculated area of the mold resistance test piece or sample (2) The area of the area of mycelial growth observed on the inoculated area of the test piece or sample (2) is one-third of the total area. The area of the above does not exceed more than one-third. 1 The area of the above covers the entire area. 0

【table】

[Table] Test Example 3 Mold resistance test of wallpaper The test method was conducted according to the method of JISZ-2911.
That is, a test chemical prepared according to Example 1 is added to a commercially available wallpaper paste without the addition of a fungicide to a predetermined concentration, and the mixture is stirred and mixed, and the paste is applied to the wallpaper and dried. This wallpaper was then cut to 4 cm x 4 cm and pasted on the center of the culture surface of an agar plate (glucose 4%, peptone 1%, agar 2.5%) in a Petri dish (inner diameter 9 cm). ATCC9642, Penicillium luteum ATCC9644, Trichoderma T-1 ATCC9645)
1 ml of the mixed spore suspension was inoculated by spraying evenly onto the surface of the medium and the test piece. Thereafter, the Petri dish was covered and cultured in a thermostat at 28°C±2°C, and after 3, 5, and 7 days, the growth state of mold on the test piece was investigated in the same manner as in Test Example 2. Comparative drugs were also tested in the same manner as the drugs of the present invention. The results are shown in Table 3.

【table】

[Table] Next, examples of preservative effect tests for the preservative and fungicidal agent of the present invention are shown. Test Example 4 Preservative effect test of casein solution Casein 10.0 parts, water 88.0 parts, Examples 1 to 3
of drug 0.1 part and ammonia water 1.9 parts 200
Pour into a ml flask and heat while stirring.
The temperature was raised to 80°C, and then gradually cooled 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, 6 and 10 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 4.

[Table] Means the state of beginning.

Claims (1)

[Claims] 1. An industrial preservative and fungicide characterized by containing a mixture of bis(dimethylthiocarbamoyl) disulfide and 2,4,5,6-tetrachloroisophthalonitrile as an active ingredient.