JPS6054301A - Antiseptic mildewproofing agent - Google Patents

Abstract

PURPOSE:To produce the titled agent exhibiting excellent synergistic effect for the control of bacteria belonging to Rhizopus genus, etc., and useful for preventing the degradation of carpet, activated industrial materials and products, by using a mixture of diiodomethyl p-tolylsulfone and another compound as an active component. CONSTITUTION:The objective agent contains (A) diiodomethyl p-tolylsulfone of formula I useful as an agent for preventing the degradation of paints, wood, cutting oil, plastics, etc. with mircoorganisms belonging to Aspergillus genus, Penicillium genus, Cladosporium genus, etc. and (B) 2,4,5,6-tetrachloroisophthalonitrile of formula II as active components. 1-9pts. of the former compound is mixed with 9-1pts. of the latter compound, and the mixture is added to various industrial materials and products such as emulsion paint, organic adhesive, etc. An exterminating antiseptic and fungicidal effect can be achieved, and bacteria and fungi belonging to e.g. Aspergillus genus, Penicillium genus, Chaetomium genus, Alternaria genus, Bacillus genus, can be controlled.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a short methyl paratolyl sulfone (compound A) represented by the following chemical structural formula and 2.4,5.6
-J with titrachloroisophthalonitrile (compound B)
The present invention relates to a preservative and fungicide characterized by containing an IN compound as an active ingredient.

1] Targets of the present invention include emulsion paints, oil-based paints, electrodeposition paints, organic adhesives, pastes, clays, inks, cutting oils, grinding oils, wood, leather, fibers, plastics,
To provide a new antiseptic and fungicidal agent to prevent various industrial raw materials and products, such as Tatami and Shutan mats, activators, and white water used in paper manufacturing, from deteriorating due to a wide variety of bacteria and mold. There is a particular thing.

Compounds A and B used in the present invention are known as preservatives and fungicides, and are described in "Basics of Applied Microbiology", for example.
(Bunkyo Publishing, written by Takashi Yamakake et al.), pages 204 to 213. Aspergillus (Asp.
ergillus), Penicillium
llium), Cladosporium (Cladosp)
It is used to prevent deterioration caused by microorganisms such as bacteria of the genus Orrum.

Conventionally, in the above-mentioned industrial field, various antiseptic and fungicides have been used because materials deteriorate due to various bacteria. However, especially Rhizopus stolonify (Rhiz
Bacteria of the genus Rhizopus, including Rhizopus opus 5tolonifer, have strong vitality and decomposition ability, so completely suppressing the occurrence and proliferation of these fungi is difficult to achieve using normal methods. This is extremely difficult to do with fungicides. In particular, the reality is that it is difficult to completely suppress Rhizopus genus bacteria, not only by the single use of general fungicides, but also by the mixed use of two or more fungicides.

In addition, as a preservative and fungicide in the industrial field,
Organomercury compounds, organotin compounds, polychlorophenol (PCP), -i'ildrin, formalin, etc. have been used. However, these drugs are not suitable for human stockpiling, from the viewpoint of sexual and environmental hygiene,
Its use has come to be considered undesirable. Therefore, it is desired to develop a new antiseptic and fungicidal agent that is highly safe in place of these drugs, has low concentration, is non-selective, and has the property of eradicating various microorganisms. In order to develop a new antiseptic and fungicidal agent that meets these demands, the present inventors tested many chemicals and conducted extensive research. As a result, when a mixture of Compound A and Compound 111y B is added to various industrial raw materials or products such as Emulsion Paint I/Y44 MA adhesives, it has the following excellent anti-corrosive and anti-fungal effects. I found out. That is, when Compound A and Compound B were used alone, there was a drawback that microbial deterioration of industrial materials could not be sufficiently prevented. However, in the present invention, as shown below, the above-mentioned two When used as a mixture of known preservative and antifungal ingredients, it is more effective against Rhizopus and other molds than when each compound is used alone, and it provides eradicative antiseptic effects. They discovered that it has an excellent property of exerting a mold effect. Representative examples of bacteria and molds that can be effectively inhibited by the preservative and fungicide of the present invention include Aspergillus, Penicillium, haetomium (C), Alternaria, and Bacillus. i
1us), and particularly effective ones are as shown in the test examples below. However, it is not limited to these, and it goes without saying that the antiseptic and antifungal activity that Compounds A and H naturally possess can be fully exhibited even when used in combination.

As described above, even a person skilled in the art would not be able to predict the antiseptic and fungicidal effects of the antiseptic and fungicidal agent of the present invention against various bacteria and molds based on the effects when each of Compounds A and B is used alone. It is expressed with a remarkable synergistic control effect.

In addition to having such a strong antiseptic and fungicidal effect, the antiseptic and fungicidal agent of the present invention has an acute oral toxicity L n 5o fft of 20 for mice, as described later.
It has low toxicity of less than 00 mg/kg, and is extremely safe in terms of toxicity compared to conventional drugs.

The present invention was made based on such new findings, but even those skilled in the art could not easily have made such new findings based on publicly known documents, and the present inventors This is the first time it has been done.

In carrying out the present invention, in order to efficiently express the above-mentioned excellent microbial deterioration 11- effect, it is necessary to use compound A.
and Compound B may be formulated into emulsions, wettable powders, flowables (sols), etc. in accordance with conventional methods and used simultaneously with general preservatives and fungicides, and there are no special uses. In such a case, the mixing ratio of Compound A and Compound B is preferably 89 to 1 part of Compound Al to 9 parts of Compound Al. In addition, it is preferable to change the mixing ratio as appropriate depending on the type of industrial material.

Furthermore, the preservative and fungicide of the present invention can be mixed or used in combination with other antibacterial agents. For example, the chemical names are zinc dimethyl dithiocarbamate, tetramethylthiuram disulfide, 2-(4-thiazolyl)benzimidazole, methyl benzimidazole carbamate, 1
．． 2-benzisothiazolin-3-one, parachloro-
metaxylenol, bis(2-pyridylthiol-1-
oxide), 1,2-dibromo-2,4-dicyanobutane, 5-chloro-2-methyl-4-isothiazoline-3
-one, N', N'-dimethyl-N-phenyl-N-(
Examples include fluorodichloromethylthio)sulfamide, but are not limited to these examples. In addition, the preservative and fungicidal agent of the present invention can be used in combination with or in combination with an insecticidal compound to kill preservatives and fungi! J2 (or insect repellent) can also be used as secondary.

Next, some examples of the present invention will be shown.

4. Mix and dissolve 2.5 parts of Compound A, 2.5 parts of Compound B, 5 parts of Tsurpol 800A (trade name of emulsifier manufactured by Toho Chemical Industry Co., Ltd.), 80 parts of xylene, and 10 parts of ethyl cellosolve. An emulsion was obtained.

1 3 parts of cloth compound A, 2 parts of compound B, Tsurupol 800A
(Product name of emulsifier made by Toho Chemical Industry) 5 parts, xylene 8
0 parts of ethyl cellosolve and 10 parts of ethyl cellosolve were mixed and dissolved to form an emulsion.

1 Garden 1 4 Measurements Compound A 2 parts, Compound B 3 parts, Tsurupol 800A
(Product name of emulsifier made by Toho Chemical Industry) 5 parts, xylene 8
0 parts and 10 parts of ethyl cellosolve were mixed and dissolved to obtain an emulsion.

Flowable Compound A 10 parts, Compound B 10 parts (the particle size of both compounds was 10 μ or less), lauryl sulfate 2 parts, alkylnaphthalene sulfonate sodium 2 parts
1 part of hydroxypropylcellulose and 75 parts of water were uniformly mixed to obtain a flowable.

20 parts of Compound A, 20 parts of Compound B, 10 parts of lauryl sulfate, and 50 parts of clay were ground and mixed uniformly to obtain an aquarium.

Next, test examples of the present invention will be shown.

Dissolve the drug in 3 mJ1 of dimethyl sulfoxide (DMSO) and use a sterilized 0.075% agar solution at 50°C.
Prepare a 500 ppm drug agar solution. This 500p
50'C that sterilized the pm concentration agar solution! It is diluted with potato dextrose agar medium (pH 6.0) and immediately dispensed into petri dishes with a diameter of 9 cm and solidified to prepare an agar medium containing a drug at a predetermined concentration. Culture in trunk medium in advance (
A spore suspension of the test bacteria (28°C for 14 days) is streaked onto the drug-treated medium using a platinum loop. This was cultured at 28°C for 10 days, and the presence or absence of growth in each plot was examined. The lowest drug concentration (minimum inhibitory concentration ppm for bacterial growth) was determined.

The results are shown in Tables 1 to 3, and it was found that the mixture of Compound A and Compound B clearly had a synergistic bactericidal effect, and effectively inhibited the growth of bacteria at extremely low concentrations. It turned out to be possible.

Table 1 Table 2 Table 3 Table U Emulgin: ・J test method is J
It was carried out according to the method of I5-Z-2911. That is, the test agent was added to vinyl acetate emulsion white paint to a predetermined concentration of 1 cm, and then mixed with a homogenizer for 30
A coating liquid was prepared by stirring and mixing for seconds. A filter paper (Toyo Roshi No. 2) having a diameter of 12 cm was immersed in the obtained coating liquid, and the sample was evenly applied to the filter paper, and then air-dried at room temperature for 48 hours. In this case, the thickness of the coating was uniform and the liquid weight was 90-110% of that of the filter paper type. This filter paper was used as a circular test piece with a diameter of 3 cm.
Prepare one beaker and add 200mM water to it.
was kept at about 20°C, and the test piece was immersed therein for 18 hours. Thereafter, the test piece was taken out and dried at room temperature for 2 hours and then in a dryer (80 to 85°C) for 2 hours.

Test piece 11 was attached to the center of the culture area of an agar plate (4% glucose, 1% peptone, 2.5% agar) in a Petri dish and cultured separately! i (Rhizopus stolonif γ FE
RM S-7, Gliocladii 1 Rum virens FERM 5-10, Aspergillus niger SERM S-2, Penicillium feniculonum FERM S-6, Cladosporium cladosporioides FE RM S-8, Aureobazium pullulans FERM
The mixed spore suspension of 5-9) was sprayed and inoculated evenly onto the medium surface and the test piece in an amount of 1 mJl. Then, the petri dish was covered with a lid and cultured in a constant temperature chamber at 28°C ± 2°C with a humidity of 95% or higher, and after 3 and 7 days, the state of mold growth on the test piece was investigated according to the following criteria. . In addition, comparative drug A in the table
, B, C, and D are the following prescriptions and commercially available drugs.

-7, No mycelial growth is observed on the inoculated part of the test piece or sample.3 The area of the part of mycelia growth observed on the inoculated part of the test piece or sample is 3 of the total area. 2 The same area exceeds 1/3 l Comparative drug A contains 5 parts of compound A Emulsion comparative drug B contains 5 parts of compound B Emulsion comparative drug C contains tributyltin oxide 10 A commercially available emulsion containing 20% of methyl benzimidazole carbamate compared to an emulsion containing 20%.The results are shown in Table 4.

3 4 Kuyu''(-4!3!JL(')!rμθ A predetermined concentration of the test chemical was added to 700 g (manufactured by Kogyo Co., Ltd.), mixed, 5 g of water was added, and the mixture was stirred and mixed again. The mixture was applied to a gypsum board 3.3 rn'. After air drying (coating thickness 1 mm)
, Cut this plasterboard into 4cm x 4cm, [9cm after 1
Agar plate in a Petri dish of m (4% sugar, 1 peptone)
%, agar 2.5%), and separately cultured test bacteria (Aspergillus niger SERM1≦Yumiichigo chromo1um FERM S-6, Rhizopus stronipha FERM S-7, Glioclarabium A mixed spore suspension of P. virens FERM S-10) was inoculated by spraying evenly onto the medium surface and the test piece at a distance of 1 mm.

This was immediately placed in a constant-humidity thermostat at a temperature of 28° C. and a humidity of 95% or higher, and cultured for 7 days. And after 3 days, test piece-1
- The growth state of mold was investigated in the same manner as Test Example 2. Further, a comparative drug was also tested in the same manner as in Test Example 2.

The results are shown in Table 5.

6 Samaki■-” [I can write about hunger! -1= Each of the following test IKs (1 section, 1 rn' area) were made indoors at a temperature of 25° C. to 35° C. and a humidity of 80% to 100%. That is, test area 1 was a test area where the concrete surface was coated with vinyl acetate white paint, test area 2 was a test area where the board surface was coated with the same uAm jlt material as in test example 3,
Then, a veneer board area was created as test area 3, and Rhizopus stroniphae FERM S-7 and Gliocladium virens FERM S 101 were added to each test area.
11! A synspore solution (10 ml Id mixture) was sprayed at a rate of 3.3 tn'J and 100 m.

After spraying, 1 g of the drugs of Examples 1 to 5 was diluted 100 times and sprayed onto each test plot (width of lrn'). and 3
After FI and 1.0 [After 1, stamp agar (manufactured by Eiken Kizai Co., Ltd.) was used for each test area, and from 1 to 2
0 molds were collected. The collected stamped agar was re-stamped onto a potato dextrose agar medium (manufactured by Eiken Kizai Co., Ltd.).

After culturing this at 27°C for 1 to Z11, the grown 7 The number of colonies was measured and the presence or absence of mold growth was detected.

The results are shown in Table 6.

Table 6 8 Next, examples of preservative effect tests for the preservative and fungicidal agent of the present invention are shown.

10.0 parts of casein, 88.0 parts of water, and 0.1 part of the drugs of Examples 1 to 3 were placed in a 200 ml flask, heated with stirring, and heated to 80°C. did. This casein solution was placed in a beaker, covered with aluminum foil, and stored in a thermostat at 30'O. After 3 and 10 days, add 1 casein solution
+nJl were taken out at a time, and the increase in bacteria was measured by the agar 6-pitch method.

The results are shown in Table 7.

Table 7 9 Next, the acute toxicity 5° value of the preservative and fungicide of the present invention is shown.

Table 8 0

Claims (1)

[Claims] Short methyl paratolyl sulfone and 2゜4.5.6
- A preservative and fungicide characterized by containing a mixture with chitrachloroinphthalonitrile as an active ingredient.