JP2000103709A - Industrial mildewproofing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an industrial mildewproofing agent capable of preventing an industrial raw material and the product from putrefying or being polluted due to microorganisms, esp. mold (or mildew), and preventing their degradation and quality deterioration. SOLUTION: This industrial mildewproofing agent includes a mixture of (A) at least one kind selected from the group consisting of 2-(4-thiazolyl)- benzimidazole, 2-benzimidazolecarbamic acid, Zn-2-pyridinethiol-1-oxide, Na-2- pyridinethiol-1-oxide, tetrachloroisophthalonitrile and 2,3,5,6- tetrachloro-4-(methylsulfonyl)-pyridine and (B) 1-(β)-alloyloxy-2,4- dichlorophenethyl)-imidazole, as an active principle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is to prevent spoilage and contamination of industrial raw materials and products caused by microorganisms, especially mold,
The present invention relates to an industrial antifungal agent for preventing such deterioration and quality deterioration.

[0002]

2. Description of the Related Art Decay and contamination caused by microorganisms, especially mold, are caused by deterioration and quality of industrial materials and products such as paints, building materials, adhesives, cutting oils, artificial leather, electronic components, and various latexes. Causes a decline. Conventionally, many antifungal agents have been used to prevent such damage.

Examples thereof include chlorinated phenol compounds such as pentachlorophenol and trichlorophenol; organotin compounds such as tributyltin oxide and tributyltin acetate; diiodomethyl-p-trisulfone; 4-chlorophenyl-3-iodopropargyl. Formal; benzimidazole compounds such as 2- (4-thiazolyl) -benzimidazole and 2-benzimidazole carbamic acid; Zn-2-pyridinethiol-1-
Oxide; Na-2-pyridinethiol-1-oxide; tetrachloroisophthalonitrile; 2,3,5,6
-Tetrachloro-4- (methylsulfonyl) -pyridine and the like.

[0004]

However, chlorinated phenol compounds and organotin compounds have a serious problem of high toxicity, for example, fish toxicity, and have a problem of diiodomethyl-p-type.
Trisulfone and 4-chlorophenyl-3-iodopropargyl formal are problematic in that they cause strong discoloration by ultraviolet light. In contrast, benzimidazole compounds, Zn-2-pyridinethiol-1-oxide, Na-2-pyridinethiol-1-oxide, tetrachloroisophthalonitrile, 2,3,5,6-tetrachloro-4- (Methylsulfonyl) -pyridine has been evaluated as a highly safe drug, but because of its selectivity in the antifungal spectrum, it is a fungicide for industrial products that are exposed to various types of mold contamination. Was inadequate.

Accordingly, an object of the present invention is to solve the above-mentioned problems and to propose an industrial fungicide capable of effectively preventing rot and contamination of industrial raw materials and products.

[0006]

Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventor has found that by using a mixture of two specific compounds and applying them to industrial materials and products, Having a broad spectrum of antifungal spectrum, and also having high durability, it was found to be excellent in fungicidal properties and could be used as a highly safe industrial fungicide, and completed the present invention. .

That is, the industrial fungicide of the present invention comprises:
(A) pyridinethiol-1-oxide or its metal salt, methyl 2-benzimidazolecarbamate or its dodecylbenzenesulfonate, 2- (4-thiazolyl) -benzimidazole, tetrachloroisophthalonitrile, 2,3,3 At least one selected from 5,6-tetrachloro-4- (methylsulfonyl) -pyridine
A mixture of a seed and (B) 1- (β-allyloxy-2,4-dichlorophenethyl) -imidazole is contained as an active ingredient.

[0008] The industrial fungicide composition of the present invention comprises two types of mixtures of the following components (A) and (B) as the active ingredients. As the component (A), pyridinethiol-
1-oxide or a metal salt thereof such as Zn, Na, Cu, Ag (hereinafter, Zn-2-pyridinethiol-1-oxide is referred to as Zn-pt and Na-2-pyridinethiol-1
-Oxide is referred to as Na-pt, Cu-2-pyridinethiol-1-oxide is referred to as Cu-pt, and Ag-2-pyridinethiol-1-oxide is referred to as Ag-pt), 2-benzimidazole carbamine Acid methyl (hereinafter abbreviated as MBC) or its dodecylbenzenesulfonate (hereinafter abbreviated as DBSBC), 2
-(4-thiazolyl) -benzimidazole (hereinafter referred to as T
BZ), tetrachloroisophthalonitrile (hereinafter abbreviated as TPN) and 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine (hereinafter abbreviated as TMP) At least one
Use seeds. Two or more of these may be used at the same time. In that case, the respective actions and the following (B) will be described.
A combination that does not inhibit the action of the components is used.

[0009] Each of these compounds is highly safe, and Aspergillus, Penicillium, Cladosporium (Cl)
adosporium), Aureobasidium (Aur)
eobasidium), Gliocladium (Glio)
It exhibits a growth inhibitory effect against many molds such as Cladium (hereinafter referred to as a general fungicidal effect). However, when only the component (A) is used, the practical concentration (0.
1 to 1.0%: JIS Z-2911 "Mold resistance test method"), Alternaria (Alternar)
ia), Ulocladium and the like do not show any growth inhibitory effect (hereinafter, this may be referred to as a special antifungal effect).

[0010] Of the component (A), pyridinethiol-1-oxide or a metal salt thereof has a strong anti-algal activity as well as the general antifungal properties described above. The other component (A) alone does not show strong algal protection activity, but when two or more of them are used at the same time, the reason is not understood in detail, but it shows some algal protection activity. Therefore, when it is desired to have anti-algal properties as well as anti-fungal properties, pyridine thiol-1 may be used as the component (A).
It is suitable to use the oxide or its metal salt alone or to use two or more components (A) other than these.

As the component (B), 1- (β-allyloxy-2,4-dichlorophenethyl) -imidazole (hereinafter abbreviated as ADPI) is used. This compound is known as an agricultural and horticultural fungicide, is highly safe, and grows against the above-mentioned molds in which each compound of the component (A) has no effect, such as Alternaria and Ulocladium. It has a suppressing effect (special anti-mold effect). However,
When only the component (B) is used, the above general antifungal effect is not exhibited.

The present invention provides a highly practical industrial antifungal agent having a wide spectrum of antifungal spectrum by combining both of the above highly safe components (A) and (B). . At this time, it is important to determine the mixing ratio of both components (A) and (B) so as to exhibit the most effective antifungal spectrum when both components (A) and (B) are mixed.

From this viewpoint, the present inventors have further studied and found that the mixing ratio of the two components for exhibiting an effective antifungal spectrum differs depending on the type of the component (A) used. Was. In other words, (A),
(B) a synergistic action that is not less than a mere sum of the actions of both components alone without specifically inhibiting the above-mentioned excellent actions of the two components (specifically, the action of component (A)) There is an optimum ratio according to the type of the component (A) for expressing a broader spectrum than the sum of the mold spectrum and the antifungal spectrum of the component (B) and maintaining the broad spectrum over a long period of time. I found to do.

That is, in the industrial fungicide of the present invention, the component (A) and the component (B) are weight ratio of the component (A), and the component (A) is TBZ, TPN, Zn-pt, Cu-pt, Ag-
90:10 to 60:40, at least one of pts (hereinafter referred to as a first group), MBC, DBSB
Of C, Na-pt, and TMP (hereinafter, the second group)
In the case of at least one of the above, the ratio of 90:10 to 70:30 synergistically increases the action of both components as described above. When the proportions of both components (A) and (B) are outside these ranges, the effect of either component is excessive, while
Not only is the action of the other component inhibited but insufficient, but also the synergistic action of both components is not exhibited, the broad antifungal spectrum is not exhibited, and the high persistence is also lost. When two or more components (A) are used in the first group or the second group, the mixing ratio of each component (A) is not particularly limited, and may be any ratio (A If both components (B) and (B) are blended in the above proportions, the above synergistic effect can be obtained. Further, when the component (A) of the first group and the component (A) of the second group are used together, the mixing ratio of each component (A) is not particularly limited. The sum of the component (A) of the second group and the component (B):
When the ratio is 90:10 to 70:30, the synergistic effect can be obtained.

The industrial fungicide of the present invention comprises the above (A),
An anti-algal agent can be blended together with the component (B).
Examples of the anti-algal agent include 2-methylthio-4-t-butylamino-6-cyclopropylamino-5-S-triazine and N, N-dimethyldichlorophenylurea. These may be used alone or in combination. Can be used. The blending ratio of the anti-algal agent is not particularly limited and is appropriately selected according to the desired algal-inhibiting action, but is generally 5 to 25% by weight, preferably 10 to 10% by weight in the industrial antifungal agent of the present invention.
Suitably it is 20% by weight. If the content is less than 5% by weight, the technical significance of blending the anti-algae agent does not occur, and 25% by weight.
If it is larger, not only the antialgal effect is saturated, but also the amount of the components (A) and (B) is relatively reduced, so that the antifungal effect, which is the original object of the present invention, is reduced.

The industrial fungicide of the present invention comprising the above components is used in an amount of 500 to 1 with respect to the target industrial material or product.
0000 ppm, preferably 1000-5000 ppm
Add and use so that If the amount to be added is too small, a sufficient growth-inhibiting effect may not be obtained.If the amount is too large, the effect is saturated, which is not only disadvantageous economically but also impairs safety. There is a possibility.

The method for using the industrial fungicide of the present invention is not particularly limited, and may be added to the target material or product as it is. Alternatively, for example, alcohols such as methanol and ethanol, ethylene glycol, propylene glycol, polyethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, glycols such as diethylene glycol monobutyl ether, dimethyl sulfoxide, dimethylformamide, ethylene glycol diacetate, diethylene glycol monoethyl ether It may be dissolved or suspended in various solvents such as acetate. Further, for example, it may be mixed with a solid such as talc, pyrophyllite, mica, kaolinite, montmorillonite, atavulgite, vermiculite, and silicon dioxide. Further, for example, a fatty acid salt, an alkyl sulfate salt, an alkylbenzsulfonic acid salt, an alkylnaphthalenesulfonic acid salt, a dialkylsulfonesuccinate salt, an alkylphosphate salt,
Anionic surfactants such as naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl sulfate, sodium acylmethyltaurate, and polycarboxylic acid; polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, and polyoxyethylene fatty acid ester Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, nonionic surfactants such as oxyethylene-oxypropylene block polymer and the like, dispersing agents, wettable powders, powders, suspending agents, etc. May be formulated.

The above-mentioned wettable powders and powders are obtained by pulverizing both the components (A) and (B), if necessary, an anti-algal agent and the above-mentioned dispersant.
Obtained by mixing. The suspending agent is (A),
(B) It is preferable to wet-pulverize and mix both components, and if necessary, the anti-algal agent and the dispersant together with water or the various solvents described above using a ball mill or a roll mill. To improve the stability in the case of aqueous suspensions, CMC-N
Pastes such as a (carboxymethylcellulose Na salt), guar gum and xanthan gum can also be used.

[0019]

EXAMPLES Preparation Example 1 Both components (A) and (B) were pulverized and mixed according to the composition shown in Table 1 to obtain a fungicide according to the present invention and a comparative antifungal agent (60 of 1A to 6J).
Seed) was prepared as a dust.

[0020]

[Table 1-1]

[0021]

[Table 1-2]

Antifungal Test Example 1 The antifungal agent of the present invention obtained in Preparation Example 1 and a comparative antifungal agent (1A to 6)
J) and (B) component (ADPI) alone,
The mold resistance to the acrylic resin emulsion paint was evaluated according to JIS Z-2911 "Paint Mold Resistance Test Method" (water penetration was omitted). However, the concentration of the fungicide added to the paint was 3000 ppm, 5000 p
pm, and the test bacteria were Aspergillus niger,
Seven mixed spore suspensions of Penicillium citrinum, Cladosporium cladosporioides, Aureobasidium brulans, Gliocladium pyrens, Alternaria alternanata, and Ulocladium sp were used.

The results are shown in Table 2. The indication of the mold resistance in Table 2 is as follows. Judgment 5: No growth of bacteria was observed on the test piece Judgment 4: Growth area of bacteria on the test piece was 1/4 or less Judgment 3: Growth area of bacteria on the test piece was 1/4 to 1/2 Judgment 2: Test The growth area of the bacteria on the test piece is 1/2 to 3/4 Judgment 1: The growth area of the bacteria on the test piece is 3/4 or more

[0024]

[1 of Table 2]

[0025]

[Table 2-2]

As is clear from Table 2, the component (A)
The component (B) alone does not show a good effect on the test bacterium, but the combination of both at a specific ratio according to the type of the component (A) makes each other insufficient. Not only complement each other, but also have a synergistic effect,
It can be seen that it exhibits excellent mold resistance.

Formulation Example 2 Each compound of component (A): A mixture of component (B) at a ratio of 8: 2 (six kinds of fungicides 1 to 6H in Table 1), each component (A) alone, The component (B) alone is used as an active ingredient, and these are each 30.0% by weight, and β-naphthalenesulfonic acid formalin condensate Na salt (trade name “Demol N” manufactured by Kao Corporation) 2.0% by weight , Xanthan gum 0.2% by weight, diethylene glycol monomethyl ether 2.0% by weight, and water 65.8% by weight were mixed and wet-pulverized to obtain 13 kinds of fungicide suspending agents. In addition, the active ingredient is a suspension of a combination of TBZ: ADPI 1H-1, a suspension of a combination of MBC: ADPI 2H-1, and a suspension of a combination of Zn-ADPI 3H-.
1. Suspension of the combination of Na-ADPI was added to 4H-1, TP
N: The suspension of the combination of ADPI was 5H-1, TMP: A
The suspending agent for the DPI combination is 6H-1.

Antifungal Test Example 2 (1) Preparation of Sample (Test Piece): Modified Silicon Polymer 1
00 parts by weight, di- (2-ethylhexyl) phthalate 3
5 parts by weight and 100 parts by weight of calcium carbonate
The mixture was heated under reduced pressure at 0 ° C./1 to 2 mmHg for 2 hours and mixed.
Subsequently, the mixture was cooled under reduced pressure, and dibutyltin oxide and
2 parts by weight of an equimolar reaction product with (2-ethylhexyl) -phthalate (acting as a reaction catalyst and a stabilizer) and the fungicide suspending agent (1H-1 to 6H-1) prepared in Preparation Example 2 6 types, 6 types of component (A) alone, and 1 type of component (B) alone
5,000 ppm of each of them (13 kinds in total) and remixed under reduced pressure for 15 minutes to obtain a modified silicone sealing agent. Next, these were extruded on a Teflon sheet by a filling machine, formed into a sheet by a roll, and these sheets were cut into test pieces of 3 cm × 3 cm square.

(2) Preparation of a test bacterial solution: Aspergillus niger slant-cultured in 10 ml of sterile water to which 0.005% of dioctyl sodium sulfosuccinate was added and dissolved.
Take five platinum ears of each spore of Penicillium citrinum, Cladosporium cladosporioides, Aureobasidium brulans, Gliocladium pyrens, Alternaria alternanata, Urocladium sp, shake the container vigorously, The spores were well dispersed and the contents were filtered through sterile gauze. The filtrate was made into each single spore suspension, and these were mixed in equal amounts. The suspension and the Sabouraud liquid medium (10 g of peptone,
40 g of glucose, 1000 ml of ion-exchanged water; pH5.
6) was mixed at a volume ratio of 1: 9 to prepare a test bacterial solution.

(3) Test method: Sabouraud agar medium (1.8% by weight of agar added to Sabouraud liquid medium) 25 m
1 was poured into a 90 mm Petri dish to prepare a plate medium. The 13 kinds of test pieces prepared in the above (1) were placed in the center of the medium, and 0.1 ml of the test bacterial solution prepared in the above (2) was uniformly inoculated on the surface of the test pieces. 28 ± 2 ℃
Was cultured in an incubator for 4 weeks to evaluate mold resistance. Table 3 shows the results. In addition, the display of mold resistance in Table 3 is as follows.
Same as Table 2.

[0031]

[Table 3]

From the test results shown in Table 3, the components (A) and (B)
Both components show almost no effect on the test bacterium at the fourth week, but it can be seen that the combination of both components imparts high durability to the fungicide resistance.

Formulation Example 3 The components (A) and the anti-algal agent were used in the amounts shown in Table 4, and the component (B) was used in the remaining amounts with the total amount being 100, and these were pulverized and mixed. Invention and comparative antifungal agent (1K
６6P) were prepared as powders.

[0034]

[Table 4-1]

[0035]

[Table 4-2]

Algae prevention test example 1 (1) Preparation of test algal suspension: For green algae (using Chlorella vulgaris and Chlamydomonas pyrenoidsa), the subcultured liquid was diluted with sterile physiological saline to 1 × 10 5 ⁶ /
The resulting suspension was used as a test algae suspension. For blue-green algae (using Oshiratoria tenuis and Anabaena varialis), the filaments in the subculture were dispersed with a homogenizer, and the optimum density of the algae was 0.4 ± 0 at 440 nm with sterile physiological saline. 1 was used as a test algae suspension.

(2) Preparation of sample (test piece): 3000 ppm, 5000 ppm of antifungal agent of the present invention obtained in Preparation Example 3
And, for comparison, 3000 ppm of component (A) alone, 5
000 ppm, algal protection agent alone 3000 ppm, 5000
ppm and (B) component alone 5000 ppm, 10,000
ppm was added to the vinyl acetate emulsion paint, and 0.09 g of each of these paints was applied to one side of a 3 cm circular paper so that the thickness of the coating was uniform, and was naturally dried for 48 hours. Prepared.

(3) Test method: The above-mentioned (2) was placed at the center of a previously prepared agar plate medium (prepared by pouring a Sabouraud agar medium obtained by adding 1.8% by weight of agar to a Sabouraud liquid medium into a 90 mm petri dish). ) Was placed, and 0.5 ml of the test algal suspension prepared in the above (1) was uniformly inoculated on the entire surface of the test piece. This is called a plant incubator (EYELA manufactured by Tokyo Rika Kikai Co., Ltd.)
FLI-301N) at 25 ± 1 ° C, 2000 Lu
The culture in which the light of x was applied for 16 hours and extinguished for 8 hours was performed for 28 days, and the algal resistance to the vinyl acetate emulsion paint was evaluated.

Table 5 shows the results. The display of algae resistance in Table 5 is as follows. Judgment 4: Algae growth was not observed on the test piece Judgment 3: Algae growth was observed on a part of the test piece Judgment 2: Algae growth was observed on the entire surface of the test piece, but growth was weak Judgment 1: Algae growth is observed on the entire surface of the test piece

[0040]

[Table 5-1]

[0041]

[Table 5-2]

Mold-proof test example 3 For the case of the mildew-proofing agent of the present invention obtained in Preparation example 3 and the alga-proofing agent alone, JIS Z-2911 "Testing method for paint-mold resistance" (water penetration was omitted). The mold resistance to the vinyl acetate emulsion paint was evaluated in accordance with the above. However, the concentration of the fungicide added to the paint was 3000 ppm and 5000 ppm for the fungicide of the present invention, 5000 ppm and 10000 ppm for the algicide alone, and the test bacterium was the same as in Fungal Test Example 1. Was used. Table 6 shows the results. The display of the mold resistance in Table 6 was the same as that of the anti-mold test example 1.

[0043]

[Table 6]

As apparent from Tables 5 and 6, (A),
(B) It is found that the industrial fungicide of the present invention containing both components exhibits not only fungicidal properties but also excellent algae-proofing properties.
It can also be seen that the addition of an anti-algal agent to both of these components provides even better anti-algal properties. In addition, when two kinds of component (A) are used in combination, the antifungal property shows excellent results, but the anti-algal property shows Zn-pt and N in component (A).
a-pt, TMP or any two of them,
It can be seen that excellent results are obtained by using any one of the three components and any one of the other components (A) in combination.

[0045]

The industrial antifungal agent of the present invention exhibits a synergistic effect which cannot be expected when these compounds are used alone when used in combination. That is,
The antibacterial spectrum against microorganisms, particularly mold, which causes deterioration and quality of industrial materials and products, is broadened and strengthened, and it also exhibits sustainability, thereby exhibiting excellent fungicide resistance. Further, the industrial fungicide of the present invention, since each compound used has low toxicity,
It does not cause environmental pollution.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 47/18 101 A01N 47/18 101C

Claims (3)

[Claims] (A) pyridinethiol-1-oxide or a metal salt thereof, methyl 2-benzimidazolecarbamate or dodecylbenzenesulfonate thereof,
At least one selected from (4-thiazolyl) -benzimidazole, tetrachloroisophthalonitrile, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine, and (B) 1- (β- An industrial fungicide comprising a mixture of (allyloxy-2,4-dichlorophenethyl) -imidazole as an active ingredient. 2. Component (A): component (B) in a weight ratio, wherein component (A) is 2- (4-thiazolyl) -benzimidazole, tetrachloroisophthalonitrile, Zn-2-pyridinethiol- 1-oxide, Cu-2-pyridinethiol-1-
Oxide, at least one selected from the group consisting of Ag-2-pyridinethiol-1-oxide, 90: 10-6
0:40, methyl 2-benzimidazolecarbamate or its dodecylbenzenesulfonate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine, N
The industrial fungicide according to claim 1, wherein the ratio is 90:10 to 70:30 when at least one selected from a-2-pyridinethiol-1-oxide. 3. The industrial fungicide according to claim 1, further comprising an antialgal agent.