JPS6028907A - Fungicide composition for agricultural and horticultural use - Google Patents

Abstract

PURPOSE:To provide an agricultural and horticultural fungicidal derivative having excellent storage stability, by adding formic acid, oxalic acid or a specific organic acid as a stabilizer to a fungicidal guanidine compound and a fungicidal N-(polychloroalkylthio)-dicarboximide. CONSTITUTION:The fungicidal derivative composed of (A) one or more effective fungicidal components selected from (a) a fungicidal quanidine compound, e.g. N-dodecylguanidium acetate and (b) an N-(polychloroalkylthio)dicarboximide of formula (R1 is 4-cyclohexene or benzene residue; n1 is 1 or 2: X is H or Cl) (e.g. captan) and (B) formic acid, oxalic acid or an organic acid of formula R2(COOH)n2 (R2 is 1-3C hydrocarbon group, carbonyl or hydrocarbon group having OH group; n2 is 1 or 2) (e.g. acetic acid).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fungicidal composition for agricultural and horticultural use. More specifically, each of the fungicidal guanidine compounds and certain fungicidal N-(polychloroalkylthio)-dicarboximides - or tool 1 -. and formic acid, oxalic acid or general formula R1 (C
OOH) n☆ (Note: Here, Rt is an organic group having 1 to 3 carbon atoms, and tu is 1 or 2).

Agricultural and horticultural fungicidal compositions using a fungicidal guanidine compound and a certain fungicidal N-<s=lichloroalkylthio)-dicarboximide as single agents are known. There are two specific examples of the former: That is,
l, 1'-iminiodi(Iphtamethylene)diguanidinium triacetate (hereinafter abbreviated as guazatine) or N
-dodecylguanidinium acetate (hereinafter abbreviated as dodine). There are three specific examples of moxibustion practitioners: That is, N-(trichloromethylthio)-4
-Cyclohexene-1,2-dicarboximide (hereinafter abbreviated as cabtane), N-(1,1,2,2-tetrachloroethylthio)-4-cyclohexene-1,2-cica J
Levoximide (hereinafter abbreviated as Putafor) and N-(1
-Lichloromethylthio)phthalimide (hereinafter abbreviated as forbet). Both the former and the latter can be used as agricultural and horticultural fungicides in RLT, but by using the two in combination, It has the characteristics of stabilizing its efficacy against diseased objects and achieving a low level of 0 degree of drug.For example, guazatine is known as an agricultural and horticultural agent for treating plants infected with pathogenic fungi or pathogenic bacteria. (Special Publication No. 43-27335) and others.
In recent years, the disease has been affected by rot disease of apple, late stone disease of grapes, storage disease of citrus, discolored rice, spotted leaf disease of wheat, 1-1 smut, snow shoulder disease, and leaf blight of grass. 4r efficacy has been confirmed.

Cabtan, on the other hand, is a fungicide that has been in official use for many years. And when using a mixture of guaritin and chitobutane,
As mentioned above, in addition to stabilizing the efficacy against infections and diseases and lowering the concentration of the drug, continuous spraying also reduces the rigidity of the drug compared to a single drug. - The mixed drug can be stably applied to a wide range of diseases such as gray mold, black rot, downy mildew and powdery mildew of grapes, scab and leaf spot of apples. , molinia or peach blight, phomopsis rot, tobacco blight, powdery mildew and sclerotium, and pear black spot and sclerotia.Therefore, it is of great significance to use as a mixed drug.However, The following drawback of mixed medicines is that they have extremely poor storage stability.This problem is so large that it cannot be predicted from the stability of single-flavored medicines. Regarding the storage stability, for example, the above-mentioned guazatine is so stable that it does not decompose even when boiled under acidic conditions.However, it decomposes only in strong alkaline.On the other hand, the above-mentioned cabtan does not decompose even when boiled under acidic conditions. It is said to be unstable under stable alkaline conditions. However, 1. When both drugs are used as a single agent, they are stable and do not require the addition of storage stabilizers. However, when both drugs are mixed together, they become extremely unstable. In other words, when the mixed drug is stored in the temperature room for one year, 40% of guazatine and 5% of cabtane decompose, and the mixed drug loses its commercial value after storage. , it has not been completely elucidated.
According to research conducted by the present inventors, it has been confirmed that -C (7) various substances are generated by mixing guazatine and cabtan and heating the mixture. They are Tet
These are hydrophthalic acid, chlorine ion, inthiocyanate, and 61-acid. The reaction mechanism is that the N-(polychloroargylthio)cica J levoximide moiety of cabtane reacts with the guanidino & (-N)I < 3ii:) of guazatine, and the thiophosgene (C9Gl
z) A"IJJ Decomposition products such as elementary scum are also reactive substances, and are presumed to react with the above-mentioned 7 guanidi groups to promote the decomposition of guaridinane. Conventionally, guadicine is stable in a shuttle. However, the stable ns method is not known.

The present inventor conducted research on a method for stabilizing a mixed drug consisting of two drugs selected from the above-mentioned two groups. In particular, we researched various acids as stabilizers. As a result, various inorganic acids, such as hydrochloric acid, Vi, t'ti, and nitric acid, cannot be used because they react with the carrier of the formulation, and phosphoric acid, pyrophosphoric acid, and bab (which are usually used as acidic stabilizers) PAP) (
It was found that neither the mixture of diisopropyl phosphate and isopropyl phosphate (trade name) (trade name) and the strong acids I. luenesulfonic acid, benzenesulfonic acid, and sulfamic acid had a sufficient stabilizing effect.

Surprisingly, the inventors discovered that various organic acids described below are extremely effective, and completed the present invention.

As is clear from the above description, the present invention [first feature] is a guanidine-based fungicide and a N-based fungicide with significantly improved storage stability.
- To provide an agricultural and horticultural fungicide composition containing a (polychloroalkylthio)dicarboximide fungicide as an active ingredient.

Other purposes will become clear from the description below.

The present invention has the following main configuration (1).

(1) Group of fungicidal guanidine compounds and structural formula 5%
A bactericidal active ingredient selected from the group of N-(polychloro'fulgylthio)dicarboximides represented by - or -, respectively, and formic acid or oxalic acid or structural formula: C0011) - for II, l, a hydrocarbon group having 1 to 3 carbon atoms, or a hydrocarbon group having a carbonyl group or a hydroxyl group; Antibacterial composition for use.

The structure and effects of the present invention will be described in detail below.

B. Bactericidal guacodine compound: /+IIt! of the aforementioned guazatine or dodine! Any guacodine compound that has fungicidal properties can be used in the M1 composition of the present invention.

B, N-(polychloroalkylthi)dicarboximide represented by the structural formula (L and R+ each represent a 4-cyclohegisenno and or benzene group, nl means l or 2, and X means 11 or C1) Compounds having bactericidal properties: Specific examples include the above-mentioned cabtan, kabtapol, and folpet. However, it is not limited to these specific examples as long as it has the above-mentioned chemical structure and bactericidal properties.

C0 Right 41 acid used in the present invention: formic acid, oxalic acid, or structural formula R, (GOOII)n, where ni- is a hydrocarbon group having 1 to 3 carbon atoms, or a hydrocarbon group having a carbonyl group or a hydroxyl group. , nl is l or 2) can be effectively used.

2. Other general compounding agents and compounding methods: The composition of the present invention can be compounded with various commonly used auxiliary agents depending on the form of the intended preparation. The order of mixing with the constituents of the composition of the invention is not limited. That is, in the case of a powder, a powder improver and a carrier are added in addition to the essential ingredients of the present invention, and the powder is ground and mixed to form a preparation. In the case of granules, in addition to the above-mentioned essential ingredients, a binder, a lubricant, an extender, and a 111 compound are mixed by lambda, pulverization, and then granulated and dried to form a preparation. In the case of a wettable powder, a lubricant, a dispersant, and a carrier are added to the above-mentioned essential ingredients, and the mixture is ground and mixed to form a preparation. Furthermore, in the case of sol preparations, +iiJ
Note n M component chisel t KIFI slide/III, II? A viscous agent, W'1 foam, antifreeze agent, and water are added and pulverized and mixed to prepare a preparation. However, the effects of the present invention are independent of the use or non-use of these auxiliary agents, the grinding and mixing method, and the form of the preparation.

In formulating the composition of the present invention, the surfactant used is preferably a nonionic active agent, and the carrier is preferably one that does not have ion adsorption properties. These circumstances are the same as when a gumenisin compound is used as a single agent as a fungicidal active ingredient.

The stabilizer component Piaru organic acid used in the composition of the present invention is
When used, that is, in a practical condition at the time of spraying, no phytotoxicity to crops is observed, and the toxicity to humans and animals is normal (note: non-medicinal deleterious substances, non-medicinal deleterious substances, etc.), and it is highly safe.

The method and effects of the present invention will be explained in detail below with reference to Examples and Usage Examples, but the present invention is not limited thereto. All parts and % in the examples mean parts by weight and % by weight.

Example I Guazatine: 0 parts Cabtane 80 parts Stabilizer 5 to 10 parts Boryoglycyethylene alkylallyl needle 3 parts White carbon 14 parts Diatomaceous earth 8 to 3 parts or more of various raw materials in the proportions listed so that the total amount is 100 parts Adjust the amount of diatomaceous material according to the amount of stabilizer and add it, mix evenly to make a wettable powder. Seal this in an ampoule and hold at 40°C.
Alternatively, after being stored in a thermostat at 50°C for a predetermined period of time, the stored sample was analyzed for guazatine by high performance liquid chromatography. The results of this time course test are shown in Table 1 along with the results of a control test in which no stabilizer was added.

Example 2 Guazatine 5 parts Cabtane 30 parts Stabilizer 5 parts Polyoxyethylene higher alcohol ether 5 parts Special high molecular weight organic compound 10 parts Water 45 parts or more of various raw materials are ground and mixed using a sand grinder to prepare a sol. After sealing this in an ampoule and storing it in a 50' (1!) thermostat for 7 days, the sample after storage was analyzed for guazatine. It is shown in Table 2.

Table 2 Implementation I^3 Dojin 10? B: Kyabutan 60 parts Stabilizer 5 parts Polyoxyethylene alkylallyl needle 3 parts White carbon 14 parts Diatomaceous earth Mix 8 or more parts of raw materials uniformly to make a wettable powder. Put this in an ampoule for 4 = 1 person, 71 for 50"0 Lii Onkimon.
After 1111 days of storage, 4J1 portions of dosin were removed by high performance liquid chromatography for each test sample after the storage. The results of the iC test are shown in Table 3 along with the results of the control test in which no stabilizer was added.

Example 4 Guazatine 10 parts 60 parts of Kaptafol or Folpet Stabilizer (oxalic acid) 5 parts Polyoxyethylene.

Alkyl allyl ether 3 parts White carbon 14 parts Diatomaceous earth 8 parts or more of various raw materials are uniformly mixed to make a wettable powder. This was sealed in an ampoule and stored in a thermostat at 50° C. for 7 days, and then the sample was analyzed for guazatine. The results of this time course test are shown in Table 4 along with the results of a control test in which no stabilizer was added.

Example 5 Guazadine 10 parts Cabtan 60 parts Stabilizer 7/fII Polyoxyethylene alkyl allyl needle 3 parts White carbon 14 parts Diatomaceous earth 6 parts or more of various raw materials are uniformly mixed to prepare a wettable powder. This was placed in an ampoule and stored in a thermostat at 50° C. for a certain period of time, and then the V-butane attached to the sample after storage was analyzed by gas chromatography. The results of this time course test are shown in Table 5 together with the results of a control test in which no stabilizer was added.

Table 5 Example of use Tobacco seedlings (variety: Kanto Matsuyo, Hakuenshū) grown in a glass house were transplanted into a 115,000 a Wagnerbot, and after the trees had grown to about 7 to 8 leaves, a formulation was prepared based on Example 1. The prepared irrigation agent was distributed three times every 8 days for a week to see if it caused harm to tobacco.

Furthermore, potted apples (variety: Nistarking, Delicious, Fuji) and pears (variety: Kosui, Chojube) were placed in a glass house from the outdoors, and new long branches grew inside and outside the lOc layer. Similar to tobacco, three hydrating powders prepared based on the above were distributed every other week, and the chemical damage to apples and pears was observed.

aF, 10: I+ (1 where the opening part is slightly curled:
No adverse effects were observed on tobacco and apples, which were sprayed three times. A slight curl was observed in the pears, but this was also observed with guazatine alone and was not caused by the addition of oxalic acid. From the results shown below, the formulation containing oxalic acid as a stabilizer does not have any adverse effects on various crops.

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Claims (1)

[Claims] (1) Bactericidal guanidine compound 1■ and the structural formula (TaC,
R1 is each a 4-cyclohexene group or a benzene group,
nl is l or 2. X means H or CI. ) and formic acid or oxalic acid or a bactericidal active ingredient from the N-(polychloroalkylthio)dicarboximide group represented by - or -, respectively, and formic acid or oxalic acid or structural formula R
-(COOII) n- to nl If: , a hydrocarbon group having 1 to 3 carbon atoms, or carbonyl, (or a hydrocarbon group having hydroxyl group, nt is 1 or 2); An agricultural and horticultural disinfectant composition characterized by comprising an acid.