JPS6123164B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an agricultural and horticultural fungicide whose active ingredient is an aluminosilicate prepared by carrying and replacing metal ions, which have an effective bactericidal action against plant pathogens, through ion exchange. As is well known, copper agents are used as fungicides for rice, vegetables, fruit trees, etc. Among them, inorganic copper salts such as copper sulfate and Bordeaux liquid are frequently used because of their quick-acting properties and relatively low cost. However, since it contains more soluble copper than organic copper, it has the disadvantage that it is susceptible to chemical damage regardless of the mode of use, and that its effects are not long-lasting due to washing away and other causes. Therefore, various proposals have been made to improve this problem, including the addition and use of magnesium hydroxide, basic magnesium carbonate, fatty acids, etc.
No.), those with added paraffin (Japanese Patent Application Laid-open No. 1983-
43123) is known. These methods seem to be aimed at reducing chemical damage by suppressing the rapid dissolution of soluble copper by reducing the solubility of many soluble copper ions or adsorbing copper ions to adjuvants. On the other hand, cuprous oxide, which is a poorly soluble copper, has little phytotoxicity but is inferior in bactericidal power, so it is hardly used. In view of the above-mentioned problems, the present inventors conducted intensive research and found that aluminosilicate, which supports copper ions etc. through ion exchange, is soluble and gently releases metal ions such as copper ions, despite being poorly soluble. The present invention was completed based on the discovery that it has a long-lasting bactericidal effect. That is, the present invention provides the general formula MO・xAl ₂ O ₃
ySiO ₂ zH ₂ O (where M is Cu, Zn, Ni or
Sn, x=0.8~1.2, y=1.5~10, z=0~10)
The present invention relates to an agricultural and horticultural fungicide containing one or more aluminosilicates represented by the following as an active ingredient. In the present invention, the aluminosilicate is represented by the above general formula, but it may be either crystalline or amorphous. Crystalline materials are generally called zeolites, have a unique three-dimensional structure, exhibit molecular sheep properties, and are known to exhibit various physical properties. Useful are zeolites of the type zeolite, P-type, Y-type zeolite, On the other hand, amorphous aluminosilicates include those that are amorphous substances that are precursors when synthesizing the above-mentioned zeolites, and those that are partially or entirely amorphous by ion exchange of zeolites as described below. This includes both. Generally, aluminosilicate is sodium aluminosilicate, regardless of whether it is a synthetic or natural product, but the disinfectant according to the present invention combines sodium ions of this aluminosilicate with metal ions having a bactericidal action, such as copper, zinc, nickel, and tin. It is an aluminosilicate in which metal ions are substituted or adsorbed by ion exchange with ions, and copper-substituted aluminosilicate is particularly preferred. As mentioned above, since the disinfectant according to the present invention is made by ion-exchanging sodium aluminosilicate with metal ions such as Cu ⁺⁺ , sodium may remain due to its nature, but Na ₂ O
It is ion-exchanged so that the amount is 10% by weight or less, preferably 5% by weight or less. Therefore, although the residual sodium content is not indicated in the above general formula of the fungicide of the present invention, it should be understood that it is contained at most 10% by weight, preferably 5% by weight from the above purpose. . The aluminosilicate having a bactericidal effect can be produced by the following method. For example, a sodium alumino acid aqueous solution and a sodium silicate aqueous solution are mixed and reacted in a specific ratio in a desired manner to produce a gel of sodium aluminosilicate, which is a zeolite precursor, and then the gel is aged to crystallize it. zeolite is obtained.
Not only zeolite, but also its amorphous precursor has cation exchange ability, and bactericidal agents can be prepared by ion exchange with metal ions such as Cu. Ion exchange is carried out by contacting an aqueous slurry of aluminosilicate with an aqueous solution of a soluble metal salt. These metal salts are generally mineral acid salts such as sulfates, chlorides, or nitrates, and the necessary For example, it may be an organic acid salt. In the case of copper, it is often preferable to replace it with an aqueous ammonia copper complex salt solution. In addition, depending on the contact conditions of the metal salt aqueous solution used to carry out the substitution reaction between sodium aluminosilicate and metal ions, a hydrous oxide of the metal may be deposited on the surface or pores of the particles in addition to the substituted metal. In the case of zeolite, although it may become amorphous, there is no problem with its effectiveness as a bactericidal agent of the present invention, and any of these cases is included. Furthermore, the disinfectant according to the present invention deposits amorphous silica or a metal hydrated oxide such as calcium, magnesium, aluminum or iron on the particle surface after ion exchange in order to adjust the release of metal ions having a disinfecting effect. It also includes those that have been subjected to coating treatment. The fungicide according to the present invention is sparingly soluble in itself, but it gradually releases soluble copper ions under the influence of organic acids secreted by animals and plants or acids such as carbon dioxide gas in the air, and exerts a bactericidal action. last. On the other hand, in general, silica is an important fertilizing ingredient that strengthens the stems and leaves of plants, such as rice, and prevents rice blast disease, but since the silica component in the fungicide of the present invention is soluble, it is absorbed and becomes harmful to young plants. It also strengthens the stems and leaves of seedlings and young seedlings, and provides resistance to the caterpillar fungus. Furthermore, since this fungicide has a large adsorption capacity, it is itself effective as a carrier for various fungicides, insecticides, fertilizers, and the like. For example, depending on the purpose of use, it can be used in combination with various fungicides such as other inorganic or organic copper agents, zinc agents, tin agents, organic sulfur agents, antibacterial agents, organic phosphorus agents, organic arsenic agents, soil fungicides, etc. The effect can be further improved. When using the fungicide according to the present invention, granules, tablets, powders,
It can be applied in any form such as an emulsion or a wettable powder. Examples of these carriers include clay, carrion, bentonite, acid clay, activated clay, diatomaceous earth, calcium carbonate, white carbon, sodium zeolite, calcium zeolite, magnesium zeolite, starch, benzene, alcohol, xylene kerosene, and the like. . In addition, various metal soaps, sulfuric ethers of higher alcohols, alkyl sulfonates, alkylaryl sulfonates, quaternary ammonium salts, etc. are used as surfactants such as spreading agents, emulsifiers, and dispersants that are commonly used in formulations. can give. The fungicides of the present invention can target a wide range of diseases, but the main diseases include: Rice: blast, rice mildew, sesame leaf blight; Tomato: late blight, ring spot, leaf spot; Eggplant: brown spot. Diseases; Cucurbits: anthracnose, downy mildew, black spot; mandarin oranges: scab, black spot; pears: black spot, black spot; grapes: brown spot, downy mildew; apples: black spot, Red star blight; Strawberry: Gray mold, etc. Production Example 1 A sodium aluminate aqueous solution and a sodium silicate aqueous solution were mixed and reacted at a temperature of 60°C with a molar ratio of SiO ₂ /Al ₂ O ₃ of 2.0 to obtain a gel-like sodium aluminosilicate reaction product. Ta. Next, this gel was aged at 80°C to obtain A-type sodium zeolite. Next, 100 g of the above-mentioned gel-like or A-type zeolite water-containing cake was treated with 30 g/CuO of cupric nitrate or its ammine complex salt solution for sufficient ion exchange to obtain copper-substituted aluminosilicate fungicides. The chemical composition of the product and the crystal-amorphous identification by X-ray diffraction are shown in the table below:

[Table] Production example 2 A sodium aluminate aqueous solution and a sodium silicate aqueous solution are reacted to form SiO ₂ /Al ₂ O ₃ = 3, Na ₂ O /
An aluminosilicate gel with SiO ₂ =1.4 and H ₂ O/Na ₂ O = 40 was prepared. Next, this gel was aged at room temperature and then heated to crystallize it to obtain X-type sodium zeolite. Next, add 100g of this zeolite water-containing cake.
A bactericide was obtained by treating and ion-exchanging with a cupric chloride solution containing 30 g/CuO, an ammine complex salt solution thereof, and a stannous chloride solution containing 50 g/SnO. The chemical analysis values and X-ray diffraction crystal form of the obtained product are shown in the table below:

[Table] Formulation Example 1 Powder Product 1... 15 parts by weight Calcium A type zeolite 82 parts by weight White carbon 2 parts by weight Calcium stearate 1 part by weight were mixed uniformly to obtain a powder. Formulation Example 2 Powder In Formulation Example 1, Product 2 was used in place of Product 1. Formulation example 3 Powder product 3... 15 parts by weight Clay... 82 parts by weight White carbon... 2 parts by weight tallow fatty acid... 1 part by weight Formulation example 4 Powder Product in place of product 3 in Formulation example 3 4 was used. Formulation example 5 Powder product 5... 15 parts by weight Clay... 52 parts by weight Calcium type A zeolite 30 parts by weight White carbon 2 parts by weight Calcium stearate 1 part by weight Formulation example 6 Wettable powder product 6... 35 parts by weight Basic copper chloride... 10 parts by weight Amorphous calcium aluminosilicate...
20 parts by weight Sorbitan monooleate... 2 parts by weight Polyoxyethylene nonyl phenyl ether...
By uniformly mixing 1 part by weight, a wettable powder containing 40% of metallic copper is obtained. Test Example 1 Tomato leaf mold control test One-month old potted tomato seedlings were sprayed with the prescribed concentration of the chemical solution of Formulation Example 6, and one day later, a spore suspension of Tomato leaf mold was spray inoculated. Then, it was left in a humid room at room temperature for 2 days, and then transferred to a greenhouse. 20 days after inoculation, the number of infected leaves was investigated according to the degree of disease on all leaves in 3 pots in 1 area. Number of leaves Disease severity a: Significant disease b: Moderate disease c: Slight disease d: No disease disease severity = 3 x a + 2 x b + c + 0 x d / Number of leaves examined The presence or absence of chemical damage was evaluated by visual observation. .

[Table] Test Example 2 When the first true leaves of cucumber (variety: Kaga Aonaga Setsei) grown in a 10 cm diameter flower pot began to appear, each test drug was applied to the pinched true leaves. It was diluted with water and sprayed at a rate of 15ml per pot. After 2 days, the spore solution of the powdery mildew fungus was spray inoculated, and the disease state was observed 20 days later, and the disease severity was evaluated using the same evaluation method as in Test Example 1, and the following results were obtained.

【table】

Claims (1)

[Claims] 1 General formula MO・xAl ₂ O ₃・ySiO ₂・zH ₂ O (where M is Cu, Zn, Ni or Sn, x=0.8 to 1.2, y=
1 represented by 1.5 to 10, z = 0 to 10)
A fungicide for agriculture and horticulture that contains seeds or two or more types of aluminosilicate as an active ingredient. 2. The agricultural and horticultural fungicide according to claim 1, wherein the aluminosilicate is zeolite. 3. The agricultural and horticultural fungicide according to claim 1, wherein the aluminosilicate is amorphous. 4 Aluminosilicate has Mg,
Claims 1 to 3 in which one or more oxides or hydrous oxides of Ca, Cu, Ni, Sn, Zn, Al, Fe, Zr, or Si are precipitated. The agricultural and horticultural fungicide according to any of the above.