WO2014026504A1

WO2014026504A1 - Use of metal salt of 2-mercaptobenzothiazole

Info

Publication number: WO2014026504A1
Application number: PCT/CN2013/077600
Authority: WO
Inventors: 徐振元; 郭世俭; 许丹倩; 朱洪斌; 魏方林; 王益锋; 张传清; 朱国念; 戴金贵; 应小锋
Original assignee: 浙江新农化工股份有限公司; 浙江工业大学
Priority date: 2012-08-16
Filing date: 2013-06-20
Publication date: 2014-02-20
Also published as: AU2013228038A1; CN103461348B; CN103461348A

Abstract

The present invention relates to use of a metal salt of 2-mercaptobenzothiazole. In particular, the present invention provides a fungicide for controlling diseases of crops, characterized in that the fungicide comprises the metal salt of 2-mercaptobenzothiazole shown as the following formula (I) and a carrier for a pesticide, wherein: M is Zn, Mn, Fe, Sn or Al; n is 2, 3 or 4. The fungicide shows very high biological activity against most bacteria, has excellent inhibitory effect on fungi as well, and is an ideal drug for integrated control of diseases of crops.

Description

Use of a 2-mercaptobenzothiazole metal salt

The invention belongs to the field of pesticides, and relates to an agricultural fungicide containing 2-mercaptobenzothiazole metal salt as an active ingredient, in particular to a use of a 2-mercaptobenzothiazole metal salt. Background technique

Among the three major types of pesticides, herbicides and fungicides, fungicides account for the least proportion, and bactericides are seriously deficient. At present, the main agents for controlling bacterial diseases are copper preparations (such as: copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, chlorhexidine, tonin, copper noble, acrylate copper, copper rosinate, Quinoline copper, copper amide, thidium copper and thiabium copper, agricultural antibiotics (eg streptomycin, oxytetracycline hydrochloride, neutrophin, ningnanmycin, polymycin, etc.), and Thiadiazole fungicides (eg thiazolazole and zinc thiazide). Copper preparations have a wide spectrum of bactericidal activity, but their safety is poor. There is a risk of phytotoxicity in the flowering and young fruit stages of the crop, and the copper preparation will stimulate the proliferation and mites of mites, rust tick and scale insects, and crops. Safety production will have an impact; agricultural antibiotics are traditional bactericides, chemically stable and efficient, but the target is narrow, easy to produce drug resistance problems and there is a large dietary risk; thiazolyl internal absorption is strong, holding The effect period is long, but drug resistance is increasingly apparent.

The 2-mercaptobenzothiazole salt is mainly used as a rubber vulcanization accelerator, and a rubber vulcanizing agent containing 2-mercaptobenzothiazole copper is disclosed in the US Patent (US004012332). The Chinese patent (CN101463018A) discloses a 2-mercapto group. A method for preparing a rubber vulcanization accelerator dibenzothiazole disulfide using sodium benzothiazole as a raw material, and a method for preparing a 2-mercaptobenzothiazole transition metal cluster by a Chinese patent (CN1861617A), and revealing the cluster The compound can be used as a nonlinear optical material and a rubber vulcanization accelerator. There are also a large number of reports on the mechanism of action of 2-mercaptobenzothiazole salt to promote rubber vulcanization (Applied Catalysis A: General 2001, 207, 55-68; Journal of Applied Polymer Science 2003, 89, 47-54; Materials Herald 2008, 22(8), 29-32). In addition to being widely used in the field of rubber vulcanization, the Chinese patent (CN101514210B) discloses a copper-2-mercaptobenzothiazole having a specific crystal form. And its use in the control of agricultural plant diseases. However, a 2-mercaptobenzothiazole salt composed of a metal element such as zinc, manganese, iron, tin, and aluminum and 2-mercaptobenzothiazole has not been reported as an agricultural fungicide alone. Copper-2-mercaptobenzothiazole is not ideally effective in controlling diseases, and it is difficult to provide metal elements such as zinc, manganese, iron, tin and aluminum which are required for crops.

The applicant successfully developed thiazole zinc (ZL001321196) in 1999 and has been industrialized for many years. The product has good control effect on bacterial diseases, can also promote crop growth, improve resistance to stress, increase yield, and improve quality. It is a low-toxic, low-residue environmental pesticide. After ten years of vigorous promotion, it has entered the market in large quantities and serves agriculture. However, this product has a problem of poor control of fungal diseases, and there is a risk of resistance in the rice area. Therefore, the development of alternatives to thiazol zinc will be of great significance.

Summary of the invention

In order to overcome the deficiencies of the prior art, the present invention provides a bactericide for controlling crop diseases, characterized in that the bactericide comprises a 2-mercaptobenzothiazole metal salt represented by the following formula (I) and a carrier for pesticides :

Wherein: M is Zn, Mn, Fe, Sn or Al; n is 2, 3 or 4.

Preferably, in the above bactericide, the 2-mercaptobenzothiazole metal salt is selected from the group consisting of bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) manganese, bis(2-mercaptobenzothiazole) iron , bis(2-mercaptobenzothiazole) tin, tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum and tetrakis(2-mercaptobenzothiazole) tin.

In the above bactericide, the term bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) manganese, bis(2-mercaptobenzothiazole) iron, bis(2-mercaptobenzothiazole) Tin, tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum and tetrakis(2-mercaptobenzothiazole) tin are respectively represented as:

Bis(2-mercaptobenzothiazole) Zinc refers to a compound of the formula:

Bis(2-mercaptobenzothiazole) Manganese refers to a compound of the formula: n

Bis(2-mercaptobenzothiazole) iron refers to a compound of the formula:

Bis(2-mercaptobenzothiazole) tin refers to a compound of the formula:

Tris(2-mercaptobenzothiazole) Iron refers to a compound of the formula:

Tris(2-mercaptobenzothiazole) Aluminium refers to a compound of the formula:

Tetrakis(2-mercaptobenzothiazole) Tin refers to a compound of the formula:

In the above bactericide, the weight of the 2-mercaptobenzothiazole metal salt is from 0.1 to 99.9%, preferably from 1 to 90%, based on the total weight of the bactericide.

In the above bactericide, the preparation method of the compound 2-mercaptobenzothiazole metal salt is a preparation method known in the art, for example, the preparation method of bis(2-mercaptobenzothiazole) zinc is disclosed in the Hungarian patent (HU17036A2). And the US patent (US ² 0100168 ² 30A1), etc., using a similar preparation method to produce bis(2-mercaptobenzothiazole) manganese, bis(2-mercaptobenzothiazole) iron, bis(2-mercaptobenzene) And thiazole) tin, tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum and tetrakis(2-mercaptobenzothiazole) tin. Methods for the preparation of these compounds have been disclosed in the prior art. The present invention also provides a use of a 2-mercaptobenzothiazole metal salt for controlling crop diseases, wherein the 2-mercaptobenzothiazole metal salt is a compound of the structure represented by the following formula (I):

Wherein: M is Zn, Mn, Fe, Sn or Al; n is 2, 3 or 4.

Preferably, the 2-mercaptobenzothiazole metal salt is selected from the group consisting of bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) manganese, bis(2-mercaptobenzothiazole) iron, and di(2- Mercaptobenzothiazole) One of tin, tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum and tetrakis(2-mercaptobenzothiazole) tin. In the above use, the crop disease is a bacterial disease and a fungal disease, and preferably, the crop disease is rice bacterial blight (Xanthomonas oryzae pv. oryzae), rice bacterial leaf streak

(Xanthomonas oryzae pv.oryzicolae), Xanthomonas axonopodis pv. citri, Xac), cucumber bacterial keratosis (Pseudomonas syringae pv. lachrymans), watermelon bacterial fruit spot disease. Acidovorax avenae subsp.citrulli ), Xanthomonas campestris pv. Pruni, Botryosphaeria dothidea, Bacterial wilt

(Pseudomanas solanacearum Smith) ^ Chinese cabbage soft rot {Erwinia carotovora) and / or peanut bacterial wilt Pseudomanas solanacearum Smith). In the above uses, the crops are cereal wheat, barley, rice, sorghum, corn; fruit trees apples, pears, peaches, pecans, citrus, grapes, glutinous rice, bananas, mangoes, alfalfa; vegetable cucumbers, watermelons, Hanging melon, loofah, melon, spinach, celery, tomato, pepper, eggplant, ginger, onion, garlic, leeks, kale, Chinese cabbage, sweet potato, strawberry, lettuce, kidney bean, kidney bean, broad bean, radish, carrot, potato, yam,芋, lotus root, lotus root, glutinous rice; sugar plant beet, sugar cane; oil crop soybean, peanut, rape, sesame, sunflower; or tobacco, tea, etc., but the scope of the disease control crop referred to in the present invention is not limited The above crops.

The present invention also provides a use of a metal salt of 2-mercaptobenzothiazole for use against harmful microorganisms, wherein the metal salt of 2-mercaptobenzothiazole is a compound of the structure represented by the following formula (I):

Wherein: M is Zn, Mn, Fe, Sn and Al; n is 2, 3 or 4.

Preferably, the 2-mercaptobenzothiazole metal salt is selected from the group consisting of bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) manganese, bis(2-mercaptobenzothiazole) iron, and di(2- Mercaptobenzothiazole) One of tin, tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum and tetrakis(2-mercaptobenzothiazole) tin. In the above anti-harmful microorganisms, the harmful microorganisms are preferably Fusarium moniliforme, Rhizoctonia solani, Gibberella zeae, Fusarium oxysporum f. Sp. vasinfectum) ^ Botrytis cinerea, Alternaria solani, Fulvia fulva, Gloeosporium orbicular e, Sclerotinia sclerotiorum , Phytophthora melonis, Alternaria cucumerina, Thanatephorus cucumeris^ Colletotrichum capsici ^ Alternaria mall ^ Technical cream Phytophthora litchii ^ Pestalotiopsis microspora, Sphaceloma ampelium and Colletotrichum ampelinum, etc., but the range of anti-harmful microorganisms of the present invention is completely absent Limited to the described bacteria. The above bactericides are used in the form of general conventional preparations, depending on the nature of the target disease, by spraying, seed dressing, watering, spreading or brushing, the amount of active active ingredient applied is in accordance with weather conditions, crop condition or The bactericidal agent is generally prepared as a preparation of a suspending agent, a suspoemulsion, a water-dispersible granule, and a wettable powder.

Preferably, the above sterilizing agent is prepared as a suspending agent or a suspoemulsion, which comprises the following mass percentage of the substance: the 2-mercaptobenzothiazole metal salt 10~60%, the oil 0-20%, the dispersing agent 3~ 10%, wetting agent 2~6%, emulsifier 0~8%, thickener 0~4%, antifreeze 0~5%, defoamer 0~2%, water to 100%; The oil is one or more of soybean oil, rapeseed oil, cottonseed oil, turpentine oil, white oil, methyl oleate; the dispersing agent is sodium starch octenyl succinate, sodium acrylate homopolymer salt, Nonylphenol polyoxyethylene ether carboxylate, polycondensation naphthalenesulfonate, nonylnaphthalenesulfonate, lignosulfonate, polyoxyethylene polyoxypropylene ether block copolymer, nonylphenol polyoxyethylene ether phosphate One or more of the esters; the wetting agent is one of tallow ethoxylated amine salt, sodium dibutylnaphthalene sulfonate, sodium decylnaphthalene sulfonate, and fatty alcohol polyoxyethylene ether. Or several; the emulsifier is calcium dodecylbenzenesulfonate, potassium fatty acid phosphate, nonylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether One or more of polyoxyethylene ether sorbitan fatty acid ester and propylene glycol polyoxyethylene polyoxypropylene ether block copolymer; the thickener is xanthan gum, aluminum magnesium silicate, alginic acid One or more of polyvinyl alcohol and carboxymethyl cellulose; the antifreeze agent is one or more of ethylene glycol, propylene glycol, glycerin, urea; and the antifoaming agent is One of polyethoxy nonylphenol, silicone, polyoxypropylene polyoxyethylene glyceryl ether, polyether modified silicone ray defoamer Several.

Preferably, the sterilizing agent is prepared as a water-dispersible granule and a wettable powder, which comprises the following mass percentage of the substance: the 2-mercaptobenzothiazole metal salt is 10 to 80%, and the dispersing agent is 4 to 12%. Wetting agent 2~7%, disintegrating agent 0~10%, binder 0~5%, filler to 100%; wherein the dispersing agent is fatty alcohol polyoxyethylene ether carboxylate, Malay One of acid-acrylic acid copolymer sodium salt, nonylphenol polyoxyethylene ether carboxylate, polycondensation naphthalenesulfonate, fatty alcohol polyoxyethylene ether sulfonate, nonylnaphthalenesulfonate, lignosulfonate One or more; the wetting agent is one or more of tallow ethoxyamine salt, sodium dibutylnaphthalene sulfonate, sodium decylnaphthalene sulfonate, sodium lauryl sulfate; The disintegrant is sodium carboxymethyl starch; the binder is one or more of starch, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol; the filler is diatomaceous earth, bentonite, One or more of attapulgite, kaolin, and silica.

Compared with the prior art, the bactericide provided by the invention has the following outstanding advantages: (1) The bactericide provided by the invention exhibits high biological activity for most bacteria, and has excellent inhibitory effect on fungi, and is a comprehensive crop disease. The ideal agent for prevention and treatment; (2) The bactericide provided by the invention has good compatibility with crops, and particularly has good compatibility with seedlings, young shoots, flowers and young fruits which are particularly sensitive to crops, and allows seeds to be treated and The flowers and fruits in the aerial part significantly improve the drug resistance and drug-receiving properties of the crop, and make the drug more safe for crops; (3) The fungicide provided by the present invention has different action mechanism with the thiadiazole fungicide, Effectively slow down the resistance of the disease to thiadiazole fungicides, reduce the length of fungicides such as thiabendazole and thiazole zinc (4) The fungicide provided by the present invention can supplement trace elements such as S, Zn, Mn, Fe and Al necessary for crop growth, has strong seedlings of backen, stimulates crop growth, and improves crop resistance. The unique efficacy of reversal and disease resistance.

detailed description

The present invention will be described in detail with reference to the preferred embodiments of the invention, All modifications and variations made within the basic spirit and principles of the invention are intended to be within the scope of the invention. Therefore, the scope of protection of the invention should be determined by the appended claims.

Biometric example:

The thiazole zinc and thiabend copper used in this test were produced by Zhejiang Xinnong Chemical Co., Ltd.; bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) copper, double (2 - mercaptobenzothiazole) iron, bis(2-mercaptobenzothiazole) tin, bis(2-mercaptobenzothiazole) manganese, tris(2-mercaptobenzothiazole) aluminum, tris(2-mercaptobenzothiazole) Iron, tetrakis(2-mercaptobenzothiazole) tin is provided by the laboratory of Zhejiang University of Technology; the preparation used in the invention is provided by the laboratory of Zhejiang University; the strains of the bioassay are all from the plant of Zhejiang Agriculture and Forestry University. Provided by the protection laboratory, usually stored at 4 ° C on the (PDA) bevel.

Bioassay Example 1: Rice Bacterial Blight

Test method: Refer to "The Agricultural Industry Standard of the People's Republic of China NY/T 1156.16-2008», Turbidity Method. The test agent was 98% bis(2-mercaptobenzothiazole) zinc powder, 97% bis(2-mercaptobenzothiazole) manganese, 97% bis(2-mercaptobenzothiazole) copper powder, 97% double (2-mercaptobenzothiazole) iron powder, 97% tris(2-mercaptobenzothiazole) iron powder, 97% bis(2-mercaptobenzothiazole) tin powder, 97% tetrakis(2-mercaptobenzene) And thiazole) tin powder, 97% bis(2-mercaptobenzothiazole) manganese powder, 60% tris(2-mercaptobenzothiazole) aluminum powder, 97% thiazole zinc powder; series concentration is 100, 25 , 12.5, 6.25, 1.5625 mg/L. The test results show: bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) copper, bis(2-mercaptobenzothiazole) iron, bis(2-mercaptobenzothiazole) tin, double ( 2-mercaptobenzothiazole) manganese, tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum, tetrakis(2-mercaptobenzothiazole) tin and thiazole The EC ₅₀ values of zinc to rice bacterial blight were 0.23 mg/L, 5.46 mg/L, 1.03 mg/L, 0.98 mg/L, 0.28 mg/L, 0.86 mg/L, 0.18 mg/L, and 0.74 mg/L, respectively. , 3.46 mg/L; indicates bis(2-mercaptobenzothiazole) zinc and bis(2-mercaptobenzothiazole) iron, bis(2-mercaptobenzothiazole) tin, bis(2-mercaptobenzothiazole) manganese , tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum, tetrakis(2-mercaptobenzothiazole) tin have high antibacterial activity against rice bacterial blight, better than Bis(2-mercaptobenzothiazole) copper and the current conventional control agent thiazole zinc.

Bioassay Example 2: Peanut Bacterial Wilt

Test method: Refer to "The Agricultural Industry Standard of the People's Republic of China NY/T 1156.16-2008», Turbidity Method. The test agent was 98% bis(2-mercaptobenzothiazole) zinc powder, 97% bis(2-mercaptobenzothiazole) manganese, 97% bis(2-mercaptobenzothiazole) copper powder, 97% double (2-mercaptobenzothiazole) iron powder, 97% tris(2-mercaptobenzothiazole) iron powder, 97% bis(2-mercaptobenzothiazole) tin powder, 97% tetrakis(2-mercaptobenzene) And thiazole) tin powder, 97% bis(2-mercaptobenzothiazole) manganese powder, 60% tris(2-mercaptobenzothiazole) aluminum powder, 97% thiazole zinc powder; series concentration is 100, 25 , 12.5, 6.25, 1.5625 mg/L. The test results show: bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) copper, bis(2-mercaptobenzothiazole) iron, bis(2-mercaptobenzothiazole) tin, double ( 2-mercaptobenzothiazole) manganese, tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum, tetrakis(2-mercaptobenzothiazole) tin and thiazole zinc on peanut bacterial wilt EC ₅₀ were 0.87 mg/L, 2.27 mg/L, 1.02 mg/L, 1.22 mg/L, 0.79 mg/L, 0.90 mg/L, 0.56 mg/L, 0.95 mg/L, 21.34 mg/L, respectively; (2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) copper, bis(2-mercaptobenzothiazole) iron, bis(2-mercaptobenzothiazole) tin, bis(2-mercaptobenzophenone) Thiazole) manganese, tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum, tetrakis(2-mercaptobenzothiazole) tin have high antibacterial activity against peanut bacterial wilt, Better than the current control agent thiazole zinc.

Bioassay Example 3: Watermelon Bacterial Fruit Spot Disease

Test method: Refer to "The Agricultural Industry Standard of the People's Republic of China NY/T 1156.16-2008», Turbidity Method. The test agent was 98% bis(2-mercaptobenzothiazole) zinc powder, 97% bis(2-mercaptobenzothiazole) manganese, 97% bis(2-mercaptobenzothiazole) copper powder, 97% double (2-mercaptobenzothiazole) iron powder, 97% Tris(2-mercaptobenzothiazole) iron powder, 97% bis(2-mercaptobenzothiazole) tin powder, 97% tetrakis(2-mercaptobenzothiazole) tin powder, 97% bis(2-fluorenyl) Benzothiazole) manganese powder, 60% tris(2-mercaptobenzothiazole) aluminum powder, 97% thiazole zinc powder; series concentrations of 100, 25, 12.5, 6.25, 1.5625 mg / L. The test results show: bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) copper, bis(2-mercaptobenzothiazole) iron, bis(2-mercaptobenzothiazole) tin, double ( 2-mercaptobenzothiazole) manganese, tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum, tetrakis(2-mercaptobenzothiazole) tin and thiazole zinc on watermelon bacterial fruit spots EC _5Q were 16.65 mg / L, 91.56 mg / L, 25.49 mg / L, 18.97 mg / L, 15.79 mg / L, 19.60 mg / L, 10.49 mg / L, 14.63 mg / L, 83.34 mg / L; Indicates bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) iron, bis(2-mercaptobenzothiazole) tin, bis(2-mercaptobenzothiazole) manganese, tris(2-mercapto) Benzothiazole) Iron, tris(2-mercaptobenzothiazole) aluminum, tetrakis(2-mercaptobenzothiazole) tin have higher antibacterial activity against watermelon bacterial spot disease, better than double (2-mercapto) Benzothiazole) Copper and conventional control agent thiazole zinc.

Bioassay Example 4: Chinese cabbage soft rot

Test method: Refer to "The Agricultural Industry Standard of the People's Republic of China NY/T 1156.16-2008», Turbidity Method. The test agent was 98% bis(2-mercaptobenzothiazole) zinc powder, 97% bis(2-mercaptobenzothiazole) manganese, 97% bis(2-mercaptobenzothiazole) copper powder, 97% double (2-mercaptobenzothiazole) iron powder, 97% tris(2-mercaptobenzothiazole) iron powder, 97% bis(2-mercaptobenzothiazole) tin powder, 97% tetrakis(2-mercaptobenzene) And thiazole) tin powder, 97% bis(2-mercaptobenzothiazole) manganese powder, 60% tris(2-mercaptobenzothiazole) aluminum powder, 97% thiazole zinc powder; series concentration is 100, 25 , 12.5, 6.25, 1.5625 mg/L. The test results show: bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) copper, bis(2-mercaptobenzothiazole) iron, bis(2-mercaptobenzothiazole) tin, double ( 2-mercaptobenzothiazole) manganese, tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum, tetrakis(2-mercaptobenzothiazole) tin and thiazole zinc against Chinese cabbage soft rot The EC ₅₀ was 30.49 mg/L, 34.62 mg/L, 41.65 mg/L, 30.12 mg/L, 34.62 mg/L, 33.74 mg/L, 24.62 mg/L, 22.63 mg/L, 30.99 mg/L, respectively; Bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) copper, bis(2-mercaptobenzothiazole) iron, bis(2-mercaptobenzothiazole) tin, bis(2-mercaptobenzene) And thiazole) manganese, tris(2-mercaptobenzothiazole) iron, three (2- Mercaptobenzothiazole) Aluminum and tetrakis(2-mercaptobenzothiazole) tin have high antibacterial activity against Chinese cabbage soft rot, which is equivalent to the current control agent thiazole zinc.

Bioassay example 5: Rice seedling disease

Test method: Refer to the "Agricultural Industry Standard of the People's Republic of China NY/T1156.2-2006" mycelial growth rate method. The test agent was 98% bis(2-mercaptobenzothiazole) zinc original powder, 97% bis(2-mercaptobenzothiazole) copper original powder, 97% thiazole zinc original powder; each treatment concentration was 2000, 500, 250 , 125 and O mg / L ; The test results show that: bis( ² -mercaptobenzothiazole) zinc, bis( ² -mercaptobenzothiazole) copper and thiazole zinc have an EC ₅₀ of 35.18 mg/L for rice seedling disease, 134.98 mg / L, 9271.67 mg / L; indicating that bis(2-mercaptobenzothiazole) zinc has a good inhibitory effect on the mycelial growth of rice seedling disease, and bis(2-mercaptobenzothiazole) copper shows a certain The activity of thiazole zinc is not active.

Bioassay Example 6: Wheat Scab

Test method: Refer to the "Agricultural Industry Standard of the People's Republic of China NY/T1156.2-2006" mycelial growth rate method. The test agent was 98% bis(2-mercaptobenzothiazole) zinc original powder, 97% bis(2-mercaptobenzothiazole) copper original powder, 97% thiazole zinc original powder; each treatment concentration was 400, 200, 100 , 50, 25 and O mg / L; The results showed that: bis ⁽² - mercapto benzothiazole) zinc, bis ⁽² - mercapto benzothiazole) Cu and Zn thiazole of wheat scab EC ₅₀ were 305.42mg / L, 886.45 mg / L, 975.93 mg / L; indicating that bis(2-mercaptobenzothiazole) zinc has a certain inhibitory effect on the growth of wheat scab, while bis(2-mercaptobenzothiazole) copper and thiazole Zinc is not active.

Bioassay Example 7: Pecan Black Spot

Test method: Refer to the "Agricultural Industry Standard of the People's Republic of China NY/T1156.2-2006" mycelial growth rate method. The test agent was 98% bis(2-mercaptobenzothiazole) zinc original powder, 97% bis(2-mercaptobenzothiazole) copper original powder, 97% thiazole zinc original powder; each treatment concentration was 400, 200, 100 , 50, 25 and O mg/L; test results show that: bis( ² -mercaptobenzothiazole) zinc, bis( ² -mercaptobenzothiazole) copper and thiazole zinc have an EC ₅₀ of 59.13 mg for pecan black spot disease, respectively. /L, 205.79mg/L, 341.95mg/L; indicating that bis(2-mercaptobenzothiazole) zinc has a strong inhibitory effect on the growth of pecan black spot, while bis(2-mercaptobenzothiazole) Copper and zinc thiazole are essentially inactive. Bioassay Example 8: Botrytis cinerea

Test method: Refer to the "Agricultural Industry Standard of the People's Republic of China NY/T1156.2-2006" mycelial growth rate method. The test agent was 98% bis(2-mercaptobenzothiazole) zinc original powder, 97% bis(2-mercaptobenzothiazole) copper original powder, 97% thiazole zinc original powder; each treatment concentration was 2000, 500, 250 , 125 and O mg / L; test results show that: bis( ² -mercaptobenzothiazole) zinc, bis( ² -mercaptobenzothiazole) copper and thiazole zinc have an EC ₅₀ of 69.10 mg/L for Botrytis cinerea, 117.18 mg/L, 1303.69 mg/L; indicating that bis(2-mercaptobenzothiazole) zinc has a certain inhibitory effect on the growth of Botrytis cinerea, and bis(2-mercaptobenzothiazole) copper shows a certain degree. Active, while thiazolyl zinc is inactive. Summary table of test results of test agents for bacterial diseases:

Summary table of test results of test agents for fungal diseases:

Field efficacy test:

Field trial example 1: Cucumber bacterial angular leaf spot Test method: The field efficacy test was carried out with reference to the National Standard of the People's Republic of China GB/T 17980.26-2000. The test was conducted in April 2011 in Wuzhou, Zhejiang. The test agent is 20% thiazolyl zinc SC (produced by Zhejiang Xinnong Chemical Co., Ltd.), 20% thiabend copper SC (produced by Zhejiang Longwan Chemical Co., Ltd.), 50% Wangtong WP (Jiangxi Heyi Agrochemical Co., Ltd.); 40% bis(2-mercaptobenzothiazole) zinc SC, 20% bis(2-mercaptobenzothiazole) iron SC, 20% tris(2-mercaptobenzothiazole) iron SC, 20% bis(2-mercaptobenzene) And thiazole) tin SC, 20% tetrakis(2-mercaptobenzothiazole) tin SC, 20% bis(2-mercaptobenzothiazole) manganese SC, 10% tris(2-mercaptobenzothiazole) aluminum SC (Zhejiang University provide);

Field trials showed: 40% bis(2-mercaptobenzothiazole) zinc SC800 solution, 20% bis(2-mercaptobenzothiazole) iron SC 400 solution, 20% tris (2) for cucumber bacterial angular plaque - mercaptobenzothiazole) iron SC 400 times solution, 20% bis(2-mercaptobenzothiazole) manganese SC 400 times solution, 20% bis(2-mercaptobenzothiazole) tin SC 400 times solution, ²⁰ % four ( ² -mercaptobenzothiazole) tin SC 400 times solution, 10% tris( ² -mercaptobenzothiazole) aluminum SC 300 times solution, 20% thiazole zinc SC400 times solution, 20% thiabend copper SC 400 times solution The difference is not significant, but the control effect is significantly higher than 20% bis(2-mercaptobenzothiazole) copper SC 400 times Liquid, 50% Wang Tong WP 250 times solution.

Field test example 2: Peach tree bacterial perforated leaf disease

Test method: The field efficacy test was carried out with reference to the National Standard of the People's Republic of China GB/T 17980.26-2000. The experiment was conducted in Jinhua City, Zhejiang Province from May to July 2011. The test variety was very early red (genus nectarine series). The test was sprayed three times, and the third dose was investigated 14 days later. The test reagent is 20% thiazolyl zinc SC (produced by Zhejiang Xinnong Chemical Co., Ltd.), 33% quinoline copper SC (produced by Zhejiang Haizheng Chemical Co., Ltd.), 40% bis(2-mercaptobenzothiazole) zinc SC , 20% bis(2-mercaptobenzothiazole) iron SC, 20% bis(2-mercaptobenzothiazole) tin SC, 20% bis(2-mercaptobenzothiazole) manganese SC, 10% tris(2- fluorenyl) Benzothiazole) Aluminum SC (provided by Zhejiang University);

Field trials showed: bacterial perforated leaf disease on peach trees, 20% bis(2-mercaptobenzothiazole) zinc SC800 solution, 20% bis(2-mercaptobenzothiazole) iron SC 800 solution, 20% double ( 2-mercaptobenzothiazole) Manganese SC 800 times solution, 20% bis(2-mercaptobenzothiazole) tin SC 800 times solution, 10% tris(2-mercaptobenzothiazole) aluminum SC 500 times solution and 20 % bis(2-mercaptobenzothiazole) copper SC 800 times solution, 20% thiazole zinc SC800 times solution, 33% quinoline copper SC 800 times solution significantly difference, and the test agent 20% bis(2-mercaptobenzene) And thiazole) copper SC 800 times solution, 33% quinoline copper SC 800 times solution has certain phytotoxicity to nectarine, showing abnormal leaves; 20% bis(2-mercaptobenzothiazole) zinc SC800 times solution and 20% thiazole zinc The SC800 solution treatment is not only phytotoxic, but the leaves of the nectarine are greener, more lustrous and softer. Formulation examples:

Example 1

Bis(2-mercaptobenzothiazole) zinc 10%, sodium octenyl succinate 2%, polyoxyethylene polyoxypropylene ether block copolymer 1%, dibutyl naphthalene sulfonate 2%, xanthan 0.2% of rubber, 3.8% of magnesium aluminum silicate, 2% of urea, 3% of ethylene glycol, water is added to 100%, and it is put into a sand mill for 60 minutes and then filtered to obtain 10% bis(2-mercaptobenzoene). Thiazole) Zinc suspension.

Example 2:

Bis(2-mercaptobenzothiazole) zinc 40%, acrylic acid homopolymer sodium salt 3%, lignosulfonate 2%, nonylphenol polyoxyethylene ether phosphate 5%, sodium decyl naphthalene sulfonate 6%, propylene glycol 2%, polyethoxy nonylphenol 2%, water added to 100%, put into the sander for sanding, after three-stage series sanding and filtration, 40% bis(2-mercaptobenzene) And thiazole) zinc suspension.

Example 3:

Bis(2-mercaptobenzothiazole) zinc 60%, nonylphenol ethoxylate carboxylate 3%, polycondensation naphthalene sulfonate 4%, tallow ethoxylated amine 3%, carboxymethyl cellulose 2%, glycerol 1%, polyether modified polysiloxane oxime 1%, water added to 100%, put into sanding machine for sanding, after 5 times of circulating sanding, filter to get 60% double (2 - mercaptobenzothiazole) zinc suspension.

Example 4:

Bis(2-mercaptobenzothiazole) zinc 20%, acrylic acid homopolymer sodium salt 2%, nonylphenol polyoxyethylene ether carboxylate 6%, fatty alcohol polyoxyethylene ether 4%, alginic acid 2%, 1% xanthan gum, 1% silicone, 100% water, and put into a sand mill, filtered through a two-stage series sanding to obtain a 20% bis(2-mercaptobenzothiazole) zinc suspending agent.

Soybean oil 20%, turpentine 10%, methyl oleate 10%, calcium dodecylbenzenesulfonate 6%, polyoxyethylene ether sorbitan fatty acid ester 4%, propylene glycol polyoxyethylene polyoxypropylene ether 6% of the block copolymer and 4% of glycerin were placed in a stirred tank and stirred for 20 minutes to obtain an oil.

20% bis(2-mercaptobenzothiazole) zinc suspending agent and oil are put into high speed at a mass of 1:1 In a shear emulsifier, 10% bis(2-mercaptobenzothiazole) zinc suspoemulsion was obtained by homogenization for 30 minutes by high-speed shearing.

Example 5:

Bis(2-mercaptobenzothiazole) zinc 60%, polyoxyethylene polyoxypropylene ether block copolymer 8%, nonylphenol ethoxylate phosphate 4%, polyvinyl alcohol 1%, aluminum silicate Magnesium 2%, water is added to 100%, put into a sand mill for sanding, followed by three-stage series sanding and filtration to obtain 60% bis(2-mercaptobenzothiazole) zinc suspension.

30% cottonseed oil, 5% potassium fatty acid phosphate ester, 5% fatty alcohol polyoxyethylene ether, 6% propylene glycol, water 100%, put into high-speed shear emulsifier, after high-speed shear for 50 minutes Get 30% cottonseed oil emulsion.

Mixing 60% bis(2-mercaptobenzothiazole) zinc suspending agent with 30% cottonseed oil water emulsion in a ratio of 1:1 by mass ratio, and homogenizing for 30 minutes by high-speed shearing to obtain 30% bis(2-fluorenyl) Benzothiazole) zinc suspoemulsion.

Example 6:

Bis(2-mercaptobenzothiazole) zinc 60%, rapeseed oil 5%, decyl naphthalene sulfonate 4%, sodium octenyl succinate 2%, lignosulfonate 2%, dibutyl Sodium naphthalene sulfonate 2.5%, sodium decyl naphthalene sulfonate 1.5%, nonylphenol ethoxylate ether phosphate 1%, nonylphenol ethoxylate 2%, polyoxypropylene polyoxyethylene glyceryl ether 1.0%, Water is added to 100%, put into sanding machine for sanding, filtered by three-stage series sanding, and then homogenized by high-speed shear for 30 minutes to obtain 60% bis(2-mercaptobenzothiazole) zinc suspoemulsion. .

Example 7:

Bis(2-mercaptobenzothiazole) zinc 10%, fatty alcohol polyoxyethylene ether carboxylate 4%, tallow ethoxylated amine 2%, dibutylnaphthalene sulfonate 5%, carboxymethyl starch Sodium 10%, bentonite 20%, diatomaceous earth is added to 97%, stirred in a blender and then pulverized by air flow to obtain bis(2-mercaptobenzothiazole) zinc mother powder; gum arabic 1%, polyethylene 2% alcohol is dissolved in water to prepare a flowable aqueous solution; the aqueous solution is sprayed into the mother powder in a state of stirring the mother powder, and mixed into a wet material, wherein the water content is 20-40% by weight of the dry matter; After extrusion granulation, drying, and granulation, 10% bis(2-mercaptobenzoene) is obtained. Thiazole) Zinc water dispersible granules.

Example 8:

Bis(2-mercaptobenzothiazole) zinc 50%, maleic acid-acrylic acid copolymer sodium salt 6%, decyl naphthalene sulfonate 2%, lignosulfonate 4%, tallow ethoxylated amine salt 1%, sodium dibutyl naphthalenesulfonate 1%, sodium lauryl sulfate 1%, sodium carboxymethyl starch 5%, starch 5%, attapulgite 10%, white carbon black added to 100%, into a blender After stirring evenly, it is pulverized by air flow to obtain bis(2-mercaptobenzothiazole) zinc mother powder; while stirring the mother powder, deionized water spray is added to the mother powder, and mixed into a wet material, wherein the water content is dry. 20-40% by weight of the material; the wet material is subjected to extrusion granulation, drying, and granulation to obtain 50% bis(2-mercaptobenzothiazole) zinc water dispersible granule.

Example 9:

Bis(2-mercaptobenzothiazole) zinc 80%, nonylphenol polyoxyethylene ether carboxylate 2%, polycondensation naphthalenesulfonate 1%, fatty alcohol polyoxyethylene ether sulfonate 2%, mercapto naphthalene Sodium sulfonate 2%, kaolin supplemented to 99%, stirred in a blender and then pulverized by air flow to obtain bis(2-mercaptobenzothiazole) zinc mother powder; carboxymethyl starch sodium 1% with deionized water It is formulated into an aqueous solution and sprayed into the mother powder in a state of stirring the mother powder, and mixed into a wet material, wherein the water content is 20-40% by weight of the dry matter; the wet material is subjected to extrusion granulation, drying, and granulation. , obtained 80% bis(2-mercaptobenzothiazole) zinc water dispersion granules.

Example 10:

Bis(2-mercaptobenzothiazole) zinc 10%, fatty alcohol polyoxyethylene ether carboxylate 7%, lignosulfonate 5%, decylnaphthalene sulfonate sodium salt 2%, white carbon black 20%, The diatomaceous earth was added to 100%, and the mixture was stirred in a mixer and then pulverized by a jet stream to obtain a 10% bis(2-mercaptobenzothiazole) zinc wettable powder. Example 11:

Bis(2-mercaptobenzothiazole) zinc 50%, fatty alcohol polyoxyethylene ether sulfonate 3%, polycondensation naphthalene sulfonate 3%, decyl naphthalene sulfonate 2%, sodium lauryl sulfate 4%, The bentonite is replenished to 100%, stirred in a blender and then pulverized by a jet stream to obtain a 50% bis(2-mercaptobenzothiazole) zinc wettable powder. Example 12:

Bis(2-mercaptobenzothiazole) zinc 80%, maleic acid-acrylic acid copolymer sodium salt 2%, nonylphenol poly 4% oxyethylene ether carboxylate, 2% tallow ethoxyamine salt, 1% sodium dibutylnaphthalene sulfonate, 5% attapulgite, 100% kaolin, and stirred in a blender. The air stream was pulverized to obtain 80% bis(2-mercaptobenzothiazole) zinc wettable powder.

Example 13:

Bis(2-mercaptobenzothiazole) iron 20%, acrylic acid homopolymer sodium salt 1%, lignosulfonate 3%, dibutylnaphthalenesulfonate sodium 1%, decylnaphthalenesulfonic acid sodium salt 1% , 3% glycerol, deionized water to 100%, put into a stirred tank and mix well, then pump into the sand mill, after three-stage series sanding, 20% bis(2-mercaptobenzothiazole) Iron suspending agent. Example 14: Tris(2-mercaptobenzothiazole) Iron 20%, Nonylphenol Polyoxyethylene ether carboxylate 2%, Polyoxyethylene polyoxypropylene ether block copolymer 4%, Tau fat ethoxylated amine 1% salt, 1% magnesium aluminum silicate, 0.3% xanthan gum, 3% ethylene glycol, 100% water, 100% tris(2-mercaptobenzothiazole) iron after three-stage series sanding Suspending agent

Example 15:

Bis(2-mercaptobenzothiazole) tin 20%, nonylphenol ethoxylate carboxylate 2%, sodium octenyl succinate 5%, xanthan gum 0.3%, deionized water to 100% The mixture is put into a stirred tank and mixed uniformly, and then pumped into a sand mill for 8 times to obtain a 20% bis(2-mercaptobenzothiazole) tin suspending agent. Example 16: Tetrakis(2-mercaptobenzothiazole) Tin SC 20%, decylnaphthalene sulfonate 3%, lignosulfonate 2%, dioctyl sulfosuccinate 2%, cellulose starch sodium 4%, propylene glycol 3%, water added to 100%, after three-stage series sanding, 20% tetrakis(2-mercaptobenzothiazole) tin SC suspending agent

Example 17:

Bis(2-mercaptobenzothiazole) manganese 20%, acrylic acid homopolymer sodium salt 4%, nonylphenol polyoxyethylene ether carboxylate 3%, tallow ethoxylated amine salt 2%, deionized water added to 100%, put into the stirred tank and mix well, then pump it into the sander for 80min, filter and then homogenize with high shear emulsifier for 20min. 20% bis(2-mercaptobenzothiazole) manganese suspension.

Example 18:

Tris(2-mercaptobenzothiazole) aluminum 10%, nonylphenol ethoxylate carboxylate 3%, nonylphenol ethoxylate carboxylate 2%, tallow ethoxylated amine 1%, silicon Magnesium aluminum magnesium 4%, ethylene glycol 5%, water to 100%, after three-stage series sanding to obtain 10% tris(2-mercaptobenzothiazole) aluminum suspension.

Claims

claims

1. A fungicide for preventing and treating crop diseases, characterized in that the fungicide contains a 2-mercaptobenzothiazole metal salt represented by the following formula (I) and a pesticide carrier:

Where: M is Zn, Mn, Fe, Sn or Al; n is 2, 3 or 4.

2. The fungicide according to claim 1, wherein the 2-mercaptobenzothiazole metal salt is selected from the group consisting of bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) manganese, bis(2-mercaptobenzothiazole) benzothiazole) iron, bis(2-mercaptobenzothiazole) tin, tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum and tetrakis(2-mercaptobenzothiazole) tin kind of.

3. The fungicide according to claim 1 or 2, which is made into one of a suspension, a suspoemulsion, a water-dispersible granule and a wettable powder, wherein the weight of the 2-mercaptobenzothiazole metal salt accounts for The total weight percentage of fungicide is 0.1-99.9%, preferably 1-90%.

4. The use of a 2-mercaptobenzothiazole metal salt for preventing and treating crop diseases, wherein the 2-mercaptobenzothiazole metal salt is a compound with the structure shown in the following formula (I):

Where: M is Zn, Mn, Fe, Sn or Al; n is 2, 3 or 4.

5. The use according to claim 4, wherein the 2-mercaptobenzothiazole metal salt is selected from bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) manganese, bis(2-mercaptobenzene) of tris(2-mercaptobenzothiazole) iron, bis(2-mercaptobenzothiazole) tin, tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum, and tetrakis(2-mercaptobenzothiazole) tin A sort of.

6. The use according to claim 4 or 5, wherein the crop diseases are bacterial diseases and fungal diseases. Preferably, the crop diseases are rice bacterial blight (Xanthomonas oryzae pv. oryzae), rice bacterial blight Xanthomonas oryzae pv.oryzicola ^†Cucumber canker disease (Xanthomonas axonopodis pv. citri, Xac), Cucumber bacterial angular spot (Pseudomonas syringae) pv.lachrymans ) ^ Watermelon bacterial fruit spot (Acidovorax avenae subsp.citrulli), peach tree bacterial worm disease (Xanthomonas campestris pv. Pruni), tree graft canker (Botryosphaeria dothidea), papaya bacterial wilt (Pseudomanas solanacearum Smith), Chinese cabbage soft rot (Erwinia carotovora) and/or peanut bacterial wilt (Pseudomanas solanacearum Smith).

7. The use according to any one of claims 4 to 6, wherein the crops are cereals such as wheat, barley, rice, sorghum, and corn; fruit trees such as apples, pears, peaches, pecans, citrus, grapes, lychees, and bananas , mango, loquat; vegetables cucumber, watermelon, hanging melon, loofah, melon, spinach, celery, tomato, pepper, eggplant, ginger, onion, garlic, leek, cabbage, Chinese cabbage, sweet potato, strawberry, lettuce, kidney beans, cowpea , broad beans, radish, carrots, potatoes, yams, taro, lotus root, water chestnuts, wild rice; sugar plants such as beets, sugar cane; oil crops such as soybeans, peanuts, rape, sesame, sunflower; or tobacco, tea.

8. The use of a 2-mercaptobenzothiazole metal salt for fighting harmful microorganisms, wherein the 2-mercaptobenzothiazole metal salt is a compound with the structure shown in the following formula (I):

Where: M is Zn, Mn, Fe, Sn and Al; n is 2, 3 or 4.

9. The use according to claim 8, wherein the 2-mercaptobenzothiazole metal salt is selected from bis(2-mercaptobenzothiazole) zinc, bis(2-mercaptobenzothiazole) manganese, bis(2-mercaptobenzene) of tris(2-mercaptobenzothiazole) iron, bis(2-mercaptobenzothiazole) tin, tris(2-mercaptobenzothiazole) iron, tris(2-mercaptobenzothiazole) aluminum, and tetrakis(2-mercaptobenzothiazole) tin A sort of.

10. The use according to claim 8 or 9, wherein the harmful microorganism is _Fusarium _moniliforme , Rhizoctonia solani, Gibberella zeae, Fusarium wilt of cotton Fusarium oxysporum f. sp. vasinfectum), Botrytis cinerea, Alternaria solani, Fulvia fulva, Gloeosporium orbici are), Sclerotinia sclerotiorum, Phytophthora melonis, Alternaria cucumerina, Thanatephorus cucumeris^ Colletotrichum capsici, Alternaria mali, Peronophythora litchii, Pestalotiopsis microspora, Sphaceloma ampelium and/or Colletotrichum ampelinum .