In the use of fungicides, there are many fungicides that are resistant to development, especially single-site fungicides. The long-term use of multi-action site protective fungicides is valuable because no resistance has been produced so far. Among them, the sales have been increasing so far, and the sales have been growing. The brilliant achievements that hinder the invasion of germs and protect plants from harm have made them a model for fungicides...
A protective bactericide is a plant that is applied to the surface of a plant to prevent the invasion of the bacterium before the disease occurs, so that the plant is protected. This kind of protective fungicide has been developed earlier and has the longest use time, so it is called a protective fungicide.
Among them, the protective fungicides such as sulfur, copper preparation, chlorothalonil and mancozeb, which are multi-action sites, are outstanding representatives, and most of them have a long history. For example, sulfur listed in 1882 and copper preparations listed in 1885 have a history of more than 100 years;
The mancozeb, which was launched in 1943 and the chlorothalonil, which was launched in 1963, has been in use for more than half a century. The sales of these 4 most active sites of protective fungicides have been growing, and their brilliant performance has made them a model for fungicides.
The global sales of sulphur, copper, chlorothalonil and mancozeb in 2015 were $185 million, $570 million, $310 million, and $610 million, respectively.
First, the characteristics of protective fungicides
These long-lasting protective fungicides have the following characteristics:
(1) The mechanism of action is to inhibit the respiration of pathogens, prevent energy production, and only protect and prevent germs.
(2) It can degrade or interfere with various protease activities that catalyze the respiratory process of the bacteria, while inhibiting various protease activities, but the selectivity between different organisms is poor.
(3) The inhibitory activity against spore germination of pathogens is significantly higher than that of cell growth and development.
(4) There is no selective and therapeutic activity, and there are multiple biochemical target sites for pathogenic bacteria, which are not easy to produce resistance.
(5) It is generally used before the infection of the bacteria, and it can provide a wide, continuous and stable control effect in the prevention and control of crop diseases. Compared with other new and hot fungicides, it is not the best, but it can always play a key role when needed. effect.
(6) Combination with a single site or selective fungicide in an appropriate ratio can delay or reduce the risk of resistance caused by these fungicides, with low cost and stable control effect.
Second, the application of protective fungicides in resistance management
In the use of fungicides, there are many fungicides that are resistant to resistance, especially single-site fungicides. In any case, resistance is inevitable, which is an adaptation between the agent and the target, and also a pest. An inevitable physiological phenomenon that protects its own existence in the future. The so-called fungicide resistance is due to the fact that the fungicide has anti-disease activity, and the activity of the fungicide shows a decrease or loss due to the genetic variation of the target pathogen, thereby causing a drastic reduction in the control effect of crop diseases, causing huge damage to agricultural production. Losses can even make some fungicides useless.
Although the multi-acting site protective fungicide has been used for a long time, it has not been produced so far, which is very valuable.
Therefore, they have become many popular products such as methoxy acrylates (such as pyraclostrobin, azoxystrobin, oxystrobin, trifloxystrobin, etc.), benzamides (metalaxyl / fine metalaxyl) Mainly the main types of triazoles (teproconazole, difenoconazole, hexaconazole, propiconazole, epoxiconazole, etc.), morpholine (enoylmorpholine), and other classes (creaming cyanide) Compound varieties are available at a lower cost.
Without the help of these multi-site protective biocides, the use of single-site biocides and currently appearing popular biocide products will be severely affected, and some varieties will even exit the market early.
For example, the sulphonic acid cyanide product developed by DuPont is mainly used to control the diseases caused by downy mildew and Phytophthora. It is widely used in various mixtures and has a stable market for controlling grape downy mildew and potato late blight. (2005 sales of $110 million, 2009: $145 million, 2014: $150 million), but its duration of action is very short, such as no long-lasting effect of mancozeb and stable efficacy Help each other, sulphonic acid cyanide itself can not exist independently.
In addition, BASF's pyrifluzil product listed in China, Baitai (60% azole ether·Dyson United WG), is a compound product of pyriazine and a protective site disinfectant. .
Because Daisenlian is a broad-spectrum, protective, low-toxic fungicide, it is not easy to produce resistance, and its control effect is superior to similar fungicides. It plays a major role in protecting plant growth and has been a large tonnage product in the world.
These two fungicides are combined to form a safe, solvent-free, dust-free, packaging and easy-to-use water-dispersible granule product. Because of its extensive bactericidal spectrum, it can be used to control at least 49 diseases on more than 100 crops. It includes diseases caused by ascomycetes, basidiomycetes, oomycetes, and deuteromycetes, and has a strong protective and therapeutic effect. It can improve the physiological activity of crops and is favored by users in the global market.
In 2015, Baitai's sales exceeded US$400 million, and its sales volume was approximately 1,800 tons, far exceeding the company's in-situ Kairun (250g/L pyraclostrobin EC, with sales of approximately US$300 million, sales volume) Nearly 400 tons) has become the new champion in the list of BASF products.
Another example is BASF, a new product focused on anthrax in China, which was launched in China in 2016. The active ingredient of this product is 4% pyraclostrobin + 12% dicyandiamide, and the registered targets are apple and jujube anthracnose. And is ready to expand to the prevention and control of pepper and citrus anthracnose.
Due to the multi-site protective fungicide dicyandiquinone, the new product, Bicui, has multiple mechanisms of action, which can react with sulfur-containing groups and interfere with mitochondrial cell respiration to inhibit the formation of fungal enzymes and hinder the spore germination and invasion.
The technical characteristics of the product are as follows: Firstly, because the combination of the two components can expand the sterilization spectrum, it is an excellent means of resistance management; secondly, it has excellent protective activity and makes the fruit have better quality; again, it has a strong It is resistant to rain and has a long-lasting and reliable effect. This is also a more outstanding advantage than similar fungicide products. Therefore, BASF's product positioning for Bi Cui is to build it into the “Bai Tai†in the fruit market.
Third, sulfur
In addition to bactericidal action, sulphur can kill and kill insects, and it can be used to control powdery mildew and leaf mites of various crops. The duration of action can be up to 2 weeks. In addition, sulfur can also be used to regulate the pH of the soil. For example, blueberries are suitable for growing in acidic soils. The pH of the soil is required to be between 4.5 and 5.5. As the popularity of blueberries increases, more and more growers are rapidly improving. Soil pH is of great interest.
The lowest cost of lowering the pH of the soil is to add elemental sulfur to the soil and reduce the pH of the soil by converting the sulfur into sulfuric acid through soil bacteria. It can be seen that sulfur is still a multifunctional agent that people like to use.
Sulphur sales in the world are increasing year by year, from $155 million in 2003 to $145 million in 2005, $150 million in 2007, $120 million in 2009, $180 million in 2014, and 1.85 in 2015. One hundred million U.S. dollars.
The use of sulphur in grapes is also obvious to all. For example, global sales of grape germicides in 2013 were 1.117 billion US dollars, of which 851 million in Europe, accounting for 76.2%; Asia was 106 million, accounting for 9.5%; the rest are on other continents. The second species of grape fungicides is sulfur (the first is copper), while Italy is the country with the most sulfur.
1. Principle and advantages of sulfur sterilization
The bactericidal principle of sulfur is that the sprayed agent contacts the air, and is decomposed by water, oxygen and carbon dioxide to form elemental sulfur to play a bactericidal action, and can also be reduced to form a more toxic hydrogen sulfide to sterilize. Sulfur is mainly effective against powdery mildew and rust, but not against downy mildew.
Characteristics of sulfur preparations: (1) not only has bactericidal effect, but also has anti-clay and insecticidal effects; (2) sterilization and insecticidal effects are closely related to the particle size of the preparation products; (3) powdery mildew can be prevented by spraying, Rust, while killing insects and killing.
2. Sulfur registration products
Recently, Shouguang Xinlong Bio-engineering Co., Ltd. has obtained the registration of 80% sulphur wettable powder products. It is also the first time that China has approved the registration of sulphur on cherries.
Previously, sulfur registered crops and control objects in the country were tomato blight, rickets, pepper virus disease, anthracnose, green pepper anthracnose, eggplant gray mold, cowpea rust, asparagus stem blight, cucumber powdery mildew, blight, Cantalouid powdery mildew, apple tree powdery mildew, anthracnose, ring rot, citrus tree scab, red spider, peach tree brown spot, mango powdery mildew, rice blast, sheath blight, stripe leaf blight, wheat powdery mildew , scab, mites, mites, peanut leaf spot, beet brown spot, rust spider, rubber tree powdery mildew, anthracnose and flower powdery mildew. Up to now, there have been 310 domestically approved products registered within the validity period, including 5 original drugs and 305 preparations.
Sulfur single-agent products mainly include: 91% sulfur powder, 80% sulfur wettable powder, 80% sulfur water dispersible granules, 45% and 50% sulfur suspending agent, etc., while South American Chilean Komita Industry Company is currently registered in China. 80% sulfur dry suspension.
There are many sulfur compound products, such as sulfur, tricyclazole, sulfur, carbendazim, dofu sulfur, sulfur methotrexate, sulfur triazole copper, sulfur triazole tin, fu·a·sulfur, Sulfur, sodium sulfonate, sulfur, thiram, etc. Commonly used are 70% thiophanate-sulfur WP, 10% chlorothalonil sulphur powder, 70% sulphur-manganese-zinc wettable powder, 50% sulphur-triazole copper suspension.
Fourth, copper preparations
Copper preparation is a kind of broad-spectrum and low-toxic fungicide which can prevent and cure fungal diseases and can control bacterial diseases. A few varieties can also weed and kill pests of larvae or mollusks.
In addition, copper preparations can also be used for preservation and preservation of certain fruits during storage, and thus are widely used worldwide. It has a special control effect on melon and fruit economic crop diseases caused by fungi, and it is not easy to produce resistance in long-term use.
For example, in 2013, the first variety of global grape fungicides was copper (secondarily sulfur, ethyl phosphine aluminum, mancozeb and captan), and France was the first country for grape copper.
In 2013, global sales of fungicides for pear fruit were US$619 million. Among them, Europe was US$301 million, accounting for 48.6%; Asia was US$203 million, accounting for 32.8%; the rest were on other continents. The second variety of fungicides for pear fruit is copper (the first one is captan), and Japan is the country with the first copper for pear fruit.
Because the copper preparation fungicide has the characteristics of low toxicity, pollution-free and environmental protection, it has become the first choice of excellent fungicide for producing green food, organic fruit and pollution-free food.
1. Variety of copper preparations
Copper preparations are used in agriculture. The earliest developed inorganic copper compounds are: copper sulfate (used to prepare the main components of Bordeaux liquid), basic copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide, copper amide , copper oxide, sterilized copper (copper sulfate, bismuth sulfate, double salt). At present, due to copper as a heavy metal, some copper preparation fungicides have been withdrawn from the market in consideration of environmental issues.
At the same time, many organic copper fungicides have been developed. The main varieties are copper acetate, copper rosinate, copper thiabium, copper sputum, copper quinolate, copper rosinate, copper humate, copper amber, copper, and bacteria. Copper, 8-hydroxyquinoline copper and domestically developed thidium copper.
The sales of copper preparation products are mainly based on inorganic copper preparations, and the sales of organic copper preparations are still very low. This can be confirmed by the following data. Global sales of inorganic copper preparations were US$165 million in 2003, US$230 million in 2005, US$305 million in 2007, US$385 million in 2009, US$485 million in 2011 and US$535 million in 2012.
Global sales of organic copper preparations were US$13 million in 2003, US$0.1 billion in 2005, US$15 million in 2007, US$0.30 million in 2009, and US$0.30 million in 2011. <0.35 billion US dollars.
2. Advantages and disadvantages of copper preparations
Advantages: (1) Wide spectrum of sterilization, strong adhesion, rapid formation of film, rain-resistant, long-lasting effect; (2) can prevent the invasion of bacteria for a long time, so the effect on bacteria and fungi is better Good; (3) 200 years of use without resistance, which is conducive to organic agriculture management; (4) Convenient source, low price, low cost of use, and high cost performance.
Disadvantages: poor mixability and poor security.
However, inorganic copper preparations and organic copper preparations each have their own different characteristics and sterilization methods. Therefore, when ensuring the eradication of diseases, crop safety must also be considered, so they should play their roles according to their respective advantages.
3. Market for copper preparations
Although copper preparation is a long-established fungicide, it can still exert a good bactericidal effect after using it for a hundred years, so it still maintains a large market share.
Due to the copper resources and copper itself is a heavy metal, there is little chance of developing a new copper-containing fungicide. Current measures to develop such copper formulations are:
(1) Expand the application range of the original copper preparations, especially for the prevention and control of crops and the detection of newly discovered crop diseases. For example, apple ring disease has always been a difficult disease on apples, which is difficult to control. Zhejiang Haizheng Chemical Co., Ltd. is one of the manufacturers of quinoline copper, which expands quinoline copper to a variety of crop applications.
Tests show that the use of 33.5% quinoline copper SC is better than that of mancozeb in the prevention and control of apple ring disease. It is expected to solve the problem of long-term troubled apple ring disease prevention and treatment.
For example, 36% quinoline copper and tebuconazole SC can effectively control citrus black spot disease, and the effect is similar to that of mancozeb. Similarly, 36% quinoline copper and tebuconazole SC can effectively control citrus ulcers. Disease, control effect is better than copper hydroxide.
(2) Expanding its application in non-agriculture, such as copper oxyquinolate, which is not only used in agriculture, but also in applications such as papermaking, wood preservation, coatings, textiles, etc. The market for copper preparations.
Global sales of copper preparations have been rising, from $165 million in 2003 to $230 million in 2005, $385 million in 2009, $595 million in 2014, and $560 million in 2016, making it a global sales platoon. The bactericide at the 7th position (the first 6 positions are azoxystrobin, prothioconazole, pyraclostrobin, mancozeb, trifloxystrobin, tebuconazole). This is mainly due to the multi-site mechanism of action of this type of preparation, long-term use is not easy to produce resistance, and it is stable development, becoming a large variety in the field of fungicides.
Five, chlorothalonil
Chlorothalonil is a substituted benzene fungicide (produced and sold by Syngenta), which was discovered by Diamond Alkali Corporatron in the United States in 1962 and developed and marketed in 1963. In the 1970s, two sets of 3000t/a production facilities were established, so chlorothalonil is also an old variety with more than 50 years.
Later, the United States, Italy, Japan and South Korea have chlorothalonil production. In China, the Yunnan Institute of Chemical Industry first started researching chlorothalonil in the early 1980s. In 1984, through the technical appraisal and basic design review conducted by the former Ministry of Chemical Industry, in 1989, 100t/a production of chlorothalonil was established. The drug (96%) pilot plant has since started the production and sales of chlorothalonil in China.
1. Mechanism and application of chlorothalonil
The mechanism of action of chlorothalonil and the current three major fungicides (triazoles, methoxy acrylates and SDHIs) is different, and its mechanism of action is to interact with glyceraldehyde triphosphate dehydrogenase in fungal cells. Combined with the cysteine-containing protein in the enzyme, the activity of the enzyme is destroyed, and the metabolism of the fungus is destroyed and the vitality is lost.
Although chlorothalonil has no systemic conduction after spraying on the foliage of the crop, it has good adhesion on the surface of the crop and is not easily washed away by rain. Therefore, its long-lasting effect is long.
Chlorothalon is mainly used in economic crops such as fruits, vegetables, potatoes, tobacco, etc., and secondly for large crops such as wheat, soybeans, rice and other cereals and dryland crops to control rust, anthracnose, powdery mildew, downy mildew, leaf spot Many diseases such as diseases and diseases. It has a special control effect on melon and fruit economic crop diseases caused by fungi, and thus has been widely used in the world. In addition, chlorothalonil is also used as an antifungal agent for leather, electrical appliances, paints, paper and fabrics.
2. chlorothalonil market
Chlorothalonil is a broad-spectrum, low-residue, contact-killing, low-toxic multi-site protective fungicide. It is not as resistant to other therapeutic fungicides. Its market is relatively stable and will not be too Big fluctuations. The production capacity of chlorothalonil has already met the market demand as early as 2011. In 2011, the global demand was about 20,000 tons, and the capacity at that time had exceeded 30,000 tons, of which Syngenta had a capacity of 9,000 tons.
Domestic enterprises have reached 25,000 tons of production capacity at this time, and the domestic market demand is about 3,000 tons of preparations (equivalent to 2,000 tons of original drugs). Therefore, the price competition in the domestic chlorothalonil market is fierce, and domestic enterprises mainly rely on exports to release. In 2011, the annual export volume was about 13,500 tons.
The global sales of chlorothalonil was US$205 million in 2005, US$295 million in 2009, US$310 million in 2011, US$325 million in 2014, and US$333 million in 2016, showing year-on-year growth. Its high-end market is mainly distributed in the United States, Japan, France and Brazil, accounting for more than half of the entire market. For example, global potato sales in 2013 were 1.658 billion US dollars, and Europe's largest was 364 million US dollars, accounting for 42.3%.
In recent years, the importance of chlorothalonil in the prevention and treatment has been increasing due to the development of resistance to triazoles, methoxy acrylates and SDHIs and some oomycetes. At present, some of the most important resistance management, such as European wheat powdery mildew, barley leaf spot, and Brazilian soybean rust, require the use of chlorothalonil fungicide in addition to mancozeb.
For example, in 2015, Fame-CR (Fluorostrobin + chlorothalonil) products, which are listed on the company, have a broader spectrum of control and can control more than 30 diseases including anthracnose and brown spot. On May 16, 2017, Alice Star Life Science Co., Ltd. launched 51% fluoropyrimidine chlorothalonil SC in China. The trade name is “Yiweiå“šâ€, which is expected to become a new hot product in China.
3. chlorothalonil dosage form
At present, chlorothalonil domestically registered products, single agent powder (5%), wet powder (50%, 60%, 75% chlorothalonil WP), smoke agent (10%, 20%, 45% for greenhouse treatment) And greenhouse downy mildew) and suspending agents (40%, 54% chlorothalonil SC, 720g/L chlorothalonil SC, 18% chlorothalonil, cymoxanil SC). The compounded product is at most a suspending agent, followed by a wet powder and a smoke agent.
The compound with chlorothalonil is procymidone, metalaxyl (fine metal cream), thiram, azoxystrobin, tebuconazole, mancozeb, sulfur, aluminum triethylphosphonate, cymoxanil, Dimethomorph, pyrimethanil, iprodione, fluoxastrobin and fluopyram.
Six, mancozeb
Mancozeb is the most important variety of dithiocarbamate fungicides. Since it entered the market in 1943, it has been able to effectively control more than 400 diseases of nearly 90 crops due to its extensive germicidal spectrum. good effect. Mancozeb is extremely cost-effective and has been used in the global market for more than 50 years without resistance. It is still a hot spot in the global market.
Mancozeb can be used to control stem rot in rice, grape downy mildew, black rot, potato to control black shank, early blight, potato late blight; also used for fruit, vegetable, plantation crops and pear fruit A variety of diseases. The general application method is foliar application to protect crop stems and leaves from Phytophthora, downy mildew, leaf mold, rice bran, rust and other infections; it can also be used for soil disinfection and control of soil fax bacteria and arthropods.
It has long been favored by users all over the world due to its extensive bactericidal spectrum, multiple sites of action, resistance to chemicals, the ability to supplement trace elements (zinc and manganese) required for crops, and improved crop quality.
1. Mancozeb sterilization mechanism and biological activity
Mancozeb has been the world's largest tonnage product. Mancozeb is mainly sterilized by metal ions. Its sterilization mechanism is to inhibit the oxidation of bacterial pyruvate during the metabolism of bacteria, and participate in the sulfhydryl group in the oxidation of pyruvate. (-SH) combines to inhibit the growth of pathogens.
There are multiple action sites in the inhibition process, which makes the resistance risk in the application low, and the bacteria are extremely difficult to produce drug resistance; and can be continuously used, the control effect is obviously superior to other similar fungicides, and the manganese deficiency of the fruit trees, Zinc deficiency symptoms have a therapeutic effect.
The protective effect of mancozeb is mainly to provide Zn to plants. In addition to solving the symptoms of zinc deficiency in plants, it can also enhance the ability of plants to resist disease. After application, a protective film layer is formed on the surface of the plant to inhibit the germination and invasion of the spores of the pathogen, inhibit the spread of the pathogen, and have a protective and therapeutic effect on diseases caused by various fungi.
Whether it is a single agent of mancozeb or a compounding agent, it has good biological activity, and the use effect is remarkable, and it is not easy to produce resistance. Therefore, mancozeb is a low-risk, excellent protection for youthfulness. Sex fungicide varieties.
2. Mancozeb market
Mancozeb is a multi-action site bactericide, so it is often used with a variety of other fungicides, such as dimethomorph, thiophanate-methyl, metalaxyl, cymoxanil, propofol, benzene. Compounds such as sedative, benzilamide, aluminum triethylphosphinate, imidacloprid, chlorothalonil, oxacillin, and some of the agents for controlling oomycetes are used in combination.
In particular, it is used in crops such as fruits and vegetables to avoid disease resistance, which is one reason for the higher global sales of mancozeb. For example, the global market for fungicides for potatoes has grown from US$632 million in 2007, US$688 million in 2009, US$774 million in 2011, and US$861 million in 2013, an annual increase of 25.93%. It is expected that by 2018, the global market for fungicides for potatoes will reach $10.2 billion.
Europe is the largest market for fungicides for potatoes, accounting for 42.3% of fungicides, followed by South America, North America, Asia, Africa and Central Asia. In 2013, the world's top sales of fungicides for potato use was mancozeb, and Brazil was the first country to use sales of mancozeb.
The global market sales of mancozeb was USD 290 million in 2003, USD 365 million in 2005, USD 40 million in 2007, USD 550 million in 2009, USD 570 million in 2010, USD 630 million in 2012 and 5.90 in 2014. In the year of 2015, it was US$610 million, and in 2016 it reached US$665 million. It is now the fourth largest biocide in the world (the first three are azoxystrobin, prothioconazole, pyraclostrobin).
3. Mancozeb dosage form
Domestically registered mancozeb-type products are mainly wettable powders (more than 90% of all dosage forms), and the rest are suspensions and water-dispersible granules. There are also many compound products of mancozeb. The registered products include nail cream, manganese zinc, carbendazim, manganese zinc, enoyl manganese zinc, aluminum aluminum, manganese zinc, frost urea, manganese zinc, and frost. ·Manganese zinc, sulfur, manganese zinc, methyl sulfide, manganese zinc, benzate, manganese zinc, poly·fu·manganese zinc, fine nail cream, manganese zinc, manganese zinc, nitrile, manganese zinc, diniconazole, manganese Zinc·flumorpholine and other varieties.
The operation of mancozeb suspension in China has been carried out earlier, and many companies such as Hebei Shuangji, Jiangsu Limin, Xi'an Modern, Jiangsu Baoling, Shanxi Yuncheng Lvkang have registered 30% mancozeb suspension products. . The US Dow AgroSciences and Guangdong Deli Company registered as 430g/L Mancozeb SC products, while the US Xiannong Company and Guangdong Jinnongda Company registered 420g/L Mancozeb SC products.
Conclusion
In the use of fungicides, there are many fungicides that are resistant to resistance, especially single-site fungicides. In any case, prevention is inevitable, and it is also an inevitable behavior and physiological phenomenon of pest protection.
The bactericide resistance is caused by the bactericidal agent which has anti-disease activity, and the bactericidal activity shows a decrease or loss due to the genetic variation of the target pathogen, thereby causing a drastic reduction in the control effect of the crop disease, causing huge damage to agricultural production. Losses can even make some fungicides useless.
However, the long-term use of multi-site protective fungicides is valuable because no resistance has been produced so far. Among them, the protective fungicides such as sulfur, copper preparation, chlorothalonil and mancozeb, which are multi-action sites, are outstanding representatives, and most of them have a long history (sulphur and copper preparations have a history of more than 100 years, and Daisen Manganese zinc and chlorothalonil have been used for more than half a century.
The sales of these four most active sites of protective fungicides have been increasing to date, and they have hindered the invasion of germs and protected plants from their harmful achievements. They have become the model for the young fungicides. (Magazine pesticide market information Author: China is the shock)
This article URL: What is a protective fungicide? What kinds of characteristics and effect characteristics
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