The present patent application is Application No. 2013106143470, filing date on November 26th, 2013, invention entitled
The divisional application of " tetramycin complex and application ".
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail, content mentioned in embodiment
Not limitation of the invention, material prescription select can suit measures to local conditions and on result without substantial impact.In these embodiments
In, unless otherwise indicated, all percentages are all weight percentage.
Tetramycin includes with the compound of amides compound: tetramycin and active material;Described active material is acid amides
Class, described amide-type includes one or more of: benzamides, dicarboximide class, benzamide type, strobilurins, N-halogen
For methyl mercapto-dicarboximide class, dimethomorph.
The embodiment of the present invention additionally provides the application of a kind of tetramycin and the compound of amides compound, plants for preventing and treating
Thing disease, insect pest and weeds, and/or for preventing and treating fungi in timber, paper, leather, fiber, composite, bacterium, worm
Evil.
Biological pesticide tetramycin is a kind of high-effective broad-spectrum fungicide, to the various plants on the crops such as cereal, fruit tree, vegetables
Disease is respectively provided with protection and therapeutic activity, especially to gray mold crops such as () tomato, cucumber, capsicums, powdery mildew (wheat class, melon,
Fruit tree etc.), the fungal disease such as scab (apple, pears etc.) there is good prevention effect.But this series bactericidal agent action site list
One, germ easily produces adaptive variation to medicament, makes the preventive effect of medicament reduce.Can rise after tetramycin is compounding with active material
To synergistic function, reduction refractory fungal bacterial strain in combination by the active material that will have the different mechanism of action selects
Property danger, extend active component service life, add the fungicidal spectrum of single component, expand prevention and treatment range;Improve
Protection effect;Can delay or overcome the resistance to the action of a drug of germ;Not only save cost but also reduce the application times of agricultural chemicals, actively rung
Country should advocate green and environment-friendly pesticide.
It follows that the present invention will describe this tetramycin complex, and tetramycin in detail by some specific embodiments
The concrete applicable cases of compound:
Tetramycin and the compound of amides compound, including: tetramycin and active material;
Described active material is amide-type, and described amide-type includes one or more of: benzamides, dicarboximide
Class, benzamide type, strobilurins, N-halogenmethylthio-dicarboximide class.
In certain embodiments, when active material includes benzamides, benzamides includes one or more of: benzene
Frost spirit, metalaxyl, R-metalaxyl, Wakil, chlorine worm benzamide;
In certain embodiments, when active material includes dicarboximide class, dicarboximide class includes following one
Or multiple: chlozolinate, sclex, isopropyl are fixed, myclozolin, procymidone, vinclozolin;
In certain embodiments, when active material includes benzamide type, benzamide type includes one or more of: wither
Rust spirit, first furan anilide, flutolanil, mebenil, oxycarboxin or thifluzamide, alachlor, Acetochlor, pretilachlor;
In certain embodiments, when active material includes strobilurins, strobilurins includes one or more of: nitrile
Fluoxastrobin, imines bacterium, fork amine benzamide, pyraclostrobin, ZEN 90160,2 [(2-trifluoromethyl)-pyridine-6-Ji Yangjijia
Base]-3-methoxy group-methyl acrylate, Lonster, Flumiclorac pentyl, trifloxystrobin;
In certain embodiments, when active material includes N-halogenmethylthio-dicarboximide class, N-halo first sulphur
Base-dicarboximide class includes one or more of: difoltan, captan, Euparen, fluoromide, folpet or first
Dichlofluanid;
In certain embodiments, active material is dimethomorph.
Wherein tetramycin mass concentration in the tetramycin compound with amides compound can be in 0.15-99%
Arbitrarily adjust, according to compound and the type of desirable effect, reach preferable by adjusting mass concentration (or the concentration that weighs)
Equilibrium toxicity and residual.
The rate of application of inventive mixture is 0.6-400 gram/ha.
Such as: in certain embodiments, the mass concentration of tetramycin is 0.15%, and concentration is relatively low.
In certain embodiments, the mass concentration of tetramycin is 15%, or 35%, or 50%, or 70%.
In certain embodiments, the mass concentration of tetramycin is 99%, and concentration is higher, at tetramycin and amides compound
Compound in play Main Function.
The finished product of the compound of this tetramycin and amides compound can make one or more in various forms, than
As: aqua, dispersible agent, missible oil, microemulsion, emulsion, suspension, gel formulation, ultra-low volume solvent (ULV).Make
Various forms is become to facilitate the storage of compound, transport and the subsequent use of tetramycin and amides compound.
Such as:
A) aqua
10 weight portions are compounded mixture be dissolved in 90 weight parts waters or water-soluble solvent.Or, add wetting agent or its
Its auxiliary agent, compounding mixture dissolves through water dilution, obtains the compound quality hundred of tetramycin and amides compound in this way
Proportion by subtraction content is the aqua of 10%.
B) dispersible agent
20 weight portions compound mixture be dissolved in 70 weight portion cyclohexanone, and add 10 parts per weight dispersing agent such as polyethylene
Base pyrrolidones, dilute with water obtains dispersion, obtains the compound quality hundred of tetramycin and amides compound in this way
Proportion by subtraction content is the dispersible agent of 20%.
C) missible oil
15 weight portions are compounded mixture and is dissolved in 75 parts by weight of xylene and adds calcium dodecyl benzene sulfonate and castor-oil plant
Oil ethoxylate (being 5 weight portions in each case), dilute with water obtains emulsion, obtains tetramycin and acid amides in this way
The missible oil that compound mass percentage content is 15% of compounds.
D) microemulsion
10 weight portions compound mixture be dissolved in 20 weight portion cyclohexanones and add calcium dodecyl benzene sulfonate (at every kind
In the case of be 20 weight portions), dilute with water obtains microemulsion, obtains the compound of tetramycin and amides compound in this way
Mass percentage content is the microemulsion of 5%.
E) emulsion
25 weight portions are compounded mixture and is dissolved in 35 parts by weight of xylene and adds calcium dodecyl benzene sulfonate and castor-oil plant
Oil ethoxylate (being 5 weight portions in each case).By emulsifying agent (Ultraturrax), this mixture is introduced 30 weights
Measure in part water and make equal phase emulsion.Dilute with water obtains emulsion, obtains answering of tetramycin and amides compound in this way
Join the emulsion that thing mass percentage content is 25%.
F) suspension
In the ball mill of stirring, 20 weight portions are compounded mixture and pulverizes and add 10 parts per weight dispersing agent and wetting agent
And 70 weight parts water or organic solvent, obtaining reactive compound suspension in small, broken bits, dilute with water obtains stable active ingredient
Thing suspension, obtains the suspension that compound mass percentage content is 20% of tetramycin and amides compound in this way
Liquid.
G) gel formulation
In ball mill, 20 weight portions are compounded mixture, 10 parts per weight dispersing agent, 1 weight portion gelling agent and 70 weight portions
Water or organic solvent grind and obtain delicate suspensions, and dilute with water is obtained tetramycin and amides compound in this way
Compound mass percentage content is the stabilized with mixture suspension of 20%.
H) ultra-low volume solvent
10 weight portions are compounded mixture be dissolved in 90 weight parts organic solvent such as dimethylbenzene, obtain the compounding mixing of tetramycin
Thing mass percentage content is the product used without dilution of 10%.
This tetramycin can be used for the mode controlling disease similar to other preparations, insect pest to the compound of amides compound
And weeds etc..Simultaneously compared with unitary agent, can preferably controlling disease, insect pest and weeds, play the effect of Synergistic.
Both the compound that can use tetramycin and amides compound also can use tetramycin and active material successively.
This tetramycin, with the application of the compound of amides compound, may be used for for controlling plant diseases, insect pest
And weeds, it is also used for the fungi in preventing and treating timber, paper, leather, fiber, composite, bacterium, insect pest.
This tetramycin and the compound of amides compound can as prevent and treat the plant in different seasons and plant part (fruit,
Flower, leaf, stem, stem tuber, root) on disease, insect pest, weeds, also protection plant late growing stage part encroach on from germ and for planting
Thing provides growth required energy.
The tetramycin of present invention protection generally includes with the application target crop of the compound of amides compound but does not limits
In following plants kind: cereal (wheat, barley, rye, oat, paddy rice, corn, Chinese sorghum and relevant species);(sugar is with sweet for beet
Dish and fodder beet);The operatic circle, drupe and berry (Kiwi berry, strawberry, raspberry, gooseberry, really mulberry, fig, pomegranate, carambola, kind
Pomegranate etc.);Legume (Kidney bean, little inclined beans, pea, soybean, red bean);Oilseed plant (rape, shepherd's purse, opium poppy, olive, to
Day certain herbaceous plants with big flowers, coconut, castor oil plant, cocoa bean, peanut);Mellon plant (pumpkin, cucumber, muskmelon, balsam pear, wax gourd, watermelon);
Fibre plant (cotton, flax, hemp, jute);Citrus fruit (orange, lemon, glucose shaddock, bar tangerine);Vegetables (spinach, lettuce
Bamboo shoot, asparagus, wild cabbage, carrot, onion, tomato, potato, pimiento);Lauraceae (avocado, Chinese cassia tree, camphor) or such as tobacco,
Nut, coffee, eggplant, sugarcane, tea, pepper, trailing plant including grape, banana, grass roots and natural rubber plant with
And ornamental plant (flowers, shrub, broad leaf tree and aithullium) etc..It should be noted that this inventory is not offered as any restriction.
The tetramycin of the present invention and the compound of amides compound can also be used for preventing and treating industrial materials fungal infection (especially
By mould microbial), bacterium or insect pest, safeguard industries material reduces after occurring from fungi invasion and attack and infecting at this or eradicates
The fungal infection of industrial materials.Industrial materials include but not limited to organic and inorganic materials timber, paper, leather, natural or conjunction
Become fiber and composite, such as particieboard, glued board, wallboard etc..The present invention can be applied to this with the consumption of effectively suppression
Material.
The compounding mixture of the present invention occur in plant, seed, soil, region, material and spatial dimension disease, worm,
The prevention of crop smothering and treatment, provide growth required energy for plant simultaneously.
In use, its application form is the compound of this tetramycin and amides compound: preparaton, spray solution,
Any one in emulsion, paste, oil.Type of service depends on specifically being intended to purpose;Under certain conditions, it should be ensured that tetramycin
Finely and it is evenly distributed with the compound of amides compound.
In certain embodiments, when the application form of tetramycin Yu the compound of amides compound is preparaton, four
After the compound of mycin and amides compound and solvent and/or carrier and/or emulsifying agent and/or surfactant are blended
Use.
In certain embodiments, when using after tetramycin is blended with the compound of amides compound and solvent, solvent
Including one or more of: water, arsol (such as toluene, dimethylbenzene), paraffin (such as mineral oil fractions), alcohols are (such as first
Alcohol, butanol, amylalcohol, benzylalcohol), ketone (such as cyclohexanone, gamma-butyrolacton), pyrrolidones (NMP, NOP), acetic acid esters (ethylene glycol two
Acetic acid esters), dihydroxylic alcohols, fatty acid dimethylamides, aliphatic acid and fatty acid ester.
In certain embodiments, when using after tetramycin is blended with the compound of amides compound and emulsifying agent, breast
Agent includes one or more of: nonionic and anion emulsifier are (such as polyoxyethylene aliphatic alcohol ether, alkylsulfonate and virtue
Base sulfonate);
In certain embodiments, use after tetramycin is blended with the compound of amides compound and surfactant
Time, surfactant includes one or more of: lignosulphonic acid, naphthalene sulfonic acids, phenolsulfonic acid, the alkali metal of dibutyl naphthalenesulfonic acid
Salt, alkali salt, ammonium salt, alkylaryl sulfonates, alkyl sulfate, alkylsulfonate, aliphatic alcohol sulfate, aliphatic acid and
Sulphated fatty alcohol glycol ether, sulfonated naphthalene and naphthalene derivatives and the condensation product of formaldehyde, naphthalene or naphthalene sulfonic acids and phenol and formaldehyde
Condensation product, NONIN HS 240, ethoxylated isooctyl-phenol, octyl phenol, nonyl phenol, alkyl phenyl polyglycol ether,
Tributyl phenyl polyglycol ether, three stearyl phenyl polyglycol ethers, alkyl aryl polyether alcohol, alcohol and fatty alcohol/oxidation second
Alkene condensate, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylation polyoxypropylene, laruyl alcohol polyglycol ether acetal,
Sorbitol ester, lignin sulfite waste liquor, methylcellulose.
When vegetable seeds is acted on by the compound of tetramycin Yu amides compound, preparaton can be fabricated to
Mode, in addition to above-mentioned each blending constituent, it is also possible to mix with adhesive and/or gelling agent and/or colouring agent.
When the application form of tetramycin Yu the compound of amides compound is spray solution, emulsion, paste, oil, dispersion
The material of body is that mid-boiling point arrives high boiling mineral oil fractions, such as kerosene or diesel oil, in addition with coal tar and plant or animal
Source oil, aliphatic, ring-type and aromatic hydrocarbon, such as toluene, dimethylbenzene, paraffin, tetrahydronaphthalene, alkylated naphthalene or derivatives thereof,
Methyl alcohol, ethanol, propyl alcohol, butanol, cyclohexanol, cyclohexanone, isophorone, intensive polar solvent, such as dimethyl sulfoxide (DMSO), N-methyl pyrrole
Pyrrolidone and water.
Tetramycin and the compound of amides compound use aqueous type of service can make by adding water in the application
Emulsion concentrates, paste.For preparation emulsion, paste or oil dispersion, can should by wetting agent, thickener, dispersant or emulsifying agent
Material directly or is homogenized after being dissolved in oil or solvent in water.However, it is also possible to preparation is by compounding mixture, wetting agent, thickening
Agent, dispersant or emulsifying agent and suitably solvent or the concentrate of oil composition and this concentrate are suitable to dilute with water.
In certain embodiments, the compound of tetramycin and amides compound can be used for controlling disease and includes following one
Or multiple: fungal disease, bacterial disease, virosis, nematodiasis.
When the compound of tetramycin Yu amides compound is used for preventing and treating fungal disease, fungal disease includes following
One or more: Deuteromycotina fungi, Basidiomycotina fungi, Ascomycotina fungi, Zygomycotina fungi, mastigomycetes
Subphylum fungi;
When the compound of tetramycin Yu amides compound is used for preventing and treating bacterial disease, bacterial disease includes following
One or more: pseudomonas, bacillus;
When the compound of tetramycin Yu amides compound is used for preventing and treating virosis, virosis includes following one or many
Kind: double-stranded DNA virus, single-stranded DNA viruses, diplornavirus, single strand RNA virus;
When the compound of tetramycin and amides compound is for pest control, insect pest includes one or more of:
Insect, mite class, snail, muroid;
When the compound of tetramycin and amides compound is for controlling weeds, weeds include one or more of:
Grass, cyperus, broad-leaf weeds;
The specific embodiment of several tetramycin and the compound of amides compound is given below, it should be appreciated that these are implemented
Example is only used for further illustrating the present invention, rather than limits the scope of the present invention, without departing from the above-mentioned technology of the present invention
Under the state of mind, the various replacements made according to ordinary skill knowledge and customary means or change, all should be included in this
In the range of invention.
Example one tetramycin compounds with procymidone
Wherein, active material component selects procymidone.Procymidone is interior absorption fungicide, to Botrytis and sclerotinite
Belonging to fungi and have special efficacy, can prevent and treat fruit tree, the gray mold of vegetable crop, sclerotiniose, the fungi that benzimidazole produces resistance also has
Effect.Use that rear protected effect is good, the lasting period is long, scab developmenting spread can be stoped.
The embodiment of the present invention is the method using Toxicity Determination and field test to combine.First pass through indoor virulence to survey
Fixed, after clear and definite two kinds of medicaments are compounding by a certain percentage synergy ratio (SR), SR < 0.5 is antagonism, 0.5≤SR≤1.5
For summation action, SR > 1.5 is synergistic effect, on this basis, then carries out field test.
After prerun determines each medicament effective inhibition concentration scope, medicament is set at 5 dosage respectively by active constituent content
Reason, if clear water comparison.Carry out with reference to " farm-chemical indoor determination test rule bactericide ", use mycelial growth rate method to measure
The medicament virulence to crop germ.Measure bacterium colony footpath by right-angled intersection method after 72h, calculate each process net growth, mycelial growth
Inhibiting rate.
Net growth (mm)=measurement colony diameter-5
Mycelial growth inhibition rate (%)=control group net growth-process group net growth/control group net growth
Mycelial growth inhibition rate is converted into probit value (y), and liquor strength (μ g/mL) is converted into logarithm value (x), with minimum
Square law tries to achieve virulence regression equation (y=a+bx), and thus calculates the EC50 value of every kind of medicament.Simultaneously according to Wadley method
Calculating two medicaments different ratio synergy ratio (SR), SR < 0.5 is antagonism, and 0.5≤SR≤1.5 are summation action,
SR > 1.5 is synergistic effect.
Computing formula is as follows:
SR=EC50(th)/EC50(ob)
Wherein: a, b are respectively the ratio that tetramycin and procymidone are shared in combination;A is tetramycin, and B is procymidone.
Tetramycin is compounding with procymidone to cucumber downy mildew Toxicity Determination.
Experimental design: determine that through pilot study the effectively suppression of tetramycin, procymidone and the two different ratio mixture is dense
Degree scope.
Toxicity test result
The compounding toxicity test analysis of results table to cucumber downy mildew of table 1 0.15% tetramycin, procymidone
As shown in Table 1, tetramycin, procymidone is respectively 2.57mg/L and 0.51mg/L to the EC50 of cucumber downy mildew.Four
Mycin, when procymidone joins 80: 1 to 1: 80, synergy ratio SR is all higher than 1.5, illustrates that both tetramycin procymidones are 80: 1 to 1
: in the range of 80, mixture all shows synergistic effect, and especially when the proportioning of the two is 20: 1 to 1: 10, synergistic effect is the brightest
Aobvious prominent, wherein when tetramycin procymidone weight ratio is 10: 1, synergy ratio SR is maximum, and synergistic effect is the most obvious.
As a example by the tetramycin compound 42% tetramycin procymidone with amides compound
Formula: tetramycin 40%, procymidone 2%, 3-methyl cyclohexanol ketenes 5%, diethylene glycol (DEG) 6%, xanthans 3%, fat
Alcohol APEO 5%, aryl phenol polyoxyethylene succinate sulfonate 4%, silicone 0.5%, deionized water is supplied
100%, prepare 42% tetramycin procymidone microemulsion.
Tetramycin, procymidone and the 42% tetramycin procymidone compound preventing and treating fresh kidney beans gray mold test of pesticide effectiveness thereof
This EE is in Chaoyang County, Chaoyang City, and test medicine is provided by the research and development of Liaoning Wei Ke bio-engineering corporation, comparison
Medicament 0.3% tetramycin aqua, 50% procymidone wettable powder (commercial).
Investigating the fresh kidney beans gray mold state of an illness before medicine, in the dispenser for the first time of state of an illness initial stage, dispenser in every 7 days once, is total to dispenser 2 times.
Within after dispenser 3 days, 7 days, 14 days for the second time, investigate disease index respectively and calculate preventive effect.Experimental result is as follows:
Table 2 tetramycin, procymidone and the compound preventing and treating fresh kidney beans gray mold test of pesticide effectiveness thereof
Thus table is it can be seen that can effectively prevent and treat fresh kidney beans gray mold after tetramycin is compounding with procymidone, and prevention effect is better than
The preventive effect of single dose, and the preventive effect phase is long.In test scope of medication, target crop is had no adverse effects.
After draw through tests different local throughout the country, tetramycin and procymidone, chlozolinate, sclex, isopropyl
To the powdery mildew of all kinds of crops, droop, downy mildew, gray mold, epidemic disease, anthrax after fixed, myclozolin, vinclozolin etc. are compounding
The preventive effect of the Common Diseases such as disease, ring spot, banded sclerotial blight, spot defoliation, scab, brown rot, leaf blight, rust is all 95%
Above, being better than single dose preventive effect, synergistic effect is obvious.
Example two tetramycin and azoxystrobin compound
Wherein, active material component selects Fluoxastrobin