CN103271039A - Synergetic herbicidal composition - Google Patents

Synergetic herbicidal composition Download PDF

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CN103271039A
CN103271039A CN2013102215094A CN201310221509A CN103271039A CN 103271039 A CN103271039 A CN 103271039A CN 2013102215094 A CN2013102215094 A CN 2013102215094A CN 201310221509 A CN201310221509 A CN 201310221509A CN 103271039 A CN103271039 A CN 103271039A
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methoxone
pyribenzoxim
herbicidal compositions
synergistic herbicidal
weeds
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CN103271039B (en
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宋文明
刘建华
刘学军
陈绍娥
吴一凡
刘智忠
冯秀珍
谭瑞成
殷爱云
罗昌炎
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Jiangsu Rotam Chemical Co Ltd
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Jiangsu Rotam Chemical Co Ltd
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Abstract

The invention relates to a synergetic herbicidal composition which comprises herbicidal active components of pyribenzoxim and 2-methyl-4-chloro-phenoxyacetic acid or a derivative thereof, wherein a weight ratio of pyribenzoxim to 2-methyl-4-chloro-phenoxyacetic acid or the derivative thereof is 100 : 1-1 : 100. The synergetic herbicidal composition is suitable for selective weed control weeds in beneficial crops such as rice. The synergetic herbicidal composition also can comprise a safety agent. Through binary compound of pyribenzoxim and 2-methyl-4-chloro-phenoxyacetic acid or the derivative thereof, the obtained novel composition can effectively overcome the defects that pyribenzoxim is used individually, enlarge herbicidal spectrum for weeds and delay the generation of resistance. The weeds in rice fields can be largely eradicated by applying the synergetic herbicidal composition at one time. The synergetic herbicidal composition is labor-saving, time-saving and effort-saving and has a certain effect for increasing both production and income for the rice. An enhanced effect in prevention of broad leaf weeds, grassy weeds and cyperaceae weeds in the rice fields is obtained.

Description

A kind of synergistic herbicidal compositions
Technical field
What the present invention relates to is a kind of synergistic herbicidal compositions, and said composition contains herbicidal active component pyribenzoxim and methoxone or derivatives thereof, is applicable to that selectivity prevents and treats for example weeds in the rice of useful crop.
Background technology
Paddy rice is one of world's staple food crop, and nearly half population in the world comprises the almost population in whole East Asia and Southeast Asia, all is food with rice, produces each continent that spreads all over except the South Pole.Eighties of last century late period, about 4,000 hundred million kilograms of world's rice annual production average out to, about 1.45 hundred million hectares of cultivated area.Also be most important cereal crops in China paddy rice.China's rice growing face accounts for 1/4 of national cereal crops, and annual about more than 3,500 ten thousand hectares, output then accounts for over half.No matter cultivated area and output all rank first in China cereal crops.
The rice field of all rice workspaces of China always has a large amount of weeds to take place.Paddy rice all has plantation in China various places, and the weeds in paddy field kind is a lot, and various places are because of factor weeds kind differences such as weather, soil.According to statistics, kind surplus the weeds that national rice field can form harm have 200, wherein the most common, take place general, harm is serious have 40 surplus kind.According to investigations, crop smothering area of (2~5 grades) crop smothering more than medium in national rice field reaches 1546.7 ten thousand hm 2, accounting for more than 46% of total cultivated area, (4~5 grades) area of wherein seriously causing harm is 3,800,000 hm 2, account for more than 11.5% of paddy rice cultivated area.It is maximum with harm with the barnyard grass grass area to take place in these weeds, also have the hazard area utmost point orders of severity such as difformed galingale herb, Monochoria vaginalis, flat stalk Fischer grass, moleplant seed, pondweed, Monochoria korsakowii to take second place, water silk floss, duckweed, Chinese scholartree leaf duckweed, little najas marina, short arrowhead, eel grass, bent grass, Herba Cyperi Glomerati, firefly Lin, water pepper, alternanthera philoxeroides, water three-coloured amaranth, hornwort, Eclipta prostrata, Sculellaria barbata etc. in addition that various places are common.
Along with the development of agricultural cience and farming techniques and the enforcement of mechanization, live field (water direct seeding and direct-sowing dry) is the planting patterns that reduces artificial and the amount of lightening one's labor, but relies on the chemical weed control in later stage more; Popularization and the application of chemical herbicide simultaneously, as the saving of labor, one of the strong well stimulation that saves time, reduce cost supporting the enforcement of the new mode of heavily planting.
The pyribenzoxim chemical name is O-(2,6-two (4,6-dimethoxypyridin-2-base oxygen base) benzoyl) oxime benzophenone or be O-[2, two (4,6-dimethoxy-2-pyrimidine radicals) the oxygen bases of 6-] the benzoyl diphenyl-ketoxime, its structural formula is
Figure 194897DEST_PATH_IMAGE002
Pyribenzoxim belongs to novel oxime ester compound, is the wide spectrum selective post-emergence herbicide.Mechanism of action is similar to sulfonylurea and the slow-witted ketone weed killer herbicide of imidazoles, all belongs to acetolactate synthestase (ALS) inhibitor.Paddy rice, common wheat, Korea lawn grass are had activity of weeding behind the selectivity super-high-efficient bud, activity of weeding before the no bud, it is distinguished to be used for preventing and kill off various grassy weeds such as barnyard grass grass, big fringe amur foxtail, polygonum flaccidum and the assorted effect of drawing of broad-leaved.
Pyribenzoxim is the broad-spectrum herbicide that can be used for transplanting rice, direct seading rice, rice transplanting paddy rice, to rice safety.Can effectively prevent and kill off grassy weeds such as barnyard grass grass (comprising the barnyard grass grass to Stam F-34, dichloro quinolinic acid and anti-acetyl-CoA carboxylase tool resistance), agrostis stolonifera, rice Li Shi standing grain, lady's-grass, moleplant seed, and annual sedge weed and part broad leaved weed.Pyribenzoxim is pyrimidine salicylic acid inner sucting conduction type weed killer herbicide, absorb through cauline leaf, in plant corpus, conduct, it is amino acid whose synthetic to suppress sensitive plant, and after susceptible weeds absorbed medicament, young shoot and root stopped growing, the lobus cardiacus jaundice of tender tissue, whole strain subsequently is withered, annual weed 5 to 15 days, and perennial weed will grow.
Methoxone, English name 2-Methyl-4-chlorophenoxyacetic acid, chemical formula: CH3 (Cl) C6H3OCH2COOH; Methoxone is widely used on the crops such as paddy rice, corn, wheat, is used for preventing and kill off broad leaved weed, and crop is had good safety.
Methoxone is to inhale the conduction hormone herbicide in the phenoxy acetic acid class selectivity, and Yi Weigen and leaf portion absorb and conduction, can destroy the conducting tissue of dicotyledon, making grows is interfered, chap or cracking are expanded in cauline leaf distortion, basal part of stem, and swollen splitting gone rotten and dead.Suitable paddy rice can be prevented and kill off most of sedge weed and broad leaved weed.The methoxone derivative is methoxone isopropyl acid, tetra chloro-butyric acid of dimethyl, tetra chloro-butyric acid of dimethyl butyl ester, the different monooctyl ester of methoxone, methoxone second thioesters, methoxone sulfo-ethyl ester, mcpa sodium, methoxone sylvite, methoxone isopropyl amine salt.
In actual use, pyribenzoxim is low to the perennial nutgrass flatsedge activity of part, uses for many years the rear section perennial weed to cause harm seriously continuously separately, as flat stalk Fischer grass, needle spikesedge herb, Japanese Fischer grass etc.Above weeds are needed control again, take a lot of work, time-consuming, effort.In addition, the speed of its weeding is slower, though can suppress the growth of weeds after the dispenser, weeds just can be dead afterwards generally to need for 2 weeks.
Summary of the invention
The present invention seeks to provides a kind of synergistic herbicidal compositions at above-mentioned weak point, and said composition is carried out pyribenzoxim, methoxone or derivatives thereof composite.Can disposablely prevent and kill off all weeds in field, enlarge the restriction of killing the grass spectrum of pyribenzoxim, methoxone derivative, improve pyribenzoxim and methoxone derivative to the careless speed of killing of grass family, sedge family and broad-leaved section weeds.The discovery that the present invention is surprised, the new compositions that obtains has been obtained gain effect at control paddy field malignant weed, significantly reduces the amount of the required active component of control of weeds, and the phytotoxicity of crop is not produced unacceptable toxicity.
In order to solve the problems of the technologies described above, the invention provides a kind of synergistic herbicidal compositions, said composition is by carrying out binary built with pyribenzoxim and methoxone or derivatives thereof, make resultant composition obtain gain effect in the control of paddy field broad leaved weed, grassy weed and sedge weed, especially to having special efficacy in long-term weeds of using sulfonylureas weed killer herbicide area to develop immunity to drugs, to succession crop safety.
A kind of synergistic herbicidal compositions comprises (a) pyribenzoxim of herbicidally effective amount and (b) methoxone or derivatives thereof, and wherein the weight proportion of pyribenzoxim and methoxone or derivatives thereof is 100:1 to 1:100.
As a further improvement on the present invention, described two kinds of active component weight proportions are 50:1 to 1:50, more preferably 20:1 to 1:20.
Described methoxone derivative is methoxone isopropyl acid, tetra chloro-butyric acid of dimethyl, tetra chloro-butyric acid of dimethyl butyl ester, the different monooctyl ester of methoxone, methoxone second thioesters, methoxone sulfo-ethyl ester, mcpa sodium, methoxone sylvite, methoxone isopropyl amine salt.
Described a kind of synergistic herbicidal compositions, also comprise safener, safener is selected from benoxacor, fenclorim, dichlormide, mefenpyrdiethyl, and wherein said safener is 1:100 to 20:1 with respect to the mixture weight proportioning of pyribenzoxim and methoxone or derivatives thereof.
Described a kind of synergistic herbicidal compositions can be mixed with agricultural and go up any formulation that allows.
Described synergistic herbicidal compositions can be mixed with agricultural and go up any formulation that allows.Preferred liquor, wetting powder, missible oil, suspending agent, oil-suspending agent, microcapsules, microemulsion, aqueous emulsion, suspended emulsion, water dispersible granules, ZC, ultra low volume liquids, the agent of kind clothing.
The present invention also provides a kind of synergistic herbicidal compositions, and the reactive compound combination that comprises described cooperative effective quantity mixes with at least a preparation technique usual auxiliaries.
The present invention also provides the method for a kind of collaborative control of undesirable plant, comprises described synergistic herbicidal compositions is applied on the growth place or leaf or stem of undesirable plant.Described undesirable plant is grassy weed, broad leaved weed and sedge weed.As Stellaria, bean cotyledon Lepidium, Agrostis, knotgrass, Avena, setaria, Europe sinapsis alba genus, Lolium, Solanum, Brome, amur foxtail genus, Matricaria, Tong fiber crops genus, chrysanthemum harvest spp, Xanthium, Amaranthus, Chenopodium, Ipomoea, crowndaisy chrysanthemum genus, Bedstraw, Viola and Veronica.
Described undesired plants is flat bar rattan grass, needle spikesedge herb, Japanese Fischer grass, Herba Cyperi Glomerati, cyperus iria, difformed galingale herb, barnyard grass grass, lady's-grass, eleusine indica, moleplant seed, green foxtail, annual bluegrass, needle spikesedge herb, firefly Lin, Monochoria vaginalis, mexicana, water starwort, dragon's tongue, cyperus iria L. rhizoma scirpi, angustifolia arrowhead herb, pondweed, clearvers, shepherd's purse, field thistle, Siberian cocklebur, the rhizome of nutgrass flatsedge, acalypha copperleaf, lamb's-quarters, thorn amaranth and branch amaranth, holds back blue dish, grass of meadow rue, kitchen garden etc.
The present invention also provides the method for a kind of collaborative control of undesirable plant, comprises described synergistic herbicidal compositions is used in the presence of other breeding part of the seed of useful crop plant, useful crop or useful crop.Wherein said useful crop is paddy rice, wheat, corn.
The present invention also provides the method for a kind of collaborative control of undesirable plant, comprises with the safener of pyribenzoxim, methoxone or derivatives thereof and the weed killer herbicide antagonism effective dose of herbicidally effective amount handling useful plants, its seed or transplanting, or its cultivation area.Safener is optional from benoxacor, fenclorim, dichlormide and mefenpyrdiethyl.Can be subjected to the crop of above-mentioned weed killer herbicide infringement to consider cereal, cotton, soybean, sugar beet, sugar sugarcane, kind plant, rape, corn, rice, wheat especially by safener benoxacor, fenclorim, dichlormide and mefenpyrdiethyl protection.
The combination of active principles of different agricultural chemicals is made agricultural chemicals, is a kind of mode effectively and efficiently that exploitation at present and development novel pesticide and control agricultural go up resistant weed.The agricultural chemicals of different cultivars shows three kinds of type of action: summation action, synergistic effect and antagonism after mixing usually.But be specially which kind of effect, unpredictable, have only by a large amount of experiments and just can know.Compound synergic is good prescription, owing to obviously improved actual control efficiency, reduced the usage amount of agricultural chemicals, thereby delayed drug-fast generation speed widely, and be the important means of integrated control disease.
The invention provides a kind of synergistic herbicidal compositions, comprise pyribenzoxim and the methoxone or derivatives thereof of herbicidally effective amount.
Above-mentioned two kinds of herbicide components weight proportions are 100:1 to 1:100.Be preferably 50:1 to 1:50, more preferably 20:1 to 1:20.
The combination of pyribenzoxim and methoxone or derivatives thereof has surpassed the addition to the desire controlling weeds of expection in principle, therefore particularly widened the sphere of action of two kinds of active components aspect following two: at first, reduce the consumption of individualized compound, kept good exposure level simultaneously; Secondly, under the situation that becomes invalid from the viewpoint of agricultural under the low amount ranges, the present composition also can obtain high control of weeds level at single material.The result has significantly widened the weeds spectrum, has increased the selectivity to the useful plants crop in addition, and this is required and expectation under the situation that is not intended to excessive use active component just.The present composition also has bigger adaptability to succession crop in the weeds that keep preventing and treating well in the useful plants.
The present invention also provides a kind of synergistic herbicidal compositions, and the reactive compound combination that comprises described cooperative effective quantity mixes with at least a preparation technique usual auxiliaries.
The auxiliary agent that uses in the synergistic herbicidal compositions of the present invention comprises that liquid-carrier, solid carrier, dispersant, emulsifier, stabilizing agent, antifreezing agent, thickener etc. and other are of value to the known substance that active ingredient is stablized and drug effect is brought into play in preparation, all be the various compositions of using or allow use in the agricultural chemicals always, be not particularly limited, concrete composition and consumption require to determine by simple experiment according to prescription.
The liquid-carrier that is fit to preparation synergistic herbicidal compositions of the present invention comprises aromatic hydrocarbons, aliphatic hydrocarbon.Particularly suitable be polar solvent, as alcohols and their ether and ester.Also have vegetable oil and the molten fiber of methyl in addition.Simultaneously, mixtures of different liquids also is suitable for.
The solid carrier that is fit to synergistic herbicidal compositions of the present invention is diatomite, Magnesiumaluminumsilicate, atlapulgite, kaolin, clay, gypsum, bentonite, white carbon, precipitated calcium carbonate, lime stone, wood chip, corn starch, soluble starch etc.
The emulsifier that is fit to preparation synergistic herbicidal compositions of the present invention can be anion and/or non-example type emulsifier, for example alkylphenol polyoxyethylene, alkylphenol-polyethenoxy polyethenoxy ether, benzylphenol APEO, polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyoxyethylene fatty amine, alkyl phenol polyglycol ether etc.
The dispersant that is fit to preparation synergistic herbicidal compositions of the present invention can be alkylnaphthalene sulfonate, two (alkyl) naphthalenesulfonate formaldehyde condensation compound, naphthalene sulfonic acid-formaldehyde condensation product, the alkylphenol-polyethenoxy based phosphates, alkylphenol-polyethenoxy base ether formaldehyde condensation products sulphate, the alkylphenol polyoxyethylene phosphate, alkylphenol polyoxyethylene, the castor oil ethylene oxide adduct, oxirane-propylene oxide block copolymer, the dirt of alkylphenol polyoxyethylene formaldehyde condensation, octylphenol polyethylene oxyethylene group ether sulfate and methylcellulose.For example sodium lignin sulfonate, calcium lignosulfonate, methyl naphthalene sulfonate formaldehyde condensate, the dirt of sodium naphthalene sulfonate formaldehyde condensation, methanonaphthalene sodium sulfonate etc.
Other additive can be enumerated the carboxymethyl cellulose that uses with the auxiliary agent form usually, ethylene glycol and propane diols etc. when preparation.
Synergistic herbicidal compositions among the present invention can also contain colouring agent, for example inorganic pigment iron oxide, titanium oxide or Prussia orchid; Organic dyestuff alizarin, azo dyes, metal phthalocyanine orchid or kiton colors etc.
Can any form commonly used use composition of the present invention.The blade face formulation example of premix composition is:
GR: granule
WP: wetting powder
WG: but the water dispersible granule
SG: solvable granula
SL: soluble concentrate
EC: missible oil
EW: emulsion, aqueous emulsion
ME: microemulsion
SC: suspending agent
CS: microcapsule suspending agent
OD: oil-based suspension
SE: suspension emulsion
FS: plant the clothing agent
The preferred formulation of the present invention can be liquor, wetting powder, missible oil, suspending agent, oil-suspending agent, microcapsules, microemulsion, aqueous emulsion, suspended emulsion, water dispersible granules, ZC, ultra low volume liquids, the agent of kind clothing.
For water dispersible granules, those skilled in the art are familiar with the corresponding auxiliary agent of use and finish the present invention very much.Dispersant is selected from polycarboxylate, lignosulfonates, alkylnaphthalene sulfonate, alkylphenol polyoxyethylene, EO/PO block polyether; Wetting agent is selected from alkyl sulfate, alkylsulfonate, naphthalene sulfonate, sodium lignin sulfonate, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene; Disintegrant is selected from ammonium sulfate, sodium sulphate, sodium chloride, ammonium chloride, urea, sucrose, glucose, carboxymethyl cellulose, soluble starch, polyvinylpyrrolidone; Binding agent is selected from polyvinyl alcohol, soluble starch, dextrin, xanthans, carboxymethyl (ethyl) cellulose family; Filler is selected from diatomite, kaolin, white carbon, precipitated calcium carbonate, talcum powder, attapulgite, potter's clay.
To wetting powder, spendable auxiliary agent has: dispersant is selected from polycarboxylate, lignosulfonates, alkylnaphthalene sulfonate; Wetting agent is selected from alkyl sulfate, alkylsulfonate, naphthalene sulfonate; Filler is selected from ammonium sulfate, urea, sucrose, glucose, diatomite, kaolin, white carbon, precipitated calcium carbonate, talcum powder, attapulgite, potter's clay.
To suspending agent, spendable auxiliary agent has: dispersant is selected from polycarboxylate, lignosulfonates, alkylnaphthalene sulfonate, TERSPERSE 2425 (U.S. Huntsman Corporation produces, the alkyl naphthalene sulfonic acid salt); Alkyl phenol formaldehyde resin polyoxyethylene ether), farming breast 2201, this dish-60# (common name: sorbitan monostearate), emulsifier T-60 (common name: the sorbitan monostearate APEO), agricultural newborn 1601# (common name: phenethyl phenol polyoxyethylene poly-oxygen propylene aether), TERSPERSE 4894 (U.S. Huntsman Corporation product) emulsifier is selected from Nongru-700 # (common name:; Wetting agent is selected from alkylphenol-polyethenoxy base ether formaldehyde condensation products sulphate, alkylphenol-polyethenoxy base ether phosphate, phenethyl phenol polyethenoxy base ether phosphate, alkyl sulfate, alkylsulfonate, naphthalene sulfonate, TERSPERSE2500 (U.S. Huntsman Corporation product); Thickener is selected from xanthans, polyvinyl alcohol, bentonite, aluminium-magnesium silicate; Preservative is selected from formaldehyde, benzoic acid, Sodium Benzoate; Defoamer is silicone based defoamer; Antifreezing agent is selected from ethylene glycol, propane diols, glycerine, urea, inorganic salts (as sodium chloride).
But to the dispersed oil suspending agent, spendable auxiliary agent has: dispersant is selected from polycarboxylate, lignosulfonates, alkylnaphthalene sulfonate (dispersing agent NNO), TERSPERSE 2425, and emulsifier is selected from the serial emulsifier (BY-110 of BY (castor oil polyoxyethylene ether), BY-125, BY-140) Nongru-700 # (common name: alkyl phenol formaldehyde resin polyoxyethylene ether), farming breast 2201, this dish-60# (common name: sorbitan monostearate), Tween-60 # (common name: the sorbitan monostearate APEO), the newborn 1601# of farming (common name: phenethyl phenol polyoxyethylene poly-oxygen propylene aether), TERSPERSE4894; Wetting agent is selected from alkylphenol-polyethenoxy base ether formaldehyde condensation products sulphate, alkylphenol polyoxyethylene phosphate, phenethyl phenol polyethenoxy base ether phosphate, alkyl sulfate, alkylsulfonate, naphthalene sulfonate, TERSPERSE 2500; Thickener is selected from white carbon, polyvinyl alcohol, bentonite, aluminium-magnesium silicate; Antifreezing agent is selected from ethylene glycol, propane diols, glycerine, urea, inorganic salts (as sodium chloride); Stabilizing agent is selected from epoxidized soybean oil, epoxychloropropane, triphenyl phosphate; Dispersion medium is selected from soybean oil, rapeseed oil, corn oil, methyl oleate, diesel oil, machine oil, mineral oil.
The formulation example that is fit to the bucket mixing composition is solution, dilution emulsion, suspending agent or its mixing and pulvis.
Usually, the bucket mixing composition is to contain different agricultural chemicals and one or more premix compositions of further auxiliary agent randomly with what solvent (as water) dilution formed.
Generally, blade face bucket mixture comprises 0.1-20%, the reactive compound of 0.1-15% particularly, and 99.9%-80%, solid-state or the liquid flux of 99.9-85% (comprising ratio of solvent such as water) particularly, wherein auxiliary agent can be based on the bucket mixture, the surfactant of content 0-20%, particularly 0.1-15%.
Usually the pre-mixing agent of foliage applying comprises 0.1-99.9%, the active compound component of 1-95% particularly, and 99.9-0.1%, solid-state or the liquid flux of 99-5% (comprising as ratio of solvent such as water) particularly, wherein auxiliary agent can be based on pre-mixing agent, the surfactant of content 0-50%, particularly 0.5-40%.
Of the present inventionly comprise 0.5-99.9% through composition prepared, 1-95% particularly, the active compound component of 1-50% advantageously, and 99.5-0.1%, the particularly solid of 99-5% quality or liquid assistant agent (comprising as solvent such as water), wherein said auxiliary agent (or assistant agent) can be based on the surfactant of the 0-50%, particularly 0.5-40% of pre-mixing agent quality.
The present invention also provides the method for a kind of collaborative control of undesirable plant, comprises described synergistic herbicidal compositions is applied on the growth place or leaf or stem of undesirable plant.Described undesirable plant is grassy weed, broad leaved weed and sedge weed.As Stellaria, bean cotyledon Lepidium, Agrostis, knotgrass, Avena, setaria, Europe sinapsis alba genus, Lolium, Solanum, Brome, amur foxtail genus, Matricaria, Tong fiber crops genus, chrysanthemum harvest spp, Xanthium, Amaranthus, Chenopodium, Ipomoea, crowndaisy chrysanthemum genus, Bedstraw, Viola and Veronica.Preferred flat bar rattan grass, needle spikesedge herb, Japanese Fischer grass, Herba Cyperi Glomerati, cyperus iria, difformed galingale herb, barnyard grass grass, lady's-grass, eleusine indica, moleplant seed, green foxtail, annual bluegrass, needle spikesedge herb, firefly Lin, Monochoria vaginalis, mexicana, water starwort, dragon's tongue, cyperus iria L. rhizoma scirpi, angustifolia arrowhead herb, pondweed, clearvers, shepherd's purse, field thistle, Siberian cocklebur, the rhizome of nutgrass flatsedge, acalypha copperleaf, lamb's-quarters, thorn amaranth and branch amaranth, hold back blue dish, grass of meadow rue, kitchen garden etc.
The present invention also provides the method for a kind of collaborative control of undesirable plant, comprises synergistic herbicidal compositions is used in the presence of other breeding part of the seed of useful crop plant, useful crop or useful crop.Wherein said useful crop is paddy rice, corn, wheat.
The present invention also provides the method for a kind of collaborative control of undesirable plant, comprises with the safener of pyribenzoxim, methoxone or derivatives thereof and the weed killer herbicide antagonism effective dose of herbicidally effective amount handling useful plants, its seed or transplanting, or its cultivation area.Safener is optional from benoxacor, fenclorim, dichlormide and mefenpyrdiethyl.Can be subjected to the crop of above-mentioned weed killer herbicide infringement to consider cereal, cotton, soybean, sugar beet, sugared with sugarcane, kind plant, rape, corn and rice especially by safener benoxacor, fenclorim, dichlormide and mefenpyrdiethyl protection.
The cultivation area be cultivated plant in the soil that growth or the seeds of those cultivated plants have been sowed, and plan the soil of the above-mentioned cultivated plant of cultivation.
According to the application of expection, the safener that is selected from benoxacor, fenclorim, dichlormide and mefenpyrdiethyl can be used for anticipating cultivated plant seed material (seed dressing or dressing transplant) can be prior to seeding or after mix in the soil.But, also can behind plant germination, use separately or with weed killer herbicide.Dimension is not subjected to the influence of herbicide application time in principle with safener processing plant or seed.And, also can carry out the processing of plant by using weed killer herbicide and safener (for example mixing the form of thing with bucket) simultaneously.Safener depends primarily on application process with respect to the consumption of weed killer herbicide.Under the situation of field processing, the bucket mixed thing or safener is used in distribution and weed killer herbicide is handled that can contain the composition of safener and weed killer herbicide by use, the ratio of weed killer herbicide and safener is 100:1 to 1:20 normally, preferred 20:1 to 1:10. is under the situation of field processing, usually use 0.001-1.0kg safener/ha, preferred 0.001-0.25 kg safener/ha.
The cooperative effective quantity that is applicable to the combination of composition of the present invention can be according to the variations such as kind of at that time condition such as weed pressure, time of application, method of application, weather, soil regime, features of terrain, target crop.In practicing, about 0.001kg/ha-1.00kg/ha enough is provided, the rate of application of the active component of preferred about 0.01 kg/ha-0.075 kg/ha is suitable.
For seed dressing, use 0.001-10g safener/kg seed usually, preferred 0.05-2g safener/kg seed.If safener is used by seed soaking with liquid form prior to seeding soon, it is favourable using the safener solution of the active component that contains concentration 1-10000ppm, preferred 100-1000 ppm so.
In order to use conveniently, be mixed with preparation with being selected from the safener of benoxacor, fenclorim, dichlormide and mefenpyrdiethyl or these safeners with auxiliary agent conventional in the composition of pyribenzoxim and methoxone or derivatives thereof and the preparation processing technology.
According to the preparation characteristic, can be selected from application process according to expection object and popular environment, as the blade face, soak into, spray, dust, scattering selects.
The inventive method most preferably is used for control plant growth district maybe will be for the weeds in the zone of kind of plant.When being used for the plant growth district, amount of application should be enough to control weed growth but can be to not do the serious nonvolatil injury of deposits yields.
Herbicidal combinations of the present invention can also can be at postemergence application at preemergence application, preferred postemergence application, and particularly weed growth is early stage.Also be one of feature of the inventive method with Herbicidal combinations early time treatment before plantation (particularly soil surface is used).
The present invention compared with prior art has following beneficial effect:
The combination of pyribenzoxim and methoxone or derivatives thereof has surpassed the addition to the desire controlling weeds of expection in principle, therefore particularly widened the sphere of action of two kinds of active components aspect following two: at first, reduce the consumption of individualized compound, kept good exposure level simultaneously; Secondly, under the situation that becomes invalid from the viewpoint of agricultural under the low amount ranges, the present composition also can obtain high control of weeds level at single material.The result has significantly widened the weeds spectrum, has increased the selectivity to the useful plants crop in addition, and this is required and expectation under the situation that is not intended to excessive use active component just.The present composition also has bigger adaptability to succession crop in the weeds that keep preventing and treating well in the useful plants.
From the following examples as can be seen, herbicide composition of the present invention shows good weeding activity, and the activity of weeding of single reactive compound or binary activity of weeding a little less than, the activity of combination of the present invention surpass simply adding of each single compound activity and binary combination activity and.
During active sum when the activity of weeding of reactive compound combination surpasses each reactive compound and uses separately, then always there is synergy.
The present invention compared with prior art has following beneficial effect:
The invention provides a kind of synergistic herbicidal compositions, said composition is by carrying out binary built with pyribenzoxim and methoxone or derivatives thereof, make resulting new compositions can solve the defective of independent use pyribenzoxim effectively, has synergistic function, expansion is composed the grass that kills of weeds, simultaneously suspension of pesticide resistance generation.Once use and can solve paddy field weed substantially, the saving of labor, save time, laborsaving, can partly alleviate the situation of rural area recruitment anxiety, simultaneously increasing production of rice is increased income tool and has certain effect.Control at paddy field broad leaved weed, grassy weed and sedge weed has obtained gain effect.
Embodiment
From the following examples as can be seen, herbicide composition of the present invention shows good weeding activity, and the activity of weeding of single reactive compound or binary activity of weeding a little less than, the activity of combination of the present invention surpass simply adding of each single compound activity and binary combination activity and.
During active sum when the activity of weeding of reactive compound combination surpasses each reactive compound and uses separately, then always there is synergy.
Embodiment 1:60% pyribenzoxim+3% methoxone sodium oil-suspending agent
Pyribenzoxim 60%
Methoxone sodium 3%
Methyl naphthalene sulfonate formaldehyde condensate 10%
Bentonite 1%
Glycerine 5%
Corn oil complements to 100%
Active component, dispersant, wetting agent and each component of corn wet goods ratio according to prescription is mixed, after grinding and/or high speed shear, obtain 60% pyribenzoxim+3% methoxone sodium oil-suspending agent.
Embodiment 2 2% pyribenzoxims+10% methoxone potassium wetting powder
Pyribenzoxim 2%
Methoxone potassium 10%
Lauryl sodium sulfate 10%
Sodium lignin sulfonate 5%
White carbon 10%
Kaolin complements to 100%
Ratio composition in prescription such as active component, various auxiliary agent and filler is mixed, after ultrafine crusher is pulverized, namely obtain 2% pyribenzoxim+10% methoxone potassium wetting powder.
Embodiment 3 2% pyribenzoxims+60% methoxone sodium wetting powder
Pyribenzoxim 2%
Methoxone sodium 60%
Calcium dodecyl benzene sulfonate 1%
Sodium lignin sulfonate 2%
White carbon complements to 100%
Ratio composition in prescription such as active component, various auxiliary agent and filler is mixed, after ultrafine crusher is pulverized, namely obtain 2% pyribenzoxim+60% methoxone sodium wetting powder.
Embodiment 4 5% pyribenzoxims+50% methoxone isopropyl amine salt water dispersible granules
Pyribenzoxim 5%
Methoxone isopropyl amine salt 50%
Sodium lignin sulfonate 4%
Lauryl sodium sulfate 5%
Urea 5%
Kaolin complements to 100%
Active component, dispersant, wetting agent, disintegrant and the filler ratio in prescription is mixed, be ground into wetting powder through air-flow, add a certain amount of water mixing extruding again and make material.Obtain 5% pyribenzoxim+50% methoxone isopropyl amine salt water dispersible granules after the drying screening.
The embodiment 5 50% pyribenzoxims+different monooctyl ester missible oil of 5% methoxone
Pyribenzoxim 50%
The different monooctyl ester 0.1% of methoxone
Ethoxylated castor oil 5%
Calcium dodecyl benzene sulfonate 3%
Dimethyl sulfoxide (DMSO) complements to 100%
Mentioned component is proportionally prepared, and stirring obtains the phase of homogeneous.
Embodiment 6 50% pyribenzoxims+0.5% methoxone isopropyl acid oil suspension emulsion
Pyribenzoxim 50%
Methoxone isopropyl acid 0.5%
Methyl naphthalene sulfonate formaldehyde condensate 5%
Ethoxylated castor oil 3%
Bentonite 1%
Aromatic solvent 100 20%
Soybean oil complements to 100%
Pyribenzoxim, methyl naphthalene sulfonate formaldehyde condensate are obtained the pyribenzoxim oil-suspending agent after grinding and/or high speed shear; Methoxone isopropyl acid, aromatic solvent 100, ethoxylated castor oil mixing and stirring are obtained the missible oil of methoxone isopropyl acid; The methoxone isopropyl acid missible oil that obtains is joined in the pyribenzoxim oil-suspending agent, obtain 50% pyribenzoxim+0.5% methoxone isopropyl acid suspension emulsion.
Embodiment 7 0.5% pyribenzoxims+50% mcpa sodium wetting powder
Pyribenzoxim 0.5%
Mcpa sodium 50%
Lauryl sodium sulfate 10%
Sodium lignin sulfonate 5%
White carbon 10%
Kaolin complements to 100%
Said components is mixed in proportion, and grind, pulverize, be prepared into wetting powder.
Embodiment 8 4% pyribenzoxims+80% tetra chloro-butyric acid of dimethyl butyl ester water dispersible granules
Pyribenzoxim 4%
Tetra chloro-butyric acid of dimethyl butyl ester 80%
MODIFIED LIGNOSULPHONATE 5%
Lauryl sodium sulfate 5%
Urea 5%
Kaolin complements to 100%
Pyribenzoxim active component, dispersant, wetting agent, disintegrant and the filler ratio in prescription is mixed, be ground into wetting powder through air-flow; Adding the tetra chloro-butyric acid of dimethyl butyl ester again mixes; Add a certain amount of water mixing extruding again and make material.Obtain 4% pyribenzoxim+80% tetra chloro-butyric acid of dimethyl butyl ester water dispersible granules after the drying screening.
Embodiment 9 1% pyribenzoxims+50% methoxone sodium aqueous emulsion
Oil phase:
Pyribenzoxim 1%
Methyl oleate 10%
Ethoxylated castor oil 5%
Water:
Methoxone sodium 50%
The sodium salt 1% of the naphthalene sulfonic acids-formaldehyde condensation products of sulfonation
Water complements to 100%
Pyribenzoxim is dissolved in the methyl oleate, adds ethoxylated castor oil and obtain oil phase; According to the sodium salt of prescription with the naphthalene sulfonic acids-formaldehyde condensation products of mcpa sodium and sulfonation, water, mix and obtain water; Under agitation oil phase is added water and obtain aqueous emulsion.
Embodiment 10 20% pyribenzoxims+40% methoxone sodium wetting powder
Pyribenzoxim 20%
Methoxone sodium 40%
Sodium lignin sulfonate 1%
NaLS 2%
The silicic acid 1% of high degree of dispersion
Kaolin complements to 100%
Said components is mixed in proportion, and grind, pulverize, be prepared into wetting powder.
Embodiment 11 50% pyribenzoxims+1% methoxone sodium coated granule
Pyribenzoxim 50%
Methoxone sodium 1%
Polyethylene glycol 3%
The silicic acid 1% of high degree of dispersion
Calcium carbonate complements to 100%
In blender, levigate active component evenly is applied to by on the wetting carrier of polyethylene glycol.Can obtain dustless coated granule in this way.
Embodiment 12 2% pyribenzoxims+40% methoxone potassium wetting powder
Pyribenzoxim 2%
Methoxone potassium 40%
Lauryl sodium sulfate 1%
Sodium lignin sulfonate 1%
Kaolin complements to 100%
Said components is mixed in proportion, and grind, pulverize, be prepared into wetting powder.
Embodiment 13 30% pyribenzoxims+6% mcpa sodium is extruded granule
Pyribenzoxim 5%
Methoxone sodium 30%
Sodium lignin sulfonate 4%
Carboxymethyl cellulose 2%
Kaolin complements to 100%
Active component is mixed with auxiliary agent and grind the mixture water-wet.This mixture is extruded, dry in air stream then.
Embodiment 14 10% pyribenzoxims++ 10% methoxone sodium kind clothing agent
Pyribenzoxim 10%
Methoxone sodium 10%
Fatty alcohol-polyoxyethylene ether sulfosuccinic acid monoesters disodium 10%
MODIFIED LIGNOSULPHONATE 5%
Xanthans 1%
Bentonite 1%
Glycerine 5%
PVP-K30 1%
Water complements to 100%
Above-mentioned each component is mixed in proportion, and through sand milling, be prepared into kind of a clothing agent.
Embodiment 15 2% pyribenzoxims+48% methoxone sulfo-ethyl ester ZC
Atlox 4913 4%
Citric acid 0.05%
Catalyzer 0.1%
Water 13%
Methoxone sulfo-ethyl ester 48%
PAPI 1.35%
Solvesso 200 10%
Atlox4913 16%
Dispersant LFH 0.3%
Defoamer 0.16%
Urea 8.4%
Pyribenzoxim 2%
Water complements to 100%
The oil phase adding that PAPI, methoxone sulfo-ethyl ester, Solvesso 100 are formed contains in the aqueous solution of Atlox4913, forms emulsion.Heat then and be incubated under 50oC and added catalyst reaction 2 hours.Obtain the microcapsules of methoxone sulfo-ethyl ester after the cooling.
Atlox 4913, dispersant LFH, and defoamer, urea, pyribenzoxim and water mix in proportion, and through sand milling, are prepared into suspending agent.
The methoxone sulfo-ethyl ester microcapsules that obtains is added in the suspending agent of pyribenzoxim, and stirring obtains 2% pyribenzoxim+48% methoxone sulfo-ethyl ester ZC.
Embodiment 16 5% pyribenzoxims+30% tetra chloro-butyric acid of dimethyl suspended emulsion
Pyribenzoxim 5%
Tetra chloro-butyric acid of dimethyl 30%
Solvesso 200 10%
Ethoxylated castor oil 4%
Fatty alcohol-polyoxyethylene ether sulfosuccinic acid monoesters disodium 5%
MODIFIED LIGNOSULPHONATE 5%
Xanthans 1%
Bentonite 1%
Glycerine 5%
Water complements to 100%
Tetra chloro-butyric acid of dimethyl is dissolved among the Solvesso 200, adds ethoxylated castor oil, obtain the missible oil of tetra chloro-butyric acid of dimethyl;
With pyribenzoxim, fatty alcohol-polyoxyethylene ether sulfosuccinic acid monoesters disodium, above-mentioned each component mixes in proportion, and through sand milling, is prepared into suspending agent.
The oil phase that will contain tetra chloro-butyric acid of dimethyl joins and contains in the pyribenzoxim suspending agent, obtains suspended emulsion.
Embodiment 17 6% pyribenzoxims+20% methoxone second thioesters missible oil
Pyribenzoxim 6%
Methoxone second thioesters 20%
Ethoxylated castor oil 5%
Calcium dodecyl benzene sulfonate 3%
Solvesso100 complements to 100%
Above-mentioned each component is mixed, be stirred to and obtain transparent homogeneous phase.
Embodiment 19 20% pyribenzoxims+80% methoxone sodium
Pyribenzoxim 20%
Methoxone sodium 80%
Pyribenzoxim, methoxone sodium are proportionally mixed.
Embodiment 20 20% pyribenzoxims+60% methoxone sodium+20% benoxacor
Pyribenzoxim 20%
Methoxone sodium 60%
Benoxacor 20%
Embodiment 21 49% pyribenzoxims+50% methoxone sodium+1% fenclorim
Pyribenzoxim 49%
Methoxone sodium 50%
Fenclorim 1%
Embodiment 22 2% pyribenzoxims+2.8% methoxone sodium+95.2% dichlormide
Pyribenzoxim 2%
Methoxone sodium 2.8%
Dichlormide 95.2%
Embodiment 23 40% pyribenzoxims+58% methoxone sodium+2% mefenpyrdiethyl
Pyribenzoxim 40%
Methoxone sodium 58%
Mefenpyrdiethyl 2%
Proportioning is the weight per distribution ratio among the above embodiment.
The biological test example
When the effect of active compound combinations surpasses the summation of the effect when each reactive compound is used separately, there is synergistic function.The predictive role of the particular combination of two kinds of reactive compounds can use so-called " Colby formula " (referring to S.R. Colby, " Calculating Synergistic and Antagonistic Responses of Herbicide Combinations ", Weeds 1967,15,20-22) following calculating: if
X be when use consumption as mg/ha or concentration the activity during as the reactive compound A of mppm;
Y be when use consumption as ng/ha or concentration the activity during as the reactive compound B of nppm, be expressed as the percentage that accounts for untreated control;
E be when use consumption as m and n g/ha or concentration the activity during as the reactive compound A of m and n ppm and B,
So
Figure DEST_PATH_IMAGE004A
If the activity of actual observation (O) is greater than expection active (E), so said composition super add and, namely have synergistic effect.
The inventor is by a large amount of screening tests, the different proportionings of pyribenzoxim and methoxone or derivatives thereof test and preventive effect analysis have been carried out a large amount of, discovery is in certain ratio range, resulting Herbicidal combinations has synergistic effect, and be not only the simple addition of two kinds of medicaments, be illustrated with following biologicall test example.
Test before the seedling:
Under greenhouse experiment, test plant is seeded in the jar.Use standard soil is as cultivation matrix.In the seedling last stage, weed killer herbicide is administered to soil surface separately or with the form of mixture.Consumption depends on determined optium concentration under field or greenhouse experiment.(100% effect=plant is dead fully in 2-4 week post-evaluation test; 0% effect=plant-less toxicity effect).The mixture of Shi Yonging shows than using good result separately in this test.
Test behind the seedling:
As long as during the summation of the effect the when effect of the combination of pyribenzoxim and methoxone or derivatives thereof is used respectively greater than each active component, just have synergistic effect.
Field trial has on the water saturated soil of about 5cm water (saturation conditions) thereon carries out.At seedling after-stage (2-to 3-leaf phase), use the back type sprayer that weed killer herbicide is administered on the test plants that is under the water saturation soil condition separately or with the form of mixture.Consumption depends on determined optium concentration under field condition.(100% effect=plant is dead fully in post-evaluation in 30-50 days test; 0% effect=plant-less toxicity effect).The mixture of Shi Yonging shows good result in this test.
Table 1: contain the postemergence weed control effect of the present composition of pyribenzoxim and methoxone sodium after the dispenser 49 days the time:
Safety effect
Under greenhouse experiment, test plant is grown to the 4-leaf phase in plastic tank.In this stage, with independent pyribenzoxim, the composition of pyribenzoxim and safener, and the mixture of pyribenzoxim and methoxone or derivatives thereof, or pyribenzoxim and methoxone or derivatives thereof are administered to test plant with the mixture as the material of safener test.Using with the aqueous solution of use test material, described solution is by embodiment 18 14% pyribenzoxims+22% methoxone or derivatives thereof water dispersible granules preparation, and per hectare is used 500 premium on currency.After using for 3 weeks, use percentage to measure and estimate weed killer herbicide to the phytotoxicity of crop such as corn and cereal.100% expression test plant is dead fully, 0% expression plant-less toxicity effect.
Unexpected discovery, specific safener is applicable to that synergistic composition of the present invention mixes.Therefore; the invention still further relates to a kind of for the selectivity control useful plants selective herbicidal composition of the weeds of rice crops particularly; said composition contains pyribenzoxim, methoxone or derivatives thereof; with the safener that is selected from benoxacor, fenclorim, dichlormide and mefenpyrdiethyl; said composition can protect useful plants (but not weeds) to avoid the phytotoxicity effect of weed killer herbicide, also relates to the application of the weeds of described composition in control useful plants crop.
Safener is selected from benoxacor, fenclorim, dichlormide, mefenpyrdiethyl, and wherein said safener is 1:100 to 20:1 with respect to the mixture weight proportioning of pyribenzoxim and methoxone or derivatives thereof.

Claims (14)

1. synergistic herbicidal compositions, it is characterized in that: comprise activity of weeding component pyribenzoxim and methoxone or derivatives thereof, wherein the weight proportion of pyribenzoxim and methoxone or derivatives thereof is 100:1 to 1:100.
2. a kind of synergistic herbicidal compositions according to claim 1, it is characterized in that: described two kinds of active component pyribenzoxims and methoxone or derivatives thereof weight proportion are 50:1 to 1:50.
3. a kind of synergistic herbicidal compositions according to claim 1, it is characterized in that: described two kinds of active component pyribenzoxims and methoxone or derivatives thereof weight proportion are 20:1 to 1:20.
4. a kind of synergistic herbicidal compositions according to claim 1, it is characterized in that: described methoxone derivative is methoxone isopropyl acid, tetra chloro-butyric acid of dimethyl, tetra chloro-butyric acid of dimethyl butyl ester, the different monooctyl ester of methoxone, methoxone second thioesters, methoxone sulfo-ethyl ester, mcpa sodium, methoxone sylvite, methoxone isopropyl amine salt.
5. a kind of synergistic herbicidal compositions according to claim 1, it is characterized in that: also comprise safener, safener is selected from benoxacor, fenclorim, dichlormide, mefenpyrdiethyl, and wherein said safener is 1:100 to 20:1 with respect to the mixture weight proportioning of pyribenzoxim and methoxone or derivatives thereof.
6. a kind of synergistic herbicidal compositions according to claim 1 or 5, it is characterized in that: described collaborative Herbicidal combinations can be mixed with agricultural and go up any formulation that allows.
7. want 1 or 5 described a kind of synergistic herbicidal compositions according to right, it is characterized in that: the formulation of described synergistic herbicidal compositions is wetting powder, missible oil, suspending agent, oil-suspending agent, microcapsules, microemulsion, aqueous emulsion, suspended emulsion, water dispersible granules, ZC, ultra low volume liquids, the agent of kind clothing.
8. synergistic herbicidal compositions is characterized in that: the reactive compound combination that comprises the cooperative effective quantity in claim 1 or 5 mixes with at least a preparation technique usual auxiliaries.
9. the method for a collaborative control of undesirable plant is characterized in that: comprise that the synergistic herbicidal compositions with claim 1 or 5 is applied to growth place or leaf or stem or the seed of undesirable plant.
10. the described method of claim 9, it is characterized in that: undesirable plant is grassy weed, broad leaved weed and sedge weed.
11. method according to claim 9 is characterized in that: comprise the synergistic herbicidal compositions of claim 1 or 4 is used in the presence of other breeding part of the seed of useful crop plant, useful crop or useful crop.
12. method according to claim 11 is characterized in that: wherein said useful crop is cereal, cotton, soybean, sugar beet, sugar sugarcane, rape, corn.
13. method according to claim 11 is characterized in that: wherein said useful crop is rice.
14. method according to claim 9 is characterized in that: undesirable plant is moleplant seed, barnyard grass grass, broadleaved herb, nutgrass flatsedge.
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