CN103271061A - Synergistic weeding composition - Google Patents

Synergistic weeding composition Download PDF

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Publication number
CN103271061A
CN103271061A CN2013102201903A CN201310220190A CN103271061A CN 103271061 A CN103271061 A CN 103271061A CN 2013102201903 A CN2013102201903 A CN 2013102201903A CN 201310220190 A CN201310220190 A CN 201310220190A CN 103271061 A CN103271061 A CN 103271061A
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pyrazosulfuron
pyribenzoxim
weeds
herbicidal compositions
synergistic herbicidal
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CN103271061B (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 synergistic weeding composition. The synergistic weeding composition comprises weeding activity components consisting of pyribenzoxim and pyrazosulfuron-ethyl, and is suitable for selective control of weeds in beneficial crops such as rice. The synergistic weeding composition comprises the weeding activity components consisting of the pyribenzoxim and the pyrazosulfuron-ethyl, wherein the weight ratio of the pyribenzoxim to the pyrazosulfuron-ethyl is 100: 1 to 1:100. The synergistic weeding composition also can comprise a safety agent. The novel weeding composition is prepared through ternary complex formulation of the pyribenzoxim and the pyrazosulfuron-ethyl, so that defects caused by single use of the pyribenzoxim can be effectively overcome, a weed killing spectrum for the weeds is enlarged, and at the same time generation of drug resistance is postponed. The weeds in rice fields can be basically removed by one-time use of the weeding composition, so that the weeding composition is labor saving, time saving, and effort saving, can alleviate some of the rural labor shortage, and at the same time can play a certain role in increase of both production and income of the rice. The weeding composition shows an enhanced effect on the control of broadleaf weeds, gramineae weeds and cyperaceae weeds of the rice fields.

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 activity of weeding component pyribenzoxim and pyrazosulfuron, 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 2013102201903100002DEST_PATH_IMAGE001
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 belong to acetolactate synthestase (ALS) inhibitor, selectivity efficient pyrimidine ether weed killer herbicide, paddy rice, common wheat, Korea lawn grass 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, needle spikesedge herb, difformed galingale herb, Monochoria vaginalis, mexicana, pondweed, carp intestines and broad leaved weed effect.Pure product are tasteless white solid, and fusing point is 128-130oC; Solvability in the water: 3.5ppm; Pyribenzoxim acute LD 50 (mg/kg): rat oral〉5000 (female); Through the skin mouse〉2000; To rabbit skin and eyes nonirritant; Animal there are not teratogenesis, mutagenesis, carcinogenesis.
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.
The pyrazosulfuron Chinese name makes careless jinx, rice song or the rice moon give birth to again, its chemical name be 5-(the amino sulphur of 4,6-dimethoxypyridin base-2-carbamyl-1-methylpyrazole-4-carboxylic acid (ethyl ester), its structural formula is:
Figure 265377DEST_PATH_IMAGE002
Pyrazosulfuron is the efficient selective herbicide for paddy field, belongs to the side chain amino acid synthetic inhibitor.Its active ingredient can spread rapidly in water, being transmitted to the biosynthesis that suppresses acetolactate synthestase, the necessary amino acid valine of plant and isoleucine in the plant body after the root of weeds the absorption stops cell division, suppress the growth of weeds leaves and stems and the stretching, extension of root rapidly, withered fully then.Though weeds still present green after the dispenser sometimes, grow and receive inhibition, lose the competitive ability with paddy rice.Paddy rice absorbs the back and carry out hydroxylating in the plant body, and is degraded to the compound of non-activity rapidly, so pyrazosulfuron is to rice safety.Its drug effect is temperature influence not, and lasting medicine is disposable employed, can control the multiple weeds harm of rice growing season.Better to broad leaved weed, sedge weed control efficiency.Can prevent and treat rice direct seeding field, transplant field, seedling throwing field weeds, as difformed galingale herb, Herba Cyperi Glomerati, firefly Lin, Monochoria vaginalis, Chinese celery, mexicana, angustifolia arrowhead herb, pondweed, blue or green duckweed, Eclipta prostrata etc.But because long-term use continuously, rice field main weeds such as difformed galingale herb, firefly Lin, arrowhead, Monochoria korsakowii, Monochoria vaginalis, Procumbent Falsepimpernel resistance in various degree occurred to pyrazosulfuron.Pyrazosulfuron only has strong inhibitory action to the barnyard grass grass.
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.
In order disposablely to prevent and kill off all weeds in field, enlarge the restriction of killing the grass spectrum of pyribenzoxim, pyrazosulfuron, improve pyribenzoxim and pyrazosulfuron to the careless speed of killing of grass family, sedge family and broad-leaved section weeds.The invention provides a kind of synergistic herbicidal compositions, said composition is carried out pyribenzoxim, pyrazosulfuron composite.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.
Summary of the invention
The present invention seeks at above-mentioned weak point, a kind of synergistic herbicidal compositions is provided, said composition is by carrying out binary built with pyribenzoxim and pyrazosulfuron, 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.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of synergistic herbicidal compositions comprises activity of weeding component (effective dose) pyribenzoxim and pyrazosulfuron, and wherein the weight proportion of pyribenzoxim and pyrazosulfuron is 100:1 to 1:100.
As a further improvement on the present invention, described two kinds of active component pyribenzoxims and pyrazosulfuron weight proportion are 50:1 to 1:50, more preferably 20:1 to 1:20.
A kind of synergistic herbicidal compositions also comprises safener, and 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 pyrazosulfuron.
Described a kind of 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 novel built Herbicidal combinations 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, flat stalk Fischer 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 and wheat.
The present invention also provides the method for a kind of collaborative control of undesirable plant, comprises with the safener of pyribenzoxim, pyrazosulfuron 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, wheat, rice especially by safener benoxacor, fenclorim, dichlormide and mefenpyrdiethyl protection.
Embodiment
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 pyrazosulfuron of herbicidally effective amount.
Above-mentioned two kinds of herbicide components scope by weight ratio are 100:1 to 1:100.Preferred 50:1 to 1:50, more preferably 20:1 to 1:20.
The combination of pyribenzoxim and pyrazosulfuron 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 novel built Herbicidal combinations, 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 novel built Herbicidal combinations 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 novel built Herbicidal combinations 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 novel built Herbicidal combinations 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 novel built Herbicidal combinations 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 novel built Herbicidal combinations 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.
Novel built Herbicidal combinations 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 novel built Herbicidal combinations 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 clearvers, white dead nettle, Veronica, piemarker, Armstrong, lamb's-quarters, the red heart lamb's-quarters, blank pipe is led a cow, the weasel hemp nettle, pale persicaria, willow leaf thorn knotweed, volume stem knotweed, Amaranthus retroflexus, acalypha copperleaf, precious leaf mustard, corn sow thistle, white dead nettle, fruitlet flax, summer cypress, black nightshade, sinapsis alba, the barnyard grass grass, rice Li Shi standing grain, needle spikesedge herb, Herba Cyperi Glomerati, difformed galingale herb, Monochoria vaginalis, Monochoria korsakowii, rhizoma alismatis, short arrowhead, pondweed, firefly Lin, duckweed, bur beggar-ticks, the floating life water starwort, not careless, take turns hot-tempered, little najas marina, three calyx waterworts, the horsefly eye, the sweet wine intestines, mexicana, Chinese celery etc.
The present invention also provides the method for a kind of collaborative control of undesirable plant, comprises the novel built Herbicidal combinations 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.
The present invention also provides the method for a kind of collaborative control of undesirable plant, comprises with the safener of pyribenzoxim, pyrazosulfuron 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 pyrazosulfuron 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 pyrazosulfuron 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, has synergistic function 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.
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.
FORMULATION EXAMPLE
Embodiment 1:20% pyribenzoxim++ 1% pyrazosulfuron oil-suspending agent
Pyribenzoxim 20%
Pyrazosulfuron 1%
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 20% pyribenzoxim+1% pyrazosulfuron oil-suspending agent.
Embodiment 2 10 % pyribenzoxims+2% pyrazosulfuron wetting powder
Pyribenzoxim 10%
Pyrazosulfuron 2%
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 10% pyribenzoxim+2% pyrazosulfuron wetting powder.
Embodiment 3 1% pyribenzoxims+50% pyrazosulfuron wetting powder
Pyribenzoxim 1%
Pyrazosulfuron 50%
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 1% pyribenzoxim+50% pyrazosulfuron wetting powder.
Embodiment 4 0.1% pyribenzoxims+1% pyrazosulfuron salt water dispersible granules
Pyribenzoxim 0.1%
Pyrazosulfuron 1%
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 0.1% pyribenzoxim+1% pyrazosulfuron water dispersible granules after the drying screening.
Embodiment 5 5% pyribenzoxims+0.1% pyrazosulfuron missible oil
Pyribenzoxim 5%
Pyrazosulfuron 0.1%
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 10% pyribenzoxims+0.1% pyrazosulfuron oil suspension emulsion
Pyribenzoxim 10%
Pyrazosulfuron 0.1%
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; Pyrazosulfuron, aromatic solvent 100, ethoxylated castor oil mixing and stirring are obtained the missible oil of pyrazosulfuron; The pyrazosulfuron that obtains is joined in the pyribenzoxim oil-suspending agent, obtain 10% pyribenzoxim+0.1% pyrazosulfuron suspension emulsion.
Embodiment 7 30% pyribenzoxims+1% pyrazosulfuron wetting powder
Pyribenzoxim 30%
Pyrazosulfuron 1%
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 40% pyribenzoxims+4% pyrazosulfuron water dispersible granules
Pyribenzoxim 40%
Pyrazosulfuron 4%
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 pyrazosulfuron again mixes; Add a certain amount of water mixing extruding again and make material.Obtain 40% pyribenzoxim+4% pyrazosulfuron water dispersible granules after the drying screening.
Embodiment 9 2% pyribenzoxims+60% pyrazosulfuron suspension emulsion
Oil phase:
Pyribenzoxim 2%
Methyl oleate 10%
Ethoxylated castor oil 5%
Water:
Pyrazosulfuron 60%
MODIFIED LIGNOSULPHONATE 1%
Water complements to 100%
Pyribenzoxim is dissolved in the methyl oleate, adds ethoxylated castor oil and obtain oil phase; With pyrazosulfuron, MODIFIED LIGNOSULPHONATE and water, sand milling obtains the suspension water of pyrazosulfuron according to prescription; Under agitation oil phase is added water and obtain suspension emulsion.
Embodiment 10 5% pyribenzoxims+10% pyrazosulfuron wetting powder
Pyribenzoxim 5%
Pyrazosulfuron 10%
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 1% pyribenzoxims+20% pyrazosulfuron coated granule
Pyribenzoxim 1%
Pyrazosulfuron 20%
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 1% pyribenzoxims+5% pyrazosulfuron wetting powder
Pyribenzoxim 1%
Pyrazosulfuron 5%
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 20% pyribenzoxims+10% pyrazosulfuron is extruded granule
Pyribenzoxim 20%
Pyrazosulfuron 10%
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 1% pyribenzoxims++ 20% pyrazosulfuron kind clothing agent
Pyribenzoxim 1%
Pyrazosulfuron 20%
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 0.1% pyribenzoxims+10% pyrazosulfuron ZC
Atlox 4913 4%
Citric acid 0.05%
Catalyzer 0.1%
Water 13%
Pyrazosulfuron 10%
PAPI 1.35%
Solvesso 200 10%
Atlox4913 16%
Dispersant LFH 0.3%
Defoamer 0.16%
Urea 8.4%
Pyribenzoxim 0.1%
Water complements to 100%
The oil phase adding that PAPI, pyribenzoxim, 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 pyribenzoxim after the cooling.
Atlox 4913, dispersant LFH, and defoamer, urea, pyrazosulfuron and water mix in proportion, and through sand milling, are prepared into suspending agent.
The pyribenzoxim microcapsules that obtains is added in the suspending agent of pyrazosulfuron, and stirring obtains 0.1% pyribenzoxim+10% pyrazosulfuron ZC.
Embodiment 16 30% pyribenzoxims+5% pyrazosulfuron suspended emulsion
Pyribenzoxim 30%
Pyrazosulfuron 5%
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%
Pyribenzoxim is dissolved among the Solvesso 200, adds ethoxylated castor oil, obtain the missible oil of pyribenzoxim;
With pyrazosulfuron, 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 pyribenzoxim joins in the suspending agent that contains pyrazosulfuron, obtains suspended emulsion.
Embodiment 17 10% pyribenzoxims+2% pyrazosulfuron missible oil
Pyribenzoxim 10%
Pyrazosulfuron 2%
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 18 50% pyribenzoxims+50% pyrazosulfuron
Pyribenzoxim 50%
Pyrazosulfuron 50%
Pyribenzoxim, pyrazosulfuron are proportionally mixed.
Embodiment 19 40% pyribenzoxims+40% pyrazosulfuron+20% benoxacor
Pyribenzoxim 40%
Pyrazosulfuron 40%
Benoxacor 20%
Embodiment 20 49% pyribenzoxims+50% pyrazosulfuron+1% fenclorim
Pyribenzoxim 49%
Pyrazosulfuron 50%
Fenclorim 1%
Embodiment 21 2% pyribenzoxims+2.8% pyrazosulfuron+95.2% dichlormide
Pyribenzoxim 2%
Pyrazosulfuron 2.8%
Dichlormide 95.2%
Embodiment 22 40% pyribenzoxims+48% pyrazosulfuron+2% mefenpyrdiethyl
Pyribenzoxim 40%
Pyrazosulfuron 48%
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 120201DEST_PATH_IMAGE004
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 pyrazosulfuron 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 pyrazosulfuron 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 pyrazosulfuron 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, with the composition of pyribenzoxim and safener, and the mixture of pyribenzoxim and pyrazosulfuron, or pyribenzoxim and pyrazosulfuron are administered to test plant with the mixture as the material of safener test.Using with water slurry of use test material, described water slurry is extruded the granule preparation by embodiment 13 20% pyribenzoxims+10% pyrazosulfuron, 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, pyrazosulfuron; 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 pyrazosulfuron.

Claims (13)

1. synergistic herbicidal compositions, it is characterized in that: include activity of weeding component pyribenzoxim and pyrazosulfuron, wherein the weight proportion of pyribenzoxim and pyrazosulfuron 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 pyrazosulfuron 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 pyrazosulfuron weight proportion are 20:1 to 1:20.
4. 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 pyrazosulfuron.
5. 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.
6. a kind of synergistic herbicidal compositions according to claim 4, 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.
7. synergistic herbicidal compositions is characterized in that: the reactive compound combination that comprises the cooperative effective quantity in claim 1 or 4 mixes with at least a preparation technique usual auxiliaries.
8. the method for a collaborative control of undesirable plant is characterized in that: comprise that the synergistic herbicidal compositions with claim 1 or 4 is applied to growth place or leaf or stem or the seed of undesirable plant.
9. the described method of claim 8, it is characterized in that: undesirable plant is grassy weed, broad leaved weed and sedge weed.
10. method according to Claim 8 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.
11. the method according to claim 10 is characterized in that: wherein said useful crop is cereal, cotton, soybean, sugar beet, sugar sugarcane, rape, corn.
12. the method according to claim 11 is characterized in that: wherein said useful crop is rice.
13. the 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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CN103503899A (en) * 2013-09-12 2014-01-15 广东中迅农科股份有限公司 Pesticide composition containing pyribenzoxim and halosulfuron-methyl
CN103583540A (en) * 2013-10-14 2014-02-19 广东中迅农科股份有限公司 Weeding composition for preventing and weeding gramineae and broad-leaf weeds of paddy field
CN103609581A (en) * 2013-11-13 2014-03-05 山东滨农科技有限公司 Herbicide composition containing pyrazosulfuron-ethyl, pyribenzoxim and S-metolachlor
CN103636649A (en) * 2013-10-30 2014-03-19 广东中迅农科股份有限公司 Ternary mixed weeding composition
CN107372560A (en) * 2017-08-04 2017-11-24 安徽圣丰生化有限公司 A kind of herbicidal composition of pyribenzoxim, dichloro quinolinic acid and pyrazosulfuron
CN108235988A (en) * 2016-12-27 2018-07-03 江苏龙灯化学有限公司 A kind of Herbicidal combinations and its application
CN108235990A (en) * 2016-12-27 2018-07-03 江苏龙灯化学有限公司 A kind of Herbicidal combinations and its application
CN110100835A (en) * 2019-05-13 2019-08-09 台州煜农生物科技有限公司 A kind of mixed herbicidal composite containing trifluoro ketone grass ether and pyrazosulfuron

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CN1247703A (en) * 1998-07-08 2000-03-22 罗纳-普朗克农业公司 Novel herbicide composition
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103503899A (en) * 2013-09-12 2014-01-15 广东中迅农科股份有限公司 Pesticide composition containing pyribenzoxim and halosulfuron-methyl
CN103503899B (en) * 2013-09-12 2017-01-04 广东中迅农科股份有限公司 Containing pyribenzoxim and the composition pesticide of halosulfuronmethyl
CN103583540A (en) * 2013-10-14 2014-02-19 广东中迅农科股份有限公司 Weeding composition for preventing and weeding gramineae and broad-leaf weeds of paddy field
CN103636649A (en) * 2013-10-30 2014-03-19 广东中迅农科股份有限公司 Ternary mixed weeding composition
CN103609581A (en) * 2013-11-13 2014-03-05 山东滨农科技有限公司 Herbicide composition containing pyrazosulfuron-ethyl, pyribenzoxim and S-metolachlor
CN108235988A (en) * 2016-12-27 2018-07-03 江苏龙灯化学有限公司 A kind of Herbicidal combinations and its application
CN108235990A (en) * 2016-12-27 2018-07-03 江苏龙灯化学有限公司 A kind of Herbicidal combinations and its application
CN114027312A (en) * 2016-12-27 2022-02-11 江苏龙灯化学有限公司 Weeding composition for preventing and treating gramineous weeds
CN107372560A (en) * 2017-08-04 2017-11-24 安徽圣丰生化有限公司 A kind of herbicidal composition of pyribenzoxim, dichloro quinolinic acid and pyrazosulfuron
CN110100835A (en) * 2019-05-13 2019-08-09 台州煜农生物科技有限公司 A kind of mixed herbicidal composite containing trifluoro ketone grass ether and pyrazosulfuron

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