WO2017084233A1 - 增效除草组合物 - Google Patents

增效除草组合物 Download PDF

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Publication number
WO2017084233A1
WO2017084233A1 PCT/CN2016/077953 CN2016077953W WO2017084233A1 WO 2017084233 A1 WO2017084233 A1 WO 2017084233A1 CN 2016077953 W CN2016077953 W CN 2016077953W WO 2017084233 A1 WO2017084233 A1 WO 2017084233A1
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WIPO (PCT)
Prior art keywords
active ingredient
methyl
herbicidal composition
acid
synergistic herbicidal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2016/077953
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English (en)
French (fr)
Inventor
金涛
王金信
路兴涛
彭学岗
张景远
赵德
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao Kingagroot Resistant Weed Management Co Ltd
Original Assignee
Qingdao Kingagroot Resistant Weed Management Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao Kingagroot Resistant Weed Management Co Ltd filed Critical Qingdao Kingagroot Resistant Weed Management Co Ltd
Priority to EP16865416.8A priority Critical patent/EP3378314B1/en
Priority to AU2016356028A priority patent/AU2016356028B2/en
Priority to US15/775,868 priority patent/US10506810B2/en
Priority to CA3004797A priority patent/CA3004797C/en
Publication of WO2017084233A1 publication Critical patent/WO2017084233A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N2300/00—Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
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    • A01N37/34—Nitriles
    • A—HUMAN NECESSITIES
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    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
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    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/48—Nitro-carboxylic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
    • A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
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    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
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    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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Definitions

  • the invention belongs to the technical field of pesticide synergy, and particularly relates to a synergistic herbicidal composition comprising a 4-benzoylpyrazole compound.
  • herbicide chemical weeding is the most economical and effective means of controlling weeds in farmland.
  • long-term continuous high-dose use of single-species or single-acting chemical herbicides is likely to cause problems such as weed resistance and resistance evolution.
  • Rational compounding or compounding of herbicide compounds has the advantages of expanding weed spectrum, improving control effect, delaying the occurrence and development of weed resistance and drug resistance, and is one of the most effective methods to solve the above problems.
  • HPPD P-hydroxyphenylpyruvate dioxygenase
  • ACCase acetyl-CoA carboxylase
  • ALS acetolactate synthase
  • Protox protoporphyrin oxidase
  • HPPD inhibitors Another class of new herbicides.
  • the action of HPPD inhibitors is characterized by a broad spectrum of herbicidal activity, which can be used before and after emergence, and the weeds die after whitening. Although the symptoms are very similar to those of carotenoid bioinhibitors, their chemical structural features such as polarity and ionization are significantly different from known carotenoid bioinhibitors.
  • PPO Protoporphyrinogen oxidase
  • PDS phytoene dehydrogenase
  • Photosynthesis photosystem II herbicides in wheat field are: bromoxynil, octanoyl bromoxynil, iodobenzonitrile, bentazone, isoproturon, chloromeron, tertidine, chlorpyrifos, oxalofen
  • Photosynthetic photosystem II herbicide is a selective herbicide for post-emergence stem and leaf treatment. It is mainly absorbed by the leaves. It can quickly make tissue necrosis by inhibiting various processes of photosynthesis.
  • the above-mentioned medicaments can be used for controlling broad-leaved weeds such as sage, leeks and piglets in wheat fields, but when the medicaments are used alone, the dosage is large, and there is a heavier safety risk to wheat, and the weeds are prevented when the dosage is small. Poor effect, need to strictly grasp the application technology and dosage.
  • Photosynthesis photosystem II herbicides and ALS inhibitors such as bensulfuron-methyl, bensulfuron-methyl and diflufenacil have no cross-resistance resistance caused by target resistance.
  • Common phytoene dehydrogenase inhibitor herbicides in wheat field include: flufenacetate, flufenacetin, etc., which are carotenoid biosynthesis inhibitors, causing chlorophyll destruction and cell rupture. Plant death is a broad-spectrum selective wheat field herbicide. It is suitable for barley and wheat fields to control broadleaf weeds such as sage, leeks, piglets and cattle. However, when the medicament is used alone, the dosage is large, and there is a heavier safety risk to the wheat. When the dosage is small, the weed control effect is poor. Strict control of the application technique and dosage. Photosynthesis photosystem II herbicides and ALS inhibitors such as bensulfuron-methyl, bensulfuron-methyl and diflufenacil have no cross-resistance resistance caused by target resistance.
  • the present invention provides a synergistic herbicidal composition
  • a synergistic herbicidal composition comprising a 4-benzoylpyrazole compound, which is effective for controlling broad-leaved weeds in a wheat field, and has an enlarged It has the characteristics of killing grass spectrum, obvious synergistic effect, reducing application rate and safety to crops.
  • a synergistic herbicidal composition comprising a herbicidally effective amount of active ingredient A and active ingredient B, wherein
  • Active ingredient A is a compound
  • the active ingredient B may be selected from one or more of the following compounds:
  • Phenoxycarboxylic acids 2 methyl 4-chloro, 2 methyl 4-chloroethyl sulfide, MCPB, 2 methyl 4-chloropropionic acid, 2 methyl 4-chloro sodium, 2 methyl 4-chloroisooctyl ester, 2,4-D Ester, 2,4-D isooctyl ester, 2,4-dichlorophenoxyacetic acid, 2,4-DB, 2,4-D-propionic acid;
  • pyridine carboxylic acid chloroflupiroxyacetic acid, isooctyl chlorofluoxetine, fluorochloropyridinium ester, triclopyridinic acid, chloropicolinic acid;
  • Hydroxybenzonitriles bromoxynil, octanoyl bromoxynil, iodobenzonitrile;
  • pyridines pyridoxal, flufenacetate
  • acetamides acetochlor, flufenacet, mefenacet, metolachlor, and naphthylamine;
  • aryloxyphenoxypropionates fenoxapropin, clodinafop, acetyl oxalic acid
  • Sulfonylureas bensulfuron-methyl, bensulfuron-methyl, thifensulfuron-methyl, chloropyrazine, methyl disulfuron, sulfonylsulfuron, propofuron, flufensulfuron;
  • Triazines oxazinone, chlorpyrifos, and tertidine;
  • Sulfonamides diflufenacil, sulfometrimine, acesulfame
  • Phenylpyrazoline oxazolin
  • the active ingredient B is 2 methyl 4 chlorine, sodium 2 methyl chloride, 2 methyl 4-chloroisooctyl ester, 2,4-D butyl ester, 2,4-D isooctyl ester, chlorofluoropyridin Acetic acid, isooctyl clofibrate, fluorochloropyridinium, isoproturon, flufenacetate, flufenic acid, oxazolone, acesulfame, fenoxapropion, alkyne Herbyl ester, acetyl oxalic acid, oxadiazon, chlorpyrifossulfonate, methyl disulfuron, flufensulfuron, oxazinone, chlorpyrifos, tertidine, diflufenacil, acesulfame, One or more of oxazolin, bentazone, bromoxynil, octanoy
  • the weight ratio of A to B is 1-100:1-100, preferably the weight ratio of A to B is 1-80:1-80, 1-50:1-50, 1-30:1-30, Preferably, the weight ratio of A to B is from 1 to 20:1-20, 1-10:1-10, and the synergistic effect of the active ingredient A and the active ingredient B is synergistically achieved within a defined weight ratio. .
  • the mass percentage of A and B in the synergistic herbicidal composition is from 1 to 95%, preferably from 10 to 80%, based on the total amount.
  • the herbicidal compositions of the present invention comprise from 1 to 95 parts by weight of active ingredient and from 5 to 99 parts by weight of a conventional pesticide adjuvant.
  • auxiliaries of the compositions of the present invention may be carriers, surfactants and the like.
  • carrier refers to an organic or inorganic, natural or synthetic material. They aid in the administration of the active ingredient which is generally inert and must be agriculturally acceptable, especially accepted by the treated plant.
  • the carrier may be solid, such as clay, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.; or liquid, such as water, alcohols, ketones, petroleum fractions, aromatic or waxy hydrocarbons, chlorine Hydrocarbons, liquefied gases, etc.
  • Surfactants may include emulsifiers, dispersants or wetting agents, which may be ionic or nonionic. Examples which may be mentioned are salts of polyacrylic acid, lignosulfonates, salts of phenolsulfonic or naphthalenesulfonic acid, ethylene oxide with aliphatic alcohols or with aliphatic acids or with aliphatic amines and substituted phenols (especially a polymer of an alkylphenol or an arylphenol, a sulfosuccinate, a taurine derivative (especially a taurine alkyl ester), a phosphate ester of an alcohol or a phosphate of a polyhydroxyethylated phenol, Alkyl sulfonates, alkyl aryl sulfonates, alkyl sulfates, lauryl ether sulfates, fatty alcohol sulfates, and sulfated hexadecane, hepta-
  • compositions may also contain various other components such as protective colloids, binders, thickeners, thixotropic agents, penetrants, stabilizers, chelating agents, dyes, colorants, and polymers.
  • compositions of the present invention may be diluted or used directly by the user prior to use.
  • the preparation can be prepared by a usual processing method, that is, after mixing the active material with a liquid solvent or a solid carrier, and then adding one or more of a surfactant such as a dispersing agent, a stabilizer, a wetting agent, a binder, an antifoaming agent, and the like.
  • a surfactant such as a dispersing agent, a stabilizer, a wetting agent, a binder, an antifoaming agent, and the like.
  • Specific formulations of the herbicidal compositions are emulsifiable concentrates, suspensions, microemulsions, suspoemulsions, aqueous emulsions, dispersible oil suspensions, wettable powders or water-dispersible granules (dry suspensions).
  • the content of the following components is: 1 to 70% of the active ingredient A, 1 to 50% of the active ingredient B, 5 to 10% of the dispersing agent, 2 to 10% of the wetting agent, and the balance of the filler.
  • the active ingredient A, the active ingredient B, the dispersing agent, the wetting agent, and the filler are mixed, uniformly mixed in a mixing tank, pulverized by a jet mill, and then uniformly mixed to obtain a wettable powder product of the composition of the present invention.
  • the content of the following components is as follows: active ingredient A 1 to 70%, active ingredient B 1 to 50%, dispersant 3 to 12%, wetting agent 1 to 8%, disintegrating agent 1 to 10%, binder 1 to 8%, filler balance.
  • the active ingredient A, the active ingredient B, a dispersing agent, a wetting agent, a disintegrating agent, a filler, and the like are pulverized together to obtain a desired particle diameter, and then a binder or the like is added to obtain a granulation material.
  • the water-dispersible granule product of the composition of the present invention is obtained by quantitatively feeding the product into a fluidized bed granulation dryer, granulating and drying.
  • composition When the composition is formulated into a suspending agent, the content of the following components is included: active ingredient A 0.1-40%, active ingredient B 0.1-30%, dispersing agent 2-10%, humectant 2-10%, antifoaming agent 0.1-1%.
  • the binder is 0.1 to 2%, the antifreeze is 0.1 to 8%, and the deionized water is added to 100%.
  • Dispersing agent, wetting agent, antifoaming agent, thickening agent and antifreezing agent in the above formula are uniformly mixed by high speed shearing, adding active ingredient A and active ingredient B, and ball milling in a ball mill for 2 to 3 hours to make the particles
  • the suspension product of the composition of the present invention was obtained in all of the diameters below 5 ⁇ m.
  • composition When the composition is made into a suspoemulsion, the content of the following components is included: active ingredient A 0.1-40%, active ingredient B 0.1-30%, emulsifier 2-12%, dispersant 2-10%, defoamer 0.1-2% , thickener 0.1 to 2%, antifreeze 0.1 to 8%, stabilizer 0.05 to 3%, water to 100%.
  • Dispersing agent, antifoaming agent, thickening agent, antifreeze agent and stabilizer in the above formula are uniformly mixed by high speed shearing, adding active ingredient B to the original drug, and ball milling in a ball mill for 2 to 3 hours to make the particle size all
  • the active ingredient B suspending agent is prepared at 5 ⁇ m or less, and then the active ingredient A original drug, emulsifier and various auxiliary agents are directly emulsified into a suspension by a high-speed stirrer to obtain a suspoemulsion product of the composition of the present invention.
  • composition When the composition is made into an aqueous emulsion, the content of the following components is included: active ingredient A 0.1% to 40%, active ingredient B 0.1% to 30%, solvent 2% to 10%, emulsifier 2% to 12%, dispersant 2%. ⁇ 10%, co-emulsifier 0.2% to 5%, antifreeze 0.1% to 8%, antifoaming agent 0.1% to 2%, thickener 0.1% to 2%, deionized water to 100%.
  • the original drug, solvent, emulsifier and co-emulsifier are added together in the above formula to dissolve into a uniform oil phase. Will go away
  • the water, the dispersing agent, the antifreezing agent, the antifoaming agent and the thickener are mixed together to form a uniform aqueous phase, and the aqueous phase is slowly dropped into the oil phase under high-speed stirring to obtain a dispersion of the composition of the present invention.
  • composition When the composition is made into a microemulsion, the content of the following components is included: active ingredient A 0.1% to 40%, active ingredient B 0.1% to 30%, emulsifier 5% to 15%, solvent 2% to 10%, antifreeze 5 % ⁇ 10%, stabilizer 0.5% ⁇ 3%, deionized water added to 100%.
  • the original drug, solvent and emulsifier in the above formula are added into the mother liquor to prepare a uniform oil phase, and the deionized water and the antifreezing agent are uniformly mixed and injected into the product preparation kettle, and the mixture is uniformly mixed to form the combination of the invention.
  • compositions of the present invention can be combined with solid and liquid additives conventionally used in prior art formulations.
  • the herbicidal composition further comprises a safener C selected from the group consisting of pyrazolium, detoxification quinone, dibenzoxazole acid, cyclopropanesulfonamide, naphthalic anhydride (NA), Chlorfenac, R-28725, AD-67, CGA-154281 (Benoxacor), CGA-43089 (Cyometrinil), CGA-43089 (Cyometrinil), Hoe-70542 (Fenchlorazole), Fenclorim, and grass An, BAS-145138, MON-13900, quinoline derivatives, sulfonylurea (amine) safeners, 2,4-D (organic acids), new antidote T (main component 4% Ti 4+ ) and One or more of gibberellins (GA).
  • a safener C selected from the group consisting of pyrazolium, detoxification quinone, dibenzoxazole acid, cyclopropanesulfonamide,
  • composition of the present invention can be applied to the leaves of the plants to be treated by spraying, i.e., to the weeds, especially on the surface which is infesting or susceptible to weeds which are harmful to the growth of the crop, and the dosage of these active ingredients is usually applied. It is between 15 and 1500 g/ha, preferably between 30 and 750 g/ha.
  • the herbicidal composition of the present invention has passed the 2-year field efficacy test, and it shows that in the period from the 3rd leaf stage to the regreening stage of wheat, the weeds 1-5 leaves are not in the same period, and the symptoms of phytotoxicity are not seen in the wheat from application to maturity. Wheat is safe.
  • the control effect of weeds reached more than 90% in 45 days. With the increase of drug dosage, the control effect increased significantly. Once applied, the weeds could be controlled during the whole growth period of the crop. Not only the herbicidal effect was significant, but also environmentally friendly. No impact on the next crop.
  • composition of the present invention is an environmentally friendly herbicide which is easily degraded in the environment and is safe for both glutinous wheat and post-crop crops.
  • the herbicidal composition of the invention has low cost and convenient use, and has great economic and social benefits for its popularization and application.
  • the herbicidal composition of the present invention can prevent the resistance of broadleaf weeds and prevent ALS inhibitors produce resistant broadleaf weeds and are an effective solution for weed resistance management in wheat fields.
  • active ingredient A when active ingredient B is acesulfame.
  • composition of the formula is: 2.5% A + 0.5% acesulfame + 5% cyclohexanone + 5% calcium dodecylbenzenesulfonate + 5% phenethyl phenol polyoxyethylene ether + 100 # aromatic hydrocarbon solvent oil .
  • active ingredient A when active ingredient B is 2,4-D butyl ester.
  • Formula composition 2.5% A + 23% 2, 4-D butyl ester + 10% isopropanol + 4% calcium dodecylbenzene sulfonate + 6% castor oil polyoxyethylene ether + 150 # aromatic hydrocarbon solvent oil .
  • active ingredient A when active ingredient B is octanoyl bromoxynil.
  • Formulation composition 2.5% A+25% octanoyl bromoxynil + 5% N-methylpyrrolidone + 4% calcium dodecylbenzenesulfonate + 5% fatty alcohol polyoxyethylene ether + 100 # aromatic hydrocarbon solvent oil .
  • active ingredient A when active ingredient B is 2,4-D isooctyl ester.
  • Formulation composition 2.5% A + 25% 2,4-D isooctyl ester + 5% cyclohexanone + 4% calcium dodecylbenzenesulfonate + 6% nonylphenol polyoxyethylene ether + 100 # aromatic solvent Oil to make up.
  • the above processing equipment for the emulsifiable concentrate a vacuum pump, a batching kettle, and a storage tank.
  • active ingredient A active ingredient B is flufenoxyacetic acid.
  • composition of the formula is: 5% A + 12% flufenoxyacetic acid + 10% cyclohexanone + 10% ethanol + 8% sodium dodecyl octyl sulfonate + 8% phenethyl phenol polyoxyethylene ether + 3% phenethyl phenol polyoxyethylene ether formaldehyde resin condensate + water to make up.
  • active ingredient A active ingredient B is benzoxazole.
  • composition of the formula is: 2.5% A + 6% carbazole oxacillin + 6% cyclohexanone + 6% 150 # solvent oil + 10% ethanol + 8% lauryl calcium sulfonate + 8% nonyl phenol Oxyethylene vinyl ether + 5% phenethyl phenol polyoxyethylene ether formaldehyde resin condensate + water to make up.
  • active ingredient A active ingredient B is clodinafop.
  • composition of the formula is: 4% A + 10% clodinafolate + 10% cyclohexanone + 10% ethylene glycol butyl ether + 8% calcium dodecyl sulfonate + 8% castor oil polyoxyethylene ether + 5% benzene Ethylphenol ethoxylate ether formaldehyde resin condensate + water to make up.
  • active ingredient A active ingredient B is oxazolin.
  • composition of the formula is: 5% A + 12% oxazolin + 10% cyclohexanone + 5% 150 # solvent oil + 10% ethylene glycol butyl ether + 8% lauryl calcium sulfonate + 8% fatty alcohol Polyoxyethylene ether + 5% phenethyl phenol polyoxyethylene ether formaldehyde resin condensate + water to make up.
  • microemulsion processing equipment vacuum pump, batching kettle, storage tank.
  • the original drug and the solvent are put into the batching kettle, stirred and dissolved until completely transparent, then the emulsifier is added, and the mixture is evenly stirred. Finally, water is added, and the mixture is stirred until the solution is completely transparent. After the test is passed, the solution is transferred to the tank for filling.
  • active ingredient A active ingredient B is 2 methyl 4-chloroisooctyl ester.
  • Formulation composition 2.5% A+24.5% 2 methyl 4-chloroisooctyl ester + 5% cyclohexanone + 3% phenethyl phenol polyoxyethylene ether phosphate triethanolamine salt + 2% phenethyl phenol polyoxyethylene ether +3% castor oil polyoxyethylene ether + 3% ethylene glycol + water to make up.
  • active ingredient A active ingredient B is fluorochloropyridinium ester.
  • Formulation composition 2.5% A + 0.5% fluorochloropyridinate + 10% cyclohexanone + 10% 150 # solvent oil + 3% nonylphenol polyoxyethylene ether phosphate triethanolamine salt + 2% phenethyl phenol poly Oxyethylene ether + 3% castor oil polyoxyethylene ether + 3% ethylene glycol + water to make up.
  • the above water emulsion processing equipment vacuum pump, batching kettle, storage tank, shearing kettle.
  • the above water emulsion processing process the original drug and the solvent are put into the batching kettle, stirred and dissolved until completely transparent, and then the emulsifier is added, and the mixture is uniformly stirred into an oil phase, and then the ethylene glycol, the defoaming agent and the water are pumped into the shearing kettle. Finally, in the shear state, the oil phase is slowly drawn into the shearing tank. After all the materials are drawn in, the cutting is continued for 1 hour. After the test is passed, the oil is transferred to the tank for filling.
  • composition of the formula is: 1.5% A + 33.5% isoproturon + 5% sodium lignosulfonate + 2% pull powder + 0.2% xanthan gum + 5% glycerol + water to make up.
  • active ingredient A when active ingredient B is tertidine.
  • composition of the formula is: 2.5% A + 47.5% tertidine + 5% naphthalene sulfonate + 2% fatty alcohol polyoxyethylene ether + 0.1% xanthan gum + 5% glycerol + water to make up.
  • active ingredient A when active ingredient B is piracetamide.
  • composition of the formula is: 5% A+30% flufenacetamide + 5% nonylphenol polyoxyethylene ether phosphate triethanolamine salt + 2% fatty alcohol polyoxyethylene ether + 0.15% xanthan gum + 5% propylene Alcohol + balance water to make up.
  • active ingredient A when active ingredient B is flufenacetamide.
  • the formula consists of: 25% A+15% fluroxypyramine + 5% polycarboxylate dispersant + 2% nonylphenol ethoxylate + 0.2% xanthan gum + 5% glycerol + balance Water complements.
  • active ingredient A when active ingredient B is 2 methyl 4-chlorodimethylammonium salt.
  • the formula consists of: 2.5% A+19.5% 2 methyl 4-chlorodimethylammonium salt + 5% polycarboxylate dispersant + 2% fatty alcohol polyoxyethylene ether + 0.3% xanthan gum + 5% glycerol + The remaining amount of water is added.
  • the above suspension processing equipment mixing tank, colloid mill, sand mill, shearing machine and the like.
  • the above suspending agent processing process all materials are put into the mixing tank, stirred and mixed, then passed through the colloid mill, then enter the sand mill three-stage sanding, and finally cut evenly in the shearing machine, and after passing the test, transfer to the storage tank Filling.
  • active ingredient A when active ingredient B is bromoxynil.
  • Formulation composition 2.5% A+17.5% bromoxynil + 5% phenethyl phenol polyoxyethylene ether phosphate triethanolamine salt + 5% fatty acid polyoxyethylene ester + 8% castor oil polyoxyethylene ether + 2% organic Bentonite + methyl oleate to make up.
  • Formulation composition 1.5% A+36% bentazone + 5% sodium sec-butyl dioctyl sulfonate + 5% nonylphenol ethoxylate + 8% castor oil polyoxyethylene ether + 0.5% organic bentonite + Methyl oleate to make up.
  • active ingredient A when active ingredient B is isoproturon.
  • Formulation composition 1.5% A + 35% isoproturon + 5% fatty alcohol polyoxyethylene ether phosphate triethanolamine salt + 5% sorbitan fatty acid polyoxyethylene ester + 2% castor oil polyoxyethylene ether + 0.6 % organic bentonite + methyl oleate to make up.
  • active ingredient A when active ingredient B is methyl disulfuron.
  • composition of the formula is: 5% A + 1.8% methyl disulfuron + 5% sodium sec-butyl dioctyl sulfonate + 5% sorbitan fatty acid polyoxyethylene ester + 6% castor oil polyoxyethylene ether + 3% organic bentonite + 3% fumed silica + 20% soybean oil + methyl oleate to make up.
  • active ingredient A when active ingredient B is flufensulfuron.
  • composition of the formula is: 5% A + 6% flufensulfuron + 5% fatty alcohol polyoxyethylene ether phosphate triethanolamine salt + 5% fatty alcohol polyoxyethylene ether + 4% castor oil polyoxyethylene ether + 3% organic Bentonite + 20% soybean oil + methyl oleate to make up.
  • active ingredient A when active ingredient B is diflufenacil.
  • composition of the formula is: 5% A+1% diflufenacil + 5% sodium sec-butyl dioctyl sulfonate + 5% sorbitan fatty acid polyoxyethylene ester + 4% nonyl phenol polyoxyethylene ether +2.6% organic bentonite + 25% soybean oil + methyl oleate to make up.
  • active ingredient A when active ingredient B is acesulfame.
  • Formulation composition 2.5% A + 0.9% acesulfame + 5% fatty alcohol polyoxyethylene ether phosphate triethanolamine salt + 5% sorbitan fatty acid polyoxyethylene ester + 6% nonylphenol ethoxylate +3% organic bentonite + 25% soybean oil + methyl oleate to make up.
  • the above dispersible oil suspension processing equipment mixing tank, colloid mill, sand mill, shearing machine and the like.
  • composition of the formula is: 1.5% A + 50% green mellon + 10% sodium lignosulfonate + 5% pull powder + 5% precipitation method white carbon black + diatomaceous earth to make up.
  • active ingredient A when active ingredient B is chlorpyrifos.
  • composition of the formula is: 3% A + 30% chlorpyrifos + 8% naphthalene sulfonate + 5% fatty alcohol polyoxyethylene ether + 5% precipitation method white carbon black + calcined kaolin to make up.
  • active ingredient A when active ingredient B is sodium 2-methyltetrachloride.
  • composition of the formula is: 5% A + 35% 2 sodium tetrachloride + 6% polycarboxylate dispersant + 5% fatty alcohol polyoxyethylene ether + 5% precipitation method white carbon black + calcined kaolin to make up.
  • the above wettable powder processing equipment a mechanical pulverizer and a jet mill.
  • the above wettable powder processing process the original drug, the auxiliary agent, the white carbon black, the kaolin, etc. are put into the mechanical pulverizer, and then passed through the airflow pulverizer, and the sample is tested and qualified for use.
  • active ingredient A when active ingredient B is oxadiazon.
  • composition of the formula is: 2.5% A + 0.5% oxalofenone + 10% naphthalene sulfonate + 5% pull-open powder + 1% disintegrant polyvinyl alcohol + filler diatomaceous earth to make up.
  • active ingredient A when active ingredient B is oxazinone.
  • composition of the formula is: 2.5% A+11.5% oxazinone + 10% polycarboxylate + 5% polyethylene glycol + 1% disintegrant polyvinyl alcohol + filler diatomaceous earth to make up.
  • active ingredient A when active ingredient B is 2 to 4 chlorine.
  • composition of the formula is: 2.5% A+16% 2 methyl 4 chlorine + 12% polycarboxylate + 5% fatty alcohol polyoxyethylene ether + 1% disintegrant polyvinyl alcohol + filler kaolin complement.
  • active ingredient A when active ingredient B is humulones.
  • composition of the formula is: 5% A + 60% oxaloin + 15% polycarboxylate + 5% pull powder + 1% disintegrant polyvinyl alcohol + filler bentonite to make up.
  • active ingredient A when active ingredient B is chlorpyrifossulfuron.
  • composition of the formula is: 15% A + 24% chloropyrazine: 20% polycarboxylate + 5% polyethylene glycol + 1% disintegrant polyvinyl alcohol + filler diatomaceous earth to make up.
  • the above water dispersible granule processing equipment jet mill, coulter mixer, basket granulator, drying box, screening machine Wait.
  • the above water-dispersible granule processing process the above materials are uniformly mixed and pulverized by air flow, added with water to knead and granulate, then dried, and finally sieved to obtain a finished product.
  • Amaranth Capsella bursa-pastoris
  • Myosoton aquaticum and Alopecurus japonicus were collected from the cornfield of the test site in Huangdao District, Shandongzhou.
  • the above weeds were cultured by pot culture, and placed in an enamel pan with 180 ⁇ 140mm plastic nutrient bowl.
  • the surface soil was collected from the farmland and passed through the air-screened surface (4/5).
  • the initial humidity of the soil was controlled at 20%.
  • the seeds with full and uniform seeds were soaked in warm water at 25 ° C for 6 hours, germinated in a 28 ° C biochemical incubator (dark), and the white weed seeds were evenly placed on the soil surface, and then covered with soil 0.7 cm.
  • the medicine is placed in a controllable solar greenhouse, and a certain amount of water is regularly added to the enamel tray to keep the soil moist.
  • the desired active ingredient B is a commercially available original drug, and the active ingredient A is a compound of the formula (I) which is produced by the company.
  • the original drugs were all treated with acetone as a solvent, diluted with 0.1% emulsifier T-80 aqueous solution, and now diluted.
  • the characteristics of the two agents and their virulence should be measured, and the main purpose of the formulation should also be considered.
  • the active ingredient A and the active ingredient B were used alone and mixedly in the table. A total of 15 groups were designed. Containing no pharmacy, containing the same solvent and emulsifier Water as a blank control.
  • Each treatment was repeated 4 times, and each time 3 pots were treated, 20 seeds of weed seeds were planted per pot, and 60 plants per treatment.
  • the cultured test materials were evenly placed on a platform with an area of 0.5 m 2 , and sprayed with a 3WP-2000 type walking spray tower, and the spray amount was 30 kg/ha.
  • the spray pressure was 0.3 MPa. After all the liquid medicines have been sprayed, close the air valve. After 30 seconds, open the spray tower door and take out the nutrient bowl. Then open the air valve, spray 50ml of water, and clean the spray tube.
  • the whole seedlings of the living weeds were cut along the surface of the soil with a blade, and the fresh weight of the weeds was weighed by an analytical balance. For dead weeds, the fresh weight is zero.
  • the investigation was conducted 20 days after the treatment, and a total of 1 investigation was conducted.
  • E measured inhibition rate
  • the E-E0 value is greater than 10% for synergism, less than -10% for antagonism, and between -10% and 10% for additive effect. According to the actual control effect and the characteristics of the herbicide, the balance of the formula and other factors determine the best ratio.
  • X is the fresh weight inhibition rate when the amount of the active ingredient A is P; and Y is the fresh weight inhibition rate when the amount of the active ingredient B is Q.
  • Test method the weed seeds are uniformly germinated, and the pre-treated test weed seeds are evenly spread on the soil surface. Before the application, the seedlings were planted, and each pot was fixed to 30 plants, and each pot was treated with 4 pots. The weeds were sprayed with stems and leaves, the number of dead plants was investigated, and the control effect of weed plants was calculated (the average control effect of the plants in the table was the average of 4 replicates). The test was statistically analyzed 45 days later. The results are shown in Table 30:
  • composition of the present invention has a good control effect on broadleaf weeds in the wheat field, and the active ingredients A and 2, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4 Ester, 2 methyl 4-chlorodimethylammonium salt, 2,4-D butyl ester, 2,4-D isooctyl ester, flupiroxine, fluorochloropyridinium, isoproturon, pirfenamide, fluorine Pyridylamine, oxazinone, acesulfame, chlorpyrifos, oxazinone, chlorpyrifos, terbutin, diflufenacil, bentazone, bromoxynil, octanoyl bromide
  • the active ingredients A and 2, 4, 4, 4, 4, 4, 4, 4, 4, 4 Ester 2 methyl 4-chlorodimethylammonium salt, 2,4-D butyl ester, 2,4-D isooctyl ester, flupiroxine, fluoroch
  • oxazolone water-dispersible granules 40% oxazolone water-dispersible granules, 10% acesulfame emulsifiable concentrate, 48% oxazinone suspension, and 10% flufenacetate suspension are slightly medicinal to wheat using high doses. harm.
  • the active ingredient A is between the active ingredients of fenoxapropion, acetyl oxalate, oxadiazon, methyl disulfuron, flufensulfuron, acesulfame, oxazolin, and chloromeron.
  • methyl disulfuron flufensulfuron
  • acesulfame oxazolin
  • chloromeron There are obvious herbicide complements on broadleaf weeds.
  • emulsifiable concentrate As a stem and leaf treatment agent, emulsifiable concentrate, suspoemulsion, suspending agent, dispersible oil suspension agent and water-dispersible granules show good convenience in the application process, and the control effect against weeds is outstanding, and greatly improved. The safety of the crop.
  • the experimental seed wormwood seeds were collected in Sicheng, Shijiazhuang, Hebei province in 2014, and were resistant to benzenesulfuron.
  • the application treatments were carried out using Example 1.3, Example 2.1, Example 3.1, Example 5.1, and Example 5.2.
  • Test method the weed seeds are uniformly germinated, and the pre-treated test weed seeds are evenly spread on the soil surface. Before the application, the seedlings were planted, and each pot was fixed to 30 plants, and each pot was treated with 4 pots. The weeds were sprayed with stems and leaves, the number of dead plants was investigated, and the control effect of weed plants was calculated (the average control effect of the plants in the table was the average of 4 replicates). The test was statistically analyzed 45 days later. The results are shown in Table 31:
  • the application treatment examples 1.3, 2.1, 3.1, 3.2, 5.1, and 5.2 can effectively prevent the target resistance of the phensulfuron-methyl, and there is no cross-resistance with the benzosulfuron.
  • Test method wheat 3 leaves 1 heart, weed 3-5 leaf stage, manual sprayer, water consumption 15 kg / 667 m 2 , spray evenly with stem and leaf spray, the specific test agent and dosage are shown in Table 33, plot area 50 square meters Repeat 4 times per treatment. The effect of investigation on the 45th day after application is shown in Table 33, and the safety of wheat is shown in Table 34.
  • Types of weed communities in each demonstration site Shijiazhuang: Boasted wormwood + leeks; Tai'an: sown wormwood + leeks + pork stalks; Zhumadian: leeks + sown wormwood + pig ⁇ + ⁇ ⁇ ; ⁇ : ⁇ + Pork chop + lacquer; ⁇ : ⁇ + ⁇ + pork chop + broken rice bran + big nest.
  • the herbicidal composition can not only effectively prevent the non-resistant stalks of the wheat field, the leeks, the leeks, the broken rice bran, the pig mites, the sorghum, the cattle sorghum, the maijiagong, the wheat grass, the lacquer, the large Common weeds such as nest vegetables, wild old glutinous rice, mother-in-law, Baogai grass, medlar, thorn vegetable, sorghum, etc., can also effectively prevent common ALS in wheat field such as benzosulfuron, bensulfuron-methyl and diflufenacil.
  • Inhibitors are cross-legged weeds such as A. serrata, Amaranth, Indian amaranth, and broken rice bran, which are cross-resistance due to target resistance.

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Abstract

本发明属于农药增效技术领域，具体涉及一种包含4-苯甲酰吡唑类化合物的增效除草组合物。一种增效除草组合物，其包括除草有效量的活性成分A和活性成分B，其中，活性成分A为化合物（见式A）；活性成分B可选自以下化合物中的一种或多种：1）苯氧羧酸类；2）吡啶羧酸类；3）苯甲酸类；4）羟基苄腈类；5）脲类；6）吡啶类；7）三唑啉酮类；8）二苯基醚类；9）乙酰胺类；10）芳氧基苯氧基丙酸酯类；11）环己二酮类；12）磺酰脲类；13）三嗪类；14）磺酰胺类；15）苯基吡唑啉类；16）其他：灭草松。所述组合物能有效防除小麦田中的阔叶类杂草，具有扩大杀草谱、增效作用明显、减少施用量、对作物安全等特点。

Description

增效除草组合物 技术领域
本发明属于农药增效技术领域，具体涉及一种包含4-苯甲酰吡唑类化合物的增效除草组合物。
背景技术
采用除草剂化学除草是农田杂草防除中最为经济、有效的手段。但长期连续高剂量地使用单一品种或单一作用方式的化学除草剂，容易造成杂草耐药和抗性演化等问题。除草剂化合物的合理复配或混配具有扩大杂草谱、提高防除效果、延缓杂草耐药性和抗药性的发生与发展等优点，是解决上述问题的最为有效的方法之一。
对羟苯基丙酮酸双氧化酶(HPPD)是继乙酰辅酶A羧化酶(ACCase)抑制剂、乙酰乳酸合成酶(ALS)抑制剂和原卟啉原氧化酶(Protox)抑制剂等之后发现的又一类新型除草剂。HPPD抑制剂的作用特点是具有广谱的除草活性，芽前和芽后均可使用，杂草出现白化后死亡。虽其症状与类胡萝卜素生物抑制剂的作用症状极相似，但其化学结构特点如极性和电离度与已知的类胡萝卜素生物抑制剂有明显的不同。HPPD抑制剂类除草剂杂草抗性风险大大低于ACCase抑制剂和ALS抑制剂，并且与苯磺隆、苄嘧磺隆、双氟磺草胺等小麦田常用ALS抑制剂不存在靶标抗性引起的交互抗性。
原卟啉原氧化酶(PPO)抑制剂类除草剂、光合作用光系统II除草剂、八氢番茄红素脱氢酶(PDS)抑制剂类除草剂在小麦田杂草化防体系占有重要位置。
小麦田常见的光合作用光系统II除草剂有：溴苯腈、辛酰溴苯腈、碘苯腈、灭草松、异丙隆、绿麦隆、特丁净、扑草净、嗪草酮等；光合作用光系统II除草剂是作选择性芽后茎叶处理触杀型除草剂，主要由叶片吸收，通过抑制光合作用的各个过程，迅速使组织坏死。以上药剂可用于小麦田防除播娘蒿、荠菜、猪殃殃等阔叶杂草，但是该类药剂单用时，用量多，且对小麦存在较重的安全性风险，用量少时对杂草的防效较差，需要严格把握施药技术和施药剂量。光合作用光系统II除草剂与苯磺隆、苄嘧磺隆、双氟磺草胺等小麦田常用ALS抑制剂不存在靶标抗性引起的交互抗性。
小麦田常见的八氢番茄红素脱氢酶抑制剂类除草剂有：吡氟酰草胺、氟吡酰草胺等，该药属于类胡萝卜素生物合成抑制剂，导致叶绿素破坏及细胞破裂、植物死亡，是广谱的选择性麦田除草剂，适用于大麦、小麦田防除播娘蒿、荠菜、猪殃殃、牛繁缕等阔叶杂草。但是该类药剂单用时，用量多，且对小麦存在较重的安全性风险，用量少时对杂草的防效较差， 需要严格把握施药技术和施药剂量。光合作用光系统II除草剂与苯磺隆、苄嘧磺隆、双氟磺草胺等小麦田常用ALS抑制剂不存在靶标抗性引起的交互抗性。
发明内容
为解决现有技术中存在的上述问题，本发明提供一种包含4-苯甲酰吡唑类化合物的增效除草组合物，该组合物能有效防除小麦田中的阔叶类杂草，具有扩大杀草谱、增效作用明显、减少施用量、对作物安全等特点。
一种增效除草组合物，其包括除草有效量的活性成分A和活性成分B，其中，
活性成分A为化合物
Figure PCTCN2016077953-appb-000001
活性成分B可选自以下化合物中的一种或多种：
1)苯氧羧酸类：2甲4氯、2甲4氯乙硫酯、MCPB、2甲4氯丙酸、2甲4氯钠、2甲4氯异辛酯、2,4-D丁酯、2,4-D异辛酯、2,4-二氯苯氧基乙酸、2,4-DB、2,4-滴丙酸；
2)吡啶羧酸类：氯氟吡氧乙酸、氯氟吡氧乙酸异辛酯、氟氯吡啶酯、三氯吡氧乙酸、二氯吡啶酸；
3)苯甲酸类：麦草畏；
4)羟基苄腈类：溴苯腈、辛酰溴苯腈、碘苯腈；
5)脲类：异丙隆、绿麦隆；
6)吡啶类：吡氟酰草胺、氟吡酰草胺；
7)三唑啉酮类：唑草酮；
8)二苯基醚类：乙羧氟草醚；
9)乙酰胺类：乙草胺、氟噻草胺、苯噻草胺、异丙甲草胺、草萘胺；
10)芳氧基苯氧基丙酸酯类：精恶唑禾草灵、炔草酯、炔草酸；
11)环己二酮类：肟草酮；
12)磺酰脲类：苯磺隆、苄嘧磺隆、噻吩磺隆、氯吡嘧磺隆、甲基二磺隆、磺酰磺隆、丙苯磺隆、氟唑磺隆；
13)三嗪类：嗪草酮、扑草净、特丁净；
14)磺酰胺类：双氟磺草胺、唑嘧磺草胺、啶磺草胺；
15)苯基吡唑啉类：唑啉草酯；
16)其他：灭草松。
作为优选地，所述活性成分B为2甲4氯、2甲4氯钠、2甲4氯异辛酯、2,4-D丁酯、2,4-D异辛酯、氯氟吡氧乙酸、氯氟吡氧乙酸异辛酯、氟氯吡啶酯、异丙隆、吡氟酰草胺、氟吡酰草胺、唑草酮、乙羧氟草醚、精噁唑禾草灵、炔草酯、炔草酸、肟草酮、氯吡嘧磺隆、甲基二磺隆、氟唑磺隆、嗪草酮、扑草净、特丁净、双氟磺草胺、啶磺草胺、唑啉草酯、灭草松、溴苯腈、辛酰溴苯腈、绿麦隆中一种或多种。
其中，A与B的重量比为1-100:1-100，优选A与B的重量比为1-80:1-80，1-50:1-50，1-30:1-30，更优选A与B的重量比为1-20:1-20，1-10:1-10，在所限定的重量比的范围内，活性成分A与活性成分B混配取得协同增效的技术效果。
所述增效除草组合物中A和B的质量百分含量占总量的1-95％，优选10-80％。通常，本发明的除草组合物包含1-95重量份的活性成分和5-99重量份的农药常规助剂。
本发明组合物的常规助剂可以为载体、表面活性剂等。
本文中的术语“载体”表示一种有机或无机、天然或合成的物质。它们有助于活性成分的施用，该载体一般是惰性的且必须是农业上可接受的，特别是被处理的植物所接受。载体可以是固体的，如陶土、天然或合成的硅酸盐、二氧化硅、树脂、蜡、固体肥料等；或者液体的，如水、醇类、酮类、石油馏分、芳烃或蜡烃、氯代烃、液化气等。
表面活性剂可包括乳化剂、分散剂或润湿剂，它可以是离子型或非离子型的。可提及的实例是聚丙烯酸的盐、木质素磺酸盐、苯酚磺酸或萘磺酸的盐、环氧乙烷与脂肪族醇或与脂族酸或与脂肪族胺与取代苯酚(特别是烷基苯酚或芳基苯酚)的聚合物、磺基琥珀酸盐、牛磺酸衍生物(特别是牛磺酸烷脂)及醇的磷酸酯或多羟乙基化的苯酚的磷酸酯、烷基磺酸盐、烷基芳基磺酸盐、烷基硫酸盐、月桂基醚硫酸盐、脂肪醇硫酸盐，以及硫酸化十六-、十七-和十八烷醇以及硫酸化脂肪醇乙二醇醚，此外还有萘或萘磺酸与苯酚和甲醛的缩合物、聚氧乙烯辛基苯基醚、乙氧基化异辛基酚、辛基酚或壬基酚、烷基苯基聚乙二醇醚、三丁基苯基聚乙二醇醚、三硬脂基苯基聚乙二醇醚、烷基芳基聚醚醇、醇和脂肪醇/氧化乙烯缩合物、乙氧基化蓖麻油、聚氧乙烯烷基醚、乙氧基化聚氧丙烯、月桂醇聚乙二醇醚缩醛、山梨醇酯、木素亚硫酸盐废液，以及蛋白质、变性蛋白、多糖(例如甲基纤维素)、疏水改性淀粉、聚乙烯醇、聚羧酸盐、聚烷氧基化物、聚乙烯胺、聚乙烯吡咯烷酮及其共聚物。至少需要一种表面活性剂存在，以有利于活性成分在水中的分散并有利于使它们能正确地施用于植物。
上述组合物也可含有各种其他的组分，如保护胶体、粘合剂、增稠剂、触变剂、渗透剂、稳定剂、螯合剂、染料、着色剂和聚合物。
本发明的组合物可以由使用者在使用前经稀释或直接使用。其配制可由通常的加工方法制备，即将活性物质与液体溶剂或固体载体混合后，再加入表面活性剂如分散剂、稳定剂、湿润剂、粘合剂、消泡剂等中的一种或几种。
所述除草组合物的具体制剂为乳油、悬浮剂、微乳剂、悬乳剂、水乳剂、可分散油悬浮剂、可湿性粉剂或水分散粒剂(干悬浮剂)。
组合物制成可湿性粉剂时包含如下组分含量：活性成分A 1～70％、活性成分B 1～50％、分散剂5～10％、湿润剂2～10％、填料余量。
将活性成分A、活性成分B、分散剂、湿润剂、填料混合，在混合缸中混合均匀，经气流粉碎机粉碎后再混合均匀，即可制成本发明组合物的可湿性粉剂产品。
组合物制成水分散粒剂时包括如下组分含量：活性成分A 1～70％、活性成分B 1～50％、分散剂3～12％、湿润剂1～8％、崩解剂1～10％、粘结剂1～8％、填料余量。
将活性成分A、活性成分B、分散剂、润湿剂、崩解剂、填料等一起经气流粉碎得到需要的粒径，再加入粘结剂等其它助剂，得到制粒用料。将料品定量送进流化床制粒干燥机内经过制粒及干燥后，制得本发明组合物的水分散粒剂产品。
组合物制成悬浮剂时包括如下组分含量：活性成分A 0.1～40％、活性成分B 0.1～30％、分散剂2～10％、湿润剂2～10％、消泡剂0.1～1％、粘结剂0.1～2％、抗冻剂0.1～8％、去离子水加至100％。
将上述配方料中分散剂、湿润剂、消泡剂、增稠剂、抗冻剂经过高速剪切混合均匀，加入活性成分A、活性成分B，在球磨机中球磨2～3小时，使微粒粒径全部在5μm以下，制得本发明组合物的悬浮剂产品。
组合物制成悬乳剂时包括如下组分含量：活性成分A 0.1～40％、活性成分B 0.1～30％、乳化剂2～12％、分散剂2～10％、消泡剂0.1～2％、增稠剂0.1～2％、抗冻剂0.1～8％、稳定剂0.05～3％、水加至100％。
将上述配方料中分散剂、消泡剂、增稠剂、抗冻剂、稳定剂经过高速剪切混合均匀，加入活性成分B原药，在球磨机中球磨2～3小时，使微粒粒径全部在5μm以下，制得活性成分B悬浮剂，然后将活性成分A原药、乳化剂及各种助剂用高速搅拌器直接乳化到悬浮剂中，制得本发明组合物的悬乳剂产品。
组合物制成水乳剂时包括如下组分含量：活性成分A 0.1％～40％、活性成分B 0.1％～30％、溶剂2％～10％、乳化剂2％～12％、分散剂2％～10％、共乳化剂0.2％～5％、抗冻剂0.1％～8％、消泡剂0.1％～2％、增稠剂0.1％～2％、去离子水加至100％。
将上述配方中有原药、溶剂、乳化剂、共乳化剂加在一起，使溶解成均匀油相。将去离 子水、分散剂、抗冻剂、消泡剂、增稠剂混合在一起，成均一水相，在高速搅拌下，将水相慢慢滴入油相，制成本发明组合物分散良好的水乳剂产品。
组合物制成微乳剂时包括如下组分含量：活性成分A 0.1％～40％、活性成分B 0.1％～30％、乳化剂5％～15％、溶剂2％～10％、抗冻剂5％～10％、稳定剂0.5％～3％、去离子水加至100％。
将上述配方中原药、溶剂、乳化剂加入母液调制釜中，制得均匀油相，将去离子水、抗冻剂等混合均匀注入产品调制釜中，经高速搅拌，混合均匀制成本发明组合物透明或半透明的微乳剂产品。
简而言之，本发明的组合物可以和现有技术的配方中常规使用的固体和液体添加剂混合。
在进一步优选的实施形式中，所述除草组合物还包括安全剂C，其选自吡唑解草酯、解毒喹、双苯恶唑酸、环丙磺酰胺、萘二甲酸酐(NA)、氯草烯安、R-28725、AD-67、CGA-154281(Benoxacor)、CGA-43089(Cyometrinil)、CGA-43089(Cyometrinil)、Hoe-70542(Fenchlorazole)、解草酮(Fenclorim)、解草安、BAS-145138、MON-13900、喹啉衍生物、磺酰脲(胺)类安全剂、2,4-D(有机酸类)、新型解毒剂T(主要成份4％Ti4+)和赤霉素(GA)中的一种或多种。
本发明的组合物可通过喷雾的方法被施用于待处理植物叶片上，即施用于杂草，特别是对作物生长有害的杂草侵扰或易侵扰影响的表面上，这些活性成分的施用剂量通常在15-1500克/公顷，优选30-750克/公顷。
本发明所述除草组合物通过2年的田间药效试验表明，在小麦3叶期到返青期，杂草1-5叶不等期，小麦从施药到成熟期未见药害症状，对小麦安全。杂草的防效45天达到90％以上，随着用药量的增大，防效明显增加，一次施药即能控制作物整个生长期内的杂草，不仅除草效果显著，而且对环境友好，对下茬作物无影响。
当施用本发明的除草组合物时，获得了预料不到的增效效果，并且除草活性比使用单个除草剂的活性预期总和，以及单个除草剂单独活性更为显著。增效效果表现为施用量减少、更宽的杂草控制谱、除草作用更快、更持久，这些特性是杂草控制实践过程中所需要的。就所描述的特性来说，这些新组合物明显地优越于现有的除草剂。
本发明的除草组合物还具有下述优点：
(1)本发明的组合物属于环境友好型除草剂，在环境中均易于降解，对当茬小麦和后茬作物均很安全。
(2)本发明除草组合物成本低、使用方便，其推广应用有巨大的经济效益和社会效益。
(3)与现有技术相比，本发明所述除草组合物既能防除非抗性阔叶类杂草，又能防除对 ALS抑制剂产生抗性的阔叶杂草，是小麦田杂草抗性管理的有效方案。
具体实施方式
下列实施例并非限制本发明，而只是用来说明本发明是如何实现的。对于某些杂草，这些实施例显示出特别显著的有效性。
A、实施例
1)乳油
1.1)、活性成分A，当活性成分B为乙羧氟草醚。
配方组成为：2.5％A+0.5％乙羧氟草醚+5％环己酮+5％十二烷基苯磺酸钙+5％苯乙基酚聚氧乙烯醚+100#芳烃溶剂油补足。
1.2)、活性成分A，当活性成分B为2,4-D丁酯。
配方组成为：2.5％A+23％2,4-D丁酯+10％异丙醇+4％十二烷基苯磺酸钙+6％蓖麻油聚氧乙烯醚+150#芳烃溶剂油补足。
1.3)、活性成分A，当活性成分B为辛酰溴苯腈。
配方组成为：2.5％A+25％辛酰溴苯腈+5％N-甲基吡咯烷酮+4％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+100#芳烃溶剂油补足。
1.4)、活性成分A，当活性成分B为2,4-D异辛酯。
配方组成为：2.5％A+25％2,4-D异辛酯+5％环己酮+4％十二烷基苯磺酸钙+6％壬基酚聚氧乙烯醚+100#芳烃溶剂油补足。
上述乳油的加工设备：真空泵、配料釜、储罐。
上述乳油的加工过程：将所有物料投入配料釜中，搅拌溶解至完全透明，化验合格后，转移至储罐灌装。
2)微乳剂
2.1)、活性成分A，活性成分B为氯氟吡氧乙酸。
配方组成为：5％A+12％氯氟吡氧乙酸+10％环己酮+10％乙醇+8％顺丁烯二仲辛酯磺酸钠+8％苯乙基酚聚氧乙烯醚+3％苯乙基酚聚氧乙烯醚甲醛树脂缩合物+水补足。
2.2)、活性成分A，活性成分B为精恶唑禾草灵。
配方组成为：2.5％A+6％精恶唑禾草灵+6％环己酮+6％150#溶剂油+10％乙醇+8％十二烷基本磺酸钙+8％壬基酚聚氧乙烯醚+5％苯乙基酚聚氧乙烯醚甲醛树脂缩合物+水补足。
2.3)、活性成分A，活性成分B为炔草酯。
配方组成为：4％A+10％炔草酯+10％环己酮+10％乙二醇丁醚+8％十二烷基本磺酸钙+8％蓖麻油聚氧乙烯醚+5％苯乙基酚聚氧乙烯醚甲醛树脂缩合物+水补足。
2.4)、活性成分A，活性成分B为唑啉草酯。
配方组成为：5％A+12％唑啉草酯+10％环己酮+5％150#溶剂油+10％乙二醇丁醚+8％十二烷基本磺酸钙+8％脂肪醇聚氧乙烯醚+5％苯乙基酚聚氧乙烯醚甲醛树脂缩合物+水补足。
上述微乳剂加工设备：真空泵、配料釜、储罐。
上述微乳剂加工过程：将原药和溶剂投入配料釜中，搅拌溶解至完全透明，之后加入乳化剂，搅拌均匀，最后加水，搅拌至溶液完全透明，化验合格后，转移至储罐灌装。
3)水乳剂
3.1)、活性成分A，活性成分B为2甲4氯异辛酯。
配方组成为：2.5％A+24.5％2甲4氯异辛酯+5％环己酮+3％苯乙基酚聚氧乙烯醚磷酸酯三乙醇胺盐+2％苯乙基酚聚氧乙烯醚+3％蓖麻油聚氧乙烯醚+3％乙二醇+水补足。
3.2)、活性成分A，活性成分B为氟氯吡啶酯。
配方组成为：2.5％A+0.5％氟氯吡啶酯+10％环己酮+10％150#溶剂油+3％壬基酚聚氧乙烯醚磷酸酯三乙醇胺盐+2％苯乙基酚聚氧乙烯醚+3％蓖麻油聚氧乙烯醚+3％乙二醇+水补足。
上述水乳剂加工设备：真空泵、配料釜、储罐、剪切釜。
上述水乳剂加工过程：将原药和溶剂投入配料釜中，搅拌溶解至完全透明，之后加入乳化剂，搅拌均匀为油相，之后将乙二醇、消泡剂和水抽入剪切釜内，最后在剪切状态下，将油相缓缓抽入剪切釜内，全部物料抽入后，继续剪切1个小时，化验合格后，转移至储罐灌装。
4)悬浮剂
4.1)、活性成分A，当活性成分B为异丙隆。
配方组成为：1.5％A+33.5％异丙隆+5％木质素磺酸钠+2％拉开粉+0.2％黄原胶+5％丙三醇+水补足。
4.2)、活性成分A，当活性成分B为特丁净。
配方组成为：2.5％A+47.5％特丁净+5％萘磺酸盐+2％脂肪醇聚氧乙烯醚+0.1％黄原胶+5％丙三醇+水补足。
4.3)、活性成分A，当活性成分B为吡氟酰草胺。
配方组成为：5％A+30％吡氟酰草胺+5％壬基酚聚氧乙烯醚磷酸酯三乙醇胺盐+2％脂肪醇聚氧乙烯醚+0.15％黄原胶+5％丙三醇+余量水补足。
4.4)、活性成分A，当活性成分B为氟吡酰草胺。
配方组成为：25％A+15％氟吡酰草胺+5％聚羧酸盐类分散剂+2％壬基酚聚氧乙烯醚+0.2％黄原胶+5％丙三醇+余量水补足。
4.5)、活性成分A，当活性成分B为2甲4氯二甲铵盐。
配方组成为：2.5％A+19.5％2甲4氯二甲铵盐+5％聚羧酸盐类分散剂+2％脂肪醇聚氧乙烯醚+0.3％黄原胶+5％丙三醇+余量水补足。
上述悬浮剂加工设备：混料釜、胶体磨、砂磨机、剪切机等。
上述悬浮剂加工过程：将所有物料投入混料釜中，搅拌混合后过胶体磨，之后进入砂磨机三级砂磨，最后在剪切机中剪切均匀，化验合格后，转移至储罐灌装。
5)可分散油悬浮剂
5.1)、活性成分A，当活性成分B为溴苯腈。
配方组成为：2.5％A+17.5％溴苯腈+5％苯乙基苯酚聚氧乙烯醚磷酸酯三乙醇胺盐+5％脂肪酸聚氧乙烯酯+8％蓖麻油聚氧乙烯醚+2％有机膨润土+油酸甲酯补足。
5.2)、活性成分A，当活性成分B为灭草松。
配方组成为：1.5％A+36％灭草松+5％顺丁烯二仲辛酯磺酸钠+5％壬基酚聚氧乙烯醚+8％蓖麻油聚氧乙烯醚+0.5％有机膨润土+油酸甲酯补足。
5.3)、活性成分A，当活性成分B为异丙隆。
配方组成为：1.5％A+35％异丙隆+5％脂肪醇聚氧乙烯醚磷酸酯三乙醇胺盐+5％失水山梨醇脂肪酸聚氧乙烯酯+2％蓖麻油聚氧乙烯醚+0.6％有机膨润土+油酸甲酯补足。
5.4)、活性成分A，当活性成分B为甲基二磺隆。
配方组成为：5％A+1.8％甲基二磺隆+5％顺丁烯二仲辛酯磺酸钠+5％失水山梨醇脂肪酸聚氧乙烯酯+6％蓖麻油聚氧乙烯醚+3％有机膨润土+3％气相法白炭黑+20％豆油+油酸甲酯补足。
5.5)、活性成分A，当活性成分B为氟唑磺隆。
配方组成为：5％A+6％氟唑磺隆+5％脂肪醇聚氧乙烯醚磷酸酯三乙醇胺盐+5％脂肪醇聚氧乙烯醚+4％蓖麻油聚氧乙烯醚+3％有机膨润土+20％豆油+油酸甲酯补足。
5.6)、活性成分A，当活性成分B为双氟磺草胺。
配方组成为：5％A+1％双氟磺草胺+5％顺丁烯二仲辛酯磺酸钠+5％失水山梨醇脂肪酸聚氧乙烯酯+4％壬基酚聚氧乙烯醚+2.6％有机膨润土+25％豆油+油酸甲酯补足。
5.7)、活性成分A，当活性成分B为啶磺草胺。
配方组成为：2.5％A+0.9％啶磺草胺+5％脂肪醇聚氧乙烯醚磷酸酯三乙醇胺盐+5％失水山梨醇脂肪酸聚氧乙烯酯+6％壬基酚聚氧乙烯醚+3％有机膨润土+25％豆油+油酸甲酯补足。
上述可分散油悬浮剂加工设备：混料釜、胶体磨、砂磨机、剪切机等。
上述可分散油悬浮剂加工过程：将所有物料投入混料釜中，搅拌混合后过胶体磨，之后 进入砂磨机三级砂磨，最后在剪切机中剪切均匀，化验合格后，转移至储罐灌装。
6)可湿性粉剂
6.1)、活性成分A，当活性成分B为绿麦隆。
配方组成为：1.5％A+50％绿麦隆+10％木质素磺酸钠+5％拉开粉+5％沉淀法白炭黑+硅藻土补足。
6.2)、活性成分A，当活性成分B为扑草净。
配方组成为：3％A+30％扑草净+8％萘磺酸盐+5％脂肪醇聚氧乙烯醚+5％沉淀法白炭黑+煅烧高岭土补足。
6.3)、活性成分A，当活性成分B为2甲4氯钠。
配方组成为：5％A+35％2甲4氯钠+6％聚羧酸盐类分散剂+5％脂肪醇聚氧乙烯醚+5％沉淀法白炭黑+煅烧高岭土补足。
上述可湿性粉剂加工设备：机械粉碎机、气流粉碎机。
上述可湿性粉剂加工过程：将原药、助剂、白炭黑、高岭土等投入机械粉碎机中，之后过气流粉碎机，取样化验合格后备用。
7)水分散粒剂
7.1)、活性成分A，当活性成分B为唑草酮。
配方组成为：2.5％A+0.5％唑草酮+10％萘磺酸盐类+5％拉开粉+1％崩解剂聚乙烯醇+填料硅藻土补足。
7.2)、活性成分A，当活性成分B为嗪草酮。
配方组成为：2.5％A+11.5％嗪草酮+10％聚羧酸盐类+5％聚乙二醇+1％崩解剂聚乙烯醇+填料硅藻土补足。
7.3)、活性成分A，当活性成分B为2甲4氯。
配方组成为：2.5％A+16％2甲4氯+12％聚羧酸盐类+5％脂肪醇聚氧乙烯醚+1％崩解剂聚乙烯醇+填料高岭土补足。
7.4)、活性成分A，当活性成分B为肟草酮。
配方组成为：5％A+60％肟草酮+15％聚羧酸盐类+5％拉开粉+1％崩解剂聚乙烯醇+填料膨润土补足。
7.5)、活性成分A，当活性成分B为氯吡嘧磺隆。
配方组成为：15％A+24％氯吡嘧磺隆+20％聚羧酸盐类+5％聚乙二醇+1％崩解剂聚乙烯醇+填料硅藻土补足。
上述水分散粒剂加工设备：气流粉碎机、犁刀式混合机、篮式造粒机、干燥箱、筛分机 等。
上述水分散粒剂加工过程：将上述物料混合均匀过气流粉碎，加水入捏合造粒，之后干燥，最后筛分得到成品。
B、药效试验
1)试验条件
1.1)、供试靶标
荠菜(Capsella bursa-pastoris)、牛繁缕(Myosoton aquaticum)、日本看麦娘(Alopecurus japonicus)采自山东省黄岛区试验基地玉米田。
上述杂草采用盆栽法培养，用180х140mm塑料营养钵，摆放于搪瓷盘中，内装从农田采回经风干过筛的表层土壤(4/5处)，土壤湿度初期均控制在20％，挑选籽粒饱满均一的杂草种子，用25℃温水浸泡6小时，在28℃生化培养箱(黑暗)中催芽，将刚刚露白的杂草种子均匀摆放在土壤表面，然后覆土0.7cm。药剂处理后置于可控日光温室内培养，定期在搪瓷盘中加入一定量的水，保持土壤湿润。
1.2)、培养条件
在可控日光温室内进行，温度18～30℃，自然光照，相对湿度57％～72％。
土壤类型为壤土，有机质含量为1.63％，pH＝7.1，碱解氮84.3mg/kg，速效磷38.5mg/kg，速效钾82.1mg/kg。
1.3)、仪器设备
3WP-2000型行走式喷雾塔，农业部南京农业机械研究所。GA110型万分之一电子天平(德国)；ZDR2000智能数据记录仪(杭州泽大仪器有限公司)；SPX型智能生化培养箱(宁波江南仪器厂)。
2)试验设计
2.1)、试剂
2.1.1)、试验药剂
所需活性成分B均为市售原药，活性成分A为式(I)化合物，该化合物为本公司生产。
原药均采用丙酮作溶剂，用含量0.1％乳化剂T-80水溶液稀释，现用现稀释。
2.2)、试验处理
2.2.1)、剂量设置
在确定活性成分A与活性成分B各组分配比或含量时，应从两种药剂的作用特点及其毒力等衡量，还要考虑该配方的主要使用目的。本研究在前期预试的基础上，设活性成分A、活性成分B单用及混合用量分别见表格，共设计15组。以不含药剂、含相同溶剂及乳化剂 的水作为空白对照。
2.2.2)、试验重复
每处理重复4次，每次每处理3盆，每盆播种杂草种子20粒，每处理共60株。
2.3)、处理方式
2.3.1)、处理时间和次数
试验共用药1次。待杂草2叶1心期，间苗，保持每盆内杂草15株，每处理保留45株，然后继续培养至荠菜、牛繁缕3-5叶期、日本看麦娘3叶1心期进行处理。
2.3.2)、使用器械和用药方法
将培养好的试材均匀摆放在面积0.5m2的平台上，用3WP-2000型行走式喷雾塔茎叶喷雾，喷液量按30公斤/公顷计。喷雾压力0.3MPa。待全部药液喷完后，关闭气阀，30秒后，打开喷雾塔门，取出营养钵。然后打开气阀，喷清水50ml，清洗喷液管。
3)试验方法
采用盆栽法。杂草培养见2.1，参照《农药室内生物测定试验准则除草剂》进行。用药方法见3.3.2，采用茎叶处理法。
4)、数据调查与统计分析
4.1)、调查方法
采用绝对数调查法，用刀片沿土壤表面切断存活杂草整株幼苗，用分析天平称量杂草鲜重。对于已经死亡的杂草，按鲜重为零计。
4.2)、调查时间和次数
处理后20天调查，共调查1次。
4.3)、数据统计分析
用Gowing法计算各处理混合组合的理论鲜重抑制率(E0＝X+Y-X*Y/100)，然后与实测抑制率(E)相比较，评价二者混用对杂草的联合作用类型，当E-E0值大于10％为增效作用、小于-10％为拮抗作用、在-10％～10％之间为加成作用。并根据实际防效和除草剂特点、配方的平衡性等因素确定最佳配比。
式中X为活性成分A用量为P时的鲜重抑制率；Y为活性成分B用量为Q时的鲜重抑制率。
统计结果见下表。
表1 活性成分A与2甲4氯混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000002
Figure PCTCN2016077953-appb-000003
表2 活性成分A与2甲4氯钠混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000004
Figure PCTCN2016077953-appb-000005
表3 活性成分A与2甲4氯异辛酯混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000006
Figure PCTCN2016077953-appb-000007
表4 活性成分A与2甲4氯二甲铵盐混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000008
表5 活性成分A与2,4-D丁酯混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000009
Figure PCTCN2016077953-appb-000010
表6 活性成分A与2,4-D异辛酯混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000011
Figure PCTCN2016077953-appb-000012
表7 活性成分A与氯氟吡氧乙酸混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000013
表8 活性成分A与氟氯吡啶酯混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000014
表9 活性成分A与唑草酮混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000015
Figure PCTCN2016077953-appb-000016
表10 活性成分A与乙羧氟草醚混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000017
Figure PCTCN2016077953-appb-000018
表11 活性成分A与嗪草酮混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000019
表12 活性成分A与扑草净混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000020
Figure PCTCN2016077953-appb-000021
表13 活性成分A与特丁净混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000022
Figure PCTCN2016077953-appb-000023
表14 活性成分A与双氟磺草胺混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000024
表15 活性成分A与灭草松混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000025
Figure PCTCN2016077953-appb-000026
表16 活性成分A与异丙隆混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000027
Figure PCTCN2016077953-appb-000028
表17 活性成分A与吡氟酰草胺混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000029
Figure PCTCN2016077953-appb-000030
表18 活性成分A与吡氟酰草胺混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000031
表19 活性成分A与精噁唑禾草灵混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000032
Figure PCTCN2016077953-appb-000033
表20 活性成分A与炔草酯混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000034
Figure PCTCN2016077953-appb-000035
表21 活性成分A与炔草酯混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000036
表22 活性成分A与氯吡嘧磺隆混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000037
Figure PCTCN2016077953-appb-000038
表23 活性成分A与甲基二磺隆混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000039
Figure PCTCN2016077953-appb-000040
表24 活性成分A与氟唑磺隆混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000041
表25 活性成分A与啶磺草胺混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000042
表26 活性成分A与唑啉草酯混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000043
Figure PCTCN2016077953-appb-000044
表27 活性成分A与溴苯腈混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000045
Figure PCTCN2016077953-appb-000046
表28 活性成分A与辛酰溴苯腈混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000047
表29 活性成分A与绿麦隆混用对杂草的实际防效以及联合作用效应(Gowing法)
Figure PCTCN2016077953-appb-000048
Figure PCTCN2016077953-appb-000049
1)利用实施例1.1-7.5制得的除草剂组合物防除小麦田杂草试验。
试验方法：将杂草种子统一催芽，将预处理的供试杂草种子均匀撒播于土壤表面。施药前进行间苗，每盆定苗至30株，每个处理4盆试材。对杂草进行茎叶喷雾处理，调查死亡的株数，计算杂草株防效(表中株防效为4次重复的平均值)，于试验45天后统计试验情况，结果如表30：
Figure PCTCN2016077953-appb-000050
表30 本发明的除草剂对小麦田杂草的防除效果
Figure PCTCN2016077953-appb-000051
Figure PCTCN2016077953-appb-000052
Figure PCTCN2016077953-appb-000053
Figure PCTCN2016077953-appb-000054
Figure PCTCN2016077953-appb-000055
Figure PCTCN2016077953-appb-000056
Figure PCTCN2016077953-appb-000057
从表中试验结果可以看出，本发明的组合物对小麦田阔叶类杂草具有很好的防除效果，活性成分A与2甲4氯、2甲4氯钠、2甲4氯异辛酯、2甲4氯二甲铵盐、2,4-D丁酯、2,4-D异辛酯、氯氟吡氧乙酸、氟氯吡啶酯、异丙隆、吡氟酰草胺、氟吡酰草胺、唑草酮、乙羧氟草醚、氯吡嘧磺隆、嗪草酮、扑草净、特丁津、双氟磺草胺、灭草松、溴苯腈、辛酰溴苯腈活性成分之间具有显著的增效作用，对播娘蒿、荠菜的增效作用尤为明显，对小麦安全。单剂中，40％唑草酮水分散粒剂、10％乙羧氟草醚乳油、48％嗪草酮悬浮剂、10％氟吡酰草胺悬浮剂在使用高剂量对小麦有轻微的药害。活性成分A与精恶唑禾草灵、炔草酸(酯)、肟草酮、甲基二磺隆、氟唑磺隆、啶磺草胺、唑啉草酯、绿麦隆活性成分之间在阔叶杂草上有明显的的杀草互补。作为茎叶处理剂，乳油、悬乳剂、悬浮剂、可分散油悬浮剂、水分散粒剂在施药过程中表现出了很好的便利性，且对杂草的防效突出，同时大大提高了对作物的安全性。
2)对ALS抑制抗性播娘蒿的效果试验
试验播娘蒿种子于2014年采集于河北石家庄藁城，对苯磺隆存在抗性。选用实施例1.3、实施例2.1、实施例3.1、实施例5.1、实施例5.2进行施药处理。试验方法：将杂草种子统一催芽，将预处理的供试杂草种子均匀撒播于土壤表面。施药前进行间苗，每盆定苗至30株，每个处理4盆试材。对杂草进行茎叶喷雾处理，调查死亡的株数，计算杂草株防效(表中株防效为4次重复的平均值)，于试验45天后统计试验情况，结果如表31：
Figure PCTCN2016077953-appb-000058
表31 对ALS抑制抗性播娘蒿的效果试验情况
Figure PCTCN2016077953-appb-000059
施药处理实施例1.3、2.1、3.1、3.2、5.1、5.2均可有效防除对苯磺隆产生靶标抗性的播娘蒿，与苯磺隆不存在交互抗性。
3)本发明组合物防治小麦田杂草的示范试验
2014年在河北石家庄、山东泰安、河南驻马店、河南漯河、江苏泗阳5个麦区25个试验点进行示范性推广试验。不同示范区小麦品种详见表32。
表32 不同示范区小麦品种情况
示范区 小麦品种 类型
石家庄 藁优5766 硬质白麦
泰安 烟麦20 硬质白麦
驻马店 周麦26 硬质白麦
漯河 豫麦18 硬质白麦
泗阳 扬麦158 硬质红麦
试验方法：小麦3叶1心后，杂草3-5叶期，手动喷雾器，兑水量15公斤/667m2，采用茎叶喷雾均匀喷雾，具体试验药剂及剂量见表33，小区面积50平方米，每处理重复4次。施药后45天调查防除效果见表33，小麦安全性情况见表34。
Figure PCTCN2016077953-appb-000060
表33 大田示范效果情况
Figure PCTCN2016077953-appb-000061
Figure PCTCN2016077953-appb-000062
表34 大田示范小麦安全性情况
Figure PCTCN2016077953-appb-000063
Figure PCTCN2016077953-appb-000064
注：各示范点内杂草群落类型：石家庄：播娘蒿+荠菜；泰安：播娘蒿+荠菜+猪殃殃；驻马店：荠菜+播娘蒿+猪殃殃+繁缕；漯河：荠菜+猪殃殃+泽漆；泗阳：荠菜+牛繁缕+猪殃殃+碎米荠+大巢菜。
经过大量试验和探索，本发明意外地发现，4-苯甲酰吡唑类除草剂与活性成分B混用，用于小麦田苗后防除阔叶类杂草，具有令人惊讶的、意想不到的增效作用，尤其是对播娘蒿、荠菜、印度蔊菜、碎米荠等十字花科杂草具有尤其明显的增效作用，对ALS抑制剂、PPO抑制剂产生抗性的上述杂草，不存在交互抗性，防效突出，明显高于两者单用，表现出明显的增效作用，同时可降低用量，提高作物安全性，降低对环境的污染，且合理复配降低了农用成本，具有很好的前景。
除草组合物不仅能有效防除小麦田的非抗性播娘蒿、荠菜、印度蔊菜、碎米荠、猪殃殃、繁缕、牛繁缕、麦家公、麦瓶草、泽漆、大巢菜、野老鹳、婆婆纳、宝盖草、藜、刺儿菜、萹蓄等常见杂草，还能有效防除对苯磺隆、苄嘧磺隆、双氟磺草胺等小麦田常用ALS抑制剂因靶标抗性而引起交互抗性的播娘蒿、荠菜、印度蔊菜、碎米荠等十字花科杂草。

Claims (10)

  1. 一种增效除草组合物，其特征在于，包括除草有效量的活性成分A和活性成分B，其中，
    活性成分A为化合物
    Figure PCTCN2016077953-appb-100001
    活性成分B可选自以下化合物中的一种或多种：
    1)苯氧羧酸类：2甲4氯、2甲4氯乙硫酯、MCPB、2甲4氯丙酸、2甲4氯钠、2甲4氯异辛酯、2,4-D丁酯、2,4-D异辛酯、2,4-二氯苯氧基乙酸、2,4-DB、2,4-滴丙酸；
    2)吡啶羧酸类：氯氟吡氧乙酸、氯氟吡氧乙酸异辛酯、氟氯吡啶酯、三氯吡氧乙酸、二氯吡啶酸；
    3)苯甲酸类：麦草畏；
    4)羟基苄腈类：溴苯腈、辛酰溴苯腈、碘苯腈；
    5)脲类：异丙隆、绿麦隆；
    6)吡啶类：吡氟酰草胺、氟吡酰草胺；
    7)三唑啉酮类：唑草酮；
    8)二苯基醚类：乙羧氟草醚；
    9)乙酰胺类：乙草胺、氟噻草胺、苯噻草胺、异丙甲草胺、草萘胺；
    10)芳氧基苯氧基丙酸酯类：精恶唑禾草灵、炔草酯、炔草酸；
    11)环己二酮类：肟草酮；
    12)磺酰脲类：苯磺隆、苄嘧磺隆、噻吩磺隆、氯吡嘧磺隆、甲基二磺隆、磺酰磺隆、丙苯磺隆、氟唑磺隆；
    13)三嗪类：嗪草酮、扑草净、特丁净；
    14)磺酰胺类：双氟磺草胺、唑嘧磺草胺、啶磺草胺；
    15)苯基吡唑啉类：唑啉草酯；
    16)其他：灭草松。
  2. 根据权利要求1所述的增效除草组合物，其特征在于，活性成分B为2甲4氯、2甲4氯钠、2甲4氯异辛酯、2,4-D丁酯、2,4-D异辛酯、氯氟吡氧乙酸、氯氟吡氧乙酸异辛酯、氟氯吡啶酯、异丙隆、吡氟酰草胺、氟吡酰草胺、唑草酮、乙羧氟草醚、精噁唑禾草灵、炔 草酯、炔草酸、肟草酮、氯吡嘧磺隆、甲基二磺隆、氟唑磺隆、嗪草酮、扑草净、特丁净、双氟磺草胺、啶磺草胺、唑啉草酯、灭草松、溴苯腈、辛酰溴苯腈、绿麦隆中一种或多种。
  3. 根据权利要求1或2的增效除草组合物，其特征在于，A与B的重量比为1-100:1-100。
  4. 根据权利要求1或2的增效除草组合物，其特征在于，A与B的重量比为1-50:1-50。
  5. 根据权利要求1或2的增效除草组合物，其特征在于，A与B的重量比为1-20:1-20。
  6. 根据权利要求1或2的增效除草组合物，其特征在于，所述除草组合物中A和B的质量百分含量占总量的1-95％，优选10-80％。
  7. 根据权利要求1或2的增效除草组合物，其特征在于，所述除草组合物的具体制剂为乳油、悬浮剂、微乳剂、悬乳剂、水乳剂、可分散油悬浮剂、可湿性粉剂或水分散粒剂。
  8. 根据权利要求1或2的增效除草组合物，其特征在于，还包括安全剂C。
  9. 根据权利要求8的增效除草组合物，其特征在于，所述安全剂C选自吡唑解草酯、解毒喹、双苯恶唑酸、环丙磺酰胺、萘二甲酸酐、氯草烯安、R-28725、AD-67、CGA-154281、CGA-43089、CGA-43089、Hoe-70542、解草酮、解草安、BAS-145138、MON-13900、喹啉衍生物、2,4-D、新型解毒剂T和赤霉素中的一种或多种。
  10. 如权利要求1-9任意一项所述增效除草组合物在防治有害杂草中的应用。
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