A kind of Herbicidal combinations and its application containing pyraclonil and diflufenicanTechnical field
The invention belongs to technical field of pesticide, especially herbicide field, and in particular to one kind is containing pyraclonil and pyrrole fluorineThe Herbicidal combinations of acyl grass amine and its application.
Background technology
Pyraclonil (pyraclonil).Chemical name：1- (the chloro- 4,5,6,7- tetrahydro-pyrazoles of 3- simultaneously [1,5-a] pyridine-2- yls) -5- [methyl (Propargyl) amino] pyrazoles -4- nitriles, structural formula is：
Pyraclonil be rice terrace herbicide, be German Schilling company (being now Beyer Co., Ltd) find with pyrazoloThe novel structure compound of pyridine ring, it is wealthy to barnyard grass and simultaneous annual Ju Mang cyperus irias section firefly Lin, needle spikesedge herbThe wide scope weeds such as leaf weeds Chinese herbaceous peony shape Monochoria korsakowii, Procumbent Falsepimpernel and wild arrowhead for many years, water chestnut have activity very high.
Diflufenican (diflufenican), chemical name：N- (2,4 difluorobenzene base) -2- [(3- trifluoromethyls) benzeneEpoxide] -3- pyridine anilides.The medicine belongs to herxheimer-liked reaction inhibitor, absorbs class Hu trailing plants in the weeds plant of medicamentForetell cellulose content to decline, cause Destruction of Chlorophyll and cell rupture, weeds show as young shoot and decolourize or white, and last plant wilt is deadDie.Barley, wheat, rice terrace can be prevented and treated and prevent and kill off various annual gramineous weeds and some broad leaved weeds.
Current herbicide for paddy field is limited by crop safety, and herbicide controlling spectrum is also limited, and a kind of herbicide single dose is used aloneCan not completely effectively control the generation of paddy field weed, furthermore some herbicides due to the water-soluble big or field lasting period tooLong, consumption is excessive or the uneven residual hazard all easily caused to this season crop or succession crop of dispenser.Inventor is through researchIt was found that, the synergistic complex of herbicide is the effective measures for expanding weed control spectrum and improving preventive effect, so far it is not yet found thatClose the Herbicidal combinations of pyraclonil and diflufenican compounding.
The content of the invention
It is an object of the invention to provide a kind of Herbicidal combinations containing pyraclonil Yu diflufenican.
It is a further object of the present invention to provide application of the Herbicidal combinations in agent for removing grass in paddy field.
The purpose of the present invention is achieved through the following technical solutions：
A kind of Herbicidal combinations containing pyraclonil Yu diflufenican, the Herbicidal combinations are with pyraclonil and pyrrole fluorine acylCareless amine is principle active component, wherein, diflufenican is 1 with the mass ratio of pyraclonil：60~60：1.It is preferred that pyrrole fluorine acyl is carelessAmine is 1 with the mass ratio of pyraclonil：60~40：1, further preferred diflufenican is 1 with the mass ratio of pyraclonil:30~1:50、1：10~30：1.In some preferred technical schemes：Diflufenican can be 34 with pyraclonil：1、29：1、59：1、12：1、60：1、50：1、40：1、20：1、10：1、5：1、1：1、1：5、1：10、1：20、1：30、1：50、1：60 these ratiosSelected in example.
This compound weeding composition can comprise only active component pyraclonil and diflufenican, can also use or prepareWhen to other components are added in active component, the effective ingredient in the Pesticidal combination can be present in combination with enhancing effective amountIn thing.
In Herbicidal combinations, weight/mass percentage composition of the pyraclonil with both diflufenicans in Herbicidal combinations is1%~80%, preferred mass percentage composition is 10%~65%.
In the binary built composition of pyraclonil of the invention and diflufenican, except pyraclonil and pyrrole fluorine acyl grassOutside the active ingredients such as amine, conventional surfactants, thickener, solvent or the solid packing allowed on pesticidal preparations can also be addedDeng any one formulation that auxiliary agent is configured to be allowed on agricultural chemicals.It is preferred that being processed into missible oil, suspending agent, aqueous emulsion, microemulsion, moistureShot agent, wettable powder etc..
Herbicidal combinations of the present invention can be applied in rice terrace annual grassy weeds weeding, particularly prevent and kill off paddy riceUsing with remarkable result in Tanaka's grass family, Cyperaceae and broad leaved weed.
Herbicidal combinations of the invention have advantages below：
1st, activity of weeding is high.Present invention selection can herbicide controlling spectrum difference, advantage and disadvantage complementary pyraclonil and diflufenicanMixture is made into after two kinds of appropriate decrements of herbicide to use, kill weeds by two kinds of different mechanism so that Weed Resistance produces speedDegree is reduced, while two kinds of medicament collaborations work, is greatly enhanced the removing activity of herbicide.
2nd, herbicidal spectrum is wide, and the lasting period is long.After both mixing, it is possible to increase to various grassy weeds, Cyperaceae and broad-leavedThe preventing and treating of weeds.
3rd, Weed Resistance is delayed.Herbicidal combinations of the present invention reduce resistance of the weeds to medicament, and carry by binary builtThe preventive effect of antagonism weeds high, so as to extend the service life of medicament.
4th, it is safe.Because its dosage is under control, make medicament on the premise of drug effect is improve, it is to waterThe security of rice and succession crop is also improved.
Herbicidal combinations of the invention, are applied to agent for removing grass in paddy field, and it can prevent and kill off various grass family, nutgrass flatsedge in rice terraceSection and broad leaved weed, on the premise of drug effect is improve, all have security to paddy rice and succession crop.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present inventionIt is further elaborated.It should be appreciated that specific embodiment described herein is only used to explain the present invention, limit is not used toThe fixed present invention, all simple modifications under concept thereof of the invention to preparation method of the present invention belong to protection model of the inventionWithin enclosing.
Percentage is mass percent in all formulas of following examples.The processing work of the various preparations of the present compositionSkill is prior art, can be varied from according to different situations.
First, formulation prepares embodiment
Embodiment 1：35% diflufenican pyraclonil missible oil (34：1)
Diflufenican 34%, pyraclonil 1%, APES 4%, phenethyl phenol polyethenoxy ether15%, dimethylbenzene complements to 100%, and the missible oil that weight/mass percentage composition is 35% is configured to according to conventional formulation method.
Embodiment 2：30% diflufenican pyraclonil suspending agent (29：1)
Diflufenican 29%, pyraclonil 1%, methyl naphthalene sulfonate formaldehyde condensate 6%, NPE3%th, aluminium-magnesium silicate 0.5%, ethylene glycol 7%, tributyl phosphate 2%, silicone oil 0.2%, balance of water, according to conventional preparation sideMethod is configured to the suspending agent that weight/mass percentage composition is 30%.
Embodiment 3：60% diflufenican pyraclonil water dispersible granules (59：1)
Diflufenican 59%, pyraclonil 1%, NNO (sodium methylene bis-naphthalene sulfonate) 5%, ammonium sulfate 3%, polyethyleneAlcohol 2%, kaolin complements to 100%, and the water-dispersible grain that weight/mass percentage composition is 60% is configured to according to conventional formulation methodAgent (WDG).
Embodiment 4：65% diflufenican pyraclonil wettable powder (12：1)
Diflufenican 60%, pyraclonil 5%, NNO (sodium methylene bis-naphthalene sulfonate) 6%, sodium lignin sulfonate 4%,Kaolin complements to 100%, and the wettable powder (WP) that weight/mass percentage composition is 65% is configured to according to conventional formulation method.
Embodiment 5：61% diflufenican pyraclonil missible oil (60：1)
Diflufenican 60%, pyraclonil 1%, APES 4%, phenethyl phenol polyethenoxy ether15%, dimethylbenzene complements to 100%, and the missible oil that weight/mass percentage composition is 61% is configured to according to conventional formulation method.
Embodiment 6：61% diflufenican pyraclonil missible oil (1：60)
Diflufenican 1%, pyraclonil 60%, APES 4%, phenethyl phenol polyethenoxy ether15%, dimethylbenzene complements to 100%, and the missible oil that weight/mass percentage composition is 61% is configured to according to conventional formulation method.
Embodiment 7：51% diflufenican pyraclonil suspending agent (50：1)
Diflufenican 50%, pyraclonil 1%, methyl naphthalene sulfonate formaldehyde condensate 6%, NPE3%th, aluminium-magnesium silicate 0.5%, ethylene glycol 7%, tributyl phosphate 2%, silicone oil 0.2%, balance of water, according to conventional preparation sideMethod is configured to the suspending agent that weight/mass percentage composition is 51%.
Embodiment 8：51% diflufenican pyraclonil suspending agent (1：50)
Diflufenican 1%, pyraclonil 50%, methyl naphthalene sulfonate formaldehyde condensate 6%, NPE3%th, aluminium-magnesium silicate 0.5%, ethylene glycol 7%, tributyl phosphate 2%, silicone oil 0.2%, balance of water, according to conventional preparation sideMethod is configured to the suspending agent that weight/mass percentage composition is 51%.
Embodiment 9：31% diflufenican pyraclonil water dispersible granules (1：30)
Diflufenican 1%, pyraclonil 30%, NNO (sodium methylene bis-naphthalene sulfonate) 5%, ammonium sulfate 3%, polyethyleneAlcohol 2%, kaolin complements to 100%, and the water-dispersible grain that weight/mass percentage composition is 31% is configured to according to conventional formulation methodAgent.
Embodiment 10：41% diflufenican pyraclonil water dispersible granules (40：1)
Diflufenican 40%, pyraclonil 1%, NNO (sodium methylene bis-naphthalene sulfonate) 5%, ammonium sulfate 3%, polyethyleneAlcohol 2%, kaolin complements to 100%, and the water-dispersible grain that weight/mass percentage composition is 41% is configured to according to conventional formulation methodAgent.
Embodiment 11：42% diflufenican pyraclonil wettable powder (20：1)
Diflufenican 40%, pyraclonil 2%, NNO (sodium methylene bis-naphthalene sulfonate) 6%, sodium lignin sulfonate 4%,Kaolin complements to 100%, and the wettable powder that weight/mass percentage composition is 42% is configured to according to conventional formulation method.
Embodiment 12：21% diflufenican pyraclonil wettable powder (1：20)
Diflufenican 1%, pyraclonil 20%, NNO (sodium methylene bis-naphthalene sulfonate) 6%, sodium lignin sulfonate 4%,Kaolin complements to 100%, and the wettable powder that weight/mass percentage composition is 21% is configured to according to conventional formulation method.
Embodiment 13：33% diflufenican pyraclonil aqueous emulsion (1：10)
Diflufenican 3%, pyraclonil 30%, methyl naphthalene sulfonate formaldehyde condensate 6%, NPE3%th, aluminium-magnesium silicate 0.5%, ethylene glycol 7%, tributyl phosphate 2%, 150# solvent naphthas 20%, water complements to 100%, according to normalThe formulation method of rule is configured to the aqueous emulsion that weight/mass percentage composition is 33%.
Embodiment 14：33% diflufenican pyraclonil aqueous emulsion (10：1)
Diflufenican 30%, pyraclonil 3%, methyl naphthalene sulfonate formaldehyde condensate 6%, NPE3%th, aluminium-magnesium silicate 0.5%, ethylene glycol 7%, tributyl phosphate 2%, 150# solvent naphthas 20%, water complements to 100%, according to normalThe formulation method of rule is configured to the aqueous emulsion that weight/mass percentage composition is 33%.
Embodiment 15：30% diflufenican pyraclonil microemulsion (5：1)
Diflufenican 25%, pyraclonil 5%, methyl naphthalene sulfonate formaldehyde condensate 6%, NPE3%th, aluminium-magnesium silicate 0.5%, ethylene glycol 7%, tributyl phosphate 2%, water complements to 100%, matches somebody with somebody according to conventional formulation methodIt is made the microemulsion that weight/mass percentage composition is 30%.
Embodiment 16：60% diflufenican pyraclonil wettable powder (1：5)
Diflufenican 10%, pyraclonil 50%, NNO (sodium methylene bis-naphthalene sulfonate) 6%, sodium lignin sulfonate 4%,Kaolin complements to 100%, and the wettable powder that weight/mass percentage composition is 60% is configured to according to conventional formulation method.
Embodiment 17：10% diflufenican pyraclonil wettable powder (1：1)
Diflufenican 5%, pyraclonil 5%, NNO (sodium methylene bis-naphthalene sulfonate) 6%, sodium lignin sulfonate 4% is highRidge soil complements to 100%, and the wettable powder that weight/mass percentage composition is 10% is configured to according to conventional formulation method.
2nd, drug effect checking test
1), toxicity determination test
According to active ingredient diflufenican：Pyraclonil quality proportioning is：70:1,34：1、29：1、59：1、12：1、60：1、50：1、40：1、20：1、10：1、5：1、1：1、1：5、1：10、1：20、1：30、1：50、1：60,1：70 are tested, and are surveyedFixed its co-toxicity coefficient to rice terrace common weed barnyard grass.
Test method：The seed of quantitative barnyard grass is seeded in the Disposable paper cup of 9cm respectively, in every glass sow 10~15 seeds, cultivate in illumination box, when the barnyard grass 1-4 leaf phase, spraying treatment are carried out on crawler type crops sprayer.Continue to cultivate in greenhouse after treatment, routine observation respectively processes the preventive effect to weeds, and the weeds weighed after 30d after each treatment are freshWeight, calculates its toxicity regression curve and co-toxicity coefficient.Co-toxicity coefficient is more than 100, shows that two kinds of active principles have synergistic effect,Co-toxicity coefficient is more than 120, shows that two kinds of active principles have notable synergistic effect, and co-toxicity coefficient is less than 100, shows two kinds effectivelyMaterial has antagonism.Measurement result is as shown in table 1.
The toxicity measurement result of table 1
As it can be seen from table 1 pyraclonil is compounded with diflufenican being significantly improved to the herbicidal effect of barnyard grass, two are illustratedPerson's compounding has significant synergies to preventing and kill off barnyard grass.Especially the proportioning of pyraclonil and diflufenican is 1:30~1:50、1：10~30：Between 1, the co-toxicity coefficient after two kinds of active principle compoundings is optimal, illustrates that the present invention makees with obvious synergyWith.
2), field control effectiveness test.
Reagent agent：
Pyraclonil and the re-compounded binary herbicide of diflufenican different ratio prepared by embodiment 1~17.
Comparison medicament：
50% diflufenican WP (commercially available), 1.8% pyraclonil WDG (commercially available).
For studying thing：Paddy rice
Rice seedlings grow fine, robust plant, without other pest and disease damages.
Prevent and kill off object：
The weeds such as barnyard grass, clearvers, Veronica, Monochoria vaginalis, mexicana, difformed galingale herb.
Test method：
According to the area of experimental plot, the good various medicaments of precise, and be watered dilution after, using knapsack sprayer,Carry out even spraying, the special Fan spray head of sprinkler selection herbicide.During spraying, it should be noted that liquid is uniformly sprayed application to experiment smallQu Zhong, accomplishes the phenomenon without drain spray, many sprays.
20d, 40d observe weeds death condition after medicine respectively after experiment, and compare the activity of weeding of various medicaments.ThisOutward, the condition of production (consumption is every mu of consumption of ground active ingredient) of crop is also observed in 1~15d after medicine, to investigateWhether medicament has poisoning to crop.
Embodiments of the invention preparation Herbicidal Testing Trials effect see the table below 2 (20d after medicine) and table 3 (40d after medicine)
The field control effectiveness test result of table 2 (20d after medicine)
The field control effectiveness test result of table 3 (40d after medicine)
From table 2 and table 3 as can be seen that pyraclonil and diflufenican compounding have expansion herbicidal spectrum and improve weeding workThe effect of property, and extend the lasting period of medicament.Broad leaved weed and grassy weed can be effectively prevented and kill off, its preventive effect is better than singleThe preventive effect of agent, illustrates that the two compounding has significant synergy to make the preventive effect of broad leaved weed in rice terrace and grassy weedWith.
Security survey result of the medicament of table 4 to crop
The rice is doing well in each treatment cell, has no any medicine spot, illustrates that various medicaments are safe to paddy rice.