Background technology
Cyanogen insect amide (cyantraniliprole), commodity are called cyazypyr
TMThe experiment code name is DPX-HGW86, chemical name is 3-bromo-N-(4-cyano group-2-methyl-6-(amino-carbonyl) phenyl)-1-(3-chloropyridine-2-yl)-1H-pyrazoles-5-carboxylic acid amides, is a kind of novel O-formammidotiazol-benzamide insecticide that du pont company develops.Cyanogen insect amide belongs to insect ryania acceptor inhibitor, mainly discharge to show and tag and stomach poison function by the intracellular calcium ion of inducing insect ryania receptor modulators, can be used for the control of various crop insects such as paddy rice, vegetables, cotton, beet, especially the control to various lepidoptera pests has special efficacy, other commercialization insecticide varieties that its control efficiency obviously is better than using in the current production, and there are not cross resistance in other insecticides.Based on this, cyanogen insect amide is described as efficient pesticides of new generation in the world.But it is invalid substantially to phytophagous mites and aphid that the shortcoming of cyanogen insect amide is it.
Single carbonamidine (monoamitraz), chemical name is N-(2, the 4-xylyl)-N '-methyl amitraz hydrochloride, the formamidine miticide that belongs to highly effective and safe, have tag, food refusal, avoidance effect, also have stomach toxicity, stifling and systemic action, its main mechanism of action is to suppress the activity of monoamine oxidase in the insect bodies, direct excitation is brought out in non-cholinergic cynapse meeting to the insect central nervous system, has drug-fast mite, scale insect that good result is also arranged to the worm attitude of each developmental stage of Tetranychidae and to other miticides.In addition, single carbonamidine has the great aphid activity of killing, and to useful insect and natural enemies securities such as ladybug, Chrysopa, carnivorism stinkbug, food mite ladybug, cotton field spider, honeybee, silkworms.Therefore, single carbonamidine substitute of can be used as high-toxic pesticide is used to prevent and treat harmful mite and the aphid on the crops such as oranges and tangerines, apple, cotton.But the shortcoming of single carbonamidine is undesirable to the control efficiency of lepidopterous insects such as cotton bollworm, pink bollworm, paddy rice paddy stem borer and striped rice borer etc., and the control spectrum is narrow, and using dosage is big, uses separately to have the risk that produces resistance.
In order to overcome the weakness that cyanogen insect amide is wanting in control mite, aphid, the inventor has done a large amount of composite and biological screening experiments, find cyanogen insect amide and the composite effect that not only keeps cyanogen insect amide high-efficiency prevention and control crop pests of single carbonamidine, and received the characteristic of single carbonamidine highly effective and safe control agricultural evil mite, two spotted spider mite, aphid and mythimna separata are shown obvious synergistic effect.
Through looking into the composition pesticide report that newly has not yet to see relevant cyanogen insect amide and single carbonamidine.
Summary of the invention
The object of the present invention is to provide a kind of is the composition pesticide of active ingredient with insecticide cyanogen insect amide [3-bromo-N-(4-cyano group-2-methyl-6-(amino-carbonyl) phenyl)-1-(3-chloropyridine-2-yl)-1H-pyrazoles-5-carboxylic acid amides] and insecticidal/acaricidal agent list carbonamidine [N-(2, the 4-xylyl)-N '-methyl amitraz hydrochloride].
For achieving the above object, the present invention adopts modern agricultural chemicals to give birth to survey technology, and the co-toxicity coefficient method of utilization Sun Y P ﹠Johnson E R (1960) to filter out with insecticide cyanogen insect amide and insecticidal/acaricidal agent list carbonamidine be the composition pesticide of active ingredient, in mixer, add cyanogen insect amide, single carbonamidine, solvent, non-ionic surface active agent, anion surfactant in proportion, fully mix till homogeneous phase transparent, promptly get the present composition.The weight ratio of cyanogen insect amide and single carbonamidine is 1: 0.1~10, and the weight sum of cyanogen insect amide and single carbonamidine is 2~55% of a composition total weight.
Solvent of the present invention is meant one or more the mixture in water, methyl alcohol, propylene glycol, dimethylbenzene, the alkyl pyrrolidone, and its consumption accounts for 1~80% of composition total weight.
Non-surface-active agent of the present invention is meant one or more the mixture in polyoxyethylene polyoxypropylene block copolymer, alkyl phenol polyvinylether, phenethyl phenol polyethenoxy polyethenoxy ether, alkyl phenol formaldehyde resin polyoxyethylene ether, the castor oil polyoxyethylene ether, and its consumption accounts for 5~30% of composition total weight.
Anion surfactant of the present invention is one or more the mixture in dodecyl benzene sulfonate, dibutyl naphthalene sulfonate, the lignosulfonates, and its consumption accounts for 1~10% of composition total weight.
The present invention has the following advantages:
1. insect is had tangible synergy killing action, and can overcome and delay the generation of pest resistance to insecticide;
2. overcome the narrower limitation of single chemical control spectrum, enlarged the control spectrum, a dispenser can prevent and treat simultaneous various pests and evil mite.
3. be the outstanding alternative kind of high-toxic pesticide.Every mu of effective ingredient consumption is that 0.5~5g is (when active ingredient concentration is 50~200mg/L), the present composition can effectively be prevented and treated vegetables, cotton, fruit tree and flowers and other crops lepidoptera pest, aphid and two spotted spider mite, and can reduce the field dosage, reduce farming originally, lower effectively the pollution of environment and the residue of pesticide in the agricultural product.
Embodiment
In order to understand essence of the present invention better, the invention will be further described below in conjunction with embodiment, but never be limited to following embodiment.
Embodiment 1: in the 250mL round bottom four-hole bottle of agitator is housed, add entry 25g, dimethylbenzene 45.0g, cyanogen insect amide 5.0g, single carbonamidine 10.0g, stirring and dissolving; After treating that two kinds of agricultural chemicals dissolvings finish, add calcium dodecyl benzene sulfonate 10.0g, polyoxyethylene polyoxypropylene block copolymer 5.0g, alkyl phenol polyvinylether 5.0g again, continue to stir, surfactant is dissolved fully, filter, remove insoluble impurities, promptly get 15% cyanogen insect amide list carbonamidine composition pesticide.
Embodiment 2~8: the cyanogen insect amide list carbonamidine composition pesticide of pressing the composite following different content of method of embodiment 1.
Non-ionic surface active agent (g) |
Alkyl phenol formaldehyde resin polyoxyethylene ether 10, alkyl phenol polyvinylether 7 |
Phenethyl phenol polyethenoxy polyethenoxy ether 10, castor oil polyoxyethylene ether 10 |
Phenethyl phenol polyethenoxy polyethenoxy ether 5, castor oil polyoxyethylene ether 15 |
Phenethyl phenol polyethenoxy polyethenoxy ether 20, castor oil polyoxyethylene ether 5 |
Alkyl phenol formaldehyde resin polyoxyethylene ether 15, castor oil polyoxyethylene ether 10 |
Polyoxyethylene polyoxypropylene block copolymer 8, castor oil polyoxyethylene ether 10 |
Polyoxyethylene polyoxypropylene block copolymer 10, phenethyl phenol polyethenoxy polyethenoxy ether 5 |
Anion surfactant (g) |
Dibutyl naphthalene sulfonate 1 |
Dibutyl naphthalene sulfonate 10 |
Dodecyl benzene sulfonate 10 |
Lignosulfonates 3, dodecyl benzene sulfonate 7 |
Lignosulfonates 2, dibutyl naphthalene sulfonate 5 |
Dodecyl benzene sulfonate 3, dibutyl naphthalene sulfonate 3 |
Lignosulfonates 2, dodecyl benzene sulfonate 5 |
Composition levels (%) |
2 |
10 |
18 |
44 |
40 |
30 |
55 |
According to national pesticide quality industry standard such as agricultural chemicals stability of emulsion assay method GB/T1603-2001, agricultural chemicals heat storage stability assay method GB/T19136-2003, agricultural chemicals low-temperature stability assay method GB/T19137-2003 etc., present composition the key technical indexes is measured, be the results are shown in table 1.
Table 1. present composition the key technical indexes measurement result
The composition example |
Active constituent content (%) |
Outward appearance |
Stability of emulsion (200 times) |
Heat storage stability |
Low-temperature stability |
Embodiment 1 composition |
15 |
Homogeneous phase transparent |
Qualified |
Qualified |
Qualified |
Embodiment 2 compositions |
2 |
Homogeneous phase transparent |
Qualified |
Qualified |
Qualified |
Embodiment 3 compositions |
10 |
Homogeneous phase transparent |
Qualified |
Qualified |
Qualified |
Embodiment 4 compositions |
18 |
Homogeneous phase transparent |
Qualified |
Qualified |
Qualified |
Embodiment 5 compositions |
44 |
Homogeneous phase transparent |
Qualified |
Qualified |
Qualified |
Embodiment 6 compositions |
40 |
Homogeneous phase transparent |
Qualified |
Qualified |
Qualified |
Embodiment 7 compositions |
30 |
Homogeneous phase transparent |
Qualified |
Qualified |
Qualified |
Embodiment 8 compositions |
55 |
Homogeneous phase transparent |
Qualified |
Qualified |
Qualified |
Embodiment 9: the present composition is to the co-toxicity of armyworm (Mythimna separata)
Adopt spray-on process that reagent agent is made into certain density mother liquor, it is stand-by to be diluted to 5 concentration with clear water again, establishes clear water and is contrast.Get fresh and tender maize leaves and be cut into the fragment of the long big or small basically identical of about 50mm, with the blade that shears prepare for reagent liquid in dipping 10 seconds, take out allow it dry naturally after, put into the culture dish (φ 90mm) that is lined with filter paper in advance.In ware, insert mythimna separata 3 instar larvaes then, 10 in every ware, every concentration repeats for 3 times.Dispose, cover the ware lid, place the recovery indoor cultivation, routine observation, inspection record death condition behind 72hr is calculated lethality (%), and obtains virulence regression equation formula, correlation coefficient (r) and the lethal concentration of 50 (LC according to the probit value analytical method
50).Co-toxicity coefficient (CTC) method that adopts Sun﹠Johnson (1960) to propose is estimated synergy.Usually, CTC represented to have synergistic effect greater than 120 o'clock, expression tool summation action between CTC is in 80~1 20, and CTC is less than being expressed as antagonism at 80 o'clock.The computing formula of co-toxicity coefficient is as follows:
The percentage composition of B in ATI * mixture of percentage composition+medicament B of A in ATI * mixture of theoretical toxicity index (TTI)=medicament A
The present composition the results are shown in Table 2 to the toxicity test of armyworm.As seen, in the combination that is mixed of cyanogen insect amide and single carbonamidine at 1: 1,1: 2,1: 4,1: 8,1: 10,1: 0.1,1: 0.25,1: 0.5, except that 1: 10 and 1: 0.1 virulence show the summation action, all the other combinations that are mixed all show as the different synergistic effect of degree to armyworm.
Table 2 present composition is to the toxicity test result (72hr) of armyworm
C∶M 1∶1 Y=6.5613+1.7919x 0.9231 0.484 236.82
C∶M 1∶2 Y=5.1610+1.4517x 0.9989 0.895 160.57
C∶M 1∶4 Y=4.5386+2.31 08x 0.9797 1.221 147.07
C∶M 1∶8 Y=3.7972+2.1004x 0.9667 1.773 122.52
C∶M 1∶1 0 Y=2.9799+2.1414x 0.9991 2.309 98.69
C∶M 1∶0.1 Y=5.7932+1.8747x 0.9992 0.655 116.88
C∶M 1∶0.25 Y=6.31 30+2.0257x 0.9905 0.523 160.62
C∶M 1∶0.5 Y=6.1115+1.9711x 0.9596 0.569 167.50
Embodiment 10: the present composition is to the co-toxicity of two-spotted spider mite (Tetranychus urticae)
Adopt infusion process to measure the virulence of the present composition, the results are shown in Table 3 two-spotted spider mite.As seen, in the ratio of cyanogen insect amide and single carbonamidine 1: 1,1: 2,1: 4,1: 8,1: 10,1: 0.1,1: 0.25 and 1: 0.5 is mixed combination, except that 1: 0.1,1: 0.25 and 1: 0.5 combination table reveal the summation action, all the other combinations all show as synergistic effect to two-spotted spider mite.
Table 3, the present composition are to the toxicity test result (48hr) of two-spotted spider mite
Embodiment 11: the greenhouse pot culture test of the present composition anti-eliminate aphis (Aphis fabae)
Adopt the greenhouse pot culture spray-on process to estimate the preventive effect of the present composition to aphid, the result show the present composition to the preventive effect of aphid significantly better than the contrast medicament, see table 4 for details.
Table 4, the present composition, contrast medicament are to the greenhouse pot culture preventive effect of bean aphid
Embodiment 12: the present composition is to the preventive effect of cotton bollworm (Heliocoverpa armigera)
Contained at cotton field, Jining, Shandong second-generation cotton bollworm ovum on June 20th, 2009 and incubate phase spray medicine, cotton variety is cotton No. 11 of Shandong, experimental result show the present composition to the preventive effect of cotton bollworm significantly better than the contrast medicament, see table 5 for details.
Table 5, the present composition, contrast chemical control cotton bollworm field control effectiveness test result (Jining, Shandong, 2009.6)
Annotate: with Duncan ' s multiple range test, it is not remarkable that colleague's numeral back same letter person is illustrated on 0.05 level difference.