Background technology
Lufenuron (Lufenuron), another name: chlorine is fragrant new, Lufenuron, fluorine the third oxygen urea, chemical name: N-[[[2,5-two chloro-4-(1,1,2,3,3,3-hexafluoro the third oxygen) phenyl] amino] carboxyl]-2, the 6-difluorobenzamide.Trade name: U.S.A removes.
Lufenuron belongs to the benzoyl area kind Insecticidal and acaricidal agent, is a kind of insect growth regulator, IGR, and its mechanism of action is suppress insect chitin synthetic, affects the formation of insect cuticle and reaches the insecticidal action purpose, has stomach toxicity and action of contace poison.
Lufenuron is mainly used in the crops such as corn, grape, soybean and vegetables.Lufenuron can be used to prevent and treat diamond-back moth, prodenia litura, cabbage caterpillar, beet armyworm, tomato moth, cotton bollworm, thrips, lima bean pod borer, rust mite, plant hopper, citrus leaf-miner etc., this product has outstanding preventive effect to food leaf caterpillars such as fruit trees, thrips, rust mite, trialeurodes vaporariorum there are unique mechanism of killing, are applicable to control pyrethroid and organophosphorous pesticide are produced resistant insect.The lasting period of lufenuron is long, is conducive to reduce the laxative number of times; To crop safety, corn, vegetables, oranges and tangerines, cotton, potato, grape, Soybean and Other Crops all can be used, and are suitable for Integrated pest and administer and Agricultural product without pollution.Lufenuron can not cause that sucking pest is rampant again, to the adult of beneficial insect and pounce on feeding habits mite action temperature and.The lasting medicine of lufenuron, resistance of rainwater washing against has selectivity to useful arthropods adult.Lufenuron has preferably ovicidal effect, can kill new product worm's ovum, 2~3 days visual effects after the dispenser.Lufenuron, can use during honeybee producting honey the mammal low toxicity honeybee and hornet low toxicity, and is relatively more safer than organic phosphor, carbamate chemicals for agriculture, can be used as good mixed agent and uses, and lepidoptera pest is had good control efficiency.
Worm hydrazides (Tebufenozide), chemical name: N-tertiary butyl-N '-(4-ethylamino benzonitrile acyl group)-3,5-dimethyl benzene hydrazides.Trade name: rice is full.
The worm hydrazides is the on-steroidal Novel insect growth regulator of U.S. rom Haars Co., Ltd nineteen ninety research and development, and its mechanism of action is to cast off a skin in the time should not casting off a skin behind the larval feeding, not exclusively causes larva dehydration, hungry and dead owing to casting off a skin.
The worm hydrazides is mainly used in preventing and treating the crops such as citrus, cotton, ornamental crops, potato, soybean, tobacco, fruit tree and vegetables.Tebufenozide pesticide is active high, and selectivity is strong, and speed of action is fast, and is all effective to all lepidopterous larvaes, and antagonism insect diamond-back moth, cotton bollworm, cabbage caterpillar, beet armyworm etc. have special efficacy, and extremely strong ovicidal activity is arranged, and be safer to non-target organism.The worm hydrazides is to eyes and skin nonirritant, and is without teratogenesis, carcinogenic, mutagenesis, all fool proof to mammal, birds, natural enemy to higher mammal.
The lufenuron shortcoming is that desinsection speed is slower, and the insecticide of needs and desinsection speed uses simultaneously.In addition, the lufenuron cost is higher, can not be applied to widely the crop pests control.
The long-term continuous single use of lufenuron or worm hydrazides easily causes pest resistance to insecticide, causes the pesticide resistance of insect more and more stronger, even causes pest resurgence, causes dosage to increase, and has so both increased cost accounting, has polluted again environment, has reduced crop quality.In recent years, some primary pests such as diamond-back moth, prodenia litura, beet armyworm, cabbage caterpillar, vegetable aphid, Trialeurodes vaporariorum Westwood etc. on China vegetables, rice field primary pest rice fulgorid and cotton primary pest aphid, two spotted spider mite, cotton bollworm etc., some conventional pesticide kinds have generally been produced resistance, caused that control efficiency obviously descends, pest resurgence.According to incompletely statistics, diamond-back moth produces resistance to more than the 50 kind of insecticide such as organochlorine, organic phosphor, carbamate, acylureas, bacillus thuringiensis,Bt, comprises growth regulator has also been produced resistance as pressing down hooligan, UC 62644 etc.; Prodenia litura all develops immunity to drugs to insecticides such as organochlorine, organic phosphor, carbamates, pyrethroid and Bt preparations.Therefore, development is efficient, low toxicity, low-residual complex preparation, helps to prevent and overcome pest to develop immunity to drugs, and helps to prolong the service life of pesticide species.
Summary of the invention
The object of the present invention is to provide a kind of synergistic composition that contains lufenuron and worm hydrazides.
The present invention a kind ofly is characterized in that take lufenuron and worm hydrazides as desinsection (mite) composition and the application thereof of main active effective ingredient is comprised of lufenuron and worm hydrazides, and its ratio of quality and the number of copies is 10: 1~1: 50, is preferably 1: 1~1: 20.Described active ingredient is present in the composition with the synergy effective dose, and the better mass fraction of effective ingredient lufenuron is 1%~10%, the better mass fraction of worm acyl calf is 1%~50%, and all the other are insecticides adjuvant and excipients (or filler).
The present invention can be used for preventing and treating the insects (mite) such as diamond-back moth, beet armyworm, striped rice borer, cabbage caterpillar, prodenia litura, lima bean pod borer, cotton bollworm, oriental tobacco budworm, tea geometrid, tea caterpillar, trialeurodes vaporariorum, thrips, rust mite take lufenuron and worm hydrazides as desinsection (mite) synergistic composition of primary activity composition.
The present invention is take active ingredient lufenuron and worm hydrazides as main, is mixed with microemulsion, suspending agent, aqueous emulsion, water dispersible granules, wetting powder or missible oil with suitable insecticides adjuvant, excipients (or filler).Described auxiliary agent determines that according to formulation the present invention conducts in-depth research the auxiliary agent of microemulsion and suspending agent, and scheme is respectively:
(1) when the preparation microemulsion, its auxiliary agent is: by quality of the pharmaceutical preparations emulsifier 5%~12%, solvent 3%~30%, stabilizing agent 0.1%~10%, antifreezing agent 0.1%~2%.Described emulsifier is NaLS, calcium dodecyl benzene sulfonate (agricultural newborn 500#), neopelex, lignosulfonates, carboxymethyl cellulose, Nongru-700 # (alkyl phenol formaldehyde resin polyoxyethylene ether), the newborn 400# of farming, the newborn 2201# of farming, TX-10 (Nonyl pheno (10) ether), triphen ethyl-phenol polyoxyethylene polyoxypropylene block polymer, phenethyl phenol polyethenoxy ethers (such as newborn 600# series of farming etc.), dibenzyl xenol polyethenoxy ether class (such as the newborn 300# of farming), castor oil polyoxyethylene ether is (such as the By emulsifier, peaceful breast 130 etc.), the EO-PO block copolymer, sorbitan fatty acid ester APEO (such as tween series), sorbitan fatty acid ester (such as Span series), Polypropylene Glycol Glycerin Ether, the mixture of one or more in the glycerin polyoxyethylene ether polyoxypropylene ether fatty acid ester; Described solvent is one or more the mixture in dimethylbenzene, toluene, methyl alcohol, ethanol, n-butanol, ethylene glycol, acetone, cyclohexanone, pyrrolidones, diesel oil, solvent naphtha (S-150, S-180, S-200), dimethyl formamide, dimethyl sulfoxide (DMSO), cyclohexane, the ethyl acetate, use when multiple, total usage amount can not be greater than the maximum of deal; Described stabilizing agent is one or more the mixture in methyl alcohol, benzinum, urea, wettable starch, triphenyl phosphite, epoxychloropropane, aceticanhydride, the tolyl glycidic alcohol; Described antifreezing agent is one or more the mixture in glycerine, propane diols, ethylene glycol, sodium chloride, sorbierite, the sorbic acid.
(2) when the preparation suspending agent, its auxiliary agent is: by quality of the pharmaceutical preparations wetting dispersing agent 1%~40%, thickener 0.1%~10%, defoamer 0.5%~10%, stabilizing agent 0%~10%, preservative 0%~5%, antifreezing agent 0.1%~5%.Described wetting dispersing agent is that alkylphenol polyoxyethylene formaldehyde condensation products sodium sulphate is (such as SOPA230,235 etc.), lauryl alcohol polyethylene glycol oxide base ether sodium sulfate, alkylnaphthalene sulfonate (pulling open powder etc.), dialkyl succinylsuccinate sulfonate, alkylphosphonic, alkylnaphthalene sulfonate, alkylsulfonate, the alkylaryl naphthalene sulfonate, aliphatic alcohol sulfate, lignin and derivative sulfonate thereof, sorbitan fatty acid ester polyoxyethylene ether--tween series, the glycerin polyoxyethylene polyethenoxy ether, alkylphenol polyoxyethylene, fatty alcohol polyethenoxy ether class (such as JFC), phenethyl phenol polyethenoxy ethers, the polyoxyethylene poly-oxygen propylene aether block copolymer, the alkylpolyoxyethylene phosphate, starch, gelatin, polyvinyl alcohol etc. can be one or more mixtures; Described thickener is xanthans, pectin, gelatin, gum Arabic, guar gum, polyvinyl alcohol, the basic cellulose of hydroxyl first (second), methylcellulose, sodium alginate, carrageenan, clay mineral (such as bentonite), Magnesiumaluminumsilicate, soluble starch, dispersed silica gel, gaseous state silica, gypsum etc. can be one or more mixtures; Described defoamer is higher alcohol (such as isooctanol, isoamyl alcohol etc.), fatty acid (lauric acid, stearic acid etc.), silicone etc., can be one or more mixture; Described stabilizing agent is xanthan gum, pyrogallol, salicylic acid, ascorbic acid, sodium sorbate, Sodium Benzoate, butyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, polyethylene glycol diglycidyl ether, chloropropylene oxide, hydroquinones, bisnaphthol, 1-naphthols salicylic acid, benzoic acid, rosemary oil, epoxidized soybean oil, castor oil, olive oil, linseed oil, Magnesiumaluminumsilicate etc., can be one or more mixture; Described preservative is formaldehyde, benzoic acid, Sodium Benzoate etc., can be one or more mixture; Described antifreezing agent is ethylene glycol, propane diols, glycerine, urea, diethylene glycol (DEG), polyethylene glycol, sorbierite etc., can be one or more mixture.
After the invention has the advantages that lufenuron and worm hydrazides are mixed, the one, can widen control of insect spectrum, can be in a drug doublely control crop growth two or more simultaneous insects in the phase; The 2nd, can save the labour, reduce cost accounting; The 3rd, improve preventive effect or prolong the longevity of residure; The 4th, can overcome and delay insect and develop immunity to drugs, prolong the service life of pesticide species; The 5th, green pesticide form, environmental contamination reduction has alleviated toxicity.
Embodiment
The inventor is by a large amount of Seiving Tests, and discovery lufenuron and worm hydrazides are mixed diamond-back moth, beet armyworm, cabbage caterpillar are had synergistic function, and field test results shows that also the effect of mixture preparation is better than the use of single dose.
In order better to understand essence of an invention, below in conjunction with example technology contents of the present invention is described in detail, but content of the present invention do not limit to so, can not therefore be interpreted as the restriction to claim of the present invention.
The former medicine effective content of lufenuron used in following examples is 95%, and the former medicine effective content of used worm hydrazides is 95%.
Embodiment 1:
Prepare 5% lufenuron worm hydrazides (1% lufenuron+4% worm hydrazides) microemulsion:
Take by weighing the former medicine 1.06g of lufenuron, the former medicine 4.22g of worm hydrazides, agricultural newborn 2201#8g, dimethyl sulfoxide (DMSO) 10g, acetone 5g, epoxychloropropane 6g, sorbierite 1g, surplus deionized water.
Preparation process:
Former medicine, dimethyl sulfoxide (DMSO) and acetone are added together, make and be dissolved into even oil phase; The newborn 2201# of farming, epoxychloropropane, sorbierite and deionized water are dropped in the emulsion dispersion still, under high-speed stirred, form water; Then oil phase is dropped in the emulsion dispersion still, begin to stir under 500~15000 rev/mins rotating speed, mixing time is 0.5~1.5 hour, makes homogeneous, transparent, stable 5% lufenuron worm hydrazides microemulsion through high speed shear.
It is similar to Example 1 that following examples prepare the process of microemulsion.
Embodiment 2:
Prepare 20% lufenuron worm hydrazides (1% lufenuron+19% worm hydrazides) microemulsion, the mass ratio of each component is respectively:
The former medicine 1.06g of lufenuron, the former medicine 21.04g of worm hydrazides, lignosulfonates 10g, dimethyl sulfoxide (DMSO) 20g, acetone 5g, triphenyl phosphite 6g, glycerine 0.5g, surplus deionized water.
Embodiment 3:
Prepare 20% lufenuron worm hydrazides (0.4% lufenuron+19.6% worm hydrazides) microemulsion, the mass ratio of each component is respectively:
The former medicine 0.42g of lufenuron, the former medicine 20.63g of worm hydrazides, calcium dodecyl benzene sulfonate 10g, dimethyl sulfoxide (DMSO) 20g, cyclohexanone 10g, tolyl glycidic alcohol 6g, benzinum 1g, surplus deionized water.
Embodiment 4:
Prepare 5% lufenuron worm hydrazides (4.5% lufenuron+0.5% worm hydrazides) microemulsion, the mass ratio of each component is respectively:
The former medicine 4.74g of lufenuron, the former medicine 0.53g of worm hydrazides, agricultural newborn 400#8g, acetone 5g, dimethyl sulfoxide (DMSO) 5g, methyl alcohol 6g, sorbic acid 0.5g, surplus deionized water.
Embodiment 5:
Prepare 5% lufenuron worm hydrazides (1% lufenuron+4% worm hydrazides) suspending agent, the mass ratio of each component is respectively:
Take by weighing the former medicine 1.06g of lufenuron, the former medicine 4.22g of worm hydrazides, alkylnaphthalene sulfonate 5g, polyvinyl alcohol 4g, isoamyl alcohol 4g, castor oil 5g, Sodium Benzoate 0.2g, polyethylene glycol 0.5g, surplus deionized water.
Preparation process:
The former medicine that will contain first lufenuron and worm hydrazides mixes, adding in proportion alkylnaphthalene sulfonate fully stirs again, then adding successively each component such as polyvinyl alcohol, isoamyl alcohol, castor oil, Sodium Benzoate, polyethylene glycol, deionized water in the ratio of filling a prescription mixes, stir while adding evenly, ball milling is 2.0~4.0 hours in ball mill, so that the particle diameter of lufenuron and worm hydrazides all gets 5% lufenuron Tebufenozide suspending agent when 4 μ m are following.
It is similar to Example 5 that following examples prepare the process of suspending agent.
Embodiment 6:
Prepare 20% lufenuron worm hydrazides (1% lufenuron+19% worm hydrazides) suspending agent, the mass ratio of each component is respectively:
The former medicine 1.06g of lufenuron, the former medicine 21.04g of worm hydrazides, aliphatic alcohol sulfate 15g, sodium alginate 5g, isooctanol 4g, sodium sorbate 5g, benzoic acid 0.2g, sorbierite 0.5g, surplus running water.
Embodiment 7:
Prepare 20% lufenuron worm hydrazides (0.4% lufenuron+19.6% worm hydrazides) suspending agent, the mass ratio of each component is respectively:
The former medicine 0.42g of lufenuron, the former medicine 20.63g of worm hydrazides, lauryl alcohol polyethylene glycol oxide base ether sodium sulfate 15g, gum Arabic 5g, lauric acid 4g, rosemary oil 5g, formaldehyde 0.1g, ethylene glycol 0.5g, surplus deionized water.
Embodiment 8:
Prepare 5% lufenuron worm hydrazides (4.5% lufenuron+0.5% worm hydrazides) suspending agent, the mass ratio of each component is respectively:
The former medicine 4.74g of lufenuron, the former medicine 0.53g of worm hydrazides, alkylphenol polyoxyethylene 10g, methylcellulose 5g, stearic acid 4g, sodium sorbate 5g, benzoic acid 0.1g, glycerine 0.1g, surplus running water.
Determination of activity example 1: subjects is diamond-back moth (Plutella xylostella L) larva
Test method: with reference to People's Republic of China's agricultural industry criteria (" farm-chemical indoor determination test rule " insecticidal n Y/T1154.9-2008.
Carry out first preliminary experiment, according to the concentration range of the consequence devised reagent agent of preliminary experiment.Each single dose and preparation are established respectively 5 concentration, take 3 diamond-back moth in age (Plutella xylostella L) larvas as subjects.
The Potter spray-on process is adopted in this test.Filter paper is put into the culture dish that diameter is 9cm, add an amount of distilled water, make filter paper moistening, but ponding can not be arranged, get rid of the air between filter paper and the culture dish, it is for subsequent use to make filter paper be close to the culture dish bottom, with the moisturizing of moisturizing cotton balls.The atomisation pressure of Potter spray tower is stabilized in 1.47 * 10
5Pa, fog-spray nozzle clean 2 times with acetone first, clean 2 times with distilled water again.Utilize the Potter spray tower quantitatively to spray, spray value is 1mL, and 15 diamond-back moth 3 instar larvaes of every repetition take out diamond-back moth behind the sedimentation 1min after the spraying, put into the culture dish of fresh cabbage leaves and raise, and every ware is 1 repetition, and every concentration is established 4 repetitions.Contrast is processed with the aqueous acetone solution with amount.After processing, cleans 2 times with acetone, distilled water the complete drug concentration of every spray.At last culture dish is put into constant incubator (temperature: 25 ℃, relative moisture: 70%, periodicity of illumination L: D=16: 8h).72h investigation examination worm death condition after processing.
According to the data of investigation, calculate the lethality that each is processed, calculate the corrected mortality that each is processed with the AbbottShi formula, ask for virulence regression equation with DPS software, calculate LC
50, LC
95And LC
5095% confidence limit.According to the co-toxicity coefficient (CTC) of the abundant method calculating of Sun Yun built agent, relatively the insecticidal effect of each mixture is estimated its synergistic effect.The common poison of built agent is that (CTC) 〉=120 show as synergistic effect; CTC≤80 show as antagonism; 80<CTC<120 show as summation action.
Each single dose of table 1 and mixture thereof are to the toxicity test result of diamond-back moth 3 instar larvae 72h
According to the Toxicity Determination result, lufenuron: the worm hydrazides is 10: 1 to 1: 50 o'clock, co-toxicity coefficient (CTC) is all greater than 120, illustrate that each proportioning all has synergistic effect, especially lufenuron: the worm hydrazides is 1: 1 to 1: 19 o'clock, and co-toxicity coefficient (CTC) is all greater than 200, synergistic effect is obvious, lufenuron particularly: the worm hydrazides is 1: 19 o'clock, and co-toxicity coefficient (CTC) is greater than 300, and synergistic effect is obvious especially.
Determination of activity example 2: subjects is beet armyworm (Spodoptera exigua H ü bner) larva
Test method is with determination of activity example 1, and described examination worm is beet armyworm 3 instar larvaes.
Each single dose of table 2 and mixture thereof are to the toxicity test result of beet armyworm 3 instar larvae 72h
According to the Toxicity Determination result, lufenuron and worm hydrazides are to 72 hours LC of beet armyworm 3 instar larvaes
50Be respectively: 2.14,5.31mg/L.Lufenuron: the worm hydrazides is 10: 1 to 1: 50 o'clock, co-toxicity coefficient (CTC) shows to have synergistic effect, wherein lufenuron all greater than 120: the worm hydrazides is 1: 4,1: 10,1: 19 o'clock, co-toxicity coefficient (CTC) shows that all greater than 200 synergistic effect is obvious.
Determination of activity example 3:
Utilize among the embodiment 1,2 institute's preparaton to do following field control effectiveness test:
1, dispenser object
Diamond-back moth (Plutellaxylostella L) on the brassicaceous vegetable wild cabbage (Brassica oleracea var.capitata).
2, concentration design
1000,1500,2000 times of 5% lufenuron worm hydrazides ME dilutions; 1000,1500,2000 times of 20% lufenuron worm hydrazides ME dilutions; 1500 times of contrast medicament 5% lufenuron ME dilutions, 1500 times of 20% worm hydrazides ME dilutions.
3, test method
With reference to People's Republic of China's agricultural industry criteria (" pesticide field efficacy medicine test criterion (one) " GB/T17980.13---2000.
This test is experimental field carried out in Shenzhen Nuopuxin Agricultural Chemical Co., Ltd, and 4 repetitions are established in every processing, totally 36 residential quarters, every residential quarter area 10m
2, by at random district's group arrangement.5 points of parallel great-jump-forward sampling survey are adopted in every residential quarter, and every with bamboo let fixation mark 4 strains, investigate altogether 20 strains.Treat that diamond-back moth is that 2-3 sprays medicine and processes during age, every residential quarter spraying liquid 0.75kg, spray date is on April 7th, 2009, investigation insect population radix before the medicine was investigated residual borer population on the the 1st, 3,7,14 day behind the medicine.Adopt insect population decline rate methods analyst control efficiency, the new multipole of Deng Kenshi poor (DMRT) method is adopted in significance test, carries out significance analysis with DPS software.
4, results and analysis
(1) 5% lufenuron worm hydrazides microemulsion the results are shown in Table 3 to the field control effectiveness test 5% lufenuron worm hydrazides microemulsion of brassicaceous vegetable diamond-back moth to the field control effectiveness test of brassicaceous vegetable diamond-back moth, after the dispenser 1,3 day, the control efficiency that 5% lufenuron worm hydrazides ME dilution is 1500 times was in same level with the control efficiency of 1500 times of contrast medicament 5% lufenuron ME dilutions; After the dispenser 7,14 days, the control efficiency that 5% lufenuron worm hydrazides ME dilution is 1000 times is significantly higher than the control efficiency same period of 1500 times of contrast medicament 20% lufenuron ME dilutions, and the control efficiency that 5% lufenuron worm hydrazides ME dilution is 1500 times is not obvious with the control efficiency difference of 1500 times of contrast medicament 5% lufenuron ME dilutions, be in same level with the control efficiency same period of contrast medicament 20% worm hydrazides ME.
According to result of the test, the quick-acting of 5% lufenuron worm hydrazides ME is good, and is suitable with the quick-acting of 20% worm hydrazides ME; The lasting effect of 5% lufenuron worm hydrazides ME and 5% lufenuron ME difference are not obvious, but significantly better than the lasting effect of 20% worm hydrazides ME.
(2) 20% lufenuron worm hydrazides microemulsions are to the field control effectiveness test of brassicaceous vegetable diamond-back moth
20% lufenuron worm hydrazides microemulsion the results are shown in Table 4 to the field control effectiveness test of brassicaceous vegetable diamond-back moth, after the dispenser 1 day, the control efficiency that 20% lufenuron worm hydrazides ME dilution is 1000 times was significantly higher than the control efficiency of 1500 times of contrast medicament 5% lufenuron ME dilutions; After the dispenser 3 days, the control efficiency that 20% lufenuron worm hydrazides ME dilution is 1000 times was significantly higher than the control efficiency that 1500 times of contrast medicament 5% lufenuron ME dilutions and 20% worm hydrazides ME dilute 1500 times; After the dispenser 7,14 days, the control efficiency that 20% lufenuron worm hydrazides ME dilution is 1000 times is significantly higher than the control efficiency same period that 1500 times of contrast medicament 5% lufenuron ME dilutions and 20% worm hydrazides ME dilute 1500 times, the control efficiency that 20% lufenuron worm hydrazides ME dilution is 1500 times is not obvious with the control efficiency difference same period of 1500 times of contrast medicament 5% lufenuron ME dilutions, is in same level with the control efficiency same period that contrasts 1500 times of medicament 20% worm hydrazides ME dilutions.
According to result of the test, the quick-acting of 20% lufenuron worm hydrazides ME is good, and is suitable with the quick-acting of 20% worm hydrazides ME; The lasting effect of 20% lufenuron worm hydrazides ME is significantly better than the lasting effect of contrast medicament 5% lufenuron ME difference and 20% worm hydrazides ME.
Comprehensive above-mentioned field control effectiveness test result shows that institute's preparaton 5% lufenuron worm hydrazides ME, 20% lufenuron worm hydrazides ME among the embodiment 1,2 are better than the use of single dose in actual applications, can prolong drug effect, reduces the medication number of times; In addition, institute's preparaton is microemulsion, and used organic solvent is less, has reduced the pollution of organic solvent to environment, has alleviated penetrating odor, to the also greatly raising of safety of crop.