CN103704226B - Containing the ultra low volume liquids of epoxy insect pyridine and Ivermectin HCL - Google Patents

Containing the ultra low volume liquids of epoxy insect pyridine and Ivermectin HCL Download PDF

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Publication number
CN103704226B
CN103704226B CN201310680618.2A CN201310680618A CN103704226B CN 103704226 B CN103704226 B CN 103704226B CN 201310680618 A CN201310680618 A CN 201310680618A CN 103704226 B CN103704226 B CN 103704226B
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ivermectin hcl
low volume
pyridine
ultra low
epoxy insect
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CN103704226A (en
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王群利
黄凤玲
卢镇
唐卫
朱华龙
黄华
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Guangxi Tianyuan Biochemical Co Ltd
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Guangxi Tianyuan Biochemical Co Ltd
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Abstract

The present invention discloses a kind of containing the ultra low volume liquids of epoxy insect pyridine and Ivermectin HCL, and composite by epoxy insect pyridine and Ivermectin HCL is activeconstituents, and all the other used additives and solvent complement to 100%. Ultra low volume liquids of the present invention is easy to process, lasting period length, work efficiency height, target not easily develop immunity to drugs, environmental pollution is low, economize medicine economizes water, improve agricultural chemicals utilization ratio, the various pests of paddy rice, wheat, corn, vegetables, tobacco, tea tree, fruit tree and sugarcane can be prevented and treated by ultra-low volume spray, low-gallonage spraying or ultra-low volume electrostatic spray.

Description

Containing the ultra low volume liquids of epoxy insect pyridine and Ivermectin HCL
Technical field
The invention belongs to technical field of pesticide, in particular to a kind of containing the ultra low volume liquids of epoxy insect pyridine and Ivermectin HCL.
Background technology
At present due to a kind of pesticide activity component of single use, control crop pests spectrum is narrow, and anti-effect does not reach best effect; Using as long-term frequent, insect easily develops immunity to drugs, thus shortens this pesticide activity component work-ing life. Epoxy insect pyridine and Ivermectin HCL are composite, and both mechanism of action is different, plays complementary action, expanding prevention worm is composed, dosage is few, and anti-effect is high, the advantages such as lasting period length, simultaneously, epoxy insect pyridine and these two activeconstituentss of Ivermectin HCL can be used for being prepared into the regular dosage forms such as missible oil, wettable powder, suspension agent at prior art report, and these regular dosage forms are only sprayed for routine, as used ultra-low volume spray, droplet is uneven, does not reach the effect using normal spraying. Along with the mass-producing of proportion of crop planting, it may also be useful to above-mentioned conventional agent carries out conventional spraying, and to there is work efficiency low, and dosing is big, and anti-effect is low, and medicament utilization ratio is low.
Therefore, how these two kinds of medicaments are combined, to produce new, more effective prevention effect, delay the work-ing life of these two kinds of medicaments, expanding prevention worm is composed, improving anti-effect, particularly make full use of the surplus energy of this kind of old farm chemical ingredients such as chrysanthemum ester class, the cost of development reducing novel pesticide activeconstituents is pesticide field technical problem in the urgent need to address.
The super-active of new generation of epoxy insect Ding Shi East China University of Science research and development, the agricultural insecticide of hypotoxicity. Chemical name: 9-((6-chloropyridine-3-base) methyl) assorted-10,11-glyoxalidine also pungent-3-alkene of (2,3-a) two ring (3,2,1) of-4-nitro-8-oxygen, English popular name: cycloxaprid, chemical molecular formula C14H15ClN4O3; Insect is had interior suction, stomach toxicity and contact toxicity by epoxy insect pyridine, can be used for the Homoptera on control farm crop, Coleoptera, lepidoptera pest. ?xpense mould fine horse �� cooked food there is not ? Nao to plunder to protect ? core and survey rice huller sole and ram expense mould fine horse �� when hiding Kang Tuo ? 0uM, nAChR is not shown the reaction of agonist, and show as unique agonist character, completely different from the mechanism of action of the neonicotine receptor stimulant of the neonicotinoid insecticide kind of current commercialization, therefore with other anabasine insecticides without cross resistance. This product using dosage is low, environmentally safe, without harm or endangers minimum to beneficial organism. The aphid of the crops such as wheat, cotton, paddy rice, fruit tree, vegetables, Cnaphalocrocis medinali(rice leaf roller), plant hopper, aleyrodid, leafhopper, thrips, flea beetle, bollworm, small cabbage moth, cabbage caterpillar, prodenia litura, mythimna separata etc. there is higher insecticidal activity. The synthesis of current epoxy insect pyridine and purposes have applied for Chinese invention patent and International PCT patent, but the ultra low volume liquids patent about epoxy insect pyridine and Ivermectin HCL is not also applied for.
Ivermectin HCL is Macrolide antiparasitic, and English name is Ivermectin, and molecular formula is C48H74O14, chemical name is the two hydrogen Ivermectin HCL (B1a) of 5-O-demethylation-22,23-and the two hydrogen-25-(1-methylethyl of de-(1-the methyl-propyl)-22,23-of 5-O-demethylation-25-) and Ivermectin HCL (B1b); The effect of insect is to increase the release of the inhibitory transmitter ��-aminobutyric acid (GABA) of polypide by Ivermectin HCL, and open the Cl ionic channel of L-glutamic acid control, strengthen neu to the permeability of Cl, thus the transmission of block nerves signal, final neural paralysis, make muscle cell lose contractility, and cause polypide dead. Nematode, insect and mite worm are all killed activity by it, and the injection made with Ivermectin HCL, tablet are mainly used in treating the gastrointestinal nematode disease of domestic animal, warble, heel fly maggot, sheep nose fly maggot and pig, sheep mange acariasis. In addition, Ivermectin HCL also can be used for treatment poultry body endoparasitism nematode (such as roundworm, lungworm etc.). Also can be made into agricultural insecticidal, miticide, for killing extensively parasitic mite class on plant, small cabbage moth, cabbage caterpillar, Liriomyza, wood louse, nematode etc. This medicine outstanding feature is: side effect is light, and a drug is killed in body and external multiple parasite simultaneously.
Target pest is had extremely strong synergism by the ultra low volume liquids being re-dubbed in research proof, epoxy insect pyridine and Ivermectin HCL by the present inventor.
The existing preparation of epoxy insect pyridine mainly comprises suspension agent etc., and epoxy insect pyridine ultra low volume liquids, have no report both at home and abroad.
Summary of the invention
For the existing above-mentioned defect existed in the art, it is an object of the invention to provide a kind of containing the ultra low volume liquids preparation of epoxy insect pyridine and Ivermectin HCL, and the preparation method of described ultra low volume liquids is provided; This ultra low volume liquids has obvious synergism, kills the anti-effect of worm high, spraying work efficiency height.
Technical scheme of the present invention is realized by following measure:
A kind of containing the ultra low volume liquids of epoxy insect pyridine and Ivermectin HCL, described ultra low volume liquids activeconstituents is epoxy insect pyridine and Ivermectin HCL, all the other are tensio-active agent and solvent, wherein the weight ratio of epoxy insect pyridine and Ivermectin HCL is 32:1��1:32, it is preferably 16:1��1:16, it is preferably 8:1��1:8 again, it is preferably 4:1��1:4 most.
Further, the weight content sum of described epoxy insect pyridine and Ivermectin HCL is 0.2%��40%; Wherein the weight content of epoxy insect pyridine is 0.1%��20%, and the weight content of Ivermectin HCL is 0.1%��20%, and the weight content of tensio-active agent is 1%��10%.
Preferably, the weight content sum of described epoxy insect pyridine and Ivermectin HCL is 0.2%��20%, and wherein the weight content of epoxy insect pyridine is 0.1%��10%, and the weight content of Ivermectin HCL is 0.1%��10%.
Applicable tensio-active agent is selected from fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, styroyl phenol polyethenoxy ether, alkylaryl polyoxyethylene polyoxypropylene ether, aliphatic alcohol polyoxyvinethene phosphate, alkylphenol polyoxyethylene phosphoric acid ester, styroyl phenol polyethenoxy ether phosphate, alkylaryl polyoxyethylene polyoxypropylene ether phosphate, castor oil polyoxyethylene ether, one or more combination in calcium dodecylbenzene sulphonate, preferred fat polyoxyethylenated alcohol, alkylphenol polyoxyethylene, styroyl phenol polyethenoxy ether, alkylaryl polyoxyethylene polyoxypropylene ether, castor oil polyoxyethylene ether, calcium dodecylbenzene sulphonate.
The solvent being applicable to is one or more combinations in aromatic hydrocarbon solvent, plant oil solvent and polar solvent; Aromatic hydrocarbon solvent comprises trimethylbenzene, orthodichlorobenzene, durene, diethylbenzene, methyl-propyl benzene, butylbenzene, methylnaphthalene, two wires oil; Plant oil solvent comprises soybean oil, Oleum Gossypii semen, rapeseed oil, Semen Maydis oil, Viscotrol C, turps, Witconol 2301, ethyl oleate; Polar solvent comprises methyl phenyl ketone, phenylcarbinol, methyl-sulphoxide, N-Methyl pyrrolidone, N, dinethylformamide, DMAC N,N' dimethyl acetamide, n-hexyl alcohol, n-Octanol, Terpineol 350. Volatility is low, flash-point height, the solvent that good to former medicine solvability, chemical injury of crops is low, viscosity is low by screening for ultra low volume liquids, it is not watered during dispenser, but directly uses with ultra low volume sprayer tool, low-gallonage spraying apparatus or ultra-low volume electrostatic spray apparatus. Ultra-low volume spray does not have considerable change from leaving spraying apparatus arrival target process owing to not containing high volatile volatile composition, its size and quality in droplet, decreases volatilization with elegant. Droplet is tiny and even, meets " biological best granula " requirement, significantly improves deposition.
The preparation method of ultra low volume liquids of the present invention is, in the reaction vessel that band stirs, first with solvent by after activeconstituents stirring and dissolving, then add auxiliary component, fully it is uniformly mixed, obtains containing the ultra low volume liquids of epoxy insect pyridine and macrocyclic lactone insecticides; Processing parameter is: stirring velocity is controlled to 60��150 revs/min, and churning time is 15��60 minutes, and temperature is normal temperature, and pressure is normal pressure.
The target crop being applicable to is the food crop such as paddy rice, wheat, the cash crop such as sugarcane, banana, rubber, cotton, tea tree, oranges and tangerines, apple, hawthorn, peach, the vegetable crops such as tomato, eggplant, capsicum, lettuce, celery, wild cabbage, Kidney bean, broad bean, cowpea, pea, the ground family crops such as cucumber, pumpkin, watermelon.
The application that the ultra low volume liquids of the present invention is applicable on water prevention rice pest, sugarcane insect, vegetables pest, fruit tree pest insect; Described rice grub is planthopper, Cnaphalocrocis medinali(rice leaf roller), striped rice borer, rice thrips, rice leafhopper, rice spider rafter stinkbug; Described sugarcane insect is aphid, snout moth's larva, thrips; Described vegetables pest is beet armyworm, prodenia litura, flea beetle, liriomyza bryoniae; Described fruit tree pest insect is Phytophthira, aleyrodid class, a red-spotted lizard class, unaspis shield kuwana, the green stinkbug of Zhu, small heart-eating peach worm, tangerine lyonetid, the thin moth of tea, thrips.
The preferred method using the ultra low volume liquids of the present invention is ultra-low volume spray, is secondly low-gallonage spraying and ultra-low volume electrostatic spray, determines the dosage being suitable for according to controlling object generation situation, and usual formulation rate is 75��150ga.i./hm2.
Ultra low volume liquids component of the present invention is reasonable, good disinsection effect, and its active and insecticidal effect is not the simple superposition of each composition activity, but has significant synergism;Kill worm holding effect long, with low cost, work efficiency height, (artificial conventional spraying every mu is consuming time 0.5-1 hour) is only spent 10 minutes in artificial ultra-low volume spray every mu; Save water (without the need to being watered); Environmental pollution can be reduced, it is to increase agricultural chemicals utilization ratio; Reduce applications of pesticide amount, such as control Cnaphalocrocis medinali(rice leaf roller) dosage 75��150ga.i./hm2, and alone epoxy insect pyridine consumption 480-600ga.i./hm2.
Embodiment
Below in conjunction with embodiment, the present invention is further described, but does not limit the scope of the invention.
Embodiment 16.6% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (32:1)
Preparation technology: in the reaction vessel that band stirs, first with solvent by after epoxy insect pyridine and Ivermectin HCL stirring and dissolving, then add auxiliary component, be fully uniformly mixed, obtain 0.1% epoxy insect pyridine ultra low volume liquids; Processing parameter is: stirring velocity is controlled to 60��150 revs/min, and churning time is 15��60 minutes, and temperature is normal temperature, and pressure is normal pressure.
According to the step of preparation process identical with embodiment 1, it is possible to preparation following examples.
Embodiment 217% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (16:1)
Embodiment 39% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (8:1)
Embodiment 425.0% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (4:1)
Embodiment 512% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (2:1)
Embodiment 618% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (1:5)
Embodiment 79% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (1:2)
Embodiment 815% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (1:4)
Embodiment 918% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (1:8)
Embodiment 1034% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (1:16)
Embodiment 1221% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (20:1)
Embodiment 1311% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (1:10)
Embodiment 1420% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (1:1)
Embodiment 1510.5% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (2.5:1)
Embodiment 1640% epoxy insect pyridine Ivermectin HCL ultra low volume liquids (1:1)
Comparative examples 120% epoxy insect pyridine ultra low volume liquids
Comparative examples 25% Ivermectin HCL ultra low volume liquids
The prepared ultra low volume liquids outward appearance containing epoxy insect pyridine is an equal oily liquids; Low-temperature phase capacitive is good, under 5 DEG C of conditions, and refrigeration 7d not crystallization and suspended substance; Volatility is low, and filter paper hangs sends out measurement result, and evaporation rate is lower than 30%; To plant safety, without poisoning; Employing remain silent method measure, flash-point is greater than 70 DEG C; Viscosity is less than 30mPa s; Electric conductivity is 1 �� 10-6��1 �� 10-10Within the scope of s/cm.
The Application Example of the present invention is the method adopting Toxicity Determination and field control effectiveness test to combine. First pass through Toxicity Determination, cotoxicity coefficient (CTC) after clear and definite two kinds of medicaments are composite by a certain percentage, CTC < 80 is antagonistic action, 80 < CTC < 120 are summation action, and CTC > 120 is synergism. The basis of Toxicity Determination being determined, cotoxicity coefficient (CTC) is greater than after 80 that is two kind medicament mixture reaches phase additive synergism, then carries out field control effectiveness test and verify that it is added or the effect of synergy.
Application Example 1 epoxy insect pyridine and the indoor joint toxicity measuring test of Ivermectin HCL
Effective constituent part by weight 32:1,16:1,8:1,4:1,2:1,1:1,1:2,1:4,1:8,1:16,1:32 mixture is pressed in epoxy insect pyridine and Ivermectin HCL respectively;Test method: " People's Republic of China (PRC) agricultural industry criteria NY/T1154.1-2006 ", " People's Republic of China (PRC) agricultural industry criteria NY/T1154.7-2006 ", adopts topical application. Within 48 hours, check dead worm number, calculate mortality ratio. Blank is equivalent clear water. Each process general arranges 6 concentration gradients. Carry out statistical study with SPSS statistical analysis software, calculate the LC of each medicament50, evaluate reagent agent according to this to the activity of examination worm, according to the abundant calculating cotoxicity coefficient (CTC) of Sun Yun.
The toxicity test result (48 hours) of table 1 epoxy insect pyridine and Ivermectin HCL different ratio planthopper
From measurement result table 1: planthopper is all had synergism by after effective constituent weight aforementioned proportion mixture by epoxy insect pyridine and Ivermectin HCL, cotoxicity coefficient (CTC) is all greater than 120, and wherein after both are composite in 4:1��1:4 ratio, synergism to planthopper is particularly remarkable.
Application Example 2
Using the identical method of Application Example 1, epoxy insect pyridine and Ivermectin HCL are respectively 123.5,139.7,135.1,147.6,141.3 by the cotoxicity coefficient of effective constituent part by weight 20:1,10:1,5:1,2.5:1,1:1,1:2.5,1:5,1:10,1:20 mixing orange caterpillar 3 nymph in age and show that orange caterpillar is all had synergism after composite according to the above ratio by epoxy insect pyridine and Ivermectin HCL.
Application Example 3
Epoxy insect pyridine and Ivermectin HCL are mixed by effective constituent part by weight 16:1,8:1,4:1,2:1,1:1,1:2,1:4,1:8,1:16 respectively and is made into binary built agent as mixture 10��mixture 18, test method is with reference to " People's Republic of China (PRC) agricultural industry criteria NY/T1154.14-2008 ", adopt leaf dipping method, after 48h, check death toll. Within 48 hours, check dead worm number, calculate mortality ratio. Blank is equivalent clear water. Each process general arranges 6 concentration gradients. Carry out statistical study with SPSS statistical analysis software, calculate the LC of each medicament50, evaluate reagent agent according to this to the activity of examination worm, according to the abundant calculating cotoxicity coefficient (CTC) of Sun Yun.
The toxicity test result (48 hours) of table 2 epoxy insect pyridine and Ivermectin HCL different ratio small cabbage moth
From measurement result table 2: small cabbage moth is all had synergism by after effective constituent weight aforementioned proportion mixture by epoxy insect pyridine and Ivermectin HCL, cotoxicity coefficient (CTC) is all greater than 120, and wherein after both are composite in 2:1��1:2 ratio, synergism to small cabbage moth is particularly remarkable.
Application Example 4
Reference��GB/T17980.4-2000 agricultural chemicals field test criterion (one) insecticide control water rice hopper >=; Controlling object: planthopper, test site: Yulin City Rong County rice terrace.
The application method of embodiment 1��embodiment 16 and comparative examples 1, comparative examples 2: ultra-low volume spray
Comparison medicament: 20% epoxy insect pyridine WP and 3% Ivermectin HCL EC, is diluted with water to 30L routine spraying.
Table 3: the test of pesticide effectiveness result of control planthopper
As can be seen from Table 3: the ultra low volume liquids of the present invention adopts ultra-low volume spray method control planthopper, and than compareing, medicament routine spraying quick-acting is strong, prevention effect good, the lasting period is longer.
Application Example 5
Test method: the lepidopterous larvae of reference��GB/T17980.13-2000 agricultural chemicals field test criterion (one) insecticide control brassicaceous vegetable >=; Controlling object: small cabbage moth; Test site: suburbs, Foshan; The application method of embodiment 1��embodiment 16 and comparative examples 1: ultra-low volume spray;Comparison medicament: 20% epoxy insect pyridine WP and 3% Ivermectin HCL EC, is diluted with water to 30L routine spraying.
Table 4: control small cabbage moth test of pesticide effectiveness result
As can be seen from Table 5: the ultra low volume liquids of the present invention adopts ultra-low volume spray method control small cabbage moth, and than compareing, medicament routine spraying quick-acting is strong, prevention effect good, the lasting period is longer.

Claims (7)

1. one kind contains the ultra low volume liquids of epoxy insect pyridine and Ivermectin HCL, it is characterized in that described ultra low volume liquids activeconstituents is epoxy insect pyridine and Ivermectin HCL, all the other are tensio-active agent and solvent, and wherein the weight ratio of epoxy insect pyridine and Ivermectin HCL is 32:1��1:32; Wherein the weight content sum of epoxy insect pyridine and Ivermectin HCL is 0.2%��40%; Wherein the weight content of epoxy insect pyridine is 0.1%��20%, and the weight content of Ivermectin HCL is 0.1%��20%, and the weight content of tensio-active agent is 1%��10%;
Described solvent is one or more combinations in aromatic hydrocarbon solvent, plant oil solvent and polar solvent; Aromatic hydrocarbon solvent comprises trimethylbenzene, orthodichlorobenzene, durene, diethylbenzene, methyl-propyl benzene, butylbenzene, methylnaphthalene, two wires oil; Plant oil solvent comprises soybean oil, Semen Maydis oil, Oleum Gossypii semen, rapeseed oil, Viscotrol C, turps, Witconol 2301, ethyl oleate; Polar solvent comprises methyl phenyl ketone, phenylcarbinol, methyl-sulphoxide, N-Methyl pyrrolidone, N, dinethylformamide, DMAC N,N' dimethyl acetamide, n-hexyl alcohol, n-Octanol, Terpineol 350;
Described tensio-active agent is one or more the combination in fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, styroyl phenol polyethenoxy ether, alkylaryl polyoxyethylene polyoxypropylene ether, aliphatic alcohol polyoxyvinethene phosphate, alkylphenol polyoxyethylene phosphoric acid ester, styroyl phenol polyethenoxy ether phosphate, alkylaryl polyoxyethylene polyoxypropylene ether phosphate, castor oil polyoxyethylene ether, calcium dodecylbenzene sulphonate.
2. according to claim 1 containing the ultra low volume liquids of epoxy insect pyridine and Ivermectin HCL, it is characterised in that: the weight ratio of epoxy insect pyridine and Ivermectin HCL is 16:1��1:16.
3. according to claim 2 containing the ultra low volume liquids of epoxy insect pyridine and Ivermectin HCL, it is characterised in that: the weight ratio of epoxy insect pyridine and Ivermectin HCL is 8:1��1:8.
4. according to claim 3 containing the ultra low volume liquids of epoxy insect pyridine and Ivermectin HCL, it is characterised in that: the weight ratio of epoxy insect pyridine and Ivermectin HCL is 4:1��1:4.
5. according to claim 1 containing the ultra low volume liquids of epoxy insect pyridine and Ivermectin HCL, it is characterized in that: the weight content sum of epoxy insect pyridine and Ivermectin HCL is 0.2%��20%, wherein the weight content of epoxy insect pyridine is 0.1%��10%, and the weight content of Ivermectin HCL is 0.1%��10%.
6. one kind contains the application of the ultra low volume liquids of epoxy insect pyridine and Ivermectin HCL as claimed in claim 1, it is characterized in that: this ultra low volume liquids is used for water prevention rice pest, sugarcane insect, vegetables pest, fruit tree pest insect, and described rice grub is planthopper, Cnaphalocrocis medinali(rice leaf roller), striped rice borer, rice thrips, rice leafhopper, rice spider rafter stinkbug; Described sugarcane insect is aphid, snout moth's larva, thrips; Described vegetables pest is beet armyworm, prodenia litura, flea beetle, liriomyza bryoniae; Described fruit tree pest insect is Phytophthira, aleyrodid class, a red-spotted lizard class, the green stinkbug of Zhu, small heart-eating peach worm, tangerine lyonetid, the thin moth of tea, thrips.
7. one kind prepare in claim 1 to claim 5 described in any one containing the method for epoxy insect pyridine and the ultra low volume liquids of Ivermectin HCL, it is characterized in that described method is in the reaction vessel of band stirring, first with solvent by after activeconstituents stirring and dissolving, add tensio-active agent again, fully it is uniformly mixed, obtains the ultra low volume liquids containing epoxy insect pyridine and Ivermectin HCL; Processing parameter is: stirring velocity is controlled to 60��150 revs/min, and churning time is 15��60 minutes, and temperature is normal temperature, and pressure is normal pressure.
CN201310680618.2A 2013-12-13 2013-12-13 Containing the ultra low volume liquids of epoxy insect pyridine and Ivermectin HCL Expired - Fee Related CN103704226B (en)

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