The prior art discloses the compounding of pyriproxyfen and fipronil, imidacloprid, dinotefuran, clothianidin, indoxacarb, abamectin, emamectin benzoate and the like, which are all applied to agricultural pests and agricultural formulations, no relevant patent specially aiming at sanitation pest cockroaches exists, and the cockroach gel bait or the particle bait is different from the conventional pesticide formulations and has high requirement on the palatability of effective ingredients to cockroaches; after the pyriproxyfen is added into the cockroach gel bait or the granular bait, the pyriproxyfen has certain inhibiting effect on the ingestion of the cockroaches, thereby reducing the killing effect of the cockroach gel bait or the granular bait, which is also the reason that the pyriproxyfen is not used in the cockroach gel bait or the granular bait at present in China.
The applicant prepares the compound composition of pyriproxyfen, fipronil, chlorpyrifos and the like into a bait suitable for sanitation by using special auxiliaries and processes based on own rich experience in the field of sanitary pests, and solves the problem of poor palatability of pyriproxyfen at present; the compound composition of the invention is preferably an embedding agent which is good in palatability to the cockroaches and synthesized from natural or natural components, embeds the effective components in the form of polymer microspheres, has the characteristics of high efficiency, low toxicity, long lasting period and high killing rate, is very suitable for thoroughly controlling the cockroaches, and particularly has the advantages of quick killing effect and thorough killing effect on the cockroaches after the preferable compound and preparation method is selected, and is greatly improved compared with the existing cockroach killing agent.
Object of the Invention
The invention aims to provide the insecticidal composition which has good insecticidal effect, low toxicity, low stimulation, convenient use and high killing rate, can delay the drug resistance of sanitary pests, has high palatability aiming at the sanitary pests and contains pyriproxyfen and a specific cockroach killing component, and the preparation method thereof.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
the pyriproxyfen-containing sanitary insecticidal composition is characterized by comprising active components A and B in a weight ratio of 1: 99-99: 1;
the active component A is pyriproxyfen;
the active component B is selected from one or more of fipronil, ethiprole, chlorantraniliprole, flubendiamide, acephate, chlorpyrifos, propoxur, imidacloprid, dinotefuran, clothianidin, indoxacarb, abamectin, emamectin benzoate or ivermectin;
the composition contains polylactic acid ester, polyhydroxyalkanoate or β cyclodextrin as an embedding carrier, and the weight ratio of the total amount of the active components A and B to the embedding carrier is 1:3-1: 5;
the pesticidal composition is a bait, such as a gel bait, a granular bait, a liquid bait or a concentrated bait.
Preferably, the active component B is fipronil, chlorantraniliprole, dinotefuran, indoxacarb or emamectin benzoate; more preferably, the active component B is fipronil and emamectin benzoate.
Preferably, in the sanitary insecticidal composition, the weight ratio of the pyriproxyfen to the component B is 1: 50-50: 1; more preferably, the weight ratio of the two is 1: 20-20: 1; most preferably, the weight ratio of the two is 1: 5-5: 1.
Preferably, the embedding carrier is a polyhydroxyalkanoate.
Preferably, the weight ratio of the total amount of active components a and B to the embedding vehicle is 1: 4.
Further, the present invention provides a method for preparing the above-mentioned sanitary insecticidal composition, characterized in that the method comprises the steps of:
the method comprises the following steps: preparation of polymer microspheres: dissolving active component A, B and embedding carrier in acetone, dichloroethane or water 3-5 times by weight, and spray drying to obtain polymer microsphere;
step two: preparing a base material of the gel bait, the granular bait, the liquid bait or the concentrated bait according to a conventional method, and then adding the polymer microspheres obtained in the step one to prepare the final gel bait or the granular bait.
Further, the invention provides the application of the sanitary insect killing composition for preventing and controlling sanitary insect pests, wherein the sanitary insect pests are cockroaches.
Regarding the principle explanation: the prior art generally consists in directly mixing the active principle with a base material for the formulation of gel or granular baits, but this is not true of the active principles of pyriproxyfen which are poorly palatable to sanitary pests, and it has been found by the applicant, after years of research, that when a sanitary insecticidal composition containing pyriproxyfen is mixed with a specific embedding vehicle and in a specific ratio before being mixed with the base material, on the one hand the pyriproxyfen is more compatible with the B active principle, and on the other hand the pyriproxyfen is greatly improved in palatability by masking the high compatibility of the embedding material with pyriproxyfen, in particular the odour and the bitter taste of pyriproxyfen.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with single agents, the insecticidal composition has very high killing effect on adult, nymphs and eggs of cockroaches, and has very good long-term thorough killing effect;
(2) after the pyriproxyfen and the active component B are compounded, the pyriproxyfen has the characteristics of long lasting time and high killing rate.
(3) The active component is added into the gel bait or the granular bait in the form of specific polymer microspheres, so that the palatability of the cockroach is greatly improved, and the poisoning effect is improved.
(4) The composition consists of active ingredients with complementary insecticidal mechanisms, has increased action sites, and is favorable for overcoming and delaying the generation of drug resistance.
(5) The novel compound composition is added to the field of domestic sanitary pesticides, has obvious pesticide effect and can be widely popularized and applied.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Firstly, a preparation method of polymer microspheres comprises the following steps:
a. the preparation method of the polylactic acid ester microspheres comprises the following steps:
2.5g of pyriproxyfen, 0.5g of fipronil and 9.0g of polylactate are completely dissolved by acetone, the solution is atomized into micro-droplets by a pressure type atomizer, and the solvent is instantaneously evaporated to obtain 25 percent pyriproxyfen-fipronil polymer microspheres.
b. The preparation method of the polyhydroxyalkanoate microspheres comprises the following steps:
1.0g of pyriproxyfen, 2.0g of chlorpyrifos and 12g of polyhydroxyalkanoate are completely dissolved by dichloroethane, the solution is atomized into micro-droplets by a pressure type atomizer, and the solvent is instantaneously evaporated to obtain the 20 percent pyriproxyfen-chlorpyrifos polymer microspheres.
c. β method for preparing cyclodextrin microsphere:
2.0g of pyriproxyfen, 1.0g of emamectin benzoate and 15g of β cyclodextrin are completely dissolved by 75 percent of acetone aqueous solution, the solution is atomized into micro drops by a pressure type atomizer, and the solvent is instantaneously evaporated to be solidified to obtain 16.7 percent pyriproxyfen-emamectin benzoate polymer microspheres.
Preparation examples of gel bait or granular bait (preparation examples Polymer microspheres were prepared according to the above-mentioned methods)
All formulations are referred to as "%" in the following formulations.
Formulation example 1:
completely dissolving 20g of white granulated sugar, 10g of milk powder, 20g of glycerol and 1.0g of sodium benzoate by using a proper amount of water, adding 1.5g of hydroxyethyl cellulose, fully shearing and gelling, sterilizing at the high temperature of 120 ℃ for 30min, adding polymer microspheres containing 0.05g of fipronil, 0.45g of pyriproxyfen and 2.2g of polylactic acid ester when cooling to 45 ℃, and shearing and homogenizing at a high speed to obtain the 0.5% fipronil-pyriproxyfen gel bait.
Formulation example 2:
completely dissolving 20g of white granulated sugar, 10g of milk powder, 20g of glycerin and 1.0g of sodium benzoate by using a proper amount of water, adding 1.5g of hydroxyethyl cellulose, fully shearing and gelling, sterilizing at high temperature of 120 ℃ for 30min, supplementing polymer microspheres containing 0.1g of emamectin benzoate, 0.5g of pyriproxyfen and 1.8g of polyhydroxyalkanoate when cooling to 45 ℃, and shearing at high speed and homogenizing to obtain the 0.6% emamectin benzoate-pyriproxyfen gel bait.
Formulation example 3:
completely dissolving 20g of white granulated sugar, 10g of milk powder, 20g of glycerin and 1.0g of sodium benzoate by using a proper amount of water, adding 1.5g of hydroxyethyl cellulose, fully shearing and gelling, sterilizing at the high temperature of 120 ℃ for 30min, cooling to 45 ℃, supplementing polymer microspheres containing 0.5g of chlorantraniliprole, 0.5g of pyriproxyfen and 4.5g of β cyclodextrin, and shearing at a high speed and homogenizing to obtain the 1.0% chlorantraniliprole-pyriproxyfen gel bait.
Formulation example 4:
completely dissolving 20g of white granulated sugar, 10g of milk powder, 20g of glycerin and 1.0g of sodium benzoate by using a proper amount of water, adding 1.5g of hydroxyethyl cellulose, fully shearing and gelling, sterilizing at the high temperature of 120 ℃ for 30min, cooling to 45 ℃, supplementing polymer microspheres containing 0.5g of indoxacarb, 0.5g of pyriproxyfen and 3.0g of β cyclodextrin, and shearing at a high speed and homogenizing to obtain the 1.0% indoxacarb-pyriproxyfen gel bait.
Formulation example 5:
completely dissolving 20g of white granulated sugar, 10g of milk powder, 20g of glycerin and 1.0g of sodium benzoate by using a proper amount of water, adding 1.5g of hydroxyethyl cellulose, fully shearing and gelling, sterilizing at a high temperature of 120 ℃ for 30min, adding polymer microspheres containing 0.5g of dinotefuran, 0.5g of pyriproxyfen and 3.0g of polylactic acid ester when cooling to 45 ℃, and shearing and homogenizing at a high speed to obtain the 1.0% dinotefuran-pyriproxyfen gel bait.
Formulation example 6:
20g of white granulated sugar, 15g of milk powder and 30g of soybean powder are crushed and then uniformly mixed with 1.0g of sodium benzoate, 5.0g of soybean oil and a proper amount of rice flour, then polymer microspheres containing 0.5g of dinotefuran, 0.5g of pyriproxyfen and 3.0g of polyhydroxyalkanoate are added, the mixture is fully and uniformly mixed, then water is added for granulation, the mixture is dried at 80 ℃ and screened to obtain the 1.0% dinotefuran-pyriproxyfen granular bait.
Formulation example 7:
the same preparation as in example 6 was conducted except that the polyhydroxyalkanoate was 4.0 g;
formulation example 8:
the same preparation as in example 6 was conducted except that the polyhydroxyalkanoate was 5.0 g;
third, comparative examples of gel bait or granular bait (in the comparative examples, effective ingredients are added according to the conventional method)
Comparative example 1:
and (2) completely dissolving 20g of white granulated sugar, 10g of milk powder, 20g of glycerol and 1.0g of sodium benzoate by using a proper amount of water, adding 1.5g of hydroxyethyl cellulose, fully shearing and gelling, sterilizing at the high temperature of 120 ℃ for 30min, supplementing 0.05g of powdered fipronil and 0.45g of molten pyriproxyfen when cooling to 45 ℃, and shearing and homogenizing at a high speed to obtain the 0.5% fipronil-pyriproxyfen gel bait of the comparative example 1.
Comparative example 2:
and (3) completely dissolving 20g of white granulated sugar, 10g of milk powder, 20g of glycerol and 1.0g of sodium benzoate by using a proper amount of water, adding 1.5g of hydroxyethyl cellulose, fully shearing and gelling, sterilizing at the high temperature of 120 ℃ for 30min, supplementing 0.05g of powdered fipronil when cooling to 45 ℃, and shearing and homogenizing at a high speed to obtain the 0.05% fipronil gel bait of the comparative example 2.
Comparative example 3:
and (2) completely dissolving 20g of white granulated sugar, 10g of milk powder, 20g of glycerin and 1.0g of sodium benzoate by using a proper amount of water, adding 1.5g of hydroxyethyl cellulose, fully shearing and gelling, sterilizing at the high temperature of 120 ℃ for 30min, supplementing 0.45g of molten pyriproxyfen when cooling to 45 ℃, and shearing and homogenizing at a high speed to obtain the 0.45% pyriproxyfen gel bait of the comparative example 1.
Comparative example 4:
20g of white granulated sugar, 15g of milk powder and 30g of soybean powder are crushed and then are uniformly mixed with 1.0g of sodium benzoate, 5.0g of soybean oil and a proper amount of rice flour, then 0.5g of dinotefuran-containing raw powder is added, the mixture is fully and uniformly mixed, then water is added for granulation, the dinotefuran-containing raw powder is dried at 80 ℃ and screened to obtain the 0.5% dinotefuran granular bait.
Comparative example 5:
20g of white granulated sugar, 15g of milk powder and 30g of soybean meal are crushed and then uniformly mixed with 1.0g of sodium benzoate and a proper amount of rice flour, 0.5g of pyriproxyfen is dissolved by 5.0g of soybean oil and then added, the mixture is fully and uniformly mixed, then water is added for granulation, and after drying at 80 ℃, screening is carried out to obtain the 0.5% pyriproxyfen granular bait.
Comparative example 6:
example 6 was prepared in the same manner as except that hydroxyethyl cellulose was used as the embedding vehicle in place of the polyhydroxyalkanoate;
comparative example 7:
example 6 was prepared in the same manner as except that the embedding vehicle used polyacetate instead of polyhydroxyalkanoate;
comparative example 8:
the same preparation as in example 6 was conducted except that the polyhydroxyalkanoate was 2.5 g;
comparative example 9:
the same preparation as in example 6 was conducted except that the polyhydroxyalkanoate was 5.5 g;
application example 1: indoor biological activity determination test for German cockroach
The effect of the cockroach killing in the formulation examples of the present invention and the comparative examples was tested with reference to the pesticide laboratory efficacy test for pesticide registration and the test method for evaluating bait in part 7. test insects were sensitive strains, water was not prohibited when fasted for 24 hours before the test, 30 adult females and males were half each time, transferred into a glass square box of 0.7m × 0.7m × 0.7.7 m, 2.0g (to 0.2 mg) of the same mass as the bait to be tested was placed diagonally inside the box, water was fed with a water-soaked cotton ball, the number of deaths was observed day by day, continuously observed for 12d, and the test was repeated at least three times to take an average value.A method for observing palatability was to place a contrast agent inside the box at the same time, weigh the mass (to 0.2 mg) of the remaining bait and feed at 24 hours after the test, take an average value of the three repetitions, and the measurement results were as follows (tables-1 and-2):
table-1 indoor bioactivity assay test results for german cockroach:
table-2 indoor palatability test results for german cockroach:
the test result shows that the pyriproxyfen is ineffective to the imagoes of the German cockroach, the palatability of the pyriproxyfen gel bait is poor compared with the fipronil, and the palatability and the killing speed of the 0.5 percent fipronil-pyriproxyfen gel bait prepared by the polymer microsphere process are the best, which shows that the palatability to the German cockroach is obviously improved, the killing speed is obviously accelerated and the killing effect is better after the special polymer process is adopted to embed the original drug.
It is noted that different amounts of polyhydroxyalkanoates were used in preparation examples 6, 7 and 8, with preparation example 7 being the most effective, i.e. when the weight ratio of the total amount of active ingredients a and B to the embedding vehicle was 1: 4; furthermore, in the comparative examples section, when comparative examples 6 and 7 used other materials as embedding materials, the effect was much lower than that of the specific embedding materials of the present invention, and even in comparative examples 8 and 9, when the weight ratio of the total amount of active components a and B to the embedding vehicle was outside 1:3-5, the effect was far inferior to that of the specific amount ratio of the present invention, and the palatability was also inferior;
the indoor biological activity measurement tests of formulation example 2, formulation example 3 and formulation example 5 also had similar effects as above, and the results were as follows:
table-30.6% emamectin benzoate pyriproxyfen gel bait indoor bioactivity assay test results:
remarking: ordinary 0.6% emamectin benzoate and ordinary 0.1% emamectin benzoate were prepared according to preparation example 2, wherein ordinary 0.6% emamectin benzoate and pyriproxyfen were not included in the embedding vehicle, and the rest was the same as preparation example 2, and ordinary 0.1% emamectin benzoate was not included in the embedding vehicle, and the rest was the same as preparation example 2.
Table-41.0% chlorantraniliprole pyriproxyfen gel bait indoor bioactivity assay test results:
remarking: a general 1.0% chlorantraniliprole-pyriproxyfen gel bait and a general 0.5% chlorantraniliprole gel bait were each prepared in accordance with preparation example 3, wherein the general 1.0% chlorantraniliprole-pyriproxyfen gel bait was identical to preparation example 3 except that it contained no entrapping carrier, and the general 0.5% chlorantraniliprole gel bait was identical to preparation example 3 except that it contained no entrapping carrier and no pyriproxyfen.
Table-51.0% dinotefuran-pyriproxyfen granular bait formulation indoor bioactivity assay test results:
remarking: a conventional 1.0% dinotefuran-pyriproxyfen pellet bait, a conventional 0.5% dinotefuran pellet bait, was prepared according to preparation example 5, except that the conventional 1.0% dinotefuran-pyriproxyfen pellet bait contained no encapsulating vehicle, the remainder of preparation example 5, and a conventional 0.5% dinotefuran pellet bait contained no pyriproxyfen, the remainder of preparation example 5.
Application example 2: cockroach eradication effect test on spot of German cockroach
The test method comprises the following steps: in 12 rooms of 2-3 buildings of a hotel, randomly selecting three rooms for each medicament, observing the rooms for 15min by manual lighting at 22: 00-23: 00 per night according to a timing and fixed-point observation counting method, taking the average number as the density before extinguishment (unit is head/min), recording the result 24h after the application of the medicament by the same method, continuously observing for 7d, then respectively observing for 15d, 30d, 60d, 90d, 120d, 150d and 180d once, and calculating according to the following formula:
The results of the measurements are as follows (tables 2 and 3):
TABLE-6 field cockroach eradication test result for German cockroach (within 30 d)
The determination result in 30d shows that the 0.5 percent fipronil-pyriproxyfen gel bait prepared by the preparation method has a faster and more thorough cockroach killing effect compared with a single agent and the 0.5 percent fipronil-pyriproxyfen gel bait prepared by the non-preparation method, and the killing rate in 5d can reach 100 percent; the killing rate of the 0.5 percent fipronil-pyriproxyfen gel bait and the single-dose 0.05 percent fipronil gel bait which are not prepared by the preparation method of the invention can reach 100 percent after 7 days and even 15 days, while the killing rate of the single-dose 0.45 percent pyriproxyfen gel bait in 30 days is difficult to reach 50 percent.
TABLE-7 field cockroach eradication test results (60 to 180 days)
The measurement results of 60-180 days show that the 0.5% fipronil-pyriproxyfen gel bait prepared by the preparation method can keep the killing rate of more than about 90% in 180 days, and has very good control effect on the population density of the cockroaches; the 0.5 percent fipronil-pyriproxyfen gel bait prepared by the preparation method of the invention is difficult to reach the killing rate of more than 90 percent after 60 days, and has slight defect on the control effect of the population density of the cockroaches; the population density of the single-dose 0.05% fipronil gel bait starts to recover gradually after 60 days, nearly half of the population density is recovered after 90 days, the long-term cockroach killing effect is not ideal, the killing rate of the single-dose 0.45% pyriproxyfen gel bait after 90 days can reach more than 70%, and the density control rate of the single-dose 0.05% fipronil gel bait during the whole test period can not reach more than 90%.
According to the efficacy results, compared with the pyriproxyfen single agent, the compound has a faster killing effect and a higher killing rate; compared with a single chlorpyrifos agent, the composition has better killing effect and has more absolute advantages in long-term control effect; compared with the gel bait prepared by the non-preparation method, the active ingredients of the gel bait are embedded by adopting a special polymer microsphere method, so that the palatability is improved, cockroaches prefer to eat, the quick-acting property and the killing rate are improved, and the long-acting population density control effect is improved by further compounding pyriproxyfen which has high killing capacity on nymphs and eggs.
Other combinations described herein have similar effects and are not listed herein.
The pyriproxyfen-containing sanitary insecticidal composition and the application thereof have been described by specific examples, and the corresponding other objects can be achieved by appropriately changing the links of raw materials, process conditions, active ingredient compounding combination or proportion and the like by those skilled in the art according to the contents of the invention, and the related changes do not depart from the contents of the invention, and all similar substitutions and changes are obvious to those skilled in the art and are considered to be included in the scope of the invention.