CN102450250A - Bacteriostatic mildew-resistant insecticidal sustained release agent prepared from sol/gel also used as insect attractant - Google Patents
Bacteriostatic mildew-resistant insecticidal sustained release agent prepared from sol/gel also used as insect attractant Download PDFInfo
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Abstract
The invention relates to a bacteriostatic mildew-resistant insecticidal sustained release agent prepared from a sol/gel also used as an insect attractant. The agent is prepared into a sol plastic and a sol forming preparation with a microemulsion technology, a sol technology and the like according to different use conditions. The agent which treats an insect growth regulator (IGR) as a main component and essential oil and/or a low-toxicity high-efficiency insecticide, a bactericide, a penetrant, a water-soluble solvent, a stabilizing agent, an insect attractant, a film forming sustained release agent and the like as assistant components to satisfy prevention and control demands of different places. The agent of the invention, which has the advantages of wide insecticidal spectrum, low toxicity and high efficiency, ovum killing, insect growth inhibition, long persistent period, difficult resistance generation, bacteriostasis and mildew resistance, and low residual, can eliminate the pollution caused by unbalanced drug application, and is in favor of the ecological environment. The agent which is used for killing, preventing and controlling pests, mites and mildews on storage objects of stored grains, tobaccos, medicines, leathers, clothes, books, archives, history relics and the like and plants can reduce the loss caused by the pests and the mildews of the stored objects, the grains and the plants.
Description
Technical field
The present invention relates to a kind of from antibacterial mildew-resistant desinsection sustained release agent as the preparation of insect attractant sol/gel; More specifically relate to a kind of compound microemulsion, slowly-releasing microemulsion, Ludox preparations such as insect growth regulator, IGR (IGR) and plants essential oil that contain, the invention still further relates to of the application of reserve protectant at reserves such as grain storage, tobacco, medicinal material, food, leather, clothes, books, archives and history relic.Belong to green, nuisanceless reserve protectant field.
Background technology
Generation and the harm of crop disease Chinese caterpillar fungus mouse are seriously restricting the development of high excellent agricultural and sustainable agriculture.According to FAO (Food and Agriculture Organization of the United Nation) (FAO) statistics, the world food output due to illness loss that causes of the Chinese caterpillar fungus plague of rats accounts for 20～35% of gross output greatly every year, and wherein insect pest 14%, disease 10%; Cotton is because of insect pest loss 16%, and due to illness the evil loss 12%, and a year amount of loss reaches 1,200 hundred million dollars.
According to State Grain Administration's investigation, because the peasant is in the not science of aspects such as grain storage in postpartum, transportation, Chinese grain post-harvest loss 8～10%.Wherein, mainly be the farmer storage loss, it causes damage 180～24,000,000,000 yuan with a toll of 1500～2,000 ten thousand tons.China is used for the several hundred million units of pharmacy fumigation expense of tobacco leaf storage every year, and however, the insect pest that annual storage process causes, the loss of going mouldy are about 5%, lose several hundred million units.
Along with the increase of expanding economy and population, stored goods quantity and kind increase thereupon, and stored product insect harm increases, and its population and quantity are huge, bring about great losses to World Economics.They can eat into reserves such as erosion grain storage, tobacco, medicinal material, food, leather, clothes, books, archives and history relic, bring about great losses to World Economics.
Agricultural chemicals is the requisite means of production in the agricultural production; It is again chemical substance to the organism illeffects; Unreasonable use will cause the pollution of soil, atmosphere and water resource; Produced simultaneously residual, the enrichment and the lethal effect of chemical pesticide, become a significant problem destroying ecotope, bio-diversity and agricultural sustainable development at the animal and plant body.
Minimizing, the pest resistance to insecticide of effective insecticidal agent and fumigant kind constantly increase, and they make efficient, eco-friendly Prevention Technique in the control of stored product insect, seem more and more important to the pollution of environment with to the influence of human and livestock health.
At present; Reserve, grain storage pest control mainly are to use aluminum phosphate both at home and abroad, and main grain storage pest all produces serious resistance to phosphine, and these insects are to the resistance performance of phosphine; The national resistance monitoring net that foodstuff preservation Science Institute takes the lead through Chengdu; Adopt the FOA method, the result that China part provinces and cities are investigated shows: grain storage pest has increased tens of to thousands of times to the resistance of aluminum phosphate.Can find out that from above-mentioned investigation result long-term single use aluminum phosphate constantly increases pest resistance to insecticide, drug effect descends, and dosage improves constantly, and the control cycle constantly shortens.
Grain etc. contains nutriments such as abundant carbohydrate, protein, fat and mineral salt in the reserve, is the natural medium of growth of microorganism.These microorganisms comprise virus, bacterium, actinomycetes, fungi.Wherein quantity maximum, grain is endangered mould and metabolite thereof most serious of all.This quasi-microorganism is under the suitable condition of environment; Can decompose the organic substance in the grain; Make it to go bad, mould corruption etc., go mouldy and reduced edible and feeding quality, even completely lose use value; But also possibly produce endotoxin contamination, the secondary metabolite mycotoxin of mould can threaten to human and livestock health.
According to 2004～2005 years the 6th time national grain storage insect investigation; China's grain storage grain storage pest has 226 kinds, endangers serious and widespread coleopteran pest and the lepidoptera pests such as gelechiid, Indian meal moth such as corn weevil, rice weevil, lesser grain borer, saw-toothed grain beetle and red flour beetle of mainly containing.Mould on the paddy has 41 to belong to 117 kinds.Wherein dominant bacteria is 31 kinds, 35 kinds of common bacteria, 49 kinds of rare bacterium.Wherein main storage fungi has aspergillus flavus, Aspergillus glaucus, aspergillus albicans, aspergillus versicolor, aspergillus nidulans, aspergillus niger, mould etc.
Tobacco leaf storage pests mainly contains lasioderma serricorne, cadelle, red flour beetle, attagenus piceus, cacac moth, black rice worm etc., belongs to coleoptera and Lepidoptera, and is wherein maximum to the harm of tobacco leaf and cigarette finished product with lasioderma serricorne, 2 kinds of insects of cacac moth.
In other reserves such as medicinal material and leather there be primary pest: multiple moths such as Stegobium paniceum, India rain moth, meal moth, dermestes maculatus, Trogoderma variabile Ballion, bread moth, attagenus piceus.The primary pest of books, archives and history relic has l.bostrychophila and has a liking for worm booklice etc.
Because control of insect medicament single (main aluminum phosphate) for many years, application method is not proper, causes the aggravation of pest resistance to insecticide degree, if can not in time change new medicament, changes application method, takes effective prophylactico-therapeutic measures, and then its extent of injury has the possibility of increase.
The grain protectant of U.S. Register mainly contains: β-cyfloxylate, chlorpyrifos-methyl and decis, decis (suspend and use), malathion, pyrethrins+Butacide, pirimiphos-methyl, methoprene, diatomite, bacillus thuringiensis, pyrethrins add Butacide, and the approval pleocidin was used to store cereal and seed protection in 2005.
Australia uses organophosphorus insecticide, pyrethrins or methoprene (insect growth regulator, IGR) always and is used to prevent and treat lesser grain borer except that with the phosphine fumigation.The normal grain protectant that adopts mainly contains: chlorpyrifos-methyl, Folithion, Actellic, decis+Butacide etc.Register pleocidin in 2007 and be used to prevent and treat lesser grain borer.
The protectant that China has come into operation has malathion, sumithion, malathion+decis mixture, methylpyrimidine sulphur phosphorus, decis+Butacide mixture, sumithion+decis mixture) and decis+vegetalitas volatile oil mixture etc.
In view of experience having been arranged both at home and abroad, the fumigant that can supply to substitute phosphine is difficult in the short time solve, and the protectant kind is many and have a function that excellent prevention insect pest is infected.Therefore, the control of insect strategy that all adopts fumigant to be used in combination with protectant is abroad used the protectant insect protected more; Use the fumigant desinsection less,, rationally make the medication source to guarantee insecticidal effect; Can reach and guarantee that for a long time stored grain safety does not have the requirement of worm; Fumigant is used in combination with protectant, and one anti-one controls, and has really accomplished treatment and prevention.
At present; The China and even the whole world mainly adopt chemical control to the control of grain storage pest; The residue of pesticide that cause thus, environmental pollution and cause problems such as grain storage pest resistance serious day by day; This forces people to seek other control of insect measures more safely and effectively, replaces a large amount of at present higher chemical agents of toxicity that use with the new bio insecticide, and research and development are green, the long-acting biological grain protectant is very urgent.American and Britain, method, add, grain main product state such as Australia and scientific and technological developed country adopt the chemical control way that fumigant is used in combination with protectant, and be respond well.
Summary of the invention
It is a kind of certainly as the colloidal sol of insect attractant and/or the antibacterial mildew-resistant desinsection sustained release agent of preparing gel that main purpose of the present invention is to provide; This protectant have insecticidal spectrum wide, efficient, kill ovum, suppress insect growth, consumption is little, dispenser is convenient, insect is difficult for developing immunity to drugs; It is long but to the double grading that environment does not pollute, have antibacterial mildew-resistant and desinsection dual-use function to have a lasting period.Residual low, to the person poultry safety, can eliminate the pollution that unbalance dispenser causes, the improvement of favourable ecotope.
It is a kind of certainly as the colloidal sol of insect attractant and/or the antibacterial mildew-resistant desinsection sustained release agent of preparing gel that another object of the present invention is to provide; According to different service conditions and environment; Be prepared into the plastics that water is prone to wash-out, the moulding sustained release preparation that is prone to process different shape, be used to kill and stored product insect, harmful microorganism and moulds such as prevention and control grain storage, tobacco, medicinal material, leather, clothes, books, archives and history relic.The loss that can reduce the insect pest of reserve, grain and go mouldy and cause.Have different releasing mechanisms, satisfy different places prevention and control demand.
It is a kind of certainly as the colloidal sol of insect attractant and/or the antibacterial mildew-resistant desinsection sustained release agent of preparing gel that another object of the present invention is to provide; When being used for grain storage; When putting in storage, need not increase additional process with grain, do not need airtight, directly to plastics at grain storage gunnysack, storing case, warehouse inner wall film-coating; Or adopt the moulding sustained release preparation, be placed in storing case, the warehouse and get final product.When being fit to farmer storage equally.
For realizing above-mentioned purpose; The present invention with insect growth regulator, IGR (IGR) as Main Ingredients and Appearance; With multicomponent plants essential oil, low toxicity highly effective pesticide, bactericide, synergist, bleeding agent, water-soluble solvent, stabilizing agent, insect attractant, film forming sustained release agent and moulding sustained release agent etc. is auxiliary composition, and its preparation method is following:
A. adopt microemulsion technology to prepare the method that high infiltration rate is imitated water baseization microemulsion;
B. micro emulsion is combined with the colloidal sol technology, preparation water is prone to the colloidal sol and/or the gel rubber sustained-release plastics of wash-out and/or contains the method for the sol solutions of insect attractant;
C. micro emulsion and colloidal sol technology is combined, prepare colloidal sol and/or gel forming sustained release agent and/or contain the method for the sol preparation of other insect attractants;
D. insect attractant and preparation method.
The inventor, selects for use insect growth regulator, IGR can suppress insect growth, is difficult for developing immunity to drugs, reduces dosage and number of times the discovering of this field through for a long time; Many components plants essential oil can antibacterial mildew-resistant, desinsection; Plant extracts is difficult for developing immunity to drugs, and residual low; The containing benezene water-soluble solvent is not compared with other solvents, except that toxicity is low, also helps and on reserve, does not stay trace; Water baseization microemulsion is strengthened infiltration, reduces dosage.To different targets, select the active ingredient of different insecticidal mechanisms for use, taken into full account the activity stack synergistic effect that is mixed, make insect be difficult to develop immunity to drugs.
The present invention has made full use of the multi-functional character of each component, and on the basis of the compatibility of considering each component, the plants essential oil of selecting for use was both antibacterial as mildew-resistant, insecticide, the solvent of double as part insecticide again; Propane diols phenylate and ethanol is both as outside the solvent, also the double as bactericide; Propane diols is both as stabilizing agent, again the bleeding agent of double as fortification of plants essential oil, synergist; Agar, pectin, sodium alginate had both been made colloidal sol, and self also makes insect attractant.Thereby realize the purpose efficient, that consumption is little.
The inventor is since 1998 develop fenoxycarb; The inventor is through long-term discovering in this field; In existing insect growth regulator, IGR; Fenoxycarb can suppress the growth that insect gives birth to (larva → each length of time → pupa → butterfly → lay eggs → ovum hatching → larva) process entirely, has the function that ovum, inhibition are extremely casted off a skin, suppressed pupa, inhibitionization butterfly, suppress to lay eggs, suppress the ovum hatching; Because fenoxycarb is the analog of corpus allatum hormone, insect can't be distinguished it and the natural juvenile hormone in the body and repel, and therefore is difficult for developing immunity to drugs.
Fenoxycarb toxicity is hanged down rat oral LD50＞10000 (reporting 16800 abroad) mg/kg; Insecticidal activity with wide spectrum is effective to diptera, coleoptera, Homoptera, Hymenoptera, Lepidoptera, different inferior wing order, thrips, psocopteran 50 various pests and some acarians, nematode.Fenoxycarb is compared with other insect growth regulator, IGR; Dosage is little, and (0.1～10ppm), other insect growth regulator, IGR comparative trials such as employing fenoxycarb and methoprene show, under condition; The consumption of fenoxycarb is 0.2～0.5 times of other insect growth regulator, IGR consumptions, and residual low.
Fenoxycarb almost can both be prevented and treated all reserve primary pests, and very efficient.Fenoxycarb can be prevented and treated the insect that existing protectant is had resistance, like Indian meal moth, gelechiid, and red flour beetle, cross resistance does not appear in become rusty red flat bone ostomatid, saw-toothed grain beetle, lesser grain borer, grain weevil.Fenoxycarb is 100% to the corrected mortality of the stored product insect first generation (F1) and the second generation (F2).To nearly all grain storage pest, second generation adult inhibitory rate of reproduction reaches 100%.Therefore, when being used for grain protectant, its lasting period reached more than 2 years.Though fenoxycarb has used one, vicennial history, the rarely seen so far report that resistance is arranged.
Fenoxycarb has long but double grading that environment is not polluted of lasting period.Many agricultural chemicals, this two specific character are difficult to occur simultaneously, often the lasting period long, chemical stability is all right, though favourable to desinsection, be lost in soil and the river after, often form environmental pollution.And fenoxycarb makes this two specific character be able to combine preferably; This performance can obtain explaining from the half life period of fenoxycarb under varying environment, when in water, because of it is insoluble in water, and be prone to absorbed by the organic matter in the water, and after illumination, the half life period is 5 hours.After getting into soil, can be dissipated fast, use and can not in earth, observe fenoxycarb after three days.
The inventor is through long-term discovering in this field; Fenoxycarb all has certain synergistic effect to existing insecticide; Particularly pyrethroid, carbamate insecticide are had good synergistic effect, this specific character is relevant with the molecular structure of fenoxycarb.
Fenoxycarb is used to prevent and treat stored product insect and has following characteristics: 1. have stomach toxicity and action of contace poison concurrently, insecticidal spectrum is wide; 2. to pest efficient, and to the mammal low toxicity; 3. the lasting period long, but double grading free from environmental pollution; 4. can prevent and treat the resistant strain insect.5. can suppress the full growing stage of insect.Select that thereby fenoxycarb can realize that insecticidal spectrum is wide for use, long, residual low, the purpose that is difficult for producing resistance of environmental protection, lasting period.
Methoprene is a kind of insect growth regulator, IGR, juvenoid.Toxicity is hanged down good stability, and big white mouse per os LD50＞34600mg/kg is effective to Lepidoptera, diptera, coleoptera, Homoptera various insects, is used to prevent and treat health, tobacco, stored product insect.American-European registration permission is used to prevent and treat grain storage pest.
The present invention adopts many components plants essential oil as antibacterial mildew-resistant, insecticide; Many components plants essential oil is meant the non-high-purity major constituent essential oil that from a plant species, extracts; The essential oil of multicomponent ability is compared with the essential oil of high-purity single component, plays synergy, synergy, helps preventing pest resistance to insecticide.For this reason, the present invention selects for use and contains main component citral 65～75% litsea cubeba oils, and all the other components are citrene, methyl heptenone, australene, nopinene, linalool etc.; Select the eucalyptus oil that contains main component cineole 60～80% for use, all the other components are alpha-terpineol, australene, terpinyl acetate, aromadendrene, terpinene, linalool etc.; Select for use to contain main component firpene 60～75% turpentine oil, all the other components are the essential oil of laurene, terpinene, α phellandrene; These components can play synergy, synergy, compare with high-purity citral, help preventing that insect from developing immunity to drugs.The plant essence of selecting for use can be used as flavorant, for this to the person poultry harmless.
Litsea cubeba oil is the flavorant that China GB2760-86 regulation allows use, and the oral LD50 of rat is 4960mg/kg, has the activity and the antitoxic action that suppress fungi, has Pesticidal and sterilizing, can eliminate aflatoxin in the paddy.The main component citral has stronger bacteriostasis to staphylococcus aureus, Escherichia coli, typhoid bacillus and shigella dysenteriae in the litsea cubeba oil, and Candida albicans, Candida tropicalis, candida parakrusei, Cryptococcus neoformans, fonsecaea dermatitidis, hormodendrum verrucosa, sporothrix, gypsum appearance microspore silk bacterium and trichophyton gypseum etc. are all had tangible bacteriostasis.Citral gas is smoked to stop fungi (aspergillus flavus, aspergillus niger, aspergillus ustus and penicillium chrysogenum) going mouldy to rice and traditional Chinese medicine etc.Litsea cubeba oil is to human non-toxic, and is free from environmental pollution.
Eucalyptus oil can be used as flavorant, and LD50＞5000mg/kg has mildew-resistant and sterilization and anticorrosion effect.FEMA regulation: senior staff officer considers and is soft drink 1.7mg/kg in the food; The eucalyptus oil compound prescription is all stronger to the inhibitory action of gram positive bacteria and negative bacterium.Turpentine oil, cinnamon oil have higher contact toxicity to corn weevil, lesser grain borer and red flour beetle adult.Litsea cubeba oil, eucalyptus oil, turpentine oil also have the smoked kill effect to the part stored product insect.
Add propane diols in the conventional microemulsion as antifreeze, the inventor discovers that propane diols has the effect that strengthens permeability and availability to plants essential oil, and the optimization proportioning that plants essential oil cooperates with propane diols is 0.8: 1.65.
The present invention considers diversity of organism; The bactericide of many components and the bactericide of one-component are more effective, therefore when having selected for use plants essential oil to be bactericide, have also selected ethylene glycol phenyl ether, ethanol for use; In as solvent; The double as bactericide to different occasions, can add dimethyl fumarate where necessary.
Diethanol phenylate low toxicity, rat oral: LD50=1260mg/kg is a broad-spectrum antiseptic; Can effectively kill Gram-positive and negative bacterium, mould, and saccharomycete: effective especially to the unicellular bacterium of vacation and other gram-negative bacterias; Be used with other bactericidal activity compositions; Strengthen the activity of other antibacterial agents, in addition, the diethanol phenylate also is good solvent.Therefore, have sterilization and double as solvent dual-use function among the present invention.
Dimethyl fumarate is a kind of efficient, wide spectrum newly developed, low toxicity, stable novel antibacterial mould inhibitor, and has insecticidal action concurrently.It can suppress more than 30 kind of mould, saccharomycete and bacterium, and the inhibition of multiple moulds such as aflatoxins common in the food and AN is had better effect.It can distil and have contact and stifling sterilization double action.Food and drug administration classifies these article as food additives and is used widely.China also approved is used as antimildew agent for food and food additives with it.
Plant be for a long time with insect coevolution process in; Produced the secondary metabolites of defence insect's food-taking; In the Secondary Metabolism of Plant product owing to contain the material of some biologically actives; Known have kind more than 2000 (Chiu, et al.1993 report 30,000 kinds) plant to have the insecticidal activity composition, can be divided into following several big type by its chemical constitution: 1. glucoside; 2. phenol and quinones; 3. alkaloids; 4. terpenes; 5. steroid class; 6. Coumarins; 7. xylan class; 8. polyyne class;
The present invention selects for use low toxicity efficiently to be prone to degrading pesticide, is the plant resource extract, and the pyrethroid of American-European registered registration and organophosphorus insecticides are main.Wherein: the plant resource extract adopts plant insecticide pyrethrins, rotenone, nicotine, matrine, stemonine, seal chinaberry, Celastrus angulatus, Tea Saponin, tea withered etc.; Because having in mammal (the comprising human body) body can be with the enzyme of its decomposition; Above-mentioned plant resource extract is decomposed into water and carbonic acid gas easily rapidly, noresidue, not contaminated food products and environment.
Pyrethrin (mainly be present in spend in) is a kind of typical never poison, and wherein main component is pyrethrin I and II, have tag, stomach toxicity and repellent action, can work simultaneously to peripheral nervous system, central nervous system and other organ-tissues; It is strong that insect is knocked down power, and insecticidal spectrum is wide, and working concentration is low, can very fast metabolism in mammalian body, and to the people, animal low toxicity, to plant and Environmental security.Pyrethrins has following characteristics: 1. desinsection wide spectrum; 2. desinsection speed is fast; 3. the lasting period is long; 4. nontoxic to people and animals, in people's carcass, decompose rapidly; 5. there is not pesticide resistance; 6. in natural environment, be prone to degraded, noresidue.
Celastrus angulatus is to have anesthesia, food refusal and stomach toxicity, action of contace poison from the active insecticidal components that Celastrus angulatus extracts; And characteristics such as do not develop immunity to drugs, killed natural enemies, physicochemical property be not stable; Celastrus angulatus I has the food refusal effect to insect; Celastrus angulatus II, III have the stomach toxicity toxic action to insects such as black cutworn, tomato moth, anomis flavas, and Celastrus angulatus IV has the selection anesthetic effect to insect.
Tea is withered to be the blob of slag of tea seed after oil expression, and active ingredient is that saponin is plain.The withered liquid of CHAKUBING and tea has good stomach toxicity and action of contace poison to insect, can extensively on vegetables, paddy rice, fruit tree, tealeaves, flowers and other crops, use control snail, river snail, leech, rice fulgorid, rice leafhopper, the first-class insect of Ipomoea batatas baby elephant.Pollution-free, no residual hazard, anti-storage are durable, and drug effect is permanent, but saponin is poisonous to fish, does not pollute waters such as fish pond during use.
Select for use low toxicity efficiently to be prone to degrading pesticide pyrethroid, organic phosphates, for satisfying the grain protectant requirement, the present invention is main with pyrethroid and the organophosphorus insecticides of selecting American-European registered registration for use.Wherein: β-cyfloxylate, decis belong to the pyrethroid low toxic pesticide, and the rabbit skin is had no stimulation, and eyes are had slight spread effect, and the property accumulated is very little in vivo, no teratogenesis, mutagenesis, carcinogenesis under experimental condition.To the high poison of fish, the high poison of honeybee, to the birds low toxicity; Its mode of action is inhaled fumigation action to tag and stomach toxicity is main in not having, insecticidal spectrum is wide, in alkaline medium and soil, is prone to decomposition failure.Low to higher mammal toxicity, under solar radiation, be prone to decompose.
Solvent of the present invention is selected ethylene glycol phenyl ether, ethanol, N for use, non-benzene class (toluene, xylol etc.) water-soluble solvents such as dinethylformamide, oxolane, N-N-methyl 2-pyrrolidone N-, therefore more environmental protection, safety.Plants essential oil solubilized part insecticide in the prescription, but double as solvent.Because the inventor screened above-mentioned solvent combinations, realized that microemulsion is sprayed at not stay trace on the object, do not damage the reserve outward appearance.
Surfactant of the present invention is selected nonionic and/or anion surfactant for use: wherein nonionic is NPE (TX series), polyoxyethylene 20 sorbitan monooleate (tween series), AEO (AEO series), OPEO (OP series), cocoa butter alkanolamide, Emulsifier EL-60 nonionics such as (EL series); Anion is neopelex/calcium (LAS), lauryl sodium sulfate/calcium (K12) etc., two or more their compositions, and its consumption is 15～35%.
The present invention is from the antibacterial mildew-resistant desinsection sustained release agent as the preparation of the colloidal sol of insect attractant, the film preparation method of sustained release agent, colloidal sol moulding sustained release agent of described colloidal sol:
A. adopt microemulsion technology to prepare the method that high infiltration rate is imitated water baseization microemulsion: to select 4～15% water-soluble solvent for use; At room temperature with the emulsifier thin up, all the other components are dissolved in the water baseization solvent, then two solution are mixed; Be prepared into transparent homogeneous liquid; Particle diameter 5～50nm, stable under-10～50 ℃ condition, consumption is 0.1～10ppm.Water baseization microemulsion is compared with missible oil, not containing benezene solvent and solvent naphtha, and being sprayed at does not have trace on the reserve; Do not pollute reserve; When keeping same control efficiency, reduce the consumption of effective ingredient, significantly reduced the consumption of organic solvent, made preparation more meet environmental protection requirement.
B. adopt the colloidal sol that self has the insect attractant function; Preparation water is prone to the long-acting slow-release plastics of wash-out and/or contains the method for the sol solutions of insect attractant: after the colloidal sol dilute with water described in the claim 8 is stirred; Normal temperature is regulated pH value down; The powerful stirring adds described water baseization microemulsion of a and/or insect attractant down fast, leaves standstill after stirring and forms green, long-acting reserve mildew-resistant desinsection vitreosol liquid, and sol solutions after the dilution and water baseization emulsifier proportion are 0.05～1.5; This colloidal sol can directly be coated with reserve cabinet wall, warehouse floor or body of wall on, consumption is 0.2～10g/m
2
C. adopt from sol material and prepare the method that water is prone to long-acting slow-release plastics, the moulding sustained release agent of wash-out and/or contains the sol preparation of other insect attractants: claim 8 is described from as the agar of insect attractant or pectin, sodium alginate, gelatin, cyclodextrin as insect attractant; After water is adjusted to suitable concentration and stirs; Normal temperature is regulated pH value down; The powerful stirring adds described water baseization microemulsion of a and/or insect attractant down fast; After stirring, pour in the container of definite shape, leave standstill formation and have the green of definite shape, long-acting reserve mildew-resistant desinsection sustained release preparation; During preparation long-acting slow-release plastics; Glue and water baseization emulsifier proportion from as insect attractant are 0.05～1.5, when preparing long-acting moulding sustained release preparation, are 0.6～2.5 from glue and water baseization emulsifier proportion as insect attractant.
Embodiment
The present invention comes explanation objects and advantages of the present invention further through embodiment, and described only is exemplary with illustrative, rather than the qualification of claim of the present invention.
Embodiment 1
With litsea cubeba oil 2.5g, fenoxycarb (or methoprene) 0.6g, pyrethrins 0.4g, Butacide 0.6g,, ethylene glycol phenyl ether 1.0g, propane diols 2.5g be dissolved in the 5g ethanol, is stirred to the liquid that forms transparent and homogeneous; With 16gAEO-9,5g OP-10, the 5g Tween 80 is dissolved in the 50g water, is stirred to the liquid that forms transparent and homogeneous; With the two the mixed solution that forms transparent and homogeneous that stirs, mend then and add water to 100g then, subsequent use.
Take by weighing the 0.2g xanthans and join 97.8g cold water in batches, treat xanthans swelling → complete dissolving after, be warming up to 65～85 ℃; Agitation and dilution is to all dissolvings, be cooled to≤45 ℃ after, stir; Regulate PH to 7～8; Stir then down, add in above-mentioned microemulsion and the claim 10 grain storage and use insect attractant 2g, leave standstill after stirring and just form transparent thick liquid with rice storage.
Characteristic: the colloidal sol that makes is the transparent and homogeneous thick liquid, and is stable under normal temperature condition.
Purposes: be used for grain, tobacco, medicinal material etc., can kill and stored product insect, mite class and moulds such as prevention and control grain storage, tobacco, medicinal material, leather, clothes, books, archives and history relic.Be especially suitable for use as grain, tobacco, medicinal material storage protectant.
Method for using: the colloidal sol of present embodiment preparation is applied to storehouse tube, ground, on the reserve casing.2～3 years lasting periods, consumption (0.5～5g/m2).
Embodiment 2
Litsea cubeba oil 3g, fenoxycarb 1.0g, Butacide 0.6g, ethylene glycol phenyl ether 1.5g, propane diols 3g are dissolved in the 5g ethanol, are stirred to the liquid that forms transparent and homogeneous; With 18g AEO-9,6g OP-10, the 4g Tween 80 is dissolved in the 40g water, is stirred to the liquid that forms transparent and homogeneous; With the two the mixed solution that forms transparent and homogeneous that stirs, mend then and add water to 100g then, subsequent use.
Take by weighing 2.2g pectin join the 95.6g temperature be in 90～95 ℃ the hot water agitation and dilution to all dissolvings; Be cooled to≤45 ℃ after; Stir, regulate PH to 7～8, stir then down; Add in above-mentioned microemulsion and the claim 10 grain storage and use insect attractant 2g, leave standstill after stirring and just form clear gel with rice storage.
Characteristic: make the liquid that water baseization micro emulsion is a transparent and homogeneous, particle diameter 5～25nm, stable performance under-15～+ 55 ℃ of conditions.Not containing benezene solvent and solvent naphtha are sprayed at the cotton article and go up and do not have trace basically, do not pollute spray.Making Ludox is the transparent and homogeneous body, and particle diameter 5～100nm is stable under normal temperature condition.
Purposes: be used for grain, tobacco, medicinal material etc., can kill and stored product insect, mite class and moulds such as prevention and control grain storage, tobacco, medicinal material, leather, clothes, books, archives and history relic.Be especially suitable for use as grain, tobacco, medicinal material storage protectant.
Method for using: the colloidal sol of present embodiment preparation is pressed certain arrangement mode, place storehouse tube, ground, the first-class mildew-resistant desinsection place that needs of reserve casing.2～3 years lasting periods, consumption (0.5～5g/m2).
Embodiment 3
Litsea cubeba oil 3g, fenoxycarb 0.8g, decis (or sumithion) 0.7g, Butacide 0.6g, ethylene glycol phenyl ether 1.0g, propane diols 3g are dissolved in the 5.0g ethanol, are stirred to the liquid that forms transparent and homogeneous; 6gAEO-9,4g Tween 80,16gAES are dissolved in the 40g water, are stirred to the liquid that forms transparent and homogeneous; With the two the mixed solution that forms transparent and homogeneous that stirs, mend then and add water to 100g then, subsequent use.
Take by weighing 2.0g agar join the 96g temperature be in 90～95 ℃ the hot water agitation and dilution to all dissolvings; Be cooled to≤45 ℃ after; Stir, regulate PH to 7～8, stir then down; Add in above-mentioned microemulsion and the claim 10 grain storage and use insect attractant 2g, leave standstill after stirring and just form clear gel with rice storage.
Characteristic: make the liquid that water baseization micro emulsion is a transparent and homogeneous, particle diameter 5～25nm, stable performance under-15～+ 55 ℃ of conditions.Not containing benezene solvent and solvent naphtha are sprayed at the cotton article and go up and do not have trace basically, do not pollute spray.Making Ludox is the transparent and homogeneous body, and particle diameter 5～100nm is stable under normal temperature condition.
Purposes: be used for grain, tobacco, medicinal material etc., can kill and stored product insect, mite class and moulds such as prevention and control grain storage, tobacco, medicinal material, leather, clothes, books, archives and history relic.Be especially suitable for use as grain, tobacco, medicinal material storage protectant.
Method for using: the colloidal sol of present embodiment preparation is pressed certain arrangement mode, place storehouse tube, ground, the first-class mildew-resistant desinsection place that needs of reserve casing.2～3 years lasting periods, consumption (0.5～5g/m2).
Embodiment 4
Litsea cubeba oil 2.5g, eucalyptus oil 0.5g, fenoxycarb (or methoprene) 0.8g, pirimiphos-methyl 0.7g, Butacide 0.5g, Octacide 264 0.1%, ethylene glycol phenyl ether 1.5g, propane diols 2.5g are dissolved in the 5.0g ethanol, are stirred to the liquid that forms transparent and homogeneous; With 12g AEO-9,6g OP-10,8gAES is dissolved in the 40g water, is stirred to the liquid that forms transparent and homogeneous; With the two the mixed solution that forms transparent and homogeneous that stirs, mend then and add water to 100g then.
Take by weighing 0.3g pectin join the 97.7g temperature be in 75～85 ℃ the hot water agitation and dilution to all dissolvings; Be cooled to≤45 ℃ after; Stir, regulate PH to 7～8, stir then down; Add in above-mentioned microemulsion and the claim 10 grain storage and use insect attractant 2g, leave standstill after stirring and just form transparent thick liquid with rice storage.
Characteristic: the colloidal sol that makes is the transparent and homogeneous thick liquid, and is stable under normal temperature condition.
Purposes: be used for grain, tobacco, medicinal material etc., can kill and stored product insect, mite class and moulds such as prevention and control grain storage, tobacco, medicinal material, leather, clothes, books, archives and history relic.Be especially suitable for use as grain, tobacco, medicinal material storage protectant.
Method for using: the colloidal sol of present embodiment preparation is applied to storehouse tube, ground, on the reserve casing.2～3 years lasting periods, consumption (0.5～5g/m2).
Embodiment 5
Litsea cubeba oil 2.5g, fenoxycarb 0.7g, chlorpyrifos-methyl 0.8g, Butacide 0.6g, ethylene glycol phenyl ether 1.0g, propane diols 3.0g are dissolved in the 5.0g ethanol, are stirred to the liquid that forms transparent and homogeneous; With 8g AEO-9,6g OP-10,10gK12 is dissolved in the 40g water, is stirred to the liquid that forms transparent and homogeneous; With the two the mixed solution that forms transparent and homogeneous that stirs, mend then and add water to 100g then, subsequent use.
Take by weighing 0.25g agar join the 98.75g temperature be in 75～85 ℃ the hot water agitation and dilution to all dissolvings; Be cooled to≤45 ℃ after; Stir, regulate PH to 7～8, stir then down; Add in above-mentioned microemulsion and the claim 10 grain storage and use insect attractant 2g, leave standstill after stirring and just form transparent thick liquid with rice storage.
Characteristic: the colloidal sol that makes is the transparent and homogeneous thick liquid, and is stable under normal temperature condition.
Purposes: be used for grain, tobacco, medicinal material etc., can kill and stored product insect, mite class and moulds such as prevention and control grain storage, tobacco, medicinal material, leather, clothes, books, archives and history relic.Be especially suitable for use as grain, tobacco, medicinal material storage protectant.
Method for using: the colloidal sol of present embodiment preparation is applied to storehouse tube, ground, on the reserve casing.2～3 years lasting periods, consumption (0.5～5g/m2).
Insecticidal test
With the every 1000g of paddy is a, puts into plastic containers, paddy moisture 13.6%.Respectively 60 of red flour beetles, 30 of corn weeviles, 30 of lesser grain borers, adding are filled in the container of paddy; The green, the long-acting reserve fungus-proof pesticide that then the embodiment of the invention 1,2,4,5 are prepared; 1000 times of dilute with waters; Respectively by 0.1,0.5,1,5,10,15,20ppm dosage, direct even spraying on paddy respectively, and a blank is set.Placing temperature is 25 ± 1 ℃, in the incubator of relative moisture 85%, stores 15 days under the lucifuge condition, does insecticidal test.
The upright result that measures of the virulence of 1 pair of red flour beetle of table 1 embodiment
Regression equation y=10.1529+0.7838X correlation coefficient: 0.9273,
Lethal concentration (and 95% credible limit value): LC50=0.2665ppm, LC90=10.1529ppm
The toxicity test result of 2 pairs of lesser grain borers of table 2 embodiment
Regression equation y=10.1181+0.7730X correlation coefficient: 0.9282,
Lethal concentration (and 95% credible limit value): LC50=0.2392ppm, LC90=10.1181ppm
The toxicity test result of 4 pairs of saw-toothed grain beetles of table 3 embodiment
Regression equation y=10.0313+0.7553X correlation coefficient: 0.9247,
Lethal concentration (and 95% credible limit value): LC50=0.2183ppm, LC90=10.0313ppm
Antibacterial mould proof test:
Test method: with the every 500g of paddy is a; Put into plastic containers; Then with green, the long-acting reserve fungus-proof pesticide of the embodiment of the invention 1,2,3,5 preparation, 1000 times of dilute with waters, respectively by 1,5,10,20,50ppm dosage; Direct even spraying on paddy respectively, and a blank is set.Paddy is moisture 15%, and placing temperature is 25 ± 1 ℃, in the incubator of relative moisture 85%, stores 15 days under the lucifuge condition, does antibacterial mould proof test.
The antibacterial mould proof test of table 5
Claims (10)
1. from antibacterial mildew-resistant desinsection sustained release agent as the preparation of insect attractant sol/gel; According to different service conditions and environment; Adopt technology such as micro emulsion, colloidal sol; Select for use to have the colloidal sol of luring the insect function, preparation colloidal sol slowly-releasing plastics and colloidal sol moulding slowly-releasing system, the present invention with insect growth regulator, IGR (IGR) as Main Ingredients and Appearance; With multicomponent plants essential oil and/or low toxicity highly effective pesticide, bactericide, synergist, bleeding agent, water-soluble solvent, stabilizing agent, insect attractant etc. is auxiliary composition, and its preparation method is following:
A. adopt microemulsion technology to prepare the method that high infiltration rate is imitated water baseization microemulsion;
B. micro emulsion is combined with the colloidal sol technology, preparation water is prone to the colloidal sol and/or the gel rubber sustained-release plastics of wash-out and/or contains the method for the sol solutions of insect attractant;
C. micro emulsion and colloidal sol technology is combined, prepare colloidal sol and/or gel forming sustained release agent and/or contain the method for the sol preparation of other insect attractants;
D. insect attractant and preparation method.
2. according to claim 1 from antibacterial mildew-resistant desinsection sustained release agent as the preparation of insect attractant sol/gel; It is characterized in that described insect growth regulator, IGR is fenoxycarb and/or methoprene, hydroprene etc.; More than one or theys' composition, its consumption is 0.05～2%;
3. according to claim 1 from antibacterial mildew-resistant desinsection sustained release agent as the preparation of insect attractant sol/gel; It is characterized in that described plants essential oil is that litsea cubeba oil, eucalyptus oil, turpentine oil, Chinese cassia tree wet goods contain aldehyde and many components of terpenes plants essential oil; More than one or theys' composition, its content is 1.5～15%, and selects for use propane diols to cooperate with plants essential oil; To increase the availability of permeability and active ingredient, it is 0.8: 1.65 that its plants essential oil and propane diols are optimized proportioning; Described many components plants essential oil is meant the non-high-purity major constituent essential oil that from a plant species, extracts; The multicomponent essential oil is compared with the essential oil of high-purity single component; Play synergy, synergy; Help preventive effect and prevent that pest resistance to insecticide, the present invention from selecting for use and contain main component citral 65～75% litsea cubeba oils, all the other components are citrene, methyl heptenone, australene, nopinene, linalool etc.; Select the eucalyptus oil that contains main component cineole 60～80% for use, all the other components are alpha-terpineol, australene, terpinyl acetate, aromadendrene, terpinene, linalool etc.; Select for use to contain main component firpene 60～75% turpentine oil, all the other components are the essential oil of laurene, terpinene, α phellandrene;
4. according to claim 1 from antibacterial mildew-resistant desinsection sustained release agent as the preparation of insect attractant sol/gel; It is characterized in that described 1. low toxicity efficient pesticides is that the pyrethroid insecticides of plant resource and plant resource modification agricultural chemicals (pyrethrins, Celastrus angulatus, rotenone, seal chinaberry, nicotine, matrine, stemonine, Tea Saponin, tea are withered etc.), microorganism insecticide (bacillus thuringiensis,Bt, AVM), LD50 >=500mg/kg is (when being used for grain storage; Select β-cyfloxylate, decis of American-European registered registration etc. for use) and organophosphorus insecticide (when being used for grain storage; Select Folithion, malathion, methylpyrimidine sulphur phosphorus, the chlorpyrifos-methyl of American-European registered registration for use); More than one or theys' composition, its content is 0.05～5%; 2. adopting above-mentioned insecticide simultaneously, the adding synergist is Butacide, Octacide 264, more than one or theys' composition, its content is 0.5～2.5%, with the ratio of insect growth regulator, IGR be 0.6～1.5.
5. according to claim 1, the 3 described antibacterial mildew-resistant desinsection sustained release agents that prepare as the insect attractant sol/gel certainly; It is characterized in that described bactericide is plants essential oil, ethylene glycol phenyl ether, ethanol, Triclosan, the dimethyl fumarate in the claim 3; More than one or theys' composition, its content is 2.5～15%.
6. green according to claim 1, the antibacterial mildew-resistant desinsection sustained release agent for preparing as the insect attractant sol/gel certainly; It is characterized in that described solvent for the low toxicity water-soluble solvent of containing benezene not like ethylene glycol phenyl ether, ethanol, N; Dinethylformamide, oxolane, N-N-methyl 2-pyrrolidone N-etc.; Two or more, its content is 3～15%, the plants essential oil double as oil-dissolving solvent described in the claim 3.
7. according to claim 1 from antibacterial mildew-resistant desinsection sustained release agent as the preparation of insect attractant sol/gel, it is characterized in that described stabilizing agent is a propane diols.
8. according to claim 1 from antibacterial mildew-resistant desinsection sustained release agent as the preparation of insect attractant sol/gel; It is characterized in that described to have the colloidal sol of luring the insect function be agar, pectin, sodium alginate, xanthans, gelatin, cyclodextrin etc.; The colloidal sol that contains insect happiness food compositions such as sugar and/or protein and/or starch, during preparation colloidal sol slowly-releasing plastics, the consumption of above-mentioned colloidal sol is 0.1～0.8%; Outward appearance is a transparent body thick liquid, films in the place that is used for the easy wash-out of water; When preparing described colloidal sol moulding sustained release agent, the consumption of above-mentioned colloidal sol is 0.8～5%; Wherein agar, pectin, sodium alginate, gelatin, cyclodextrin also can add known insect attractant except that self is insect attractant
9. according to claim 1 from antibacterial mildew-resistant desinsection sustained release agent as the preparation of insect attractant sol/gel; It is characterized in that described surfactant is nonionic and/or anion surfactant: wherein, nonionic is NPE (TX series), polyoxyethylene 20 sorbitan monooleate (tween series), AEO (AEO series), OPEO (OP series), polyoxyethylene nonylphenyl ether, cocoa butter alkanolamide, Emulsifier EL-60 nonionics such as (EL series); Anion is neopelex/calcium (LAS), lauryl sodium sulfate/calcium (K12) etc., and two or more, their composition, its consumption are 15～35%.
10. described from the antibacterial mildew-resistant desinsection sustained release agent as insect attractant sol/gel preparation according to claim 1～9, it is characterized in that described the film method of sustained release agent, colloidal sol moulding sustained release agent and insect attractant of colloidal sol for preparing:
A. adopt microemulsion technology to prepare the method that high infiltration rate is imitated water baseization microemulsion: select 4～15% water-soluble solvent for use, at room temperature with the emulsifier thin up, all the other components are dissolved in the water baseization solvent; Then two solution are mixed, be prepared into transparent homogeneous liquid, particle diameter 5～50nm; Stable under-10～50 ℃ condition; Be sprayed on the reserve and leave no trace, do not pollute reserve, consumption is 0.1～10ppm;
B. micro emulsion is combined with the colloidal sol technology; Prepare long-acting colloidal sol and/or gel rubber sustained-release plastics and/or contain the method for the sol solutions of insect attractant: after the colloidal sol dilute with water described in the claim 8 is stirred; Normal temperature is regulated pH value down, and powerful the stirring adds described water baseization microemulsion of a and/or insect attractant down fast, leaves standstill after stirring and forms green, long-acting reserve mildew-resistant desinsection vitreosol liquid; The ratio of micro emulsion and sol solutions is 0.5～1.5; Sol content is 0.05～1.5%, and outward appearance is a transparent body thick liquid, films in the place that is used for the easy wash-out of water; This colloidal sol can directly be coated with reserve cabinet wall, warehouse floor or body of wall on, consumption is 0.2～10g/m
2
C. micro emulsion is combined with the colloidal sol technology; Prepare long-acting colloidal sol and/or gel forming sustained release agent and/or contain the method for the sol preparation of other insect attractants: claim 8 is described from as the agar of insect attractant or pectin, sodium alginate, xanthans, gelatin, cyclodextrin etc., and after water was adjusted to suitable concentration and stirs, normal temperature was regulated pH value down; The powerful stirring adds described water baseization microemulsion of a and/or insect attractant down fast; After stirring, pour in the container of definite shape, leave standstill formation and have the green of definite shape, long-acting reserve mildew-resistant desinsection sustained release preparation; Moulding glue and water baseization emulsifier proportion are 0.5～2.5; Sol content is 0.2～3.5%, and this colloidal sol body is used to have certain profile, presses certain way and arranges; Place in good thing casing of storage or the storehouse (reserve periphery) and/or sized-multiple.
D. insect attractant and preparation method:
The preparation method of insect attractant: will be used for mixing under the prescription normal temperature of different places, add the deionized water of 1.5～2 times of composition weight after, stirring gets final product.The insect attractant that is used for different places is formed as follows:
Foodstuff preservation is with the composition of insect attractant
The tobacco storage is used insect attractant
The medicinal material storage is used insect attractant
Leather, dress ornament storage are used insect attractant
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