CN101999345A - Environmentally-friendly, long-acting, bacteriostatic, mildewproof and pesticidal sol preparation - Google Patents
Environmentally-friendly, long-acting, bacteriostatic, mildewproof and pesticidal sol preparation Download PDFInfo
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Abstract
The invention discloses an environmentally-friendly, long-acting, bacteriostatic, mildewproof and pesticidal sol preparation. A sol film coating agent, a film-forming sustained-release agent and a sol moulding sustained-release agent are prepared by technology of micro emulsion, sol and the like according to different using conditions and environments. The sol preparation meets requirements on prevention and control in different places by taking an insect growth regulator (IGR) as a main component and taking vegetable essence oil and/or a low-toxin high-efficiency pesticide, a bactericide, a synergist, a penetrating agent, a water-soluble solvent, a stabilizer, an insect attractant, a sustained-release agent, a moulding sustained-release agent and the like as auxiliary components. The preparation has wide insecticidal spectrum and high efficiency, kills eggs, inhibits insect growth, has long acting time, causes no resistance, resists bacteria, prevents moulds, has low residue and low toxin, can remove pollution caused by unbalanced preparation application, contributes to ecological environment, is used for killing and controlling insects, mites and moulds in stored objects such as rice, tobaccos, medicaments, leathers, costumes, books, files, historical relics and the like and plants and can reduce loss of the stored objects and plants caused by insects and moulds.
Description
Technical field
The present invention relates to a kind of green, long-acting bacteriostatic mildew-resistant desinsection sol preparation; more specifically relate to a kind of contain that insect growth regulator, IGR (IGR) and plants essential oil and/or low toxic pesticide etc. are compound and be prepared into water baseization microemulsion after; in the process of the colloidal sol for preparing, add water baseization microemulsion; be made into colloidal sol sustained release preparation and/or colloidal sol moulding sustained release preparation, the invention still further relates to the application of reserves such as said preparation plant protection, 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 seem more and more important in the control of stored product insect 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, these insects are to the resistance performance of phosphine, the national resistance monitoring net of taking the lead through Chengdu foodstuff preservation Science Institute, 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.From above-mentioned investigation result as can be seen, long-term single use aluminum phosphate constantly increases pest resistance to insecticide, and 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 the 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 may 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, wherein with lasioderma serricorne, 2 kinds of insects of the cacac moth harm maximum to tobacco leaf and cigarette finished product.
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 has been arranged both at home and abroad, can be difficult in the short time solve for the fumigant that substitutes phosphine, and the protectant kind be many and have a function that excellent pre-insect-pest infects.Therefore; the external control of insect strategy that all adopts fumigant to be used in combination with protectant; use 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; replace a large amount of at present higher chemical agents of toxicity that use with the new bio insecticide, 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
Main purpose of the present invention is to provide a kind of green, long-acting bacteriostatic mildew-resistant desinsection sol preparation, said preparation have insecticidal spectrum wide, efficient, kill ovum, suppress insect growth, consumption is little, dispenser is convenient, insect is difficult for developing immunity to drugs, and has antibacterial mildew-resistant and desinsection dual-use function.Residual low, to the person poultry safety, can eliminate the pollution that unbalance dispenser causes, the improvement of favourable ecotope.
Another object of the present invention is to provide a kind of new formulation, said preparation combines micro emulsion with the colloidal sol technology, according to different service conditions and environment, be prepared into the colloidal sol slowly-releasing plastics of the easy wash-out of water, easily make the moulding sustained release preparation of different shape, and/or contain insect growth regulator, IGR, have different releasing mechanisms, satisfy different places prevention and control demand.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.
Another object of the present invention is to provide a kind of green, long-acting bacteriostatic mildew-resistant desinsection sol preparation, when being used for grain storage, when putting in storage with grain, on conveyer belt, admix, need not increase additional process, when being used for farmer storage, do not need airtight, when adopting colloidal sol plastics and/or film forming sustained release agent direct plastics at grain storage gunnysack, storing case, warehouse inner wall film-coating.When adopting the moulding sustained release preparation, be placed in storing case, the warehouse and get final product.
For achieving the above object, 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 as follows:
A. adopt microemulsion technology to prepare the method that high infiltration rate is imitated water baseization microemulsion;
B. adopt the colloidal sol technology to prepare the long-acting slow-release plastics of the easy wash-out of water and/or contain the method for the sol solutions of insect attractant;
C. adopt the colloidal sol technology to prepare the moulding sustained release preparation and/or contain the method for the colloidal sol body preparation of insect attractant;
For achieving the above object, the inventor is through long-term discovering in this field, select insect growth regulator, IGR (suppress insect growth, do not develop immunity to drugs, reduce dosage and number of times), edible plants essential oil, plant extracts, containing benezene water-soluble solvent, water baseization microemulsion reinforcement infiltration for use, reduce dosage.At different targets, select the effective 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; 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, through long-term discovering to fenoxycarb, 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 be repelled, 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, as 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 combination 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 easily absorbed by the organic matter in the water, and after illumination, the half life period is 5 hours.After entering 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 extracts from a plant species, the essential oil of multicomponent energy 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 sample 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 nontoxic to human body, 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.The FEMA regulation: the highest reference quantity 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 inventor finds, because diversity of organism, the bactericide of one-component is compared with the bactericide of many components, therefore selected for use to have multi-functional ethylene glycol phenyl ether, ethanol, in as solvent, the double as bactericide, at different occasions, can add dimethyl fumarate where necessary.
Diethanol phenylate low toxicity, rat oral: LD50=1260mg/kg, it is 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 this product as food additives and is used widely.China also approved used as antimildew agent for food and food additives.
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 (a Chiu of kind more than 2000, et al.1993 reports 30,000 kinds) plant has active insecticidal components, can be divided into following several big class 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 the efficient easily degrading pesticide of low toxicity for use, 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. easily degraded in natural environment, 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 the saponin element.The withered liquid of CHAKUBING and tea has good stomach toxicity and action of contace poison to insect, can extensively use control snail, river snail, leech, rice fulgorid, rice leafhopper, the first-class insect of Ipomoea batatas baby elephant on vegetables, paddy rice, fruit tree, tealeaves, flowers and other crops.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 low toxicity efficient easily degrading pesticide pyrethroid, organic phosphates for use, for satisfying the grain protectant requirement, pyrethroid and the organophosphorus insecticides of the present invention to select 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, does not have 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 not inhaled fumigation action to tag and stomach toxicity in not having, and insecticidal spectrum is wide, easy decomposition failure in alkaline medium and soil.Low to higher mammal toxicity, under solar radiation, easily decompose.
Solvent of the present invention is selected ethylene glycol phenyl ether, ethanol, N for use, non-benzene class (toluene, dimethylbenzene 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 has screened the combination of above-mentioned solvent, 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 polyoxyethylene nonylphenol ether (TX series), polyoxyethylene 20 sorbitan monooleate (tween series), fatty alcohol-polyoxyethylene ether (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%.
Green of the present invention, long-acting reserve mildew-resistant desinsection colloidal sol sustained release agent, the colloidal sol long-acting slow-release plastics of its water baseization microemulsion, the easy wash-out of water and/or contain insect attractant, colloidal sol moulding sustained release agent and/or contain the preparation method of insect attractant:
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 technology to prepare the long-acting slow-release plastics of the easy wash-out of water 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, the powerful stirring adds described water baseization microemulsion of a and/or insect attractant down fast, leave standstill after stirring and form reserve mildew-resistant desinsection vitreosol liquid with insect attractant function, sol solutions after the dilution and water baseization emulsifier proportion are 0.05～1.5, this colloidal sol can directly be coated with and the reserve cabinet wall, on warehouse floor or the body of wall, consumption is 0.2～10g/m
2
After colloidal sol dilute with water described in the claim 8 stirred, normal temperature is regulated pH value down, the powerful stirring adds described water baseization microemulsion of a and/or insect attractant down fast, leave standstill after stirring and form green, long-acting reserve mildew-resistant desinsection vitreosol preparation, the ratio of micro emulsion and sol solutions is 0.1～1.0, sol content is 0.05～1.5%, outward appearance is a transparent body thick liquid, film in the place that is used for the easy wash-out of water, this colloidal sol can directly spray or brush on reserve cabinet wall, warehouse floor or body of wall, and consumption is 0.2～10g/m2.
C. adopt the colloidal sol technology to prepare the moulding sustained release preparation and/or contain the method for the colloidal sol body preparation of insect attractant: after the colloidal sol class moulding sustained release agent water described in the claim 8 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 and form green with definite shape, long-acting reserve mildew-resistant desinsection sustained release preparation, moulding glue and water baseization emulsifier proportion are 0.6～2.5, this colloidal sol body is used to have certain profile, pressing certain way arranges, place in reserve casing or the storehouse (reserve periphery) and/or sized-multiple;
Embodiment
The present invention further illustrates objects and advantages of the present invention by embodiment, and described only is exemplary with illustrative, rather than the qualification of claim of the present invention.
Embodiment 1
Litsea cubeba oil 3.0g, fenoxycarb (or methoprene) 0.6g, pyrethrins 0.4g, Butacide 0.6g, ethylene glycol phenyl ether 1.0g, propane diols 2.5g are dissolved in the 5g ethanol, are 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, standby.
Taking by weighing the 5.0g sodium silicate solution, to join in the 34g water agitation and dilution even, powerful down stirring of normal temperature slowly adds watery hydrochloric acid (3～5%,～8.2g) regulate PH to 7～8, powerful then the stirring down, add rice storage insect attractant 1g in above-mentioned water baseization microemulsion 60g and the claim 7 fast, after stirring, pour in four 25mL glasswares, leave standstill and just form clear gel.
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 product and go up and do not have trace substantially, 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.
Using method: 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 2
Litsea cubeba oil 3g, fenoxycarb 1.5g, 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, standby.
Take by weighing the 0.2g polyvinyl alcohol join the 98g 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, adding in above-mentioned microemulsion and the claim 7 grain storage leaves standstill after stirring and just forms clear gel with rice storage insect attractant 2g.
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.
Using method: 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 3
Litsea cubeba oil 2.5g, eucalyptus oil 0.5, fenoxycarb (or methoprene) 0.6g, rotenone 0.4g, the withered extract 0.5 of tea, Butacide 0.5g, Butacide 0.1%, ethylene glycol phenyl ether 1.0g, propane diols 2.5g are dissolved in the 5.5g ethanol, are stirred to the liquid that forms transparent and homogeneous; With 20g AEO-9,5g OP-10, the 3g Tween-80 is dissolved in the 35g 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 the 1.2g carboxymethyl cellulose join the 97g 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 rice storage insect attractant 3g in above-mentioned microemulsion and the claim, leave standstill after stirring and just form transparent thickness sol solutions.
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.
Using method: 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 4
Litsea cubeba oil 2.5g, fenoxycarb (or methoprene) 0.6g, β-cyfloxylate 0.6g, Butacide 0.6g, 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 7g AEO-9,5g OP-10,12gK12 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.
Taking by weighing the 5.5g sodium silicate solution, to join in the 34.5g water agitation and dilution even, powerful down stirring of normal temperature slowly adds watery hydrochloric acid (3～5%,～8.2g) regulate PH to 7～8, powerful then the stirring down, add rice storage insect attractant 2g in above-mentioned water baseization microemulsion 58g and the claim fast, after stirring, pour in four 25mL glasswares, leave standstill and just form clear gel.
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 product and go up and do not have trace substantially, do not pollute spray.Make green, long-acting mould-proof desinsection colloidal sol moulding sustained release agent is the transparent and homogeneous body, particle diameter 5～100nm, 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.
Using method: 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).
Insecticidal test
With the every 1000g of paddy is a, puts into plastic containers, paddy moisture 13.4%.Respectively 60 of red flour beetles, 60 addings of corn weevil are filled in the container of paddy, then with green, the long-acting reserve colloidal sol moulding fungus-proof pesticide of the embodiment of the invention 1 preparation, respectively by 0.1,0.5,1,5,10,15,20ppm dosage, place respectively in the container of containing paddy, and a blank sample is set.Placing temperature is 25 ± 1 ℃, in the incubator of relative moisture 85%, stores 30 days under the lucifuge condition, does insecticidal test; With embodiment 1 condition, with green, the long-acting reserve colloidal sol of the embodiment 2 preparation fungus-proof pesticide of filming, respectively by 0.1,0.5,1,5,10,15,20ppm dosage, brush respectively at the container inner wall of containing paddy, do insecticidal test.
The virulence of 1 pair of corn weevil of table 1 embodiment is found measurement result
Regression equation y=9.9039+0.7536X correlation coefficient: 0.9090,
Lethal concentration (and 95% credible limit value): LC50=0.3111ppm, LC90=9.9039ppm
The toxicity test result of 2 pairs of red flour beetles of table 2 embodiment
Regression equation y=11.2759+0.9289X correlation coefficient: 0.9812,
Lethal concentration (and 95% credible limit value): LC50=0.1800ppm, LC90=11.2759ppm
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 preparation, 1000 times of dilute with waters, respectively by 1,5,10,20,50ppm dosage, direct even spraying on paddy respectively, and a blank sample is set.Paddy is moisture 15%, and placing temperature is 25 ± 1 ℃, in the incubator of relative moisture 85%, stores 30 days under the lucifuge condition, does antibacterial mould proof test.
The antibacterial mould proof test of table 5
Claims (10)
1. green, long-acting bacteriostatic mildew-resistant desinsection sol preparation according to different service conditions and environment, adopt technology such as micro emulsion, colloidal sol, and the easy wash-out colloidal sol of preparation water plastics, water are difficult for wash-out film forming sustained release agent and colloidal sol moulding sustained release agent, form different releasing mechanisms; 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, film forming sustained release agent and moulding sustained release agent etc. is auxiliary composition, and its preparation method is as follows:
A. adopt microemulsion technology to prepare the method that high infiltration rate is imitated water baseization microemulsion;
B. micro emulsion is combined the long-acting colloidal sol slowly-releasing plastics of preparation water easy wash-out and/or contain the method for the sol solutions of insect attractant with the colloidal sol technology;
C. micro emulsion is combined with membrane technology, preparation water is difficult for the long-acting film forming sustained release preparation of wash-out and/or contains the method for the colloidal sol body preparation of insect attractant;
D. micro emulsion is combined with the colloidal sol technology, prepare long-acting colloidal sol moulding sustained release preparation and/or contain the method for the colloidal sol body preparation of insect attractant;
E. insect attractant and preparation method.
2. green according to claim 1, long-acting bacteriostatic mildew-resistant desinsection sol preparation is characterized in that described insect growth regulator, IGR is fenoxycarb and/or methoprene, hydroprene etc., more than one or theys' composition, and its consumption is 0.05～2%;
3. green according to claim 1, long-acting bacteriostatic mildew-resistant desinsection sol preparation, 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 adopt 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 extracts from a plant species, the multicomponent essential oil is compared with the essential oil of high-purity single component, play synergy, synergy, help preventive effect and prevent pest resistance to insecticide, the present invention adopts and contains main component citral 65～75% litsea cubeba oils, and all the other components are citrene, methyl heptenone, australene, nopinene, linalool etc.; Employing contains the eucalyptus oil of main component cineole 60～80%, and all the other components are alpha-terpineol, australene, terpinyl acetate, aromadendrene, terpinene, linalool etc.; Employing contains main component firpene 60～75% turpentine oil, and all the other components are the essential oil of laurene, terpinene, α phellandrene;
4. green according to claim 1, long-acting bacteriostatic mildew-resistant desinsection sol preparation, it is characterized in that described 1. low toxicity efficient pesticides is plant resource and plant resource modification agricultural chemicals (pyrethrins, Celastrus angulatus, rotenone, the seal chinaberry, nicotine, matrine, stemonine, Tea Saponin, tea is withered etc.), microorganism insecticide (bacillus thuringiensis,Bt, Avermectin), the pyrethroid insecticides of LD50 〉=500mg/kg is (when being used for grain storage, adopt the β-cyfloxylate of American-European registered registration, decis etc.) and organophosphorus insecticide (when being used for grain storage, adopt the Folithion of American-European registered registration, the malathion, methylpyrimidine sulphur phosphorus, chlorpyrifos-methyl), 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 1,3 described greens, long-acting bacteriostatic mildew-resistant desinsection sol preparation, 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, long-acting bacteriostatic mildew-resistant desinsection sol preparation, it is characterized in that described solvent for the low toxicity water-soluble solvent of containing benezene not as 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. green according to claim 1, long-acting bacteriostatic mildew-resistant desinsection sol preparation, it is characterized in that described insect attractant is a fluid composition, to mix under the recipe ingredient normal temperature, behind the deionized water that the adding composition weight is 1.5～2 times, stirring gets final product.Form: essence 30～60%, carbohydrate 5～30%, lactic acid 2～8%, distiller's yeast 2～8%, valeric acid 10～18%:
The foodstuff preservation composition of insect attractant
Tobacco storage insect attractant
Medicinal material storage insect attractant
Leather, dress ornament storage insect attractant
8. green according to claim 1, long-acting bacteriostatic mildew-resistant desinsection sol preparation, it is characterized in that described 1. colloidal sol slowly-releasing plastics is the colloidal sol of preparations such as low concentration silica, agar, pectin, carboxymethyl cellulose (salt), hydroxyethylcellulose, sodium alginate, gelatin, modified starch, cyclodextrin, its consumption is 0.1～1.2%, films in the place that is used for the easy wash-out of water; 2. described film forming sustained release agent is other macromolecule aqueous solution or emulsions such as polyvinyl alcohol, acrylic acid and polyacrylic, and do not produce chemical reaction, degradable polymer with above-mentioned active ingredient, its consumption is 0.05～2%, outward appearance is a thick liquid, curable film-forming is used for water and is difficult for filming of wash-out; 3. described colloidal sol moulding sustained release agent is the colloidal sol of preparations such as Ludox, agar, pectin, carboxymethyl cellulose (salt), hydroxyethylcellulose, sodium alginate, carboxymethyl cellulose (salt), its consumption is 0.8～5%, is used for any arrangement, convenient occasion of placing.
9. green according to claim 1, long-acting bacteriostatic mildew-resistant desinsection sol preparation, it is characterized in that described surfactant is nonionic and/or anion surfactant: wherein, nonionic is polyoxyethylene nonylphenol ether (TX series), polyoxyethylene 20 sorbitan monooleate (tween series), fatty alcohol-polyoxyethylene ether (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. according to the described green of claim 1～9, long-acting bacteriostatic mildew-resistant desinsection sol preparation, it is characterized in that the long-acting colloidal sol slowly-releasing plastics of described water baseization micro emulsion spray, the easy wash-out of water, easily make different shape long-acting colloidal sol moulding sustained release preparation the preparation method and and insect attractant and preparation method:
A. the preparation method of water baseization microemulsion: adopt 4～15% water-soluble solvent, 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. the preparation method of colloidal sol slowly-releasing plastics: after the colloidal sol dilute with water described in the claim 8 stirred, normal temperature is regulated pH value down, the powerful stirring adds described water baseization microemulsion of a and/or insect attractant down fast, leave standstill after stirring and form green, long-acting reserve mildew-resistant desinsection vitreosol preparation, the ratio of sol solutions and water baseization micro emulsion is 0.5～1.5, sol content is 0.05～1.5%, outward appearance is a transparent body thick liquid, film in the place that is used for the easy wash-out of water, said preparation can directly spray or brush at the reserve cabinet wall, on warehouse floor or the body of wall, consumption is 0.2～10g/m
2
C. the preparation method of film forming sustained release agent: with the film forming sustained release agent (polyvinyl alcohol described in the claim 8, other macromolecule aqueous solution or emulsions such as degradable acrylic acid and polyacrylic), after dilute with water stirs, regulate pH value, the powerful stirring adds described water baseization microemulsion of a and/or insect attractant down fast, after stirring, form the green that water is difficult for wash-out, long-acting storage subtracts thing mildew-resistant desinsection film forming sustained release agent, filming emulsion after the dilution and water baseization microemulsion ratio are 0.5～1.5, film forming agent content is 0.2～2.5%, this film forming sustained release agent can directly be coated with and the reserve cabinet wall, on warehouse floor or the body of wall, consumption is 0.2～10g/m
2
D. the preparation method of colloidal sol moulding sustained release preparation: after the colloidal sol class moulding sustained release agent water described in the claim 8 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 and form green with definite shape, long-acting colloidal sol moulding mildew-resistant desinsection sustained release preparation, moulding glue and water baseization emulsifier proportion are 0.5～1.5, sol content is 0.2～3.5%, this colloidal sol body is used to have certain profile, press certain way and arrange, place in reserve casing or the storehouse (reserve periphery) and/or sized-multiple.
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| CN109619098A (en) * | 2019-02-14 | 2019-04-16 | 浙江大学 | A kind of rice antimicrobial agent and its application |
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| CN110453020A (en) * | 2019-07-10 | 2019-11-15 | 浙江理工大学 | A kind of guard method for vegetable leather historical relic |
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