• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention describes a process for obtaining microbiocapsules of one or more pyrethrins as active substance, and is framed in the field of the technique of the production of biopesticides. Natural pyrethrin is a broad spectrum insecticide extracted from the flowers of the Chrysasnthemun genus plant and is easily broken down by air and light. The present invention increases the stability of pyrethrins, being effective for a longer time than other solutions of the state of the art. The method and procedure comprises the following steps; a first oily phase, a second emulsion phase of the mixture and a third encapsulation phase. The result is the obtaining of pyrethrin microbiocapsules with a size between 0.5 to 5 microns, with greater stability. The process does not reduce the insecticidal ability of pyrethrins. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2794124A1
    申请号:ES201930434
    申请日:2019-05-17
    公开日:2020-11-17
    发明作者:Terres Enrique Riquelme
    申请人:Grupo Agrotecnologia S L；
    IPC主号:
    专利说明:

    [0002] Method and procedure for obtaining microbiocapsules of natural pyrethrins with high stability
    [0004] TECHNICAL SECTOR
    [0006] The invention belongs to the field of application of the chemical industry sector dedicated to the production of nanobiopesticides, and specifically to methods for the production of pyrethrin nanoemulsions.
    [0008] BACKGROUND OF THE INVENTION
    [0010] With the development of society and the expansion of agricultural areas, there has been a demand for new, more efficient and safe pesticides. Some highly effective chemical formulations have emerged quickly, but a high degree of residues appear on analyzing crops. However, with the development of environmental certification and awareness along with advances in biotechnology in recent years, pesticide manufacturers have begun to adhere to guidelines for safety, efficiency, circular economy and user-friendliness, which have resulted in non-toxic, ecological and zero residue products. Biopesticides have become the priority line of the agrochemical industry.
    [0012] The use of natural pyrethrins as a pesticide has a long history and can be used to control pests that affect both humans and crops. Natural pyrethrin is an insecticide extracted from the pelitre flower ( Chrysanthemum cinerariaefolium) and is easily degradable by light, air, water and microorganisms. Pyrethrin is highly toxic to crop-damaging insects, but is safe for hot animals, is non-polluting, and leaves no residue.
    [0014] For the prevention and control of pests, pyrethrins are usually in the form of solids, oils, wettable powders, and emulsifiable concentrations. In the case of pelitre oil and concentrated emulsions, it is usually mixed with substances and plant derivatives, which are pollutants for water and the environment. The encapsulation of pyrethrins not only allows the need for lower doses of pyrethrin but also protects the environment, reduces production costs, increases the effectiveness of the insecticide in contact with other inputs or others. pesticides and blocks the unpleasant smell of active substances. Pesticide compositions containing a pyrethroid, a vegetable oil, a solvent and an emulsifying surfactant system are known (EP 567,368). Likewise, emulsifiable concentrates are known which contain a pyrethroid, an excipient that can contain vegetable oils, a surfactant system and optionally solvents and stabilizing agents (GB 2,058,569). Compositions containing a pyrethroid, a vegetable oil and a surfactant system consisting, for example, of a mixture of non-ionic and anionic surfactants are also known (US 4,617,3318), such as compositions containing pyrethroids, vegetable oils or other esters such as an organic solvent (ES 2,144,618). However, none of these documents claims, mentions or can be subtracted from the description, the microencapsulation of the pyrethroid.
    [0016] With regard to the procedure for obtaining microcapsules, microencapsulation technologies have been applied to pesticide formulation processes from the beginning of the 70s to the present day. However, the number of products with microencapsulated active substances is quite limited. In 1976 in the United States, Pennwalt launched the first microencapsulated pesticide: Methyl parathion, which significantly reduced the toxicity of the product and prolonged its effects. Pennwalt also encapsulated Pennwalt Corporation pyrethrin ES 8506420 by a complex and expensive procedure. Since then, different investigations have been carried out in the field of microcapsule development, and in particular in the field of agriculture, reaching today where there are over 200 agrochemical companies that have research projects in the development and application of microcapsules . Therefore, there is more than 40 years of history in the development of pesticide microcapsules, but compared to developments in the pharmaceutical industry this has been quite slow. As a result, there is little variety of products on the market based on pesticide microcapsules.
    [0018] Current methods of microencapsulation of pesticides mainly include: polymerization, cohesive phases of separation and evaporation of solvents. These methods are not only complicated but also expensive. Organic solvents are also used in large amounts which are polluting.
    [0019] Despite all these existing alternatives, the need continues to provide a process for obtaining pyrethrin microbiocapsules that does not affect the insecticidal capacity in such a way that they can be used for pest control.
    [0021] EXPLANATION OF THE INVENTION
    [0023] The present invention has been designed in such a way as to provide, according to a first aspect thereof, a process for obtaining microbiocapsules of one or more pyrethrins as active substance, the process of which comprises three stages:
    [0025] 1. Preparation of oil phase, which consists of a solution of one or more pyrethrin (s) as active substance with a richness between 48% -80%, in one or more vegetable oil (s) in a ratio of 1: 20, optionally stirring occurs, optionally a solvent agent can be added that can be fatty acid (s), alcohol (s), essential oil (s) or a mixture of the above, then it is applied stirring the mixture.
    [0027] 2. Emulsifying phase in which an emulsifier and optionally a stabilizing agent and / or a preservative are added, while stirring. Additionally, a co-formulating agent (s) with antioxidant property (s), preservative (s) and / or antifoam (s) can be added.
    [0029] 3. Microbiocapsule obtaining phase, where by means of a mixing process, preferably using a mixer, such as a mixer with paddle stirrer, the result is the obtaining of pyrethrin microbiocapsules at 4-25% w / v, preferably between 4-8% w / v with a size between 0.5 to 5 microns, with greater stability.
    [0031] In the present invention by pyrethrin microbiocapsule refers to; micrometric particles with an outer membrane inside which contains pyrethrin as an active substance.
    [0033] In phase (1), one or more vegetable oil (s) are added that are selected from the group consisting of sunflower, corn, soybean, avocado, jojoba, pumpkin, grapeseed, sesame, hazelnut, glycerol tricaprocaprylate, or vegetable oils of the formula R9 COOR10 in which R9 represents the residue of a higher fatty acid comprising 7 to 29 carbon atoms and R 10 represents a straight or branched hydrocarbon chain containing 3 to 30 carbon atoms in particular alkyl or alkenyl , undecylenic, myristoleic, palmitoleic, oleic, linoleic, linolenic, ricinoleic, eicosenoic, or docosenoic acids (found in pine, corn, sunflower, soy, raisin, flax, or jojoba). As preferred examples of fatty acids, mention may be made of fatty acids comprising unsaturated molecules, for example of the oleic type, which are oligomerized by a double bond condensation reaction. This reaction results in mixtures that essentially comprise dimers and trimers. By dimers and trimers of fatty acids we mean the oligomers of 2 or 3 identical or different monomers. Advantageously, these fatty acids, saturated or unsaturated, comprise 12 to 100 carbon atoms, and more advantageously 24 to 90
    [0035] In phase (1) the agitation is between 60-150RPM
    [0037] In phase (1) the temperature is 20 to 40 ° C, preferably between 25-35 ° C.
    [0039] In phase (1), a solvent agent selected from unsaturated fatty acids and their derivatives can be added: linoleic acid, linolic acid, oleic acid, folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, tocopherols and derivatives
    [0041] In step (1) a solvent agent selected from lower alcohols such as ethanol and isopropanol can be added; polyhydric alcohols such as glycerol, propylene glycol, dipropylene glycol, and sorbitol;
    [0043] In phase (1), a dissolving agent selected from natural or synthetic essential oils such as, for example, the oils of eucalyptus, hybrid of lavender, lavender, vetiver, litsea cubeba, lemon, sandalwood, rosemary, chamomile, can be added. savory, nutmeg, cinnamon, hyssop, caraway, orange, geranium, juniper and bergamot.
    [0045] In phase (2), a non-ionic emulsifying agent is added which appears in a proportion of 10 to 50% of the composition by weight, and preferably, between 15 to 30% by weight with respect to the total weight of the composition.
    [0046] By non-ionic emulsifying agent is meant; amphoteric, anionic, preferably cationic. Amphoteric or ampholytic emulsifying agents are understood to be those surfactant compounds that contain, in addition to an alkyl or acyl group with 8 to 18 carbon atoms, at least one free amino group, and at least one -COOH or -SO3H group in the molecule , and are suitable for the formation of internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodi-propionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropyl acids, 2-alkylaminopropyl acids. alkylaminoacetic compounds, in each case with about 8 to 18 carbon atoms in the alkyl group. Anionic emulsifying agent is understood to be those having a negative face, examples of anionic surfactants are, such as alkyl sulfates with a chain length of 8 to 18 C atoms, alkyl or alkylaryl ether sulfates with 8 to 18 C atoms in the hydrophobic moiety and up to 40 units of ethylene oxide or propylene oxide, alkyl or alkylaryl sulphonates with 8 to 18 carbon atoms, esters and half esters of sulphosuccinic acid with monovalent alcohols or alkylphenols, alkyl or alkylaryl sulphonates, sulphates of hydroxylalkanols, fatty acids of saturated and unsaturated chain of 8 to 24 carbon atoms and their oxy-alkylenated esters and sulfates and phosphates of polyethoxylated alkanols. By cationic emulsifying agents, those that contain a positive charge in aqueous solution are understood, amines and also quaternary compounds. Examples of cationic emulsifying agents are C7-25 alkylamines, C7-25 N, N-dimethyl-N- (hydroxyalkyl) ammonium salts, mono- and di- (with C7-25) -alkyldimethylammonium quaternized with alkylating agents, the ester quats such as the esterified, quaternary mono-, di or trialkanolamines, which are esterified with C8-22 carboxylic acids, the imidazolin quats such as the 1-alkylimidazolinium salts of general formulas I or II.
    [0048] In phase (2) the cationic emulsifying agent used is a quaternary compound, it is observed that it increases the insecticidal capacity of the product resulting from the described process.
    [0050] In phase (2), optionally, a second emulsifying agent can be added, when combinations of emulsifying agents are used, it is advantageous to use an agent relatively hydrophobic emulsifier in combination with a relatively hydrophilic agent, or use an anionic emulsifier in combination with a nonionic agent.
    [0052] In phase (2), a second emulsifying agent can be added that is present in the composition, generally, in a proportion that can range from 10 to 50% by weight and preferably 15 to 30% by weight with respect to the total weight of the composition.
    [0054] In phase (2), additionally, a coformulating agent (s) can be added that can be selected from antioxidants such as tocopherol and propyl gallate, nitroxides, BHT-butylhydroxytoluene, BHA-butylhydroxyanisole, and / or acidulants such as ; citric acid, lactic acid and malic acid, hydrochloric acid, tartaric acid, phosphoric acid, lactic acid, sulfonic acid, and / or defoamers; at least one fatty acid containing between 14 and 24 carbon atoms, silicone-based or fluorine-based.
    [0056] In phase (2) the temperature is between 10-45 ° C, preferably between 25-35 ° C.
    [0058] In phase (3) a stirring of 60-300 RPM occurs between 1 to 36 hours, preferably between 1 to 4 hours. It has been worked under controlled conditions of density between 0.910-0.980g / cm3 and pH between 5-10, preferably between 6.5-8.5. The final result of the described procedure is the obtaining of pyrethrin microbiocapsules of a size between 0.5- 5 ^ m with a regular morphology and a smooth surface.
    [0060] In another aspect, the present invention relates to the use of the microbiocapsules of the present invention as an insecticide. More particularly, the present invention relates to the use of the microcapsules of the present invention for the control of arthropod pests such as insects, preferably aphids and ants. The effectiveness of the insecticide product obtained by this procedure lasts up to 2 years.
    [0064] To complement the description that is being made and in order to help a better understanding of the characteristics of the invention, a set of drawings is attached as an integral part of said description, where with an illustrative and non-limiting, the following has been represented:
    [0066] Figural- Shows a chromatographic profile of the resulting composition under normal conditions and 14 days later in the same compound applying the MT 46.3 method
    [0068] Figure 2- Shows a photograph of pyrethrin microbiocapsules where an epifluorescence microscope (Axioplan, ZEISS) is observed. A sample drop is placed on a slide (20x40x0.25mm) with a 20x objective.
    [0070] Figure 3- Shows a photograph of pyrethrin microbiocapsules indicating their size and monodispersity:
    [0071] 1. Length 5.14 ^ m
    [0072] 2. Length 4.42 ^ m
    [0073] 3. Length 5.48 ^ m
    [0074] 4. Length 5.14 ^ m
    [0078] The invention will be illustrated below by means of tests carried out by the inventors, which demonstrate the effectiveness of the process of the invention: Example 1
    [0079] 73g of a refined extract of chrysanthemum EDEOIL P60® were mixed as a source of pyrethrins 60% (w / w); Pyrethrin I, Cinerin I, Jasmoline I, Pyrethrin II, Cinerin II and Jasmoline II, the ratio between Pyrethrin I and Pyrethrin II was 1.85, with 557g of soybean oil with 50% linoleic acid and 25% in oleic acid, also containing lauric, myristic, palmitic, stearic and linolenic acid, stirring was produced at 60rpm in HI 180x-2® at a temperature of 25 ° C and 1g of extract rich in tocopherol E306 was added, stirring continued for 20 minutes, then without stopping the stirring, 158g of 99.5% propylene glycol and 185g of 97% polysorbate 80 were added Sorbilene®. Then 15g of D-limonene of 94% richness (bitter orange) and 8g of vegetable glycerin E-422 were added, acting as a coformulant, improving the tense activity of the formulation. It was stirred at 120 rpm for about 2 hours and the appearance of the microbiocapsules was observed (Figure 2), then the microcapsules and their shapes were measured according to (Figure 3)
    [0080] Example 2
    [0081] To determine the stability of the product, obtained by the process of the present invention as described in example 1, the method MT 46.3 (J. Zhang et al. J. of Chromatography A. 1218 (2011) 6621-6629 Dean was used Ban et al. Afr. J. of Biotechnology Vol. 9 (18), pp. 2702-2708, May 3, 2010) by means of heat stimulation to age the formulations and simulate the packaged and stored product (Figure 1). Formulations that passed the test were considered viable for at least 2 years.
    [0084] Storage stability at 54 ° C
    权利要求:
    Claims (29)
    [1]
    1. A process for obtaining pyrethrin microbiocapsules comprising several stages: (1) Oily phase, which consists of a solution of one or more pyrethrin (s) as active substance with a richness between (48% -80%), in one or more vegetable oil (s) in a 1:20 ratio; (2) Emulsifying phase where an emulsifying agent is added; (3) Microbiocapsule obtaining phase, where by means of a controlled mixing process, 4-25% w / v pyrethrin microbiocapsules are obtained
    [2]
    2. A process for obtaining pyrethrin microbiocapsules according to claim 1, characterized in that in phase (1), the animal or vegetable oils are selected from the group formed by sunflower, corn, soy, avocado, jojoba, pumpkin, grapeseed, sesame, hazelnut, fish oils, glycerol tricaprocaprylate, or vegetable or animal oils of the formula R 9 COOR 10 in which R 9 represents the remainder of a higher fatty acid comprising 7 to 29 carbon atoms and R 10 represents a straight or branched hydrocarbon chain containing from 3 to 30 carbon atoms in particular alkyl or alkenyl.
    [3]
    3. A process for obtaining pyrethrin microbiocapsules according to claim 1, characterized in that in phase (1), where agitation occurs, it is between 60-150RPM
    [4]
    4. A process for obtaining pyrethrin microbiocapsules according to claim 1, characterized in that in phase (1), the temperature is 20 to 40 ° C
    [5]
    5. A process for obtaining pyrethrin microbiocapsules according to claim 1, characterized in that in phase (1), a solvent agent such as fatty acids and their derivatives can be added
    [6]
    6. A process for obtaining pyrethrin microbiocapsules according to claim 1, characterized in that in phase (1), a dissolving agent such as lower alcohols can be added.
    [7]
    7. A process for obtaining pyrethrin microbiocapsules according to claim 1, characterized in that in phase (1), a solvent agent such as natural or synthetic essential oils can be added
    [8]
    8. A process for obtaining pyrethrin microbiocapsules according to claim 1, characterized in that in phase (1), a solvent agent can be added which can be a mixture of claims 5, 6 and / or 7
    [9]
    9. A process for obtaining pyrethrin microbiocapsules according to claim 1, characterized in that in phase (2), a non-ionic emulsifying agent is added that appears in a proportion of 10 to 50% of the composition by weight with respect to to the total weight of the composition.
    [10]
    10. In claim 9 the nonionic emulsifying agent that is added is of the amphoteric or ampholytic type
    [11]
    11. In claim 9 the non-ionic emulsifying agent that is added is of the anionic type
    [12]
    12. In claim 9 the non-ionic emulsifying agent that is added is of the cationic type
    [13]
    13. In claim 9, a second relatively hydrophobic emulsifying agent may be added in combination with a relatively hydrophilic agent.
    [14]
    14. In claim 13 the emulsifying agent is anionic in combination with a nonionic agent.
    [15]
    15. In claim 13, the emulsifying agent is present in the composition, generally, in a proportion that can range from 10 to 50% by weight.
    [16]
    16. In claim 9, a co-formulating agent may additionally be added
    [17]
    17. In claim 16 the coformulating agent can be an antioxidant
    [18]
    18. In claim 16 the coformulating agent can be an acidulant
    [19]
    19. In claim 16 the coformulating agent may be an antifoam
    [20]
    20. A process for obtaining pyrethrin microbiocapsules according to claim 1, characterized in that in phase (2), the temperature is between 10 ° - 45 ° C
    [21]
    21. A process for obtaining pyrethrin microbiocapsules according to claim 1, characterized in that in phase (3), a stirring of 60-300 RPM occurs between 1 to 36 hours
    [22]
    22. A process for obtaining pyrethrin microbiocapsules according to claim 1, characterized in that in phase (3), it is produced at a density between 0.910g / cm3 and 0.980g / cm3.
    [23]
    23. A process for obtaining pyrethrin microbiocapsules according to claim 1, characterized in that in phase (3), it occurs between a pH between 5-10
    [24]
    24. A process for obtaining pyrethrin microbiocapsules according to claim 1, characterized in that in phase (3), a microbiocapsules of a size between 0.5 ^ and 5 ^ are produced
    [25]
    25. The use of the encapsulated product resulting from the process according to claim 1, for the control of pests.
    [26]
    26. The use according to claim 25 is an insecticide.
    [27]
    27. The use according to claim 26 is a pyrethroid
    [28]
    28. The use according to claim 25, with an optimal efficacy durability of at least 2 years
    [29]
    29. A use according to claim 25 where the emulsifier added in Phase (2) is a cationic emulsifier agent increases the insecticidal capacity
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    同族专利:
    公开号 | 公开日
    ES2794124B2|2021-09-14|
    WO2020234492A2|2020-11-26|
    CN114072226A|2022-02-18|
    ES2794124B8|2021-10-07|
    WO2020234492A3|2021-01-14|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB2058569A|1979-09-12|1981-04-15|Montedison Spa|Liquid insecticide compositions containing synthetic pyrethroids|
    CN103004858A|2012-11-28|2013-04-03|李建中|Insecticidal composition containing methylamino abamectin and pyrethroid compound|
    US20170105418A1|2014-02-19|2017-04-20|Fmc Corporation|High-Load Pyrethroid Encapsulated Seed Treatment Formulations|
    CN106508895A|2016-09-05|2017-03-22|广东康绿宝科技实业有限公司|Secure insecticide release control composition|
    US4617318A|1981-09-25|1986-10-14|American Cyanamid Company|Non-irritating pyrethroid formulations in vegetable oils and tall oils|
    ES535633A0|1984-09-04|1985-08-01|Pennwalt Corp|A PROCEDURE FOR MICROENCAPSULAR PYRETHRINS EXISTING IN NATURE|
    FR2689729B1|1992-04-09|1994-06-03|Roussel Uclaf|NOVEL PESTICIDE COMPOSITIONS CONTAINING A PYRETHRINOUIDE.|
    FR2721800B1|1994-07-01|1997-12-26|Roussel Uclaf|NEW EMULSIONABLE CONCENTRATES CONTAINING ONE OR MORE PESTICIDES|
    法律状态:
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    ES201930434A|ES2794124B8|2019-05-17|2019-05-17|Method and procedure for obtaining microbiocapsules of natural pyrethrins with high stability|ES201930434A| ES2794124B8|2019-05-17|2019-05-17|Method and procedure for obtaining microbiocapsules of natural pyrethrins with high stability|
    CN202080046321.9A| CN114072226A|2019-05-17|2020-05-18|Method and process for obtaining high-stability natural pyrethrin microbial capsules|
    PCT/ES2020/000026| WO2020234492A2|2019-05-17|2020-05-18|Method and procedure for obtaining micro biocapsules of natural pyrethrins with high stability|
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