CN101420848B - The application of microencapsulated essential oils - Google Patents

The application of microencapsulated essential oils Download PDF

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Publication number
CN101420848B
CN101420848B CN200780013591.4A CN200780013591A CN101420848B CN 101420848 B CN101420848 B CN 101420848B CN 200780013591 A CN200780013591 A CN 200780013591A CN 101420848 B CN101420848 B CN 101420848B
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Prior art keywords
oil
acid
preparation
microcapsule
encapsulated
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CN101420848A (en
Inventor
查尔斯·林德
阿姆农·克里茨曼
阿里·马库斯
普尼纳·斯特龙金
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Beijing China New Agriculture And High Tech Business Consulting Co ltd
BOTANOCAP Ltd
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BOTANOCAP Ltd
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Priority to CN201610411181.6A priority Critical patent/CN106070202A/en
Priority claimed from PCT/IL2007/000213 external-priority patent/WO2007094000A2/en
Publication of CN101420848A publication Critical patent/CN101420848A/en
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28Microcapsules or nanocapsules
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34Nitriles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08Magnoliopsida [dicotyledons]
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08Magnoliopsida [dicotyledons]
    • A01N65/12Asteraceae or Compositae [Aster or Sunflower family], e.g. daisy, pyrethrum, artichoke, lettuce, sunflower, wormwood or tarragon
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08Magnoliopsida [dicotyledons]
    • A01N65/28Myrtaceae [Myrtle family], e.g. teatree or clove
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/40Liliopsida [monocotyledons]
    • A01N65/44Poaceae or Gramineae [Grass family], e.g. bamboo, lemon grass or citronella grass
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
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  • Natural Medicines & Medicinal Plants (AREA)
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  • Microbiology (AREA)
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Abstract

Disclose a kind of new method preparing microencapsulated essential oils.The microcapsule comprising quintessence oil or the preparation comprising it can be used for many-sided non-agricultural application.

Description

The application of microencapsulated essential oils
Invention field
The present invention relates to be suitable to the essential oil formulation of the micro encapsulation of non-agricultural application.
Background of invention
In recent years, the potential application during some researchs have concentrated on quintessence oil control biology in microorganism and different insect pests.This quintessence oil is degraded quickly than synthesis compound in the environment, and some have the specificity being conducive to beneficial insect of enhancing.The effect of they antagonism stored product insecticides is widely studied.Although having the most attracting character, but poor about volatile problem of quintessence oil, water solublity and be prone to oxidisability and have become as the problem of reality, and it makes essential oil formulation be difficult to be used as control system, and is finally applied to target environment.
Summary of the invention
It has now surprisingly been found that some preparation comprising the single of microencapsulated essential oils or combination can be used for various non-agricultural purpose, especially for treating or preventing the uneasiness of some target or the injury to target.
It will be understood by those skilled in the art that for the preparation of desirable effect to be successfully reached, need to carry out large-scale experimental work.Although certain form of Microencapsulation Method can provide the microcapsule formulation useful to the application of some aspect, but in applying on the other hand, it may be invalid.Similarly, although some quintessence oil known can have some activity, such as, antimicrobial acivity, do not ensure that in each antimicrobial is applied effective.As those skilled in the art will readily recognize that, these difference cause due to many factors, as from the distribution in target of the rate of release of microcapsule, infiltrative degree, concentration, slowly release and a small amount of efficiency, microcapsule, the deactivation of microcapsule shell, other additives or auxiliary agent, before essential oil formulation is applied or the afterwards environment of target, pot-life, the various additives etc. that exist present in the microcapsule or the carrier containing it.
This application discloses the most many essential oil microcapsules, it is as follows:
Preparation
In a first aspect of the present invention, it is provided that a kind of method (referred to herein as " method of the present invention ") of suspension preparing microcapsule, each at least one quintessence oil self-contained, described method includes:
A at least one alkanoic acid is mixed by () with at least one quintessence oil;
B the mixture of step (a) is mixed by () with alkaline aqueous solution, obtain suspension;With
C () is mixed into the aqueous saline solution comprising at least one polyvalent cation to the suspension of step (b), thus obtain comprising the suspension of the microcapsule of at least one quintessence oil described.
In one embodiment, step (a) is carried out in the case of need not any solvent.
In another embodiment, first at least one alkanoic acid described is dissolved in or is suspended in solvent, preferably in water-immiscible liquid.
In one embodiment, described water-immiscible liquid is quintessence oil.
In another embodiment, described liquid is not quintessence oil.When described water-immiscible liquid is not quintessence oil, it is selected from the organic solvent of water-insoluble, and described solvent does not reacts under conditions of using in the method.The limiting examples of this type of water-immiscible liquid is alkane (such as hexane and petroleum ether), ether (such as Anaesthetie Ether, butyl ethyl ether), alcohol and ketone.
In another embodiment, this solid alkanoic acid is melted, then added in described quintessence oil or water-immiscible carrier.
The alkaline aqueous solution used in step (b) can be solution or the mixture of this type of alkali of two or more of single monoacidic base such as NaOH, such as, NaOH and KOH, or NaOH and Na2CO3.In one embodiment, this alkali is inorganic base.In another embodiment, this alkali is organic base.
In preferred embodiments, this monoacidic base is the alkali of sodium or potassium.
In another embodiment, the suspension obtained in step (b) is the suspension of micelle.In another embodiment, the suspension obtained in step (b) is clarified suspension.
The saline solution of the polyvalent cation added in the step (c) of the inventive method is the solution of the inorganic metal salt containing the cation with the electric charge higher than+1.In one embodiment, the ion of II race during this inorganic metal cation is those periodic table of elements.The limiting examples of this cationoid is the polyvalent cation of Ca, Mg, Fe and Al.Preferably, described polyvalent cation is Ca.
It should be appreciated that when some atom has the cation of multiple different valence state, this cation all of is included within the scope of the invention.
In one embodiment, described polyvalent cation is not Ca.
In another embodiment, described polyvalent cation is not Mg.
In another embodiment, described polyvalent cation is not Fe.
In another embodiment, described polyvalent cation is not Al.
In another embodiment, described polyvalent cation is not any one in Ca, Mg, Fe or Al.
In another embodiment, the aqueous saline solution of this step (c) comprises the mixture of two or more multivalent salts.This type of mixture can be the salt such as CaCl with different cationes2And MgCl2Mixture, or there is the salt such as CaCl of different pair anions2With Ca (OH)2Mixture, or there is the salt such as CaCl of the cation of different price2And FeCl3Mixture.
The saline solution of polyvalent cation alternatively has the organic molecule ion of the positive charge more than+1, as disclosed above.Multivalence organic cation limiting examples is diamidogen or triamine or the ammonium salt of tetramine, quaternized polyamine etc..The same with inorganic metal saline solution, this organic slat solution also can comprise the organic salt that two or more are different.
Multivalent salts can be added in this reactant mixture, pure or as aqueous solution, such as, slaine such as Ca (OH)2、CaCl2、MgCl2Or FeSO4Aqueous solution.
This at least one " alkanoic acid " is the organic carboxyl acid of general formula R-COOH, and wherein R is saturated and/or undersaturated aliphatic carbon chain, and-COOH is known hydroxy-acid group in organic chemistry.Within the scope of the invention, term alkanoic acid and fatty acid are used interchangeably.
In one embodiment, this alkanoic acid is water-immiscible compound.Typically, R is the aliphatic chain of the main chain with 10-45 carbon atom.This main chain can be substituted or unsubstituted.In preferred embodiments, this type of optionally substituted hydrophobicity to carbochain has no effect on.
In one embodiment of the invention, described alkanoic acid is selected from having the fusing point alkanoic acid higher than 25 DEG C.
Can be capric acid, dodecylic acid, tetradecanoic acid, hexadecanoic acid, octadecanoid acid, arachic acid, behenic acid and lignoceric acid by the limiting examples of the inventive method encapsulated unsaturated chain alkanoic acid.
The limiting examples of unsaturated chain alkanoic acid is vaccenic acid, Arachidonic Acid, omega-fatty acid etc..
The limiting examples of omega-fatty acid includes alpha-linolenic acid (18:3-ω-3), parinaric acid (18:4-ω-3), eicosapentaenoic acid (20:5-ω-3) (EPA), docosahexenoic acid (22:6-ω-3) (DHA), clupanodonic acid (22:5-ω-3) (DPA), eicosatetraenoic acid (20:4-ω-3), 21 carbon 5 alkene acids (21:5-ω-3), clupanodonic acid (22:5-ω-3), including its arbitrary derivant.
In one embodiment, this omega-fatty acid is the mixture of this type of fatty acid of two or more.
The possible derivant of omega-fatty acid can include ester derivant, side chain or non-branched C1-C30Arrcostab, side chain or non-branched C2-C30Alkenyl esters, or side chain or non-branched C3-C30Cycloalkyl ester such as plant sterol ester.
In one embodiment, described fatty acid extracts from following natural source and obtains, this natural source includes, but it is not limited to, aquatile such as long tail anchovy (anchovies), capelin (capelin), Atlantic Ocean morrhua, Atlantic Ocean Mylopharyngodon piceus, Atlantic mackerel, Atlantic Ocean catfish, salmon, sardine, shark and tuna;Plant such as Caulis et Folium Lini and vegetable;With microorganism such as fungus and algae.
Term " quintessence oil " within the scope of the present invention also includes vegetable oil and lipid.
nullThe limiting examples of quintessence oil is Oleum sesami、Pyrethrum、Glycerol-derivative lipid or glycerol fatty acid derivatives、Oleum Cinnamomi、Cedrus deoclar (Roxb.) G. Don oil、Oleum Caryophylli、Oleum Pelargonii Graveolentis、Indian oil of verbena、Radix Angelicae Sinensis oil、Oleum menthae、Turmeric oil、Wintergreen oil、Oil of rosemary、Fennel oil、Cardamom oil、Caraway oil (carawayoil)、Chamomile oil、Fructus Coriandri oil、Guaiac wood oil、Cymin oil、Dill oil、Oleum menthae、Parsley oil、Basil oil、Oleum Camphora、Cananga odorata oil、Citronella oil、Eucalyptus oil、Oleum Anisi Stellati、Oil of ginger、Copaiba balsam oil (copaibabalsamoil)、Perilla oil、Cedar oil、Jasmin oil、Cymbopogon martini Sofia (palmarosasofia) oil、Western Oleum menthae、Oleum Anisi Stellati (staranisoil)、Tuberose oil、Orange blossom oil、Tolu balsam oil、Patchouli oil、Palmarosa oil、Japanese cypress oil (Chamaecyparisobtuseoil)、Hiba oil、Sandalwood oil、Petitgrain oil、Laurel、Vetiver oil、Oleum bergamottae、Peru balsam oil、Rosewood oil (boisderoseoil)、Oil of grapefruit、Fructus Citri Limoniae oil、Mandarin oil、Orange oil、Herba Origani oil (oreganooil)、Essential lavender oil、Lindera oil (Linderaoil)、Pinke needle oil、Oil of pepper、Oleum Rosae Rugosae、Orris oil、Oleum Citri sinensis、Tangerine oil (tangerineoil)、Tea tree oil、Oleum Camelliae、Thyme oil、Thymol、Bulbus Allii oil、Oleum menthae (peppermintoil)、Oil of Bulbus Allii Cepae、Linaloe oil、Japanese peppermint oil、Oleum Menthae Rotundifoliae,And other are disclosed herein.
In one embodiment, this quintessence oil is ethereal oil.
In another embodiment, this quintessence oil is spice berry (spiceplant) quintessence oil.
In another embodiment, this quintessence oil is selected from citronella oil, Oleum Pelargonii Graveolentis, tea tree oil, Essential lavender oil, carnation oil (clovepineoil), Eucalyptus oil, thyme oil and Herba Origani oil.
Those skilled in the art is it will be appreciated that specific quintessence oil or the combination of quintessence oil can be selected according to concrete application.
In one embodiment, the microencapsulated essential oils microcapsule obtained from the inventive method is wax-like or solid particle.
In another embodiment, this microcapsule does not separates with medium, and said preparation the most so uses.
In another embodiment, said method also includes the step filtering and collecting microencapsulated essential oils microcapsule.When separating solid microcapsule from aqueous medium, a small amount of quintessence oil may be the most unencapsulated.In order to obtain the microcapsule of oil-free (oil-dry), generally add a small amount of pick up the oil agent that can absorb excess.This absorbent is selected from, such as, and cellulose, starch powder or AerosilTMSilicon dioxide such as AerosilTM200 or 300, it can be buied from Degussa.In some applications, AerosilTMFor preferred absorbent.
In another embodiment, the method for the present invention may also include the step adding at least one surfactant.This surfactant can be ion-type or nonionic, and can add in solution or in suspension with the form of the form of pure material or solution (such as aqueous solution), can add to promote or control the size of microcapsule during the manufacture of microcapsule, or add after microcapsule has been formed with the broken gel caused due to micro encapsulation and the preparation obtaining mobility.A kind of particularly preferred surfactant is sodium lauryl sulphate (SDS).Preferably, this surfactant is with the 0.1-10% of the gross weight of preparation, and the concentration of most preferably 0.5%-5% is added.
In another embodiment, the method also includes adding at least one additive, preferably in the front interpolation of step (c).This at least one additive can be solid, liquid, solution, suspension, or the mixture of two or more examples of such additives.
The various additives limiting examples that can use is active medicine, naturally occurring or synthetic antioxidant, dietary supplement, vitamin, coloring agent, aromatic, oil, fat, spice, non-volatile natural essential oil or other dispersants or emulsifying agent.
The limiting examples of the concrete additive that can use is gamma-Linolenic acid, Citrus oil (citrusoils) such as orange oil, nutritional supplement such as VitAVitE, vitamin C, and vitamin D, tocopherol, tocotrienol, plant sterol, vitamin K, beta-carotene, marine oil (marineoil), omega-fatty acid, CoQ10, the fat-soluble derivant of polar antioxidants, as ascorbic acid aliphatic ester, plant extract such as Herba Rosmarini Officinalis, Salvia japonica Thunb. and Herba Origani oil, algae extract, and antioxidant such as BHT, TBHQ, ethoxyquin, alkyl epicatechol gallate and the hydroquinone of synthesis or natural antioxidant.
In addition to surfactant, other limiting examples of preferred additive are space barrier polymer (stericbarrierpolymers), and it helps to maintain the dispersion of granule.These space barrier polymers can be selected from, and is not limited to, polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and poly-(ethyoxyl) nonyl phenol.When the pH of final microcapsule formulation must be regulated, such as when microcapsule suspensions is with other insecticidal compositions, it is possible to use the conventional reagent for regulating acidity and basicity.This type of reagent can such as include hydrochloric acid, citric acid, sodium hydroxide, sodium carbonate and sodium bicarbonate.
Once preparing, this liquid or solid preparation can be with preservation to using at that time.Generally it is most convenient that the bottled or canned suspension comprising encapsulated essential oil, in the case, it is intended to add the simplification of formulation auxiliary agents stability and application to improve suspension before storage.These auxiliary agents are selected from density balance agent (densitybalancingagents), surfactant, thickening agent, Biocide, dispersant, antifreezing agent, salt etc..Typically, this auxiliary agent adds with the concentration of about 0.01%-about 30% weight.
Present invention provides the microencapsulated essential oils preparation comprising multiple microcapsule, each microcapsule comprises at least one quintessence oil, wherein said preparation or microencapsulated essential oils the method according to the invention and prepares.
Within the scope of the invention, terms " formulation " refers to the combination of microcapsule and any other reagent, and this microcapsule the method according to the invention is prepared or used by arbitrary application of the present invention, and this reagent can be the medium being added thereto by microcapsule.Preparation according to the present invention may also comprise any additive as disclosed herein.This term also refers to microcapsule suspended substance in medium (such as solid or liquid) or dispersion.
The preparation of the present invention can be prepared generally according to method as known in the art.See Pharmaceutics and PharmacyPractice, J.B.LippincottCo., Philadelphia, Pa., Banker and Chalmers, eds., the 238-250 page (1982), and ASHPHandbookonInjectableDrugs, Toissel, 4thEd., the 622-630 page (1986).
Typically, when said preparation pharmaceutical preparation to be used as, it may be necessary to pharmaceutically suitable carrier such as medium, auxiliary agent, excipient or diluent.Known to this type of pharmaceutically suitable carrier is, and it is can be easily obtained for the public for those skilled in the art.Preferably pharmaceutically suitable carrier is for quintessence oil or for being contained in any other compound wherein or on the surface of microcapsule to be chemically inert carrier.The selection of pharmaceutically suitable carrier partially by concrete quintessence oil, and can be determined by the concrete method being used patient (animal or people) administration said preparation.
The preparation of the present invention, it is suitable to animal or people uses, such as, and anthelmintic, antimicrobial, food additive, it is preferably suitable to oral administration or the dermal topical application to patient.Therefore this type of preparation can be made up of following: (a) liquid suspension, as being suspended in the essential oil microcapsules of the effective dose in carrier such as water, saline or orange juice;B () capsule, medicated bag (sachets), tablet, lozenge and buccal tablet, the active component of each self-contained scheduled volume, it is solid or granule;(c) powder;(d) suitable emulsion.
Liquid preparation can include diluent, such as water and alcohol, such as, ethanol, benzylalcohol and Polyethylene Glycol, with or without adding pharmaceutically acceptable surfactant, suspending agent or emulsifying agent.
Capsule form can be common hard-or the capsule of soft-shell gelatine type, and it comprises, and such as, surfactant, lubricant and inert filler, such as lactose, sucrose, calcium phosphate and corn starch.
Tablet form can include one or more lactose, sucrose, mannitol, corn starch, potato starch, alginic acid, microcrystalline Cellulose, arabic gum, gelatin, guar gum, silica sol, cross-linking sodium carboxymethyl cellulose Talcum, magnesium stearate, calcium stearate, zinc stearate, stearic acid, and other excipient, coloring agent, diluent, buffer agent, disintegrating agent, wetting agent, preservative, aromatic and the most compatible carrier.
In another aspect of this invention, it is provided that the microcapsule prepared according to following method:
A at least one alkanoic acid is mixed by () with at least one quintessence oil;
B the mixture of step (a) is mixed to obtain suspension by () with alkaline aqueous solution;
C () is mixed into the aqueous saline solution comprising at least one polyvalent cation to the suspension of step (b);With
D () collects described microcapsule from this aqueous medium, thus obtained multiple microcapsules of at least one microencapsulated essential oils.
In one embodiment, this microcapsule prepared has amphipathic (amphiphatic) shell substantially surrounded by the nuclear core comprising at least one quintessence oil.
In another embodiment, this amphipathic shell is the multivalence alkanoate of at least one alkanoic acid and polyvalent cation.
As known in the art, amphiphile (amphipile) is for not only to have hydrophobicity but also have the molecule of hydrophilic radical.The alkanoic acid used in the methods of the invention is amphiphile.In the alkanoic acid of general formula R COOH as defined above, R is to have the aliphatic chain of hydrophobic property and have group-COOH or its salt form of hydrophilic nmature.Without being limited by theory, this amphipathic shell is to be made up of the hydrophobic group being embedded in this quintessence oil nuclear core and its outside hydrophilic radical, the surface of this hydrophilic radical outwardly microcapsule.
Additionally providing the microcapsule with the nuclear core comprising at least one quintessence oil that amphipathic shell surrounds, wherein said amphipathic shell is the multivalent salt form of at least one alkanoic acid.
Disclosed microcapsule and/or the preparation comprising them can use in broad field of application.
In one embodiment, said preparation is the pharmaceutical preparation used by people patient and non-human patients.This pharmaceutical preparation can be used for example as anti-microbial agents.
In another embodiment, said preparation is the anti-microbial agents of non-medicine.
In another embodiment, said preparation is preservative.
In another embodiment, said preparation is anthelmintic or insecticide, and it is used for, such as, and the expeling of the insecticide in family or environment or elimination.
In another embodiment, said preparation is for being delivered to food additive in the Food & Drink by people and/or animal consumption.
The present invention also provides for comprising the test kit of invention formulation or commercial packaging external member.This test kit can be a Component Kit or two Component Kit, and it includes that the suspension of volatile essential oil of at least one microcapsule micro encapsulation is contained in the first container therein, and nonvolatile carrier is contained in second container therein.Optionally, the test kit of the present invention may also comprise and how this two component is applied to target environment thus reaches the description of desirable effect.
The preparation of this kit preparation or single component can be with solid or liquid form and with that concentrate or dilution state existence, and it can pass through such as, the sponge of hands, in advance sorbent formulation or a piece of cloth, obtains manually sprinkling and is administered to target.
Various application disclosed herein can use identical or different microcapsule formulation.The selection of said preparation is determined by several respects factor, physics, chemistry and/or the biological property combined such as quintessence oil or quintessence oil;Application mode;And preparation used to the character of target.
Generally, the preparation used in the present invention comprises at least one encapsulated essential oil.Preparation can be novel formulation disclosed above or the microcapsule formulation prepared by interfacial polymerization, and it is discussed in more detail below.Not limited by classification used herein, the preparation used in each application in the present invention can be divided into following a few class:
1. the preparation of homogeneous preparations-identical microcapsule, comprises the same mixture thing of identical quintessence oil or quintessence oil;
The preparation of the most uneven preparation-the include dissimilar microcapsule of at least two, all types of different mixtures comprising different quintessence oils or quintessence oil.Different quintessence oils or the number of its mixture can change according to should be used for.
In one embodiment, this uneven preparation comprises two kinds of microcapsule, the first comprises the first quintessence oil or the first blend of essential oils, and the second comprises the second quintessence oil or the second blend of essential oils, wherein said first quintessence oil or the first blend of essential oils respectively from the second quintessence oil or different with described second blend of essential oils.Ratio between two types microcapsule, the ratio between the i.e. first and second quintessence oils or the first and second blend of essential oils, can change and can be respectively, such as 1:1,1:2,1:5,1:10,1:100,2:1,5:1,10:1,100:1 etc..
First uneven preparation can comprise the microcapsule containing only Eucalyptus oil and the microcapsule containing only Herba Origani oil with the ratio of 1:1.Second preparation can comprise the microcapsule containing tea tree oil and containing each Herba Origani oil and the microcapsule of the mixture of Eucalyptus oil, wherein this comprises the ratio between the microcapsule of tea tree oil and the microcapsule comprising mixture is 1:2, and Herba Origani oil is 1:1 with the ratio of Eucalyptus oil in described mixture.
It addition, this uneven preparation can such as comprise the microcapsule containing quintessence oil and the microcapsule containing non-essential oil agents.
In another embodiment, described uneven preparation comprises the microcapsule of at least two type, and one comprises quintessence oil and another kind comprises additive as herein defined.
In another embodiment, said preparation comprises two kinds of different microcapsules, the mixture that the first comprises quintessence oil and the second comprises quintessence oil and additive.
In another embodiment, said preparation comprises the microcapsule of at least two type, and each type is prepared by different methods, and such as, one is prepared by interfacial polymerization, and another kind is prepared by the method for the present invention.
In another embodiment, said preparation comprises the microcapsule of at least two type, uses different polymer chains to prepare each via interfacial polymerization, and such as, a type of microcapsule shell is polyurethane outer and another kind of type has polyurea shell.
3. spacer forms preparation (Barrierformingformulation)-refer to and can form physical barrier after being applied to target and becoming dry, and the preparation of required effect can be shown at the same time, such as, anthelmintic action, parasite killing, weeding, antifungal, bactericidal etc. act in required effect.
Spacer forms preparation and can change according to its intended application, to form various thickness, permeability, porosity, water solublity, heat stability, and other spacer of physical parameter that can determine quintessence oil rate of release from which or films.
In certain embodiments, the physical barrier of this formation or film to quintessence oil from described microcapsule, or the rate of release from the combination coating of microcapsule and polymeric film has an impact, so that when quintessence oil is after microcapsule discharges, and its evaporation rate also can be reduced by polymer coating.
In another embodiment, rate of release is not affected by the physical barrier of this formation, and is solely for the barrier to various microorganisms and/or the invasion and attack polluting (physics, biological or chemical).In this type of embodiment, the combination of barrier properties of quintessence oil activity and coated polymeric result subsequently can be had add with or synergism.
In other embodiments, this microcapsule comprises volatile essential oil, and carrier, and this carrier is generally selected from multiple low-volatility or nonvolatile at room temperature for the quintessence oil of liquid or solid.
In another embodiment, this carrier is not quintessence oil.
Without being limited by theory, when the preparation of encapsulated essential oil is applied in target, one contacts it becomes dry and starts to play its effect.Initial action is realized by medium (carrier), although this carrier is the most optionally high boiling, but what initial action was realized by it.Once quintessence oil starts to discharge from microcapsule, it was observed that encapsulated and not-encapsulated quintessence oil (or non-quintessence oil carrier) add with or synergism.
When difference between the most even uneven preparation is the inclusions according to microcapsule rather than carrier realizes, this film forms preparation can be somewhat dependent on the character of carrier.As previously mentioned, this film forms preparation and physical barrier or film is formed, it surrounds the object that (engulf) treats, thus stop or reduce various microorganism and the intrusion of pathogen or water and other chemical substances from the effusion (such as in the case of harvested fruits and vegetables, it is discussed in more detail below) of target.The formation of spacer such as can be sprayed by using with finite concentration in target, along with the evaporation of liquid medium (water that such as microcapsule is prepared wherein rather than carrier), forms solid matter layer, and it is preferably the shape with condensed film.The thickness of this film depends on the concentration of preparation, the size of microcapsule, carrier (solid or liquid), the number of applications on same loci or object, the method used and exsiccation degree.
This film can also be formed by the original application of invention formulation, and said preparation, in addition to encapsulated essential oil and carrier, also comprises complexation and/or the reagent of polymerization when can contact with the reagent used afterwards.Such as, the preparation of the present invention can contain or process with fatty acid such as lauric acid, is applied to afterwards on target surface.After using said preparation, the aqueous solution of chelating agent such as calcium chloride can be used in the position first used, so that the formation of film that microcapsule is embedded.
Express " encapsulated (encapsulated) quintessence oil ", " encapsulated (encapsulation) " or its any other linguistic variant as used herein and refer to the granule that can keep one or more quintessence oils wherein of arbitrary shape and size.
This type of encapsulated example is micro encapsulation.Preferably microcapsule is for having its weight 10-98%, or the microcapsule of the quintessence oil of more preferably 60-95%, and prepares according to the inventive method in a preferred embodiment.
In another embodiment, be used together with microcapsule of the present invention or replace the present invention microcapsule for the microcapsule that obtained by the interfacial polymerization of isocyanates.This Type of Collective provides the shell of the micro encapsulation of polyurethane, polyureas or a combination thereof, as disclosed in such as WO04/098767.The usual average-size of this type of microcapsule is between 0.1 and 100 micron.Other suitable microcapsules can be prepared by such as the method disclosed in WO94/13139, EP0252897, US5576009 and US5925464.
Encapsulated essential oil preparation can comprise multiple microcapsule, not only according to its inclusions, also according to its preparation method.Therefore, said preparation can comprise multiple size, the microcapsule of shape, chemically and physically parameter.
Rest in the target of process and preferably show add and or the organic reagent of cooperative effect with microcapsule after term as used herein " nonvolatile vehicle " typically refers to use.Examples of such carriers can be to have high boiling point or dystectic liquid or solid (pure material or mixture), and is less than the evaporation rate of encapsulated essential oil using its evaporation rate leaving in target after thereon.This type of medium or carrier can the most nonvolatile quintessence oil, nonvolatile vegetable oil, nonvolatile or solid terpenes class and lipids.
Generally, described carrier is only never water.But, in various embodiments, it may be necessary to use water as the key component of preparation.In this exemplary cases, when preparing microcapsule in aqueous, or when adding water so that having more preferable mobility and sprayability, or when preparation is at water intermediate package or storage, nonvolatile carrier can be added to as medium and will not to the anthelmintic of preparation, parasite killing, deinsectization, kill larva or ovicidal characteristics and produce the aqueous solution of beneficial effect.
This liquid essential oil and lipid carrier are preferably those boiling points and are higher than 250 DEG C, the material of preferably above 300 DEG C.This type of high boiling point quintessence oil can for example, cinerins.The example of lipid is Oleum sesami or Oleum Gossypii semen.
Term " solid carrier " refers to wherein be mixed with the solid reagent of microcapsule, using pure material form or as mixture solid, and before target is used its solubilized, suspend or be dispersed in as in liquid medium such as water.Solid carrier can for example, powder type.
Term " liquid-carrier " refers to neat liquid, the homogenous fluid mixture of various reagent (each reagent can be the most all solid, liquid or gas) or the heterogeneous mixture of this type of reagent, wherein suspends just like the suspension of described microencapsulated essential oils of microcapsule.Microcapsule is at liquid-carrier or at solution (such as, it is prepared by being dissolved or dispersed in by solid carrier in the suitable medium in such as water) in suspension, it should do not affect the denseness of volatile essential oil, distribution, physical state or the concentration in microcapsule.Additionally examples of such carriers is such material: described microcapsule the most therein will not dissolve, deteriorates, decomposes, leaches or experience and any physically or chemically change.
Term " suspension " or its any other linguistic variant refer to the dispersity of microcapsule in the carrier;As a limiting examples, affiliated dispersion liquid is Oleum Gossypii semen and microcapsule dispersion liquid in water.According to the size of microcapsule, this term also can refer to colloidal state.
In its most commonly form, according to concrete application, the invention discloses the mixture of a kind of quintessence oil or quintessence oil and the encapsulated of various additives.
This nonvolatile carrier can be at least one nonvolatile quintessence oil, at least one nonvolatile vegetable oil or its combination in any, and at least one of which quintessence oil has the necessary required activity of enforcement desirable effect.Such as, in the case of preparation is used as the anthelmintic of insecticide, it is contained in a kind of quintessence oil therein and there is repellency.
This group with can for example, but be not limited to following combination: the combination of the nonvolatile quintessence oil that (a) two or more are different;The combination of the different nonvolatile quintessence oil of (b) two or more and at least one vegetable oil;(c) a kind of nonvolatile quintessence oil and the combination of a kind of nonvolatile vegetable oil;The combination of (d) two kinds of different nonvolatile vegetable oil, etc..Also can the change that is similar to of subgroup specific to any one (such as lipid), it is possible to the change that its any concrete representative thing (triglycerides as different) is similar to.
Term " volatile ", " moderate is volatile " and " nonvolatile " refers to the degree of compound evaporability at ambient temperature and pressure.The lowest to the boiling point that it is known to those skilled in the art that specific compound, its volatility is the biggest.About quintessence oil, volatile low boiling oil is that those are defined as boiling point and are below about the oil of 250 DEG C.The volatile oil of moderate is that those are defined as boiling point oil between 250 DEG C and 300 DEG C.Nonvolatile or less volatile oil is that those are defined as the boiling point oil higher than 300 DEG C.
" vegetable oil " is the natural complex mixtures of the oil prepared by plant." quintessence oil " is that those generally give to its distinctive abnormal smells from the patient of plant, fragrance or the material of other similarities.In the various piece of plant, (in seed, flower, bark or leaf), vegetable oil, and the also enrichment in some specific cells or groups of cells (body of gland) of described vegetable oil it have been found that.In general, according to the character of the part being found to have quintessence oil, quintessence oil can be by the compound mixture that various mode is obtained by plant.Described method can be such as by compression, by utilizing steam to carry out to distill, by oil soluble being gone out (extraction) or absorbing them, and by pressurization with impregnate.This term also refers to the oil mixture prepared by being enriched with by the vegetable oil of natural acquisition with one or more specific components, described specific components such as monoterpene alkenes, two terpenes, triterpene alkenes, tetraterpene alkenes, sesquiterpene, and other polyterpene class and Organic Alcohol, aldehyde, ketone, acid and ester.
Although term " quintessence oil " and " vegetable oil " are used interchangeably in different literature references, but within the scope of the invention, the latter refers to the bigger compound group of lipid.
" lipid " mentioned by Ben Wen includes that the lipid (including fat and oil and phospholipid) of fatty acid, glycerol-derivative, sphingol-derivative lipid (include ceramide, cerebroside, ganglioside and sphingomyelins), steroid and derivant, terpenes and derivant thereof, some aromatic compound and long-chain alcohol and wax.This term also refers to lipoprotein (lipid being combined with protein or carbohydrate), lipopolysaccharide and the vitamin such as fatsoluble vitamin.
In preferred embodiments, this grease separation is from Oleum sesami, Pyrethrum (pyrethrum), glycerol-derivative lipid or glycerol fatty acid derivatives and at least one encapsulated essential oil described are selected from Oleum Cinnamomi, Cedrus deoclar (Roxb.) G. Don oil, Oleum Caryophylli, Oleum Pelargonii Graveolentis, Indian oil of verbena, Oleum menthae, Oleum sesami, thyme oil, turmeric oil, wintergreen oil, oil of rosemary, Oleum Anisi Stellati, Cardamom oil, chamomile oil, Fructus Coriandri oil, cymin oil, dill oil, Oleum menthae, parsley oil, basil oil, Oleum Camphora, citronella oil, Eucalyptus oil, Oleum Anisi Stellati, oil of ginger, oil of grapefruit, Fructus Citri Limoniae oil, mandarin oil, orange oil, pinke needle oil, oil of pepper, Oleum Rosae Rugosae, oleum Citri sinensis, mandarin oil, tea tree oil, Oleum Camelliae, Essential lavender oil, caraway oil, Bulbus Allii oil, Oleum menthae, oil of Bulbus Allii Cepae and Oleum Menthae Rotundifoliae.
In one embodiment, this quintessence oil is ethereal oil.In another embodiment, this quintessence oil is selected from citronella oil, Oleum Pelargonii Graveolentis, tea tree oil, Essential lavender oil, carnation oil, Eucalyptus oil, thyme oil, Herba Origani oil, and other spice plant essential oil.
In another embodiment, said preparation also can comprise additive such as auxiliary agent, binding agent, antioxidant, water repellent agent, surfactant, the space barrier polymer of prevention microcapsule aggregation and gel-cracking agent, as Component Vectors or in microcapsule.
Used additives can be made such as to improve storage life, sprayable property and the absorption to substrate.This analog assistant is selected from natural and polymer such as polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol oxide, ethylene or copolymer-maleic anhydride, methyl vinyl ether-maleic acid copolymer, water-soluble cellulose, water soluble polyamide or polyester, acrylic acid copolymer or homopolymer, water soluble starch and modified starch, natural gum such as alginate, dextrin and the protein such as gelatin and casein of synthesis.
The physical state of said preparation, that is as solid or liquid, depend on that nonvolatile carrier is liquid or solid, or nonvolatile carrier and microcapsule are to suspend or scattered in immiscible medium is such as water.Its physical state need not be considered, said preparation can be used by the dosage form needed for it being formed further, powder as wettable in emulsifiable concentrate, wettable powder, granule, flowable preparation, suspension, granule, dust (dust), fumigant etc..The character of said preparation form can determine according to following parameters: target environment, application process, the relative concentration etc. of microcapsule used in carried out condition, nonvolatile carrier.
Although the concentration of the microcapsule in nonvolatile carrier can control, but the concentration of encapsulated essential oil can change according to storage, weather conditions, dosage form, application process, the place used, targeted insect to be controlled etc..In preparation, the concentration of volatile essential oil at 0.01-90%, or can change between preferably 0.1-25%.But, the concentration of the quintessence oil needed for reaching effect after using is the lowest.This concentration can be suitably selected from the scope of the 0.1% of volatile essential oil weight, and preferably 0.25%.
Said preparation may be adapted to two kinds of release profiles (profile) of microcapsule, i.e. (1) rapid release profile;(2) and continue or postpone release profiles;(4) residual plots, wherein followed by sustained release profile after so-called " quickly release ".
As it was previously stated, the preparation used utilizes the microcapsule can prepared by disclosed or this paper either method required for protection.This microcapsule can reclaim from reactant mixture, and be resuspended in nonvolatile carrier or comprise it solution in, such as, in order to prepare the purpose of uneven preparation.Or, any medium, aqueous or other, it comprises microcapsule, at least one nonvolatile vehicle treated available and this microcapsule need not be separated.
In the case of preferably being separated from initial medium by this microcapsule, can realize reclaiming by centrifugal or filtration, this depends on the size of microcapsule.This separated microcapsule can be with many parts of suitable solvent such as distilled water washs, to remove free reactant from surface.This microcapsule also can under reduced pressure heat to remove the reactant of any remnants further in microcapsule if desired.Preferably, this step is by carrying out at the temperature of intermediate value (median) glass transition temperature higher than the polymer constituting microcapsule shell heating microcapsule.Then, these microcapsules dispersible or are suspended in described non-volatile liquid or solid carrier.
Aforesaid uneven preparation can be prepared as follows: the microcapsule that two or more the most prepared as described above are different, such as each type comprise different quintessence oils or mixture;Microcapsule is separated from the medium that they are initial;And they mixed with medium in a desired proportion, thus obtain uneven preparation.
In some cases, described nonvolatile carrier is granular solids, such as powder, is preferably disperseed by the dry microcapsule of mixing effective dose for this.In some cases, described nonvolatile carrier is liquid, and suspension is preferably prepared by the microcapsule of mechanical agitation effective dose in described carrier.Term as used herein " effective dose " refers to empirically determined amount, and this amount can apply following and described desirable effect to target environment.
" aqueous formulation of encapsulated volatile quintessence oil " is the preparation utilizing any method well known to the skilled artisan in the art to prepare.Aqueous formulation the method according to the invention of the most described encapsulated volatile quintessence oil, or prepare with claimed method according to disclosed in WO04/98767.
The method of WO04/98767 mainly includes being dissolved in quintessence oil diisocyanate or polyisocyanates (polyisocyanate), the mixture of emulsifying gained in comprising the aqueous solution of diamidogen or polyamines and/or dihydroxy compounds or polyol, thus implement the encapsulated of described quintessence oil by interfacial polymerization, thus formation polyureas and/or polyurethane film around described essential oil droplets, this film can increase the stability of described quintessence oil, reduces its evaporation rate and control its rate of release when being applied to substrate.
The physical property of this microcapsule is depended in the quintessence oil delivery mode from microcapsule and the effect therewith to the target processed.Generally, active volatile essential oil is liquid storehouse (liquiddepot) that is encapsulated by microcapsule shell and that carried by nonvolatile carrier, and described nonvolatile carrier can strengthen (adding and or collaborative) its effect played.Thinking, owing to there is the Concentraton gradient of volatile essential oil between the inside of microcapsule and outside, therefore when preparation is delivered to target, the content of microcapsule starts release.This release process and kinetics thereof can be affected by following factors: being dried of (a) microcapsule;B () contacts with aqueous medium, such as water or rainwater, reservoir as previously discussed, and it can change the permeability of micro encapsulation shell and/or cause the slow decomposition of shell;(c) variations in temperature, particularly high temperature;(d) direct sunlight.But, owing to the content of microcapsule may be spontaneous and discharge independently, it is thus possible to exist and need not any of the above described condition or it will not produce the situation of any impact.
Anti-microbial agents
Background-the effective management of dairy herd and the preparation of maintenance and milk product have become as main achievement on a large scale.The health problem causing significant economic problems relates to mastitis.Mastitis are the lactiferous ducts system caused by antibacterial intrusion in the breast of mammal (including people) and breeding or the inflammation of mammary gland tissue.Once mammal obtained mastitis, and the ability of its synthesis milk receives the infringement of inflammation.That is, this mammal starts the milk of diacrisis, and the such as leukocyte of the somatic cell in milk increases.Equally, the glandular cell of mammary gland sustains damage, thus they fall into a decline along with increasing in connective tissue, result in secretion emulsion and reduces.
Mastitis are to affect the disease of the dairy animal of 15%-20% in world wide.In the U.S., it is believed that there is the cow of 50% to have the limbs (quarters) of one or more infection.In Europe, it is estimated that there is the veterinary of 30%-40% to get involved owing to mastitis cause.Mastitis are also frequently seen in women.
Antibacterial infects, particularly bovine mastitis, is that rancher generally has to the consumption money of process and the problem of difficulty.Breast factory owner is in the face of two distinct types of mastitis infection, the most communicable and Environmental.Communicable mastitis are during the process of giving milk, and are contacted with the dairy equipment that may carry mastitis pathogens source by animal and to spread.Environmental mastitis are to be caused by the material infection animal skin coming from following place: the environment that the animals such as barnyard environment, field, stock barn inside stayed.
Communicable mastitis dip compositions by the sterilization of nipple after giving milk, thus are readily available control.This type of sterilization is dipped and is killed the antibacterial moving on to animal surface from instrument of giving milk.Environmental mastitis are exempted from infected spacer film preferably by protection sensitive organization and are treated.
Mastitis can exist with various rank intensity, from not observing the symptom inflammation to nipple, hyperpyrexia, makes animal weak and dejected, lacks appetite.These situations actually cause the drastically decline of milk yield.
Infection is caused by microorganism, but for them, in entering mammary gland and establishing the site causing infection, relates to many factors.There is this type of factor multiple (such as, health, stock barn condition, weather, instrument of giving milk, feedstuff, gene) to work simultaneously.
Substantial amounts of microorganism is there is with internal on breast.It is true that confirmed 137 kind relevant to the mammary gland of cow and subspecies microorganism;Some of which is normal flora part, and does not typically result in mastitis.On the contrary, they can protect the infection that breast causes from pathogen bacteria.
But, some other microorganism can cause infection in mammary gland.Modal, those cause about 90% mastitis infection for streptococcus agalactiae (Streptococcusagalactiae), staphylococcus aureus (StaphylococcusAureus), streptococcus dysgalactiae (StreptococcusDysgalactiae), streptococcus uberis (Streptococcusuberis), escherichia coli (Escherischiacoli) and corynebacterium pyogenes (Corynebacteriumpyogenes).
There is communicable microorganism and Environmental microorganism.Infected cow is the major source of communicable microorganism, and it is survived on skin and nipple wound and breeds.They are made up of streptococcus agalactiae (Streptococcusagalactiae), staphylococcus aureus (StaphylococcusAureus) and streptococcus dysgalactiae (Streptococcusdysgalactiae).Environmental microorganism (escherichia coli (Escherischiacoli) and other coliform, streptococcus uberis (Streptococcusuberis)) does not also end up on nipple.But, the presence of which indicates the pollution of the height of the soil, straw mattress and the water that are particularly caused by fertilizer.
Use multiple means of defence for avoiding disease in people patient and non-human patients.It can include in order to wash off or restricting bacterial and other be positioned at the gathering of microorganism of nipple expose portion and carry out give milk before the holding health of height, and therefore can pass through colostrum (foremilk) etc. and clean.
The based composition used in treating and preventing mastitis is formed from aqueous coating system.These applicator reduce, by the existence of killing activity agent, the probability that animal is contaminated.But, these nipples are dipped thing (dips) and are very easy to remove.Such as, nipple based on polyvinyl alcohol dips the water resistance that thing can not provide enough.That is, by exposure to water, these films were consume in about 3 to 4 hours.In the case of not having enough isolating membrane, this dairy animal is easily polluted by Environmental pathogen, and it can promote the mastitis in herds.
The feature of another kind of coating substance is by forming film spacer at skin surface, thus avoids the contact between vulnerable tissue and environment.Many antimicrobial materials are formed with such film multiple or polymeric material is incompatible.Such as, antimicrobial material can not be efficiently used with latex, is because this antimicrobial material and is finally precipitated out from latex.Additionally, latex can not provide the effect of the skin of lasting cladding mammal.Recently the product of exploitation provides for mammiform film forming spacer and the applicator containing antimicrobial.Liquid, polyvinylpyrrolidone and other polyvinyls that this type of applicator includes having dissolved, protein hydrolysate (proteinhydrozylate), natural and the glue of synthesis, water, ethanol, methanol, isopropanol, soluble polymer, unsaturated fatty acids oil, cellulose derivative, acrylate copolymer structure (lattice) etc..
Clay poultice, homeopathic therapeutic method, medicinal plants and oxygen therapy can be as the medicable methods to mastitis.Advise using antibiotic, and for treating ill animal.But, it is the most far from preferable solution.Problem (the problem that the pollution caused by antibiont residue is relevant to Yoghurt and cheese processing milk products caused except antibiotic, etc.) outward, antibiotic can't reduce the probability of mastitis, this is because they introduce as possible solution.It is the most real to opposing or the most invalid relevant problem in the case of the mastitis caused by coliform and staphylococcus aureus (StaphylococcusAureus).
The US patent 6,106,838 of Nitsas discloses antimicrobial compositions, and it includes the active component of the quintessence oil obtained from Origanumvulgaressp.hirtum, and it comprises thymol and carvacrol as its Main Ingredients and Appearance.The multiple disease that said composition is caused by pathogen microorganism for treatment, including the chronic mastitis caused by staphylococcus (Staphylococcus) or Streptococcus (Streptococcus) or mastitis.
The US patent 6,649,660 of Ninkov discloses pharmaceutical composition, it comprises the oily extract of the plant coming from Labiatae family, and it is used for treating microorganism and infects.The US patent 6,921,539 of Ninkov also similarly discloses therapeutic antimicrobial compositions and their methods in treatment is such as the disease of mastitis.
The use of the openest encapsulated essential oil preparation with prevention and therapeutic properties of above-mentioned document.
Content-exist in the industry is for the demand of the biocide preparation before giving milk and after giving milk, and it be the highly effective skin antiseptic for preventing mastitis, and makes breast and skin of nipple holding good environment at the same time for giving milk with low frequency or altofrequency.It addition, such composition can provide quickly kills the microorganism causing mastitis, and it is water miscible, nontoxic and not allergy.Such composition is conducive to low-frequency dairy (dairies) given milk, and eliminates the obstacle of the practice exploitation of the dairy given milk for further altofrequency.
It has been determined that, the preparation comprising the encapsulated essential oil prepared by the inventive method or interfacial polymerization be can be used for combating microorganisms and infects such as mastitis, and thus be accordingly used in prevention, controls and treat microorganism-relevant disease or disease.
Therefore, providing the anti-microbial agents comprising at least one encapsulated essential oil microcapsule prepared according to new method of the present invention or foregoing interfacial polymerization, wherein said preparation is in treatment or prevents in the disease relevant at least one microbial pathogens or disease effective.
Term " as used herein treatment " refers to the use of a certain amount of preparation comprising volatile essential oil according to the present invention, it is effectively improved undesirable symptom relevant to disease or disease, prevent the performance of the symptom before they occur, reduce disease or the progress of disease, reduce the deterioration of the symptom relevant to disease or disease, reduce the irreversible infringement caused by pathogen, palliate a disease or the severity of disease or recovery from illness, guarantee more quickly to recover, or prevent disease form generation or above two or multiple combination.
In one embodiment, described microbial pathogens is selected from escherichia coli (Escherichiacoli), staphylococcus aureus (StaphylococcusAureus), Micrococcus CNS (MicrococcusCNS), streptococcus dysgalactiae (StreptococcusDysgalactiae), Arcanobacterium pyogenes (AreanobacteriumPyrogenes), and bacillus pyocyaneus (PseudomonasAeruginos).
In another embodiment, described anti-microbial agents mastitis in treatment or the animal that giving milk of prevention and people.
In another embodiment, described anti-microbial agents is preservative.
A kind of method regulating and controlling mastitis in dairy animal of same offer, method includes using antimicrobial essential preparation to the nipple of described animal, and described preparation optionally can form sealing coat, thus substantially prevent the microorganism entrance to breast.
Term as used herein " regulation and control (modulating) " refers to the use of a certain amount of preparation comprising volatile essential oil according to the present invention, it is effectively improved undesirable symptom relevant to mastitis, prevent the performance of the symptom before they occur, reduce the progress of mastitis, reduce the deterioration of the symptom relevant to mastitis, reduce the irreversible infringement caused by pathogen, alleviate severity and the recovery from illness of mastitis, improve and give milk or more quickly recover, or prevent disease form generation or above two or multiple combination.
A kind of method also providing microbial population reduced in surface or target, described method includes using to surface or target antimicrobial essential preparation, optionally can form antimicrobial sealing coat.
In one embodiment, described surface or target are the nipple of dairy animal.
Term " dairy animal " refers to think the animal of dairy animal.This type of animal can be cattle, goat, camel, alpaca etc..But, this type of preparation also can effectively treat the mastitis in dairy animal, and in dairy animal, its milk products are generally not the part of human diet.This term also refers to people.
Preparation used can be uneven or uniformly.It addition, this microencapsulated essential oils can be executed to target together with high boiling point (active or nonactive) carrier, as applied for 11/040 author of the present invention at US, disclosed in 102, whole at this it is incorporated herein by reference.
In another embodiment, described preparation comprises at least one encapsulated antimicrobial essential and at least one not-encapsulated essential oil, as carrier.Preferably, described antimicrobial essential is one or more Herba Origani oil, basil oil, oil of rosemary, Eucalyptus oil, tea tree oil or thyme oil.
Other can encapsulated quintessence oil be those quintessence oils obtained from Labiatae (Lamiaceae), Labiatae (Labiatae) or Verenaceae (Verbenaceae).
The preparation that can form sealing coat also can comprise polymer, its spacer described in being formed that becomes dry after being applied on animal skin.Or, said preparation can comprise at least one monomer, and it once becomes dry or polymerization forms polymer spacers in the presence of initiator.
In one embodiment, the antimicrobial spacer formed after the preparation using the present invention is based on the polymer being contained in this essential oil formulation or monomer.In another embodiment, this polymer or monomer are not contained in preparation, but before administration, are and then applied on skin after using this essential oil formulation, or use with the mixture now joined before administration.
This essential oil formulation, it is for regulating and controlling microbial-relevant disease such as mastitis or is used for reducing microbial population, also can comprise other and be generally used for controlling or the antibacterial agent for the treatment of disease such as mastitis.This type of combination may result in significantly more efficient antimicrobial acivity, and its prolonged action that also can show microorganism to more wide range or effect are extensively.It addition, this type of combination can significantly decrease the valid density of described Antibacterial.Therefore, this type of preparation can be used for regulating and controlling communicable Environmental mastitis.
Being not intended to be restricted at this, other antimicrobial is selected from stability chlorine (stabilizedchlorine) such as chlorine dioxide, chlorhexidine salt, releases chlorine (chlorinerelease) compound such as alkali metal hypochlorite, oxidant such as hydrogen peroxide and peracid;Protonated carboxylic acid (i.e. fatty acid) is such as enanthic acid, octanoic acid, n-nonanoic acid, capric acid, hendecanoic acid;Acid anion (acidanionics) is such as alkyl aryl sulphonic acid;Quaternary ammonium salt, and iodine.
The preparation of this aspect can be applied to the nipple of dairy animal, by any method to know as sprayed (spraying) on nipple, dab (brushing), swab (swabbing) or bubbling (foaming), and in any time giving milk period.Said preparation can be used by nipple is dipped in the bin comprising invention formulation or container (referred to as nipple-dipping methods).
After using so that the nipple being coated with by preparation becomes dry, antimicrobial spacer and preventative barrier are formed on it.
In one embodiment, can the most immediately said preparation be sprayed on the breast of animal, now nipple be most susceptible to infect, and can upper once milk before remove from the breast of animal.This is used after milking and can prevent pathogen from immediately entering after being milked in nipple, owing to nipple-end sphincter (being responsible for closing nipple-end) keeps exposing about 30 minutes after being milked.
In another embodiment, this anti-mastitis formulations can used when the not galactopoiesis phase not carrying out milking starts and during the not galactopoiesis phase.Breast also periodically can be used, to prevent and to control mastitis by it in the whole not galactopoiesis phase.Necessary part in mastitis control program is not galactopoiesis therapy (drycowtherapy).Not galactopoiesis therapy is the treatment of the cow before childbirth cub during about 4 to 10 weeks.During this period also referred to as non-lactation period.Although during this period, mammal is also not exposed to the milking machines of potential pollution form, but the nipple of ten to five 14 percent infects and occurs during this period.Owing to the immunoreation of mammal is weakened during not galactopoiesis, thus a high proportion of infection occurs.It addition, during not galactopoiesis papillary dilation so that mammary gland is easier to invade by microorganism, and does not has lactogenic stream (flushinglactation), and the probability of infection increases.Therefore, during not galactopoiesis, treat dairy animal and can reduce the probability of infection.
Embodiment 1:
Using high-speed shearing Mixer, the solution of the quintessence oil (table 1) that 35g toluene di-isocyanate(TDI) (TDI) is mixed with 250g adds in the 500g water containing 5g polyvinyl alcohol (PVA).It is added thereto to the 120ml water with 55.6g Polyethylene Glycol (PEG) 4000.It is blended in room temperature with constant 2 hours.By the emulsion 12g guar gum obtained and 4gNefocide process.In order to destroy the hydrogel viscosity of emulsion, add the sodium lauryl sulphate (SDS) of 10g1%.
In order to evaluate its antimicrobial efficacy, particularly treat mastitis, on multiple-microorganism, next test said preparation.
Generally, find that said preparation is effective anti-microbial agents, the pathogen of all tests is all had effect.
Embodiment 2:
The 12g stearic acid being dissolved in 100g quintessence oil adds to quickly stir the 250mlH containing 2.5g polyvinyl alcohol (PVA) of (high shear agitation device)2In the solution of O.Wherein, 22.8gCaCl is added2Hexahydrate is in 20mlH2Solution in O, and stir 2 hours.Then, add 1.5g nipagin, 8mlLatronB1956 and 3g guar gum, and be further continued for stirring 2 hours.
The microcapsule that include other quintessence oils be similarly prepared:
1-tea tree oil, encapsulated in lauric acid, use CaCl2
2-thyme oil, encapsulated in stearic acid, use CaCl2
3-Eucalyptus oil, encapsulated in stearic acid, use CaCl2, containing free (withfree) Pyrethrum and Oleum sesami;
4-Herba Origani oil, encapsulated in capric acid, use CaCl2, containing free Pyrethrum and Oleum sesami;
5-tea tree oil, encapsulated in capric acid, use FeCl2
6-citronella oil, encapsulated in lauric acid, use MgCl2, containing free Pyrethrum and Oleum sesami;
7-tea tree oil, encapsulated in capric acid, use MgCl2
Testing in vitro:
Use the sample to the following pathogen coming from IsraeliDairyBoard (prepare and sell) to test the effect of above-mentioned preparation:
A) escherichia coli (Escherichiacoli),
B) staphylococcus aureus (StaphylococcusAureus),
C) Micrococcus CNS (MicrococcusCNS),
D) streptococcus dysgalactiae (StreptococcusDysgalactiae)
E) Arcanobacterium pyogenes (AreanobacteriumPyrogenes), and
G) bacillus pyocyaneus (PseudomonasAeruginos).
Every kind of different antibacterial is grown 18 hours at 37 DEG C on TSBA and Sanguis caprae seu ovis culture plate.Arcanobacterium pyogenes (ArcanobacteriumPyrogenes) is grown 42 hours at 30 DEG C.Then, by the Sterile Saline of antibacterial 0.9N from culture plate eluting, and it is suspended in Sterile Saline.The concentration of bacterial suspension is regulated to about 5x108CFU/ml。
In this suspension, use the essential oil formulation comprising Herba Origani oil, tea tree oil or thyme oil.The essential oil formulation of use variable concentrations, 0.01% to 1%.Inoculated bacteria is 5ml with the usual volume of oil formulation.
After the mixture vortex 10 minutes of this inoculum and essential oil formulation, this mixture is used vacuum pump filtered by sterile glass micro-filter (GF/C1.2 micron, purchased from Whatman filter company).
This liquid filtrate is diluted and is transferred to TSBA and Sanguis caprae seu ovis culture plate.This plate is cultivated 18-42 hour under optimum temperature;Thereafter the bacterium colony of antibacterial on each plate is counted.
Result is summarised in table 1 below and 2:
Table 1: according to the summary of the antibacterial efficacy of the different preparation of the encapsulated quintessence oil of the method for embodiment 1.
Table 2: according to the summary of the antibacterial efficacy of the different preparation of the encapsulated quintessence oil of the method for embodiment 2.
Embodiment 3:
The quintessence oil that quintessence oil such as tea tree oil, Eucalyptus oil, Herba Origani oil, the quintessence oil obtained from Herba thymi vulgaris, the herbaceous plant that obtains from origanum (origanum) obtain, and the quintessence oil that the plant of other Labiatae (Lamiaceae), Labiatae (Labiatae) or Verenaceae (Verbenaceae) belongs to is encapsulated also according to the method for embodiment 2.
These quintessence oils also can come encapsulated by the interfacial polymerization as disclosed in embodiment 1.Also being prepared for comprising the mixture of the microcapsule of polyurethane microcapsule and polyurea microcapsule, its various microcapsules have different release characteristics, to provide the release characteristics of relative broad range for preparation.
The expeling of insecticide and elimination
Background-such with insecticide only after insecticide has been positioned in target, twinge also may cause directly or postpone to infect, it is only possible to show that their effect is different, insect repellent stops insect fly into or contact and stop them to bite or suck the skin to them attractive surface, such as animal and people.Under many circumstances, drive away bite, suck blood and other harassing and wrecking insecticides be badly in need of very much because they part also can spread disease.Therefore, the active ingredient being used for driving away this type of insecticide has important cleaning, health and cosmetic function to realize its effect.
Insect repellent extensively sends out use in the U.S. and the whole world.In some areas, the use of insect repellent is the most necessary, thus is used for avoiding or reducing the appearance of the disease carried by insecticide.Such as Center for Disease Control (CDC) (CentersforDiseaseControl, CDC) about 101 are received every year, 000 example report Lai Mushi (Lyme) sick (being propagated by deer louse class) and 1,000 example report encephalitis (by mosquitoes spread).
A lot of effective anthelmintics as is generally known in the art.These one of them N, N-diethyl-m-toluamide (DEET) has shown that as extremely effective mosquito anthelmintic, and is considered one of the most the most frequently used.DEET is to be applicable to the skin of patient in design, and expels rather than kill insecticide.The many compositionss comprising this material are commercially available, and it is used for humans and animals, such as with Emulsion or aerosol combination form.
Have begun to recently pay close attention to and child on long-term is used DEET and the toxicity of other available insect anthelmintics.At present, forbid the child of less than 7 years old is used DEET.USEnvironmentalProtectionAgency (EPA) determines that no longer allowing Labels Were Marked with child of the product containing DEET is safe prompting recently.Although additionally, DEET is effective anthelmintic, but it has dual shortcoming, it must use with rather high concentration, and, prior, it can not effectively provide the protective effect that lasting antagonism insect exceedes about 6 hours.
Control in delivery formulations in the time, many encapsulated insect repellents of having reported for work.The example of this type of anthelmintic system is disclosed in the U.S. patent 4 of Munteanu et al., 548,764, and the U.S. patent 5,069,231 of Rutherford.The encapsulated system of this type of anthelmintic has very limited amount of effect in time, and generally effect duration was less than 1 week.Being usually present high volatility material such as ester, ether and aldehyde in available compositions, it makes these compositionss the most unstable, and it is thus desirable to the existence of chemical stabilizer.
It is cyano group (3-Phenoxyphenyl) the chloro-α of methyl-4--(1-Methylethyl)-phenylacetate for driving away the available anthelmintic of another kind of little blood-sucking pests from the skin of mammal, hair or hair.This reactive compound can be formulated as being suitable to be locally applied to the compositions (see for example the US patent No. 4,547,360) of the skin of mammal, hair or hair easily.
Quintessence oil the most uses in driving away insecticide.Such as, Essential lavender oil is used to be used for protecting child to attack from head louse.Piperonal (1,3-benzodioxole (benzodioxol)-5-formaldehyde) commercially introduces as anthelmintic recently.It is manufactured that the Citronella candles for driving away insecticide, although showing citronella oil is not very effective insect repellent, even if when it is from wax candle release to air.The commercially available topical composition comprising citronella oil is not highly effective, if patient perspire, it may be possible to owing to they action times are the shortest, that is, 10-20 minute or less, and if will expeling effect completely, need to cover whole health.
Report for work the use of preparation based on quintessence oil in agricultural.The PCT Publication WO04/098767 of the present inventor discloses the microcapsule of quintessence oil, and it can be used as insecticide, insect repellent and antiviral or antifungal etc..When microcapsule is applied to the material given, it is contained in quintessence oil therein and discharges over time with constant speed.The effect of this type of microcapsule depends on the usefulness of encapsulated material and the parameter that microcapsule itself is relevant, i.e., size, the thickness of encapsulated film, it is contained in the ability etc. of the sustained release of quintessence oil therein, and the aqueous medium become dry immediately after being not dependent on the target environment they carried.
The US patent application 11/040,102 of the present inventor discloses encapsulated essential oil preparation, and it comprises at least one encapsulated volatile quintessence oil and nonvolatile carrier, contains at least one volatile essential oil described in the carrier.This type of preparation is for controlling pest population in agricultural environment.
The essential oil formulation that content-have now found that manufactures according to the method for US application 11/040,102 or the method for the present invention such as those, can be used for from animal or the skin of people or surface and attractive to them can drive away the target of land or eliminate insecticide.This type of insecticide is that animal or people can be caused worry or injury, and can for example, mosquito, louse class, fly, Formica fusca and Blatta seu periplaneta.Also it is found that this type of preparation can be directly applied to animal or the skin of people or can contact or on the indoor or outdoors surface of intimate contact with animal or people.
Such as, US application 11/040, the preparation of 102, it comprises encapsulated volatile quintessence oil (such as, Herba Cymbopogonis Citrari) and nonvolatile quintessence oil is as carrier (such as, Pyrethrum), and it also can contain active agent such as insect growth regulator, IGR, Novaluron (Novaluron), (contain together with encapsulated essential oil, in the carrier, or both), it has already been proven that they or artificial reservior such as fish ponds, lake the most natural from wet or humidity environment, crawl, drink reservoir and other aquatic products industry is driven away or eliminates the effect of insecticide.
Compared with existing insect repellent, for similar purpose, it has been determined that use anthelmintic/elimination preparation can arrive one or more following advantages:
1., compared with those commercially available anthelmintics, they use more efficient for application on human skin;
2. they significantly reduce insect population in handled region, therefore eliminate or reduce significantly the use of contact skin preparation;
3. they more efficiently reduce the disease or the diffusion of infringement caused by mosquito and other insecticide;
4. they can be applied in combination have synergism at haunt serious place and skin preparation of mosquito or insecticide;
5. they can be used to reduce the population of insect in animal place, need not use single animal such as Canis familiaris L. canopy, stock barn and circus troupe;With
6. they can be used near child, has therefore avoided direct contact and has used and ensure that child more more than to the side effect being grown up.
Therefore, another aspect of the present invention provides anthelmintic or insecticidal preparation, for reducing the population of the insecticide in the nonagronomic environments processed, described preparation comprises at least one encapsulated volatile quintessence oil and nonvolatile carrier, carries at least one volatile essential oil described in this carrier.Nonvolatile carrier can be solid or liquid-carrier.
In one embodiment, the preparation of this encapsulated essential oil is according to prepared by the method for the present invention.In another embodiment, the preparation of this encapsulated essential oil is prepared by interfacial polymerization.
In another embodiment, described insecticide is the insecticide that animal or people can be caused worry or injury.This type of insecticide can, be not limited to this, selected from mosquito, louse class, fly, Formica fusca and Blatta seu periplaneta.
In another embodiment, described nonvolatile carrier is selected from nonvolatile quintessence oil, nonvolatile vegetable oil or its combination in any.
When preparing said preparation and being suitable to be directly applied on the skin of animal or people, it can also comprise at least one medicine or cosmetic agent, and when its application to skin, it can provide other advantage (such as menthol, vanillin).
In order to animal or people use, this quintessence oil is selected from: Oleum menthae, Oleum Caryophylli, Eucalyptus oil and Essential lavender oil;Fennel oil, Radix Angelicae Sinensis oil, orris oil, Oleum Anisi Stellati, orange oil, Cananga odorata oil, caraway oil, Cardamom oil, guaiac wood oil, cymin oil, lindera oil, Oleum Cinnamomi, Oleum Pelargonii Graveolentis, copaiba balsam oil, Fructus Coriandri oil, perilla oil, Cedar oil, citronella oil, Jasmin oil, Cymbopogon martini Sofia oil, Cedrus deoclar (Roxb.) G. Don oil, Oleum Menthae Rotundifoliae, western Oleum menthae, Oleum Anisi Stellati, tuberose oil, Oleum Caryophylli, orange blossom oil, wintergreen oil, Tolu balsam oil, patchouli oil, Oleum Rosae Rugosae, palmarosa oil, Japanese cypress oil, Hiba oil, sandalwood oil, petitgrain oil, laurel, vetiver oil, oleum bergamottae, Peru balsam oil, rosewood oil, Oleum Camphora, mandarin oil, Eucalyptus oil, white lemon oil, Essential lavender oil, linaloe oil, Indian oil of verbena, Fructus Citri Limoniae oil, oil of rosemary and Japanese peppermint oil.
Semen Armeniacae Amarum oil, fennel oil, basil oil, laurel, caraway oil, Cardamom oil, Cedrus deoclar (Roxb.) G. Don oil, Celery oil, chamomile oil, Oleum Cinnamomi, citronella oil, Oleum Caryophylli, Fructus Coriandri oil, cymin oil, dill oil, Eucalyptus oil, Oleum Anisi Stellati, oil of ginger, oil of grapefruit, Fructus Citri Limoniae oil, white lemon oil, Oleum menthae, parsley oil, Oleum menthae, oil of pepper, Oleum Rosae Rugosae, Oleum Menthae Rotundifoliae (menthol), oleum Citri sinensis, thyme oil, turmeric oil, and the oil of Ilicis Purpureae can be selected from by the most encapsulated and from animal or application on human skin expeling insecticide quintessence oil.
In quintessence oil, the example of active ingredient is: citronellal, methyl salicylate, ethyl salicylate, propyl salicylate, citronellol, safrol, and limonene, Organo, Herba Cymbopogonis Citrari and Garden lavender, Oleum Pelargonii Graveolentis, oil of rosemary and Oleum menthae, Oleum Menthae Rotundifoliae, pinke needle oil and Eucalyptus oil.Unsuitable for, but unspent for Fructus Citri Limoniae oil, oil of grapefruit, lavandin oil, Oleum Cinnamomi, Oleum Caryophylli, thyme oil, wintergreen oil, Cedrus deoclar (Roxb.) G. Don oil, Indian oil of verbena, mandarin oil, tangerine oil, orange oil, citrus oils, white lemon oil, Fructus Coriandri oil, Punica granatum L. oil, Oleum Juglandis, Oleum Arachidis hypogaeae semen, Semen Maydis oil, Oleum Brassicae campestris, Oleum Helianthi, Oleum sesami, Semen Lini oil, safflower oil and olive oil.
nullIt can use in the formulation and be selected from pinaster Pyrethrum as larvicide and insecticide and its quintessence oil being suitable to humans and animals、Camellia sinensis、Herba thymi vulgaris and come from the quintessence oil of following family: α-terpinol、Amyl cinnamic aldehyde、Amyl salicylate、Anisic aldehyde、Benzylalcohol、Benzyl acetate、Cinnamic aldehyde、Cinnamyl alcohol、Carvacrol、Carveol、Citral、Citronellal、Citronellol、Dimethyl salicylate ester、Eucalyptol (eucalyptole)、Acetaminol、Iso-acetaminol、Galaxolide、Geraniol、Guaiacol、Ionoionone、D-limonene、Menthol、Methyl 2-aminobenzoate、Methyl ionone、Cresotinic acid acid esters、α-phellandrene、Pennyroyal oil、Fructus Perillae aldehyde、1-or 2-phenylethyl alcohol、1-or 2-phenyl ethyl propionate ester、Piperonal、Piperitol acetate、Piperonyl alcohol、D-pulegone、Terpinen-4-ols、Tirpinyl acetate、4-t-butylcyclohexyl yl acetate、Thyme oil (Bai Hehong)、Thymol、Trans-trans-anethole、Vanillin、Ethyl vanillin etc..
The most useful has oil of rosemary and/or wintergreen oil, and it can be with plants essential oil such as thyme oil, acetaminol and 2-phenylethyl propionate, carvacrol and the β-side alcohol derived from Thujopsis dolabrata (Thujopsisdolabratavarhondai) sawdust.
Other reagent is selected from auxiliary agent, antioxidant, UV absorbent, surfactant, water-soluble polymer, and non-water-soluble polymer, solvent (such as alcohol) etc..
Any concrete preparation depends on the combination of used quintessence oil or quintessence oil as the suitability of anthelmintic or insecticide.A kind of quintessence oil combination can be only used for driving away insecticide, and another kind can eliminate them effectively.The concentration of the essential oil formulation used has impact also for expeling and the elimination ability of said preparation.
Term " is driven away " or any linguistic variant refers to expel insecticide without ensuring that kill their action.The action that term " eliminates " or the whole of insect population or its part are killed by any linguistic variant.Term " insecticide " refers to mosquito, louse class, fly, Formica fusca and Blatta seu periplaneta and other insecticide, nematode, and animal or people are caused worry or infringement by it.
Term " mosquito " as used herein refers to any kind of mosquito, such as, malarial mosquito, yellow-fever mosquito and culex, include but not limited to tiger mosquito, original inhabitants yellow-fever mosquito (Aedesaborigines), Aedes aegypti, Aedes albopictus, Aedescantator, Aedes sierrensis, aedes sollicitans (Aedessollicitans), aedes squamiger, sting thorn yellow-fever mosquito (Aedessticticus), Aedes vexans, anopheles quadrimaculatus, northern house and culex pipiens fatigans.
Term " tick " as used herein includes any kind of tick, include but not limited to, deer louse (deerticks), U.S. Canis familiaris L. louse (Dermacentor variabilis), Omithodorosparkeri, carapatos (O.moubata) and Dermacentor andersoni (Dermacentorandersoni).Term as used herein " Blatta seu periplaneta " refers to any kind of Blatta seu periplaneta, includes but not limited to American cockroaches (periplaneta americana), Germany cockroach (Groton bug), oriental cockroach (oriental cockroach), wood Blatta seu periplaneta (Pennsylvania wood Lian), brown band Lian (brownbandedcockroach) (long hair cockroach (Supellalongipalpa)) and smoke Perilpaneta americana (smokybrowncockroach) (Peroplaneta fluligginosa (Periplanetafuliginosa)).
By driving away or eliminate the population of the insecticide that can result in target environment infringement, the virus that said preparation also can be propagated by insect vector by restriction, thus contribute to reducing the infringement caused by virus.
Said preparation can be prepared as various forms, and it depends on application, the degree (be such as applied to whole skin or contain the skin of concrete organ) of environment, the concentration using preparation and covering processed.This type of dosage form can, it is not limited to this, selected from concentrate (emulsifiedconcentrate), wettable powder, granular wettable powder, flowable formulation, suspension, granule, powder, fumigant, solution, spray agent and the aqueous solution of emulsifying.
The present invention also provides for a kind of method for driving away or eliminate the insect population that animal or people can be caused worry or injury, described method includes using preparation to nonagronomic environments or the insect population in described environment, said preparation comprises at least one encapsulated volatile quintessence oil and nonvolatile carrier, carries at least one volatile essential oil described in carrier.
In one embodiment, described method relates to directly using said preparation on the skin of animal or people.
In another embodiment, described method relates to said preparation is applied to surface such as floor, wall, ceiling, furniture, net, screen, lawn, clothes, seat, the surface of animal stock barn, and aquatic products industry.
Having also been discovered that during the research causing the present application, nonvolatile carrier enhances the expeling effect applied by volatile essential oil, and volatile essential oil adds the effect applied by nonvolatile vehicle.Therefore, the present invention also provides for each comprising the anthelmintic preparation of the invention formulation of effective dose.
In another embodiment, said preparation is in addition to essential oil insect repellent, also can be comprised at least one selected from following additive: insect growth regulator, IGR (IGR), insecticide, Acaricide, antifungal, nematicide and/or ectoparasiticide, in microcapsule or as the part of carrier.Preferably, described preparation can contain at least one insecticide, and it is dissolved at least one encapsulated essential oil described or is dissolved in this nonvolatile vehicle.This insecticides can for example, carbaminate, carbamide, triazine, triazole, uracil, organic phosphate, morpholine, dinitroaniline, acylalaninies, pyrethroid thing, and organochlorine.nullConcrete example is carbofuran、Bayer 17147、Sulfentrazone (sulfentrazone)、Azoles oxadiazon (carfentrazone-ethyl)、Cypermethrin、Cyromazine (cyromazine)、β-cyfloxylate、5a,6,9,9a-hexahydro-6,9-methano-2,4、Phosmet、Bromax (chlorobromuron)、Chloroxifenidium、Chlortoluron、Fluometuron、Metobromuron、Thiazfluron、Diflubenzuron、HEXAFLUMURON、Diflubenzuron、Cascade、Octafluoro urea、UC 62644、Novaluron (novaluron)、Dimethachlor、Propisochlor、Pretilachlor (pretilachlor)、2-chloro-n-(1-methyl-2-methoxy ethyl)-acetyl group-2,6-xylidine、Alachlor、Butachlor、Propachlor、Xylenol fenacet (dimethenamid)、Bifenox、4-(4-pentyne-1-base epoxide) diphenyl ether、Acifluorfen、Oxyfluorfen、Fluoroglycofen-ethyl、Fomesafen、Cis,Trans-(+)-2-ethyl-5-(4-phenoxy-phenoxy methyl)-1,3-dioxolanes、Fluazifop、Haloxyfop-P-methyl、The spirit of fluorine pyrrole second standing grain、Fluorine torr pyrrole gram (fluorotopic)、Azoles diclofop-methyl、Quizalofop-ethyl、Propaquizafop、Diclofop-methyl、Ding Leling、The spirit of alkene fluorine、The spirit of chlorine fluorine、Isopropaline,2,6-dinitroN,N-dipropylcumidine、Pendimethalin、Profluralin、Trefanocide、Accra bacterium spirit (aclalaninesfuralaxyl)、Metalaxyl、Suffer、Methyl wheat straw is lied prostrate、Difenoconazole、Etaconazole、Propiconazole、1,2-(2,4-Dichlorobenzene base)-amyl-1-base-1h-1,2,4-triazole、Triazolone、Elacron、Furan sulfur prestige (furathiocarb)、Aldicarb、Benomyl、2-secondary butyl phenenyl methyl carbamate、Wood Fen prestige (etiofencarb)、Fenoxycarb、Mobucin、Arprocarb、Carbetamide (carbetamid)、Fourth grass is special、Avadex、Eptam (eptc)、Molinate、Benthiocarb、Triallate、Vernolate、Penta grass is clean、Anilofos、Gram climing phosphorus、Methylpyridine phosphorus、Chlorfenvinpho、Dichlorvos、Diazinon、Methidathion、Azinphos ethyl、Bayer 17147、Chlopyrifos、Chlormephos (chlorthiofos)、Crotoxyphos、Cynock、Demeton、Dialifos、Rogor、Disulfoton、Etrimfos、Famphur、Fluorine sulfur ground peace (flusulfothion)、Fluorine sulfur peace (fluthion)、Fonofos、An Guo、Heptenophos、Isofenphos、Azoles phosphorus、Malathion、Fenoxaprop-P、Menite、2-dichloroethylk dimethyl phosphate、Metilomerkaptofosoksid、Thiometan、Parathion、Phoxim、Pirimiphos-methyl (pyrimiphosmethyl)、Profenofos、Kayaphos、Propetamphos、BAY-NTN 8629 (prothiophos)、Quintiofos、Sulprofos、Fen U.S. phosphorus (phemephos)、Terbufos、Triazophos、Agrisil、Nemacur (fenamipos)、Isazofos、Sec-benzyl-neighbour,O-diisopropyl thionic phosphonate ester (s-benzyl-o,o-diidopropylphosphorothioate)、According to ground phosphorus (edinphos) and pyrazophos.
In another embodiment, the preparation of the present invention can be used for antagonism can be as the insecticide of transmitted virus of the viral vector infected.Term " viral vector " refers to any as defined herein with the insecticide of this example, and it is the organism of the plant virus (plantvirusdisease-causing) can carried and propagate and cause disease.
In another aspect of the present invention, it is provided that a kind of method for controlling insect population, described method includes using microencapsulated essential oils preparation as disclosed herein to target environment or to described insect population or to its site.
Term as used herein " non-agricultural target environment " is often referred to be different from the environment of agricultural or horticultural environments.But, this term refers to indoor or outdoors environment, wherein needs drive away or eliminate insecticide.It can be the room in house, work offices, interior of building, park, school, nursery school, public entertainment region, sports ground, traffic and transport field such as subway station, departure hall (airportterminals), yacht, automobile, bus, train etc..Sprayable surface is floor, wall, ceiling, furniture, net, screen, lawn etc..
Owing to animal or people can be caused the insecticide of worry or injury to find their site in neighbouring or wet environment is such as pond by great majority, there are the needs eliminated the insect population existed from this type of wet environment (i.e. aquatic products industry) or they driven away.
In fact, it has been found that the preparation of the present invention can be applied to multiple reservoir (waterreservoir), thus reach eliminate the population of this type of existing insecticide or from purpose reservoir, drive away opportunistic insecticide (opportunisticinsect).As pastime or using this type of reservoir as current consumption, this avoids and uses the poisonous and long-standing compound that environment and humans and animals produce environmental hazard.
Term " reservoir " or " wet environment " refer at this, are not limited to this, water system, cooling system, swimming pool, natural and artificial water reservoirs, fishing ground, water tank, crawl, irrigation system and any other water system.
In one embodiment, said preparation is added in reservoir with the amount enough controlling insect population with anhydrous form.In another embodiment, after being dissolved in suitable carrier, this anhydrous composition is added in reservoir.
The preparation eliminating insect in reservoir can also be used for controlling microorganism and preventing the root system to water source, particularly irrigation conduit from invading (rootintrusion).
Drip irrigation, on surface also under surface, the technology irrigated by a kind of referred to as underground or low discharge, for a kind of method of root area that water and nutrient are fed directly to plant.The conveying of this type of water provides accurate irrigation control and the effective use to limited water resource.This Irrigation System is installed simple, and installation cost is relatively low so that all select sub-irrigation solution for private or public consumer for pouring garden and park.
The water regenerated by use carrys out irrigating plant, the advantage providing many relatively conventional irrigation methods with the underground drip irrigation technique system controlled of suitable design, as sub-irrigation by distributing water in underground, so that the health risk relevant to being exposed to recycled water is reduced to minimum.
For prolonged application, for utilizing a main challenge of underground drip irrigation technique to be the potential of the inside blocking of Irrigation System and outside root system intrusion (rootintrusion) to drip irrigation pipe.Having been proposed for a lot of solution, such as, some use trefanocide are to prevent the root system to emitter (emitters) from invading, and root system is invaded spacer and is directly incorporated into tubing itself by other.
Although the inside blocking that the deposition of the solid that root system invades drip irrigation pipe and precipitate, suspension causes, algae and bacterial slime are by good pretreatment, sterilised filtration, and new pipeline and emitter design and greatly reducing.Existing for the demand of unified approach, it can both prevent the intrusion of opportunistic root system, also can prevent the accumulation of the deposit caused due to the growth of fungus and antibacterial.
In aquatic products industry produces and controls, a maximum problem is the antibacterial in water and fungus, and fish and shrimp are also killed in several hours or several days by its Fast-propagation.Use preparation disclosed herein to this type of aquatic products industry and contribute to controlling this type of fungus and antibacterial, and thus help to maintain in that live and healthy state.
Antibacterial and fungal infection can be by controls as discussed above.Nematode also can be by controlling to the essential oil formulation comprising natural essential oil of the soil application present invention, its control line insects and their ovum.
Have now found that introducing, to the current of subirrigation system, the preparation comprising encapsulated essential oil makes it possible to control microorganism for a long time and prevent the root system to pipeline from invading.
Therefore, present invention provides preparation, it comprises at least one quintessence oil being selected from having antimicrobial and/or fungicidal property, and as disclosed in this, it is for controlling microorganism and preventing it from invading to the root system of irrigation conduit.The example of this type of quintessence oil is tea tree oil, thyme oil, Oleum Caryophylli, Eucalyptus oil, Herba Origani oil, citronella oil, basil oil, Oleum Anisi Stellati and fennel oil.
In one embodiment, these quintessence oils can be used together for root system control with the mixture of synthetic herbicide.In another embodiment, use has the quintessence oil of herbicidal properties.The herbicide of these quintessence oils with herbicidal properties or synthesis can be the most encapsulated or encapsulated in different microcapsules.
The quintessence oil with herbicidal properties is that those comprise 6-unit monocycle, carbocyclic ring structure and are aoxidized (oxygenated) or the substituted quintessence oil of hydroxy functional group by least one.nullThe example being included in the plants essential oil in this definition includes,But it is not limited to,Selected from aldehyde C16 (pure)、Amyl cinnamic aldehyde、Amyl salicylate、Anisic aldehyde、Benzylalcohol、Benzyl acetate、Cinnamic aldehyde、Cinnamyl alcohol、α-terpinol、Carvacrol、Carveol、Citral、Citronellal、Citronellol、Cymene、Diethyl phthalate、Dimethyl salicylate ester、Dipropylene glycol、Eucalyptol (eucalyptole)、Acetaminol、Iso-acetaminol、Galaxolide、Geraniol、Guaiacol、Ionoionone、D-limonene、Menthol、Methyl 2-aminobenzoate、Methyl ionone、Cresotinic acid acid esters、α-phellandrene、Pennyroyal oil、Piperonal、1-or 2-phenylethyl alcohol、1-or 2-phenyl ethyl propionate ester、Piperonal、Piperitol acetate、Piperonyl alcohol、D-pulegone、Terpinen-4-ols、Tirpinyl acetate、4-t-butylcyclohexyl yl acetate、Thyme oil、Thymol、The metabolite of trans-trans-anethole、Vanillin、Ethyl vanillin etc..
These quintessence oils can also be used as the spacer of the encapsulated essential oil for having antimicrobial and Fungicidally active.
For antimicrobial or/and the quintessence oil of antifungal and/or weeding can be encapsulated in identical microcapsule together, or then mix with independent Protein denaturation.
The preparation of the present invention can exist as single preparation, store, pack or use, wherein, encapsulated volatile quintessence oil and nonvolatile carrier premixing, or as bicomponent agent, described bicomponent agent comprises encapsulated volatile quintessence oil as the first component, the most in a separate container or be administered alone, and nonvolatile carrier is as second component.
Therefore it provides a kind of method for controlling insect population, described method includes:
-microcapsule formulation comprising at least one volatile essential oil is used to target, and
-the second preparation comprising non-volatile agent is used to target environment.
Using of described second preparation can be carried out after using the first preparation immediately, or any time after it is applied is carried out.For concrete condition, those skilled in the art can determine herein disclosed for any being more suitable in the two kinds of methods controlling insect population.
Preparation disclosed herein can be delivered to target by any method known to those skilled in the art.This type of method can include: (a) by surface as described in such as dilute with water or unused water-reducible liquid preparation being applied to and by as described in preparation manually or mechanically be applied to the surface that gives;(b) will be applied to such as the granule of powder or wettable powder as described in surface;C () garden near many or concrete selected region are by ground or aerial spraying liquid preparation;D preparation is embedded in the topsoil of garden by (), etc..
A) for driving away the preparation of mosquito
Use lower series preparation for driving away mosquito from various surfaces and indoor or outdoors place:
Preparation 1: citronella oil, Essential lavender oil, Oleum Pelargonii Graveolentis (geraniumoil) are dissolved in almond oil with the ratio of 1:1:1, the oil solution of formation 24% is (with trade (brand) name Di-TushTM, TamarLtd., Israel buy), by these these oil by the micro encapsulation in polyurethane coated (envelope) of the method in following embodiment 1.
Preparation 2: encapsulated citronella oil and not-encapsulated Pyrethrum and Oleum sesami.
Preparation 3: encapsulated citronella oil and Novaluron (Novaluron) and not-encapsulated Pyrethrum and Oleum sesami.
Preparation 4: encapsulated citronella oil and Novaluron and not-encapsulated Pyrethrum and Oleum sesami and 20mg Novaluron.
Preparation 5: encapsulated citronella oil and Novaluron and not-encapsulated Pyrethrum and Oleum sesami and 10mg Novaluron.
Preparation 6: encapsulated citronella oil and Novaluron and not-encapsulated Pyrethrum and Oleum sesami and Novaluron.
Preparation 7: encapsulated tea tree oil.
Preparation 8: encapsulated Camellia sinensis and Novaluron and not-encapsulated Pyrethrum and Oleum sesami.
Preparation 9: Pyrethrum, citronella oil, Oleum sesami are encapsulated in lauric acid, use CaCl2
Preparation 10: encapsulated Camellia sinensis and Novaluron and not-encapsulated Pyrethrum and Oleum sesami and Novaluron.
Preparation 11: tea tree oil is encapsulated in lauric acid, uses CaCl2, with not-encapsulated Pyrethrum and Oleum sesami.
Preparation 12: tea tree oil is encapsulated in lauric acid, uses CaCl2, with not-encapsulated Pyrethrum and Oleum sesami.
Preparation 13: citronella oil is encapsulated in stearic acid, uses CaCl2, with not-encapsulated Pyrethrum and Oleum sesami.
Preparation 14: tea tree oil is encapsulated in stearic acid, uses CaCl2, with free Pyrethrum and Oleum sesami.
Preparation 15: citronella oil is encapsulated in capric acid, uses CaCl2, with not-encapsulated Pyrethrum and Oleum sesami.
Preparation 16: tea tree oil is encapsulated in capric acid, uses CaCl2, with not-encapsulated Pyrethrum and Oleum sesami.
Preparation 17: citronella oil is encapsulated in capric acid, uses MgCl2, with free Pyrethrum and Oleum sesami.
Preparation 18: tea tree oil is encapsulated in capric acid, uses MgCl2, with free Pyrethrum and Oleum sesami.
Preparation 19: above-mentioned each preparation is also used fatty acid and bivalence Ca or Mg salt such as Ca (OH)2Or Mg (OH)2With multiple other bivalence or trivalent ion and various counter ions come encapsulated.
B) repellency test
Embodiment 1:
Three kinds of active component such as Herba Cymbopogonis Citrari, Garden lavender and Herba Pelargonii Graveolentis quintessence oil being dissolved in almond oil with the mixture of the ratio of 1:1:1, form the active ingredient solution of 24%, this solution can be prepared or with trade (brand) name Di-Tush by laboratoryTM(TamarLTD, Israel) buys.
In this embodiment, by the Di-Tush of the 153g of the active essential oil concentration that has 24%TMMix with the TDI of 19.8g, and be dispersed in the aqueous solution of 270g water and 2.7gPVA.After approximately forming microcapsule 5 minutes, add the PEG4000 of the 32.3g being dissolved in 75g water, and continue mixing.Phase after the production, add 2.4gNefocide, 0.7gRodopol and enough dibastic sodium phosphates so that pH level is about 6.
In a similar fashion, the preparation 1 with 48% active concentration it is prepared for.When being sprayed on floor and wall, two kinds of preparations all demonstrate good mosquito repellency matter.Two kinds of preparations all demonstrate the active duration more longer than not-encapsulated preparation.
Embodiment 2:
Use high-speed shearing Mixer, the solution being mixed into the 35gTDI of the preparation 1 to 250g with 6% active component is added in the 500g water containing 5gPVA.Wherein, water and the 55.6gPEG4000 of 120ml are added.The most persistently mixing 2 hours.12g guar gum and the antifungal (Nefocide) of 4g is added in this dispersion.In order to crush hydrogel, add 10gSDS (1%).
When the concentration of the 0.05-1% with 50ml-1,000ml is on half acre, or spraying on the soil of the neighbouring house of 1 acre with the concentration of 0.1%-0.5%, it does not has mosquito in keeping 2 weeks, and adjacent domain suffers the serious plague of insects.This preparation show than identical quintessence oil not-encapsulated formulation or be purchased not-the longer active duration of encapsulated essential oil.
Embodiment 3:
(the high shear agitation device) that the 12g capric acid being dissolved in 100g citronella oil adds to quickly stir contains the 250mlH of 2.5gPVA2In the solution of O.Wherein, it is incorporated in 20mlH222.8gMgCl in O2Hexahydrate, and stir 2 hours.Then, add 20g Pyrethrum, 2g Oleum sesami, 1.5g nipagin, 8mlLatronB1956 and 3g guar gum, and continue to stir other 2 hours.
Embodiment 4:
Repeat embodiment 3, but without Pyrethrum.When being sprayed at the wall in surface such as room and office, floor, ceiling, furniture, net, screen, lawn, clothes, seat, the surface of animal storage canopy and aquatic products industry, preparation 3 and 4 all shows good mosquito repellency matter.
Embodiment 5:
It is similar to preparation 1, uses 93g citronella oil, l0g Pyrethrum and 1g Oleum sesami to replace Di-Tush product, prepare preparation 5.
Embodiment 6:
It is similar to preparation 1, uses Oleum Pelargonii Graveolentis as encapsulated volatile quintessence oil, replace Di-Tush product, prepare preparation 6.
Embodiment 7:
It is similar to preparation 1, uses tea tree oil as encapsulated volatile quintessence oil, replace Di-Tush product, prepare preparation 7.
Embodiment 8:
It is similar to preparation 1, uses Essential lavender oil or Oleum Caryophylli as encapsulated volatile quintessence oil, replace Di-Tush product, prepare preparation 8.
Embodiment 9:
Preparation 9 uses following ingredients with amount substantially to prepare with for the identical method disclosed in preparation 1.Use following ingredients replacement Di-Tush product: 2.1gPVA, 88g oil of ginger, 22g Oleum Gossypii semen, 15.3gTDI, 24.4gPEG4000,1.8gNefocide and 0.5gRodopol.
Embodiment 10:
Prepare preparation as the anthelmintic (MuscaDomestica) to house fly.
The TDI of 250 grams of Di-Tush with 35g with 96% active essential oil concentration is mixed, and is dispersed in the aqueous solution of the 500ml water containing 5.0gPVA.Formation microcapsule, after about 5 minutes, adds the PEG4000 of the 55.6g being dissolved in 120ml water, and persistently disperses until forming homogeneous solution (about 30 minutes to 2 hours).In the latter stage of preparation, add 4.0gNefocide and 10gSDS (sodium lauryl sulphate).Along with continuing stirring, add 12 grams of guar gums, to obtaining uniform solution.
In order to determine the expeling of said preparation, the test of each a-type double uses the ripe fly of about 400 laboratory-growths.This fly is limited in the environment of closing, and on the scraps of paper sprayed with the preparation of preparation and do not spray, counts the quantity of the fly of landing.
Can be it can be seen that repeat in experiment for all of from table 3 below, the quantity of the fly landed on spraying paper is fewer than the quantity of matched group a lot.It addition, after repeating to test Isosorbide-5-Nitrae 8 hours, it was observed that the mortality rate of about 35%.For repeating to test 2, after 1 hour, it was observed that the mortality rate of 65%, after 5 hours, it was observed that the mortality rate of 91%.After 24 hours, observe whole population dead.
Table 3: the effect of anthelmintic antagonism housefly (MuscaDomestica) of the preparation of embodiment 10.
Embodiment 11:
Preparation antagonism Formica fusca (Tapinomasimrothi) and the insecticidal preparation of Blatta seu periplaneta (GermanicaBlatella).Said preparation is the combination of preparation A and B of following preparation:
Preparation A: tea tree oil and the 18.3g chlopyrifos (pyrinex) of 112.5g are mixed with 18.7gTDI.This solution is dispersed in containing 2.5g dissolve PVA (polyvinyl alcohol) 250ml water aqueous solution in.Wherein, add 65ml water, and 4.2g ethylenediamine and 3.7g diethylenetriamines, and continue dispersion.After stirring obtains uniform dispersion, it is added thereto to 1.7gNefocide and 6.0g guar gum, and continues stirring.Then use acid such as citric acid that this solution is neutralized to pH7.Then, add 5.15g Oleum sesami and 51.5g Pyrethrum, and continue stirring until again obtaining uniform mixture.
Preparation B: tea tree oil and the 18.3g chlopyrifos of 112.5g are mixed with the TDI of 17.5g, be dispersed in containing 2.5g dissolve PVA (polyvinyl alcohol) 250ml water aqueous solution in.Wherein, add 70ml water and 23.3gPEG3350, and continue dispersion mixing, after other stirring, form uniform dispersion liquid.Then, add 2.0gNefocide, 5.0gSDS and 6.0g guar gum, and continue stirring.Finally, add 5.15g Oleum sesami and 51.5g Pyrethrum, and continue stirring until obtaining uniform mixture.
Then preparation A and B is mixed with the ratio of the B of A and 20g of 40g.In order to test the effect of said preparation, this combination of spraying in the space of the restriction that Formica fusca or Blatta seu periplaneta are placed, and determine per cent death loss.Result is given in Table 4 below.
Table 4: combination preparation is to Formica fusca (Tapinomasimrothi) and the effect of Blatta seu periplaneta (GermanicaBlatella)
Embodiment 12:
The essential oil microcapsules used in drip irrigation system can be formed by the method for interfacial polymerization and the present invention.
17.5gTDI is mixed in 125g Oleum Caryophylli, then adds in the 250g water containing 2.5gPVA, use high speed shear gaseous mixture.Wherein, the 70ml water containing 27.8gPEG4000 is added.At room temperature continue mixing 2 hours, obtain dispersion liquid.0.4g xanthan gum (xanthanegum, rodopol) and the antifungal (Nefocide) of 2g is added to this dispersion liquid.In order to crush the hydrogel properties of this emulsion, add 5gSDS (sodium lauryl sulphate, 1%).
When this preparation being given the water inlet being used for underground drip irrigation system or drip irrigation system earth's surface, ground to this, find that it has efficiently controlled antibacterial and fungus growth at the hole of pipeline and system.
Embodiment 13:
When the encapsulated essential oil of embodiment 1 is prepared together with herbicide, this herbicide is selected from 2,6-dichlorobenzonitrile (dichlobenil) and sodium dimethyldithiocar-bamate (SDDC) (sodiummethyldithiocarbamate, Metam), diquat dibromide and N,N'-dimethyl-.gamma..gamma.'-dipyridylium, grow into the root system in water hole and antibacterial and fungus growth be also efficiently controlled.
Embodiment 14:
Repeat embodiment 12, use 125g thyme oil to replace Oleum Caryophylli, in the pipeline and hole of irrigation system, in effectively controlling antibacterial and fungus growth, obtain identical good result.
Embodiment 15:
Repeat embodiment 12, use the quintessence oil with antimicrobial and activity of weeding, such as Pinaster oil, tea tree oil or Eucalyptus oil.Preparation each of comprises in these quintessence oils or combination, and its antibacterial in the pipeline effectively controlling irrigation system and hole and fungus growth all show good result.
In a still further aspect thereof, can load in packaging or covering material by said preparation, this material is as those are for comprising or accommodate the goods of various material, fruit or vegetable or any object that can be attacked by this type of insecticide.This packaging or covering material can be designed such that quintessence oil slows down to the release of the goods being contained therein from packaging or container during storage or transport or controls release.This packaging or covering material can the most bag-shaped, plastics or paper bag, nylon6 chips, polyester sheet, paper wrapper, plastics or other seal container, for either manually or mechanically packaging fruit and the paper of vegetable or plastic material, etc..
Fruits and vegetables is characterised by high-moisture.The product that can maintain for it, needs water content in a small amount.Therefore, the dehydration of fruits and vegetables affects of both having: (1) which reduces the weight of product, thus reduce it and be worth and (2) that it changes the concentration of the chemotrophy material in fruit or vegetable, thus may result in and become sour increase and mouthfeel reduces.In the case of all, this is considered as the economic loss huge to distributors or consumer.Accordingly, there exist for coating can be formed at fruit or plant surface, thus reduce the needs of the preparation of the loss of moisture evaporation and nutrition.The use of this type of preparation can have obvious action keeping fruit or vegetable storage life and fortune in terms of the time in market.
Additionally, it is known that the fruits and vegetables after Shou Huo is susceptible to the infringement of this quasi-microorganism and insecticide, they pierce through the epidermis of fruits and vegetables due to a variety of causes.Finding that the preparation used in this respect in the present invention can be used for the fruits and vegetables after protecting results and encroach on from this type of, it acts on by being formed on driving away the sealing coat of microorganism and insecticide.
Therefore it provides film forms preparation, it can form coating on fruits and vegetables after harvesting.One uses the film being formed for and the quintessence oil being contained in microcapsule, or each of which prevents independently and controls the infringement caused by microorganism and insecticide, by first providing physical barriers, secondly provides long-term parasite killing or anti-microbial protection.
After using so that the fruits and vegetables covered by said preparation becomes dry, thus form physical barrier and preventative barrier.
Comprising encapsulated essential oil with this preparation using use, this quintessence oil portability in an aqueous medium, contains other reagent such as polymer and surfactant at aqueous medium, and its existence is to stablize this suspension.
In a preferred embodiment, said preparation also comprises coating reagent, and it may or may not be equal to the polymer of stable suspension, and it can be in the upper coating forming protection of spraying substrate (i.e. fruit or vegetable).
Embodiment 16:
Use high-speed shearing Mixer, the 35gTDI solution being mixed into 250g tea tree oil is added in the 500g water containing 5gPVA.It is added thereto to the water of 120ml containing 55.6gPEG4000.The most persistently mixing 2 hours.12g guar gum and the antifungal (Nefocide) of 4g is added to this dispersion liquid.In order to crush the hydrogel properties of this emulsion, add 10gSDS (sodium lauryl sulphate, 1%).
It is designated as said preparation test comparison comparison (untreated) and commercial formulation of other entitled HPP, Oxyfor, Shemer on Bulbus Allii Cepae, Radix Dauci Sativae and Rhizoma Solani tuber osi of N262, represents with two groups of parameters: weightless and corrupt, as described in detail in table 5 below and 6.
Table 5: red and purple Bulbus Allii Cepae " weightless " test (%) after results
Table 6: red and purple Bulbus Allii Cepae " corrupt " test (%) after results
Also carry out other experiment to determine the preparation N262 impact rotted on the Radix Dauci Sativae of storage.This experiment uses the Radix Dauci Sativae being grown in KibbutzAlumim to carry out.Radix Dauci Sativae is immersed in different solution 30 seconds, stores 1 month in the storage room of 0-1C °, and under 25C °, carry out the shelf shelf life of other 6-days again.
According to the following step process Radix Dauci Sativae:
Use several groups of Radix Dauci Sativaes:
1. matched group-untreated Radix Dauci Sativae (being labeled as C);
2. process group-by Radix Dauci Sativae is immersed in pathogen: sclerotinite (Sclerotiniasclerotiorum), rod method (Alternariaalternate), A.radicina suspension in (being labeled as T);
3. the washing group being purchased-Radix Dauci Sativae is immersed in the solution of 150ppm chlorine+0.2% isopropyl fixed (iprodione) (being labeled as Com);
4. the Radix Dauci Sativae that process group II-will process in 2 groups, carries out washing (being labeled as Com+T) such as 3 groups be purchased;
5.N262 group-by Radix Dauci Sativae is immersed in the N262 solution of 2% and (is labeled as EO1);
6. Radix Dauci Sativae according to 2 groups of process, is then immersed in the N262 solution of 2% and (is labeled as EO1+T) by process group III-;
Radix Dauci Sativae is immersed in the N262 solution of 4% and (is labeled as EO2) by 7.N262 group II-;
8. Radix Dauci Sativae according to 2 groups of process, is then immersed in the N262 solution of 4% and (is labeled as EO2+T) by process group IV-;
Radix Dauci Sativae is immersed in the N262 solution of 6.6% and (is labeled as EO3) by 9.N262 group III-;With
10. Radix Dauci Sativae according to 2 groups of process, is then immersed in the N262 solution of 6.6% and (is labeled as EO3+T) by process group V-.
Result shows in table 7 below.Preparation N262 can be summed up under the concentration of 2%, compare other process decrease the corruption of Radix Dauci Sativae, and can be used as being purchased the succedaneum (if target is to replace chemicals with friendly material) of washing.
Rot-total (%) Rot-mix (%) (%) is rotted by what antibacterial was caused (%) is rotted by what fungus was caused Process
4.5 1.4 3.1 0 C
57 0 0 57 T
2.4 2.4 0 0 Com
11.9 2.8 0.3 8.8 Com+T
2.65 0.7 2.0 0 EO1
21.3 2.3 19 0 EO1+T
9.6 5.8 3.8 0 EO2
31.2 1.0 4.2 26 EO2+T
3.3 2.0 1.3 0 EO3
72.3 0.3 0 72 EO3+T
Table 7:N262 is exposed to the result that the fungus under pathogen sclerotinite (Sclerotiniasclerotiorum), rod method (Alternariaalternate) and A.radicina and antibacterial are rotted to Radix Dauci Sativae.
Carry out other experiment to determine rotting and other effects rotted of the preparation N262 Sweet Potato Against Resopous to storing.The Rhizoma Dioscoreae esculentae from AgronomiaAgricultureCompany is used to test.Rhizoma Dioscoreae esculentae is immersed in different solution the several seconds, and stores 1 month in the storage room of 0-4C °.
Rhizoma Dioscoreae esculentae is processed: Rhizoma Dioscoreae esculentae is divided into several groups according to the following step:
1. matched group-untreated Rhizoma Dioscoreae esculentae (being labeled as C);
2. process group-Rhizoma Dioscoreae esculentae is under water to (being labeled as W);
3. process group I-by by 0.5% be referred to as B262 BotanoCap preparation process Rhizoma Dioscoreae esculentae according to 2 groups of process (being labeled as B1);With
4. process group II-by by 3.0% be referred to as B262 BotanoCap preparation process Rhizoma Dioscoreae esculentae according to 2 groups of process (being labeled as B2);Then with the commercial preparations of trade name Magnet (Imazalil) according to 3 groups and 4 groups process (being labeled as M).
Result shows in table 8 below.Preparation B262 can be summed up under 0.5% concentration with 3%, compare other process decrease the corruption of Rhizoma Dioscoreae esculentae, and can be as the succedaneum being purchased washing of antagonism Resopous, during particularly when target is to replace chemicals with friendly material.
After 1 month, by Resopous and rotten (%) of other reasons Process
16.48 C
17.45 W
10.98 B1
12.33 B2
20.81 M
Table 8: B262 is to the Resopous of Rhizoma Dioscoreae esculentae and the result rotted of other reasons in storage room.
Food additive for humans and animals consumption
Background-food industry uses unsaturated fatty acid in various products; this product is suitable to the consumption of following animal: such as mice, rat, milch cow or cattle, horse, sheep, goat; and primates; including troglodyte, chimpanzee, orangutan, fish, shellfish, Crustaceans, birds (such as chickling, cock etc.), people or the animal (such as Canis familiaris L. and cat) raised and train.This type of fatty acid can for example, eicosapentaenoic acid (EPA), docosahexenoic acid (DHA), aracadonoicacid (ARA), and the linoleic acid plus linolenic acid (CLA) of conjugation.These unsaturated fatty acids demonstrate can affect they process, manufacture, store, abnormal smells from the patient, the compatibility and the character of oxidation.
Encapsulated some these problems that solve of these fatty acids, and make them suitable for directly consuming or being incorporated in food compositions.Other food ingredients, such as vitamin, nutritional supplement, mineral, herbal concoction, food additive, aminoacid, etc., including, such as, beta-carotene, phylloxanthin, zeaxanthin (zeazanthin), iron salt, mantoquita, selenium salt, flavonoid, coenzyme Q10, medicinal herbs, spice, flavorant and extract (such as allicin or Bulbus Allii extract) are it can also be used to encapsulated.
The encapsulated essential oil preparation of content-use is the quintessence oil ratified based on encapsulated film and GRASS and/or FDA.It is true that all of reagent being contained in this microcapsule or the preparation comprising them, the most nontoxic to humans and animals.This type of preparation has used fatty acid or alkanoic acid disclosed in its face to be prepared for.In short, acid is dissolved in quintessence oil, then emulsifying in aqueous solution.Then this acid is cross-linked by polyvalent cation such as Ca or Mg or Fe or other polyvalent cations being dissolved in aqueous solution.
More specifically, the method includes:
A at least one alkanoic acid is mixed by () with at least one quintessence oil;
B the mixture of step (a) is mixed to obtain suspension by () with alkaline aqueous solution;With
C () is mixed into the aqueous saline solution comprising at least one polyvalent cation to the suspension of step (b), thus obtain the waterborne suspension of the microcapsule of microencapsulated essential oils.
In one embodiment, the method also includes filtering and collecting the wax-like or step of solid particle.
In another embodiment, this granule does not separates with liquid-carrier, and said preparation uses same as before.
When being separated with aqueous medium by solid microcapsule, a small amount of quintessence oil may keep unencapsulated.In order to obtain the microcapsule of oil-free, it is usually added into the absorbent that can absorb excessive oil on a small quantity.This absorbent is selected from, such as, and cellulose, starch powder or AerosilTMSilica gel (silicas) is such as AerosilTM200 or 300, can be commercially available from Degussa.In some applications, AerosilTM is preferred absorbent.
Present invention also offers a kind of method preparing microcapsule formulation, this microcapsule formulation comprises multiple edible microcapsule, and each have the shell comprising at least one quintessence oil nuclear core with surrounding described nuclear core, and described method includes:
A at least one alkanoic acid is mixed by () with at least one quintessence oil;
B the mixture of step (a) is mixed to obtain suspension by () with alkaline aqueous solution;With
C () is mixed into the aqueous saline solution comprising at least one polyvalent cation to the suspension of step (b), thus obtain the waterborne suspension of the microcapsule of microencapsulated essential oils.
In one embodiment, this comprises at least one quintessence oil nuclear core and also comprises at least one additive, and described additive is preferably food and strengthens additive.
In another embodiment of the present invention, front in step (c), add additive to said preparation.This additive can be solid form or liquid form or the form of suspension of this type of reagent of two or more.Examples of such additives is selected from active medicine, naturally occurring or synthetic antioxidant, dietary supplement, vitamin, coloring agent, aromatic, oil, fat, spice, non-volatile natural essential oil or other dispersants or emulsifying agent.In some specific embodiments, this additive is selected from gamma-Linolenic acid, Citrus oil such as orange oil, nutritional supplement such as VitAVitE, vitamin C, with vitamin D, tocopherol, tocotrienol, plant sterol, vitamin K, beta-carotene, marine oil, and omega-fatty acid, CoQ10The derivant of the lipid soluble of the antioxidant that polarity is higher, such as ascorbic acid (ascobyl) fatty acid ester, plant extract are (such as, Herba Rosmarini Officinalis, Salvia japonica Thunb. and Herba Origani oil), algae extract, antioxidant (such as, BHT, TBHQ, ethoxyquin, alkyl gallates, hydroquinone, tocotrienol) with synthesis.
The instantiation of the oil that can add includes, but it is not limited to, animal oil (such as, fish oil, marine mammal oil etc.), vegetable oil (such as, Oleum Brassicae campestris (canola) or Oleum Brassicae campestris (rapseed)), mineral oil, its derivant or mixture.
This additive can be purification or partially purified oily mater such as fatty acid, triglyceride or its ester, or its mixture.
In another embodiment, this additive be at least one carotenoid (such as, lycopene), full abdomen agent (satietyagent), flavor compounds, medicine (such as, water-insoluble drug), granule, chemistry of pesticide product (such as, herbicide, insecticide, fertilizer), or aquatic products industry composition (such as, feedstuff, pigment).
The suitably instantiation of fish oil includes, but it is not limited to, Atlantic Ocean fish oil, Pacific Ocean fish oil, Mediterranean fish oil, (lightpressed) fish oil of light pressure, the fish oil that alkali processes, the fish oil of heat treatment, light and heavy brown (lightandheavybrown) fish oil, tunny fish oil, sea bass oil, halibut oil, sailfish oil (spearfishoil), Mugil cephalus oil, cod fish oil, herring oil, pilchard oil, long tail anchovy oil, hair scale fish oil, Atlantic cod oil, Atlantic herring oil, Atlantic mackerel oil, Atlantic herring oil, trout oil, shark oil etc..
After once oil or aqueousmiscible fluid are converted into solid or wax-like granule, can be filtered to reclaim the solid in suspension, or this suspension is the most so used.
When needs preserve capsule carburetion before use, formulation auxiliary agents can be added to said preparation.Which improve the stability of suspension and the ease of use.This type of formulation auxiliary agents is selected from, but is not limited to, density balance agent, surfactant, thickening agent, Biocide, dispersant, antifreezing agent, salt and its combination in any.Said preparation auxiliary agent can add in this capsule carburetion with the concentration of about 0.01%-about 30% weight of encapsulated oil product.
In order to preserve material; for separating active substances; in order to reduce the toxicity of material; in order to Protective substances is from oxidation; in order to material is delivered in concrete environment and/or in order to control the rate of release of material; the method of the present invention can be used for converting liquids to the solid of free-pouring powder or compression, and this powder or solid can be used as the parts in manufacturing final products.
In another preferred embodiment of the present invention; encapsulating solids granule can be used for the material to any load described here of patient delivery; described patient can include mammal such as mice, rat, milch cow or cattle, horse, sheep, goat; troglodyte, chimpanzee, orangutan, fish, shellfish, Crustaceans, birds are included (such as with primates; chickling, cock etc.), people or the animal (such as, Canis familiaris L. and cat) of domestication.
As was disclosed earlier, the alkanoic acid used in the methods of the invention is preferably selected from those fusing points alkanoic acid higher than 25 DEG C.It addition, a length of 10-45 the carbon of the preferred chain of this alkanoic acid.
The example of this type of acid being suitable to this application is the unsaturated acids selected from following (but not limited to): vaccenic acid or Arachidonic Acid and omega-fatty acid.The example of omega-fatty acid includes, but it is not limited to, alpha-linolenic acid (18:3-ω-3), parinaric acid (18:4-ω-3), eicosapentaenoic acid (20:5-ω-3) (EPA), docosahexenoic acid (22:6-ω-3) (DHA), clupanodonic acid (22:5-ω-3) (DPA), eicosatetraenoic acid (20:4-ω-3), 21 carbon 5 alkene acids (21:5-ω-3), clupanodonic acid (22:5-ω-3), including its any derivant and its combination in any.
The possible derivant of omega-fatty acid can include ester derivant, side chain or non-branched C1-C30Arrcostab, side chain or non-branched C2-C30Alkenyl ester, or side chain or non-branched C3-C30Cycloalkyl ester such as plant sterol ester and C1-C6 Arrcostab.
This fatty acid can extract from natural source, include but not limited to, aquatile is (such as, long tail anchovy, capelin, Atlantic Ocean morrhua, Atlantic Ocean Mylopharyngodon piceus, Atlantic mackerel, Atlantic Ocean catfish, salmon, sardine, shark, tuna etc.) and plant is (such as, Caulis et Folium Lini, vegetable etc.) and microorganism (such as, fungus and algae).
The concentration of the oil being contained in preparation, for the application when needing to be converted into oil solid, can change between 0.01-90%, and preferably 60% or higher, or during Pyrethrum the most encapsulated for aqueous formulation, in the range of 25%.
In a preferred embodiment of the invention, the encapsulated material being suitable to animals consuming obtained is powder type anhydrous, free-pouring.These materials have the high reactivity reagent level reaching and keeping consistent, and/or the advantage of outstanding non-oxidizability.Encapsulated material prepared by this use capsule agent of the present invention reaches consistently and keeps the activating agent of high relative contents.This activating agent can exist with amount based on encapsulated material about 5-90% (wt/wt).In another embodiment, described activating agent exists with the amount of about 15-60% (w/w).The activating agent needing high-load reduces the cost preparing final products, because encapsulated reagent is typically much more expensive.Additionally, some encapsulated reagent can produce disadvantageous or unwanted character to final system, it is therefore desirable to reduce the amount of the capsule used.
Encapsulated form at some reagent introduces some reagent and also provides and overcome the problem relevant to the insoluble or low-solubility of reagent in medium.Therefore, encapsulated food additive, such as vitamin, it is provided that the additive of a kind of form, it can be dissolved or dispersed in food with certain concentration, and this concentration is uniform and measurable.
Being important not only for the activating agent obtaining high-load, it is also important for keeping its longer storage life simultaneously.In order to increase non-oxidizability further, antioxidant and/or reducing agent can be added in oil.When as powder storage, this encapsulated material is stable, and once be exposed in dampness its release bioactive agent.The encapsulated material obtained can use in any required level, and its amount depends on the amount of activating agent to be mixed and to be used in product therein.
In an embodiment wherein using encapsulated material in food product, this encapsulated material uses with the amount of about 0.01-about 10% weight of food product, and in another embodiment, its amount is up to about 5% (w/w).
The solid encapsulated granule of the present invention can use in food.Term as used herein " food " refers to be consumed by receptor people, animal or fish any goods of (such as, eat, quote or digest).
In one embodiment, the solid encapsulated granule of the present invention can be used as nutritional supplement for food.In another embodiment of the present invention, this food can be baked goods (bakedgood), pasta, meat products, frozen dairy, milk product, cheese product, egg products, flavoring agent, powder (soupmix), dessert (snackfood), nut product, plant protein preparation, boiled goods, soft candy, poultry products, the fruit juice of processing, Saccharum Sinensis Roxb. is (such as, white or brown), sauce, gravy, syrup, nutrition bar (nutritionalbar), beverage, dry beverage powder, fruit jam or fruit jelly, the food that fish product or house pet are liked.On the other hand, this food is bread, tortilla, cereals, sausage, Carnis Gallus domesticus, ice cream, Yoghurt, milk, salad dressing, Testa oryzae, fruit juice, dry beverage powder, roll, cooky, cookies, fruit group or cake.
In another embodiment, the solid encapsulated granule of the present invention can use in pharmaceutical preparation.Pharmaceutical preparation may also comprise other carrier, and thickening agent, diluent, buffer, preservative, surfactant and other component.Pharmaceutical preparation may also comprise one or more other active component, and itself maybe can not think active medicine such as antimicrobial, antiinflammatory, anesthetis etc..
In another embodiment of the present invention, the solid encapsulated granule prepared by any one method disclosed herein can be used in personal care product, and this personal care product includes Antiperspirant, deodorizer, soap, aromatic and cosmetics;Hair care product, such as hair jelly, mousse, shampoo, cream rinse, and hair jelly;Paper product such as diaper, cotton wool, napkin, cotton paper, toilet paper;Animal care products such as cat muck;With homebrew such as carpet cleaner and air freshener.
The fatty acid (such as, capric acid, or stearic acid or Palmic acid) added in oil can be as surfactant to form oil dispersion liquid in an aqueous medium.However, it may be desirable to ion-type or nonionic surfactant.This type of surfactant can add during manufacturing microcapsule, for the convenient or size of control microcapsule, and/or adds after manufacturing microcapsule, for the broken gel formed by micro encapsulation, and obtains the non-gel preparation of flowing.A kind of preferably surfactant is sodium lauryl sulphate (SDS).It preferably adds with the concentration of 0.1-10%, and most preferably concentration is 0.5%-5%.
The limiting examples of other preferred additive, in addition to surfactant, also has stearic isolation polymer (stearicbarrierpolymer), it helps to maintain granule and separates, such as polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and poly-(ethyoxyl) nonyl phenol.In some cases, its pH needing to regulate the microcapsule formulation made, such as, when the solution of the microcapsule made is with other insecticide composition.The conventional reagent for regulating acidity or alkalescence that can use, including such as, hydrochloric acid, citric acid, sodium hydroxide, sodium carbonate and sodium bicarbonate.Other the stabilizer that can add is alginate, xanthan gum, carboxymethyl cellulose, sodium salt, xanthan gum, Karya glue and locust bean gum etc..
Available PVP has various molecular weight, its scope from about 20,000-about 90,000, and all these can use, but preferably from about 40, the PVP of 000MW.Poly-(ethyoxyl) nonyl phenol can obtain with trade (brand) name Igepal, and it has various molecular weight, and it depends on the length of oxyethyl chain.Can use poly-(ethyoxyl) nonyl phenol, but preferably Igepal630, it shows that molecular weight is about poly-(ethyoxyl) nonyl phenol of 630.Other example of surfactant includes polyether block copolymer, such as Pluronic and Tetronic, and the polyethylene oxide adducts of fatty alcohol, such as Brij surfactant, and the ester of fatty acid, such as stearate, oleate etc..The example of this type of fatty acid includes sorbitan stearate, sorbitan monooleate, Sorbitan sesquioleate etc..The example of the alcohol moiety of fatty ester includes glycerol, glucosyl group etc..Fatty ester is commercially available usually used as ArlacelC.R surfactant.Surfactant changes on the living property on their surface, and this surfactant properties affects the size of the microcapsule formed.In the case of other condition is equal, using 40, the PVP of 000MW can provide the microcapsule bigger than Igepal630.The surfactant used, and shake degree and scope, all affect the size of the microcapsule obtained.In a word, their size can be about 1-about 100 microns, and this depends on used environment.Other the surfactant forming dispersion liquid and emulsifying agent can also use, such as sodium, potassium, magnesium and calcium or the ammonium salt of lignin sulfonate.
As it was previously stated, this encapsulating solids granule can reclaim from reactant mixture or Eddy diffusion is out at described nonvolatile carrier or in the solution comprising it.Or, any medium comprising microcapsule, aqueous or nonaqueous, can be processed, and need not from its medium manufactured (water) with at least one nonvolatile carrier initially-separate out.At most of conditions, described medium is water.In the case of preferable separate, can be by centrifugal or filter and realize the collection of microcapsule, it depends on their size, and with several parts suitable solvent such as distilled water wash, thus the reactant dissociated from surface removing.
It addition, these granules dispersible or are suspended in described nonvolatile liquid or solid carrier.In some cases, described nonvolatile carrier is granular solids, such as powder, and this dispersion is preferably prepared with described carrier by the dry microcapsule of mixing effective dose.In some cases, described nonvolatile carrier is liquid, and this suspension is preferably prepared by the microcapsule of mechanical agitation effective dose in described carrier.
Therefore, also providing for a kind of method preparing edible microcapsule, described method includes:
A at least one alkanoic acid is mixed by () with at least one quintessence oil;
B the mixture of step (a) is mixed to obtain suspension by () with alkaline aqueous solution;
C () is mixed into the aqueous saline solution comprising at least one polyvalent cation to the suspension of step (b), and
D () collects described microcapsule from this aqueous medium, thus obtained the microcapsule of at least one microencapsulated essential oils.
These microcapsules may be added in food compositions (meat crossed such as sausage, Salar rice sausage (salamis) and common process, all types of cheese etc.), to prevent from or to delay being become sour by what microorganism caused or being faded.Encapsulated essential oil preparation also can comprise food preservative, and it includes, but not limited to benzoic acid, sodium benzoate, and calcium propionate, nipagin, aethyl parabenum, propyl parabene or Butyl Chemosept.
This preservative or food additive microcapsule can comprise 0.01-5% or the quintessence oil of preferably 0.1% and 1% and the benzoic acid of 0.1% or p-Hydroxybenzoate.This composition can add in food the most separately or together.Encapsulated essential oil can add under the level of taste or taste not affect, if or when needing abnormal smells from the patient or the taste of this quintessence oil, can add with high level.In some cases, using encapsulated essential oil additive or preservative, so that the concentration of its oily, derivant or active component is between 0.01% and 1%, and the concentration of benzoic acid or p-Hydroxybenzoate is 0.01%-1%.
In one embodiment of the invention, said preparation comprises fennel oil and nipagin, and wherein this fennel oil uses with the concentration of 0.2%, and this nipagin uses with the concentration of 0.1%.
Essential oil formulation as food preservative can suppress many microorganisms effectively, e.g., and is not limited to this: Listeria monocytogenes (Listeriamonocytogenes);Intestinal Salmonella (Salmonellaenteriditis);Staphylococcus aureus (StaphylococcusAureus) and vancomycin resistant enterococci belong to (Enterococcus).
This quintessence oil be selected from those with reference to other application as was disclosed earlier there is antimicrobial and/or the quintessence oil of antifungal character.The example of this type of quintessence oil that can use is tea tree oil, thyme oil, Oleum Caryophylli, Eucalyptus oil and Herba Origani oil, citronella oil, basil oil, Oleum Anisi Stellati and fennel oil.
Embodiment 1:
Capric acid (12gr) is dissolved in tea tree oil (100gr).(high shear agitation device) 250ml adding to the solution obtained quickly stir contains the H of PVA (2.5gr)2In the solution of O.Wherein, addition is dissolved in H2MgCl in O (20ml)2Hexahydrate (22.8gr), and by solution stirring 2 hours, add thereafter guar gum (3gr), it continues other 2 hours of stirring.
When said preparation is added to sausage, which prevent the growth of antibacterial and fungus.
Embodiment 2:
Repeat embodiment 1, tea tree oil 125g Oleum Caryophylli is replaced.The solution obtained is added in white and yellow cheese during white and yellow cheese manufacture, effectively controls antibacterial and fungus growth.
Embodiment 3:
Obtain the encapsulated of cod liver oil powder as steps described below:
Solution A is prepared by being dissolved in the cod liver oil of 75gr. by the stearic acid of 25gr. at 70-80 DEG C.
Solution B is by adding in solution A by the NaOH of 3.5gr. solution in 30ml water, and stirring simultaneously is prepared for 10 minutes.
Solution C is by by the CaCl of 7gr.2·2H2O solution in 70ml water adds in the mixture of solution A+B, and stirring simultaneously is prepared for 10 minutes.
Reactant mixture is filtered by Bu Shi (Buchner) funnel, and air is dried.Then 10gr dry products is mixed with 2.5grAerosil200 or 300, with absorb remaining not-capsule carburetion.Final products contain 60% cod liver oil as active component.
This encapsulated product has fishlike smell.When whole dissolving and encapsulation step being carried out under nitrogen atmosphere, product no longer has a fish like smell.
Embodiment 4:
The encapsulated oil used in manufacturing animal feed according to following preparation:
Solution A is prepared by the stearic acid of 25gr. is dissolved at 60 DEG C the vegetable oil of 75gr.
Solution B is by adding to prepare in solution A in the solution of 30ml water by the NaOH of 3.5gr under 60 DEG C and stirring.
Solution C is passed through the CaCl of 7gr at 60 DEG C2·2H2O solution in 70ml water adds in the mixture of solution A+B, and stirring simultaneously is prepared for 10 minutes.
By this reactant mixture by filtered on buchner funnel, and at room temperature air is dried.10gr. dry matter is mixed with 2.5gr.Aerosil200 or 300.Final products contain the vegetable oil of 60% as active component.
Embodiment 5:
Realize encapsulated in stearic acid/Ca salt of Pyrethrum in accordance with the following steps:
Solution A is prepared by the stearic acid of 15gr. is dissolved at 60 DEG C the Pyrethrum of 50gr..
Solution B is by adding in solution A by the NaOH of 2.1gr. solution in 20ml water, and stirring simultaneously is prepared for 10 minutes.
Solution C is by by the CaCl of 4.2gr.2·2H2O solution in 40ml water adds in the mixture of solution A and B, and stirring simultaneously is prepared for 10 minutes.
Solution D is prepared by being mixed with 10gr.SDS, 0.4gr.Irganox1076,0.4gr.Tinuvin770 and 850ml water by the mixture of solution A, B and C.High-speed shearing Mixer is used to stir 30 minutes this reactant mixture.Use citric acid by pH regulator to 7.Reactant mixture is stirred for 30 minutes, now adds 3.5gr.Rodopol24, and stir 30 minutes.

Claims (16)

1. the method preparing the essential oil formulation of micro encapsulation, the essential oil formulation of this micro encapsulation is the form of suspension of microcapsule, and the most each microcapsule comprises at least one quintessence oil, and described method includes:
A at least one alkanoic acid is mixed by () with at least one quintessence oil;
B the mixture of step (a) is mixed to obtain suspension by () with alkaline aqueous solution;With
C () is mixed into the aqueous saline solution comprising at least one polyvalent cation in the suspension of step (b), thus obtain comprising the suspension of the microcapsule of at least one quintessence oil described.
Method the most according to claim 1, the suspension of wherein said microcapsule comprises multiple microcapsule, each has the nuclear core comprising at least one quintessence oil and surrounds the outer shell of described nuclear core.
Method the most according to claim 1, wherein said alkaline aqueous solution is the aqueous solution of at least one of sodium hydroxide or potassium hydroxide.
Method the most according to claim 1, wherein said polyvalent cation is selected from the cation of Ca, Mg, Fe and Al.
Method the most according to claim 1, the melting temperature of wherein said alkanoic acid is higher than 25 DEG C and/or has 10-45 carbon atom.
nullMethod the most according to claim 5,Wherein said alkanoic acid is selected from capric acid、Dodecylic acid、Tetradecanoic acid、Hexadecanoic acid、Octadecanoid acid、Arachic acid、Behenic acid、Lignoceric acid、Vaccenic acid、5,8,11,14-eicosatetraenoic acid and omega-fatty acid,Wherein said omega-fatty acid is selected from [α]-linolenic acid (18:3-ω-3)、Parinaric acid (18:4-ω-3)、Eicosapentaenoic acid (20:5-ω-3)、Docosahexenoic acid (22:6-ω-3)、Clupanodonic acid (22:5-ω-3)、Eicosatetraenoic acid (20:4-ω-3)、21 carbon 5 alkene acids (21:5-ω-3) and clupanodonic acid (22:5-ω-3),Or described omega-fatty acid is above two or the mixture of multiple omega-fatty acid.
7. the process of claim 1 wherein that at least one described quintessence oil is antimicrobial essential, thus obtain the essential oil formulation of antimicrobial micro encapsulation.
8. the process of claim 1 wherein that at least one described quintessence oil is anthelmintic and/or insecticide, thus obtain the essential oil formulation of the micro encapsulation of anthelmintic or the essential oil formulation of the micro encapsulation of parasite killing.
Method the most as claimed in one of claims 1-8, it also includes adding carrier and/or sealing coat forming agent and/or at least one absorbent and/or at least one is selected from following additive: active medicine, naturally occurring or synthetic antioxidant, dietary supplement, vitamin, coloring agent, aromatic, oils, fat, spice and dispersant.
Method the most as claimed in one of claims 1-8, it also includes adding carrier and/or sealing coat forming agent and/or at least one absorbent and/or at least one ion-type or nonionic surfactant and/or at least one is selected from following additive: insect growth regulator, IGR (IGR), insecticide, antifungal and non-volatile natural oil.
11. methods as claimed in one of claims 1-8, it also includes adding carrier and/or sealing coat forming agent and/or at least one absorbent and/or at least one ion-type or nonionic surfactant and/or at least one is selected from following additive: Acaricide, nematicide and ectoparasiticide.
12. the process of claim 1 wherein and farther include filter from described suspension and collect this microcapsule.
The method of 13. claim 12, the most also adds in the microcapsule of described separation and a small amount of can absorb any unencapsulated pick up the oil agent.
The method of 14. claim 9, wherein said absorbent is selected from cellulose, starch powder and Aerosil silicon dioxide.
The method of 15. claim 10, wherein said absorbent is selected from cellulose, starch powder and Aerosil silicon dioxide.
The method of 16. claim 11, wherein said absorbent is selected from cellulose, starch powder and Aerosil silicon dioxide.
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