CN1875708A - Method of controlling acarian and device for use in the same - Google Patents
Method of controlling acarian and device for use in the same Download PDFInfo
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- CN1875708A CN1875708A CN 200610079834 CN200610079834A CN1875708A CN 1875708 A CN1875708 A CN 1875708A CN 200610079834 CN200610079834 CN 200610079834 CN 200610079834 A CN200610079834 A CN 200610079834A CN 1875708 A CN1875708 A CN 1875708A
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- farnesyl acetone
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Abstract
A method for controlling Acarina, which includes allowing a gaseous compound having the formula (I) wherein < > is a single bond or a double bond, to be present at a concentration of 0.001-20,000 mug/L in a space where Acarina repellence is intended, and an apparatus capable of effectively controlling Acarina are provided.
Description
Technical field
The present invention relates to control the method for Acarina mite, the device of Shi Yonging for this reason, described method comprises with having wherein
Be that the compound steam of the following formula (I) of singly-bound or two keys is full of for a long time with specific concentrations and does not expect to produce the environment that Acarina mite is disliked thus in the space that Acarina mite exists, force Acarina mite to leave this space and prevent new invasion simultaneously.
Background technology
Well-known Acarina mite not only harms the crops, and gives the people's uncomfortable feeling and the harm of sucking blood, and the disease in the brain inflammation that for example causes because of Acarina mite of propagation serious disease, relapsing fever, autumn yochubio etc. and the livestock.In recent years, along with health with increase at home popular of clean environment thought, the incidence of disease of the communicable disease that Acarina mite is propagated descends gradually.On the other hand, observed thus the increase of the anaphylactic disease that causes as anaphylactogen, the anaphylactic disease for example one of the main reasons of atopic dermatitis, bronchial astehma, rhinitis etc. is considered to indoor Acarina mite.The number increase of indoor Acarina mite is mainly owing to improved living environment, and to Acarina mite more and more advantageous environment such as the airtight dwelling house of height popular, winter indoor heating system performance improvement, the fiber product that is used for the indoor design westization more and more etc. enlarged harm.Therefore, consumingly need be at their countermeasure.
With regard to countermeasure, miticide for example organophosphorus ester, carbamate etc. is normally used widely.But, because these reagent major parts comprise the high toxicity compound as active component, so there is the problem of harm humans and livestock in they.Although occurred many hypotoxicity pyrethroid reagent in recent years,, so just can not get rid of to the problem of human and animal health and to the influence of environment as long as their validity performance mechanism is based on biocidal activity.
On the other hand, not based on biocidal activity and the Acarina mite controlling agent that is based on anthelmintic action also is known.There is not the pest repellant of biocidal activity to be considered to provide simultaneously the high security and the effective extermination of disease and insect pest.The inventor finds that the compound with following array structure has Acarina mite expulsion property, and has proposed to comprise the Acarina mite controlling agent (seeing JP-A-10-316507) of this compound.
Farnesyl acetone
With the known organophosphorus ester of routine-, pyrethroid-compare with the miticide of carbamate type and other type, this Acarina mite control agent has more advantage, because (1) it has low acaricidal activity, can drive away Acarina mite and do not stay the Acarina mite corpse in environment, this corpse is potential anaphylactogen, and (2) Acarina mite is not easy to obtain resistance, (3) it is to people and domestic animal high safety, or the like.
Above-mentioned publication discloses farnesyl acetone can be used to control Acarina mite.Yet its unexposed Acarina mite control agent can not wished in the space that insect exists and effectively effectively controls Acarina mite by farnesyl acetone is remained on the valid density scope.
Summary of the invention
The inventor has carried out detailed research, finds to make the gaseous compound (after this being also referred to as compound (I)) of formula (I)
Wherein
Be singly-bound or two key, with 0.001-20, the specific concentrations of 000 μ g/L appears at plans can to control Acarina mite especially effectively in the space of expulsion Acarina mite, compound (the phytone of formula (I ') in addition, after this be also referred to as compound (I ')) also have excellent Acarina mite control action, thus finished the present invention.
Therefore, the invention provides a kind of being included in plans the space of expulsion Acarina mite and keeps the method for effective control Acarina mite of concentration in expulsion valid density scope of compound (I), a kind of method and apparatus that obtains such valid density efficiently and a kind of inclusion compound (I ') the Acarina mite controlling agent as active component for a long time.Therefore, the invention provides following aspect.
(1) a kind of method of controlling Acarina mite, it is included in plans gaseous compound that space of expulsion Acarina mite keeps formula (I) at 0.001-20, the concentration of 000 μ g/L,
Wherein
Be singly-bound or two key.
(2) method of above-mentioned (1), wherein above-mentioned concentration are to be obtained by the compound that evaporates intensifier evaporation formula (I).
(3) method of above-mentioned (1) or (2), wherein above-mentioned concentration are that the compound by disengagement area expanding unit evaporation formula (I) obtains.
(4) method of above-mentioned (2) or (3), wherein evaporating intensifier is heater.
(5) method of above-mentioned (2) or (3), wherein evaporating intensifier is blowning installation.
(6) a kind of equipment of controlling Acarina mite comprises the storage device of reagent of a compound that comprises formula (I) and the device of the compound evaporation that strengthens formula (I).
(7) equipment of above-mentioned (6) further comprises the disengagement area expanding unit of the compound of formula (I).
(8) equipment of above-mentioned (6) or (7), wherein evaporating intensifier is heater.
(9) equipment of above-mentioned (6) or (7), wherein evaporating intensifier is blowning installation.
(10) a kind of Acarina mite controlling agent that comprises phytone as active component.
Brief description of drawings
Fig. 1 has explained the Acarina mite expulsion test of being undertaken by improved glass tube method.
Fig. 2 has explained the Acarina mite expulsion test that prevents that by improved the intrusion method from carrying out.
Embodiment
Compound (I) is a compound known, as synthesis example such as vitamin E and vitamin K
2The raw material of side chain by chemosynthesis on a large scale.Compound (I ') be wherein
It or not the compound (I) of two keys.Therefore, the reagent that is used for the inclusion compound (I) of the inventive method can be used as the Acarina mite controlling agent (after this abbreviate of the present invention reagent) of inclusion compound (I ') as active component.Therefore unless depart from context especially, also refer to compound (I ') when referring to compound (I) in this manual simply.When
When being two key, compound (I) comprises multiple geometric isomer based on the different connection site that are connected with two keys (cis, trans).Being used for compound of the present invention (I) can be any of these geometric isomers, the perhaps mixture of two or more in these geometric isomers, wherein specifically restriction of blending ratio.
Depend on evaporation conditions, ambient environmental conditions etc., " gaseous state " of gaseous compound of the present invention (I) comprises the mist attitude.
The concentration of gaseous compound (I) is not less than 0.001 μ g/L at least in being intended to drive away the space of Acarina mite, preferably is not less than 0.01 μ g/L, is no more than 20,000 μ g/L at the most, preferably is no more than 2,000 μ g/L.When concentration during less than 0.001 μ g/L, do not find the Acarina mite control efficiency, when it surpassed 20,000 μ g/L, the smell that compound (I) produces became and makes us strong and impracticable offensively.
The space that is intended to drive away Acarina mite is about size, and aspects such as shape do not have any concrete restriction, because can adjust the consumption of compound (I) and using method so that can obtain above-mentioned concentration.
The reagent of inclusion compound in this context (I) is meant the unification compound and the dilution by obtaining with thinner diluted compounds (I) of compound (I), or comprising the reagent of other carrier, described carrier not only comprises liquid but also comprises solid.As thinner, can use any inorganic or organic diluent, as long as it does not apply adverse effect to compound (I).As thinner, can use solvent, fragrance retention agent, humectant etc.Among these, preferably have high security as those of cosmetic raw materials, for example can mention alcohols such as ethanol, isopropyl alcohol etc., ketone such as acetone etc., ester class (low boiling) is as ethyl acetate etc.; Silicone oil, polyethylene glycol, polypropylene glycol, jojoba oil, saualane, atoleine, rapeseed oil, cottonseed oil, tung oil, camellia oil, other vegetable oil (high boiling point oil) etc.Additive such as emulsifier etc. can also be added the thinner of compound (I) and mixture is used as water-dispersible agents.As additive, for example, can mention alkylbenzenesulfonate, alpha-alkene sulfonate, paraffin sulfonate contains four ammonium salts of chain alkyl, aliphatic series one or diglycollic amide, the ether of (gathering) glycol ester or fatty acid, mono fatty acid glyceride, the sorbitan ester of fatty acid, polyethylene glycol oxide sorbitan fatty acid esters, alkyl phenyl polyethylene oxides ether, N-alkyl betaine-type or sulfobetaines type surfactant etc.Among these, preferably have high security as those of cosmetic raw materials, as sulfo-succinic acid monooctyl ester sodium, polyoxyethylene sorbitan monolaurate etc.In addition, as required, the reagent of inclusion compound (I) can comprise auxiliary agent in addition, stabilizing agent, thickener, colouring agent, condiment etc.
The compound that comprises formula (I) as the evaporation capacity is with the method for the liquid reagent of the concentration that obtains gaseous compound (I) in being intended to drive away the aforesaid space of Acarina mite, can use anyly can realize the method for purpose and do not have concrete restriction.Below particularly with show this method exemplaryly and realize the device of this method.
A kind of method, comprising the reagent that will contain compound (I) is placed in the container with porous wall, described container such as biscuiting pottery, sintering metal etc. ooze out at container outer surface at the reagent of inclusion compound (I) and to make compound (I) from whole outer surface evaporation on every side later on.The container that has porous wall in this method is equivalent to the storage device of the reagent of inclusion compound in apparatus of the present invention (I), and is a kind of disengagement area expanding unit.The storage device of the reagent of inclusion compound (I) is not limited to said vesse and not specifically restriction, as long as it can store the reagent of inclusion compound (I) until evaporation.For example, device can be a storage device, the reagent that is specially inclusion compound (I) is kept in container such as glass or the plastic bottle etc., reagent is assigned in the container that closes, when using, the part of container is cut, or uncap and content is transferred in disengagement area expanding unit or the container, depending on its embodiment, the disengagement area expanding unit of explained later can also be a storage device.
As distinct methods, can mention a kind of method, this method comprises cloth, rope or a spongiform end with disengagement area expanding unit of wide surface area is immersed in the storage device of reagent of inclusion compound (I), make the disengagement area expanding unit absorb the reagent of inclusion compound (I) by capillarity thus, perhaps that the reagent of inclusion compound (I) is without interruption to the disengagement area expanding unit from the storage device of the reagent of inclusion compound (I), reagent is absorbed, from the surface evaporation compound (I) of disengagement area expanding unit.The example that is used for the disengagement area expanding unit of this method comprises native fiber such as paper pulp, cotton, hemp etc.; Synthetic fibers such as polyester etc.; Paper, fabric, knitting, felt of producing by glass fibre and nonwoven etc.; Spongiotic article, it is the loose structure of being made by synthetic resin or glass; Also have in addition, by the rope of synthetic resin or glass production, knitting, doughnut fabric or the like.These are specifically restriction not, as long as they can expand the disengagement area of compound (I).Although be difficult to provide the concrete numeral that it evaporates required wide surface area, because the condition of its basis such as disengagement area expanding unit etc. changes, surface area is wide more, may promote effective evaporation more.The surface area of measuring the surface area of porous mass and fiber product is difficulty very, but 50cm at least
2, preferably be not less than 100cm
2Surface area be actual.In the situation of wide surface area, be included in the concentration of the compound (I) in the reagent by reduction, the concentration that is intended to drive away the compound (I) in the space of Acarina mite can be adjusted to and belong in the above-mentioned scope, in the situation of little surface area, be included in the concentration of the compound (I) in the reagent by enhancing, the concentration of the compound in the space (I) can be adjusted to and belong in the above-mentioned scope.
As the distinct methods of the purpose that realizes mentioning in the aforementioned paragraphs, can mention a kind of method, it comprises and will contain the reagent coating of compound (I) or be sprayed on the disengagement area expanding unit with wide surface area.In this case, the disengagement area expanding unit is equivalent to the storage device of the reagent of inclusion compound (I).As the example of this coating or sprayer unit, can mention brush, sprayer is directly sprayed from bottle container, uses dropper to drip, and uses watering can spraying etc.
Be coated with and be sprayed on the disengagement area expanding unit and can carry out one or many, and can be suitably in conjunction with coating and spraying.For repeatedly coating or spraying, calculate interval between each coating and the spraying based on the actual measurement of compound (I) extinction time or its theory hypothesis, preferably before the interval stops period or when it stops, implement coating or spray.Recommendation should attach the service manual of this method of description.
As mentioned above, also can promote the evaporation of compound (I) by the surface area that increases the disengagement area expanding unit.Because compound (I) has high boiling point, more preferably use the evaporation intensifier to come forced evaporation compound (I).Therefore, in another embodiment of the present invention, preferably, will explain this device below by using evaporation intensifier warp or obtaining above-mentioned concentration without disengagement area expanding unit forced evaporation compound (I).
Owing to, therefore can use any device as long as the evaporation intensifier can just be not specifically limited by forced evaporation compound (I).Compound (I) can be intended to evaporate separately or when evaporation is included in other material in the reagent that contains compound (I) with compound (I), compound (I) can be evaporated.
As this device, can mention heater and blowning installation.For example, when heater is used as the intensifier of evaporation compound (I), as an embodiment that realizes the object of the invention, can mention the equipment (preferably being equipped with temperature control equipment in addition) that is equipped with heater that uses, the reagent that will be included in the inclusion compound (I) of device inside by heater and temperature control equipment is heated to proper temperature, and evaporates compound (I) from the surfaces externally and internally and/or the outer surface of device.In another embodiment, operative installations, wherein this device combines with the above-mentioned disengagement area expanding unit with wide surface area, one end of disengagement area expanding unit is immersed in the holder that comprises the reagent that contains compound (I) so that absorb by capillarity, perhaps give the disengagement area expanding unit so that absorb with the reagent of inclusion compound (I) is without interruption, by heater and temperature control equipment the storage device or the disengagement area expanding unit of the reagent of inclusion compound (I) is heated to proper temperature, with forced evaporation compound (I).As above-mentioned heater, can mention by heating wires such as nichrome wire etc. and give birth to heat, low energy light source such as indicator lamp etc.As the said temperature control device, bimetallic is a most convenient, but can use by with thermocouple, and the temperature of detections such as thermistor input CPU control is supplied to the device of the electric power of heating wire.
When with blowning installation as evaporation during intensifier, can mention by blowning installation air is blowed to the use that the evaporation of reagents area expanding unit that absorbs inclusion compound (I) comes the device of forced evaporation compound (I).As this blowning installation, can mention fan such as propeller fan, sirocco fans etc. have the pump (for example being used for air is sparging into the pump of water tank when breeding goldfish) of film and valve etc.As different embodiments, can mention such device, wherein combine heater and blowning installation are paired, in the disengagement area expanding unit reagent of inclusion compound (I) is heated to proper temperature with forced evaporation compound (I) by sending hot-air.
With regard to the heating-up temperature of heater,, preferably be no less than 10 ℃ temperature than this flash-point is low because the flash-point of compound (I) is about 110 ℃ low and about 160 ℃ height.This temperature need be adjusted suitably according to the character of the thinner that uses together etc.For example it is 50-110 ℃, preferred 60-100 ℃.In addition, the wind speed of blowning installation is preferably 0.001-5m/sec, and air capacity is preferably 0.001-10L/sec.
Regularly be coated with or be sprayed at by the reagent with inclusion compound (I) and be placed on the indoor article, can make gaseous compound (I) with 0.001-20, the concentration of 000 μ g/L is present in and is intended to drive away in the space of Acarina mite.As these article, for example can mention carpet, Couch cushion (tatamimat), bed clothes, stuffed toy, cylindrical fireworks, vase is decorated statue, artificial flower and be placed on other indoor article usually.In one embodiment of the invention, can mention a kind of method, its reagent that comprises inclusion compound (I) adds in floor wax or other buffing compound, floods disposable type of mop with it, reusable mop etc., and coating window still, threshold, screen windows etc. are according to this method, can prevent the invasion of Acarina mite, and by Acarina mite being driven away from wide surface area evaporation compound (I) with the room or near the steam that coating surface is full of compound (I).The article of having used the reagent of inclusion compound (I) are equivalent to be used for the storage device and the disengagement area expanding unit of the reagent of inclusion compound (I).
The reagent of inclusion compound (I) can adopt any dosage form, as tablet, and pill, capsule, cream, ointment, aerosol, powder, liquid, emulsion, supensoid agent etc.Although reagent of the present invention can use separately, it also can use simultaneously with other Acarina mite control agent.In addition, can add effective other component of Acarina mite control so that unitary agent to be provided.
For the ease of the use of reagent of the present invention, except compound (I), preferably add solvent, carrier, emulsifier, stabilizing agent etc. to be providing preparation, and be processed into dilution etc. as required and use preparation.When needs, can add or,, keep material, paint, carrier, condiment or colouring agent etc. as antioxidant in conjunction with other component.Preferably make condiment or colouring agent play indicant, this indicant notice is replaced the opportunity of the article that use reagent control Acarina mite of the present invention.For example, have than the more lower boiling condiment of compound (I) the preferred adding, when using beginning, and the fragrance that the article of its Acarina mite out of hand have before compound (I) disappears, the perhaps clear variation that shows fragrance.
In compound (I), contain those quilt oxidations gradually in air of two keys.In order to prevent this problem, preferably add or use antioxidant simultaneously.As antioxidant, for example, use the antioxidant such as the vitamin E of phenols type, butylated hydroxytoluene, Irganox 1010, Irganox 1076 etc.; The antioxidant of polyphenol type such as tannic acid, gallic acid (gellic acid) etc.Its consumption is preferably the 0.001-10wt% with respect to compound (I), more preferably 0.1-5wt%.
As the Acarina mite control composition that except compound (I), can add, for example can mention and have compound such as the DEET that drives the Acarina mite effect, 2,3,4, two (Δ 2-the butylene)-tetrahydrofurfurals of 5-, pyridinedicarboxylic acid di-n-propyl ester, dibutyl succinate, 2-ethoxy octyl group thioether, 2-tertiary butyl-4-hydroxy anisole, 3-tertiary butyl-4-hydroxy anisole, 2,2,3,3-Tetramethylcycloprop-ne-ne carboxylic acid 1-acetenyl-2-methyl-amylene ester, N-hexyl-3,4-dichloro maleimide etc.Can use the Acarina mite control agent that comprises these components simultaneously with reagent of the present invention.
As above-mentioned solvent, can use any solvent, as long as it does not apply adverse effect to compound (I).As this solvent, for example can mention alcohols such as ethanol, isopropyl alcohol etc.; Silicone oil, polyethylene glycol, polypropylene glycol, jojoba oil, saualane, atoleine; Rapeseed oil, cottonseed oil, tung oil, camellia oil, other plant wet goods.Its consumption is preferably the 10-99wt% of whole preparation, more preferably 50-95wt%.
As above-mentioned carrier, can use any carrier, as long as it does not apply adverse effect to compound (I).As this carrier, for example can mention silica, active carbon, porous calcium phosphate zirconium, Woelm Alumina, diatomite, perlite, vermiculite, zeolite, galleon soil, wood powder, wood chip etc.
As mentioned emulsifier, can use any emulsifier, as long as it does not apply adverse effect to compound (I).As this emulsifier, for example can mention alkylbenzenesulfonate, alpha-alkene sulfonate, paraffin sulfonate contains four ammonium salts of chain alkyl, aliphatic series list or diglycollic amide, the ether of (gathering) glycol ester or fatty acid, mono fatty acid glyceride, the sorbitan ester of fatty acid, the polyethylene glycol oxide sorbitan fatty ester, alkyl phenyl polyethylene oxides ether etc.Its consumption is preferably the 5-90wt% of whole preparation, more preferably 10-50wt%.
As the aforementioned stable agent, can use any stabilizing agent, as long as it does not apply adverse effect to compound (I).As this stabilizing agent, for example can mention polyvinyl alcohol, gelatin, carboxymethyl cellulose, PVP(polyvinyl pyrrolidone), polyethylene glycol, polyethylene glycol (macrogol), Acacia, starch etc.
As the above-mentioned material of keeping, can use any material of keeping, as long as it does not apply adverse effect to compound (I), and comprise thermoplastic resin, wax, gel, various capsules etc.
The reagent of inclusion compound (I) can be solid.As adding, for example can mention thermoplastic resin, wax, gel, microcapsules, porous inorganic particulate etc. to produce the material of keeping of solid.
The reagent that comprises the compound (I) that is used for the inventive method can be the shaping solid.The shaping solid can be taked particle, ball, and rod, sheet, piece, thin slice, any form in the sponge etc., and can be used as the closet dusting flour, underground dusting flour etc., or as upholstery, as the ornamental decoration statue of alcove, vase, calendar, tapestry, candle etc.In addition, formed product can be used for allowing the container of compound (I) in the easy evaporation of indoor critical positions.By adopting the form of formed product, to compare with using as aforesaid liquid, compound (I) can evaporate over a long time.
About thermoplastic resin, the use with resin of remarkable high molding temperature cause the evaporation of compound (I) etc. and on the compound of kneading during the molding (I) or its dilution significant white cigarette generate.Therefore, preferably use molding temperature, preferably be no more than 160 ℃, more preferably no more than 140 ℃ thermoplastic resin less than 200 ℃.Contrast therewith has the use of significantly hanging down the resin of molding temperature, because the high viscosity of resin causes limited use.Therefore, preferably use molding temperature to be not less than 50 ℃ resin.As preferred thermoplastic resin, for example can mention low-melting-point resin such as soft propene acid resin, comprise (methyl) acrylate-copolymer, the soft propene acid resin, it is prepared to the nucleocapsid structure of partly being made up of rubber part and animi resin, ethylene-vinyl acetate copolymer resin, poly-(trans-isoprene) resin, thermoplastic elastomer (TPE) by preparations such as block polymerization styrene-butadiene or isoprene, poly--6-caprolactone, poly--D, the L-decalactone, polydioxinone, polyurethane resin etc.Preferably by test set one from resin, do not have seepage compound (I) but upper limit amount and in this limit, select the highest energy to determine that the amount of compound (I) of adding thermoplastic resin is to extend the expiration date.For example, when the soft propene acid resin was used as thermoplastic resin, the amount that adds compound (I) was preferably 10-50wt%.
As wax, for example can mention higher alcohol, candelilla wax, rice wax, carbawax, Japan tallow, cera flava, microwax, Tissuemat E, stearic acid, paraffin, vaseline, spermaceti, tallow etc.Preferably by test set one from wax, do not have seepage compound (I) but upper limit amount and in this limit, select the highest energy to determine that the amount of compound (I) of these waxes of adding is to extend the expiration date.For example, when stearic acid was used as wax, the amount of the compound of adding (I) was preferably 10-60wt%.
As gel, the gel that preferably can become oil-base gel is used to comprise a large amount of compounds (I).For example, with gelling composition such as odium stearate, aluminum stearate, 2 ethyl hexanoic acid aluminium, dibenzylidene sorbitols etc. add compound (I), and use a small amount of alcohol or water to prepare gel products.The amount that adds the compound (I) of this gel is preferably 10-60wt%.
As above-mentioned paint, can use any paint, as long as it does not apply adverse effect to compound (I).As this paint, for example can mention varnish; Enamel paint; The cellulose acetate lacquer; Ethyl cellulose lacquer; Alkyd resin enamel and varnish; Vinylite enamel paint and varnish such as vinyl chloride, vinyl acetate-methacrylate, styrene-butadiene etc.; Pigment oiliness paste paint etc.When compound (I) being added these paint, do not having the upper limit amount of the adhesion of painting after the drying and in this limits, selecting the highest energy to determine that an amount is to extend the expiration date but preferably set one by test.When for example it being added varnish, the amount that adds the compound (I) in the paint is preferably 1-10%.
As above-mentioned condiment, can use any natural condiment and synthetic condiment, as long as it compound (I) is not applied adverse effect and does not suppress compound (I) drive the Acarina mite effect.When reagent of the present invention is used for the living space, the condiment of special preferred heights safety.As natural condiment, for example can mention bergamot oil, peppermint oil, lemongrass oil, volatile oil extracted from eucalyptus' leaves or twigs, Japanese pitch, the lemongrass wet goods as synthetic condiment, for example can be mentioned terpenoid condiment such as linalool, lynalyl acetate, geraniol, nerolidol, citral etc.
Porous inorganic particulate is meant that preferred average particle size is 1 μ m-10mm by the porous particle of the preparation of dissolubility or insoluble inorganic powder hardly, more preferably 2 μ m-5mm, and the BET surface area is not less than 50m
2/ g more preferably is not less than 100m
2/ g.
Porous inorganic particulate comprises silica; Metal oxide such as aluminium oxide, zinc oxide, magnesia, titanium oxide, zirconia etc.; Metal hydroxides such as aluminium hydroxide, magnesium hydroxide etc.; Metal silicate such as calcium silicates, magnesium silicate, alumina silicate etc.; Metal carbonate such as calcium carbonate, magnesium carbonate etc.; Metal sulfate such as calcium sulphate, magnesium sulfate etc.; Clay mineral if you would take off stone, talcum, pyrophyllite, zeolite etc.; Or the like.
By using the sol-gel process of metal alkoxide etc., use the ion-exchange of soluble metallic salt etc. can synthesizing porous inorganic particle, perhaps can same as before or behind purifying, use naturally occurring porous inorganic particulate.When synthetic or naturally occurring inorganic material itself have been porosu solid basically, by such as pulverizing, the method for screening etc. can suitably be adjusted to this porosu solid wieldy size, and as the carrier of adsorption compound (I).When this method is not directly utilized; can will synthesize or naturally occurring inorganic material is suspended in the solvent such as water etc.; and granulate by spray drying process; or in rotating the comminutor of slurry or powder simultaneously, drying granulates into the expectation granularity; or the like, adjust size, when needs; sintering etc. are to guarantee the stability of particle, and described particle is then as carrier.As improving one's methods, can will be used as carrier by handle interlayer clay mineral at interval with four ammonium salts with expansion; Can compound (I) is introduced immediately inorganic carrier simultaneously will be by the bonding adhesive granulation that improves inorganic powder and compound (I) of organic polymer preparation; The organic polymer material as adhesive of inclusion compound (I) can be mixed with these inorganic powders, this mixture of powders can be granulated together.
Reagent preparation of the present invention can be become any formulation by known method, aerosol for example, finish, fumigant, thin slice, pulvis, microcapsules, water-dispersible agents etc.By spraying, coating, dipping is coated with the shop and waits agent administration of the present invention with these formulations in various materials such as woven cloth, looped fabric, wet type nonwoven (paper), dry type nonwoven, plywood, synthetic resin sheet, synthetic resin board, timber etc.
When the active compound component (I) with reagent of the present invention adds various resins and is processed into such as fiber film, sheet, the mechanograph of plate etc., these mechanographs are used as the raw material of producing the indoor life article that Acarina mite perches, described article such as various construction material, Couch cushion, bed clothes, carpet, cotton-wool etc., and with mechanograph as control Acarina mite assembly the time, above-mentioned mechanograph, the various assemblies of life article and performance Acarina mite control efficiency are also included among the present invention.
When forming preparation, the content of compound in the reagent of the present invention (I) is preferably 0.1-99wt%, more preferably 5-99wt%.The concrete amount of the reagent of the present invention that uses of restriction, as long as can show the Acarina mite control efficiency, but preference such as its are per unit area 1m
2Be used for spraying, coating, dipping is coated with the shop and waits the target object of operation to use about 0.01-10g, more preferably from about 0.1-3g compound (I).
In addition, when compound (I) being added various resins and is processed into such as fiber, film, when sheet, the mechanograph of plate etc., the content of compound in the mechanograph (I) is preferably about 1-60wt%, more preferably from about 10-50wt%.
In addition, reagent of the present invention can form microcapsules.As microcapsules, to use by interfacial polymerization, the bag quilt is solidified in situ polymerization, submergence, nuclear solvation, the microcapsules in conjunction with preparation of physics and machinery production method or these known methods.As the wall material of microcapsules, for example, can mention polyester, polyamide, polyurethane, polyureas, epoxy resin, polystyrene resin, ethylene-vinyl acetate copolymer, polylactic resin, acrylic resin, celluosic resin, sodium alginate, gum Arabic, polyvinyl alcohol, gelatin, albumin etc., preferred polylactic resin.
Although specifically do not limit the particle mean size of microcapsules, be preferably 10 μ m-1mm, more preferably 20 μ m-500 μ m.Its reason is when microcapsule granule is too fine, and inner compound (I) discharges at short notice, oxidation, and the term of validity of microcapsules shortens.On the other hand, when microcapsule granule is too coarse, the difficulty that becomes in the mechanograph etc. of kneading, the kind of object that can comprise particle is limited.For example, when using adhesive with microcapsules and fiber product adhesion, microcapsules are clearly thought allogenic material and are manually removed, or deliberately crushed to be infected with fiber product.
Be used to obtain the preferred every 1m of amount of microcapsules of the concentration of above-mentioned expeling Acarina mite
2The space that is intended to drive away is no less than 3g as indoor grade, more preferably is no less than 5g.Compound (I) is limited in from the release of microcapsules extremely low-level, even a large amount of the use can not go wrong in living environment yet.Yet consider economic aspect and extremely sensitive and dislike those of smell of compound (I), preferred every 1m to smell
2Be no more than 100g, more preferably no more than 50g.
By reagent of the present invention and above-mentioned thermoplastic resin are kneaded molding then, the band that can obtain to have the Acarina mite controllability, film, sheet, fiber or other mechanograph.By processing these mechanographs, the closet that can obtain to have the Acarina mite controllability is coated with the shop material, places material, clothes is coated with the shop, and the rearmounted material of furniture is coated with the shop under the Couch cushion, pedal, the blanket sheet, automotive interior material, bedding, mattress, animal Acarina mite control agent band (collar), the pet clothes, pet is coated with shop etc.In addition, by using adhesive reagent of the present invention and fiber product are adhered to, the fiber product of broad range can have the Acarina mite controllability, and it can be processed into controlled fiber product of Acarina mite such as bed clothes then, is used for the coverlet of kotatsu etc.Reagent of the present invention can be added paint, paste and spray, it can or be used as the construction material adhesive as paint, or is sprayed on the nest and furniture of pet and animal, or be sprayed on the animal body, can force the Acarina mite that is adsorbed on nest and the animal body to leave thus.
" Acarina mite " is meant the terrestrial animal that belongs to Arthropoda (phylumArthropoda), arachnids (the class Arachnida), Acarina (the order Acarina) in the present invention, for example comprises the Acarina mite for example tyrophagus putrescentiae (Tyrophagusputrescentiae), the Caloglyphus berlesei etc. that belong to Tyroglyphidae (Acaridae); The Acarina mite that belongs to dirt mite section (Epidermoptidae) is dust mite (Dermatophagoides farinae), dermatophagoides pteronyssinus (Dermatophagoidespteronyssinus) etc. for example; Belong to for example southern pawl mite of Acarina mite (Chelacaropsis moorei), Cheyletus malaccensis of cheyletidae (Cheyletidae) etc.; Belong to for example tame sweet food mite of Acarina mite (Glycyphagus domesticus) of the sweet mite section of food (Glycyphagidae) etc.; The Acarina mite that belongs to Tarsonemidae (Tarsonemidae) is Tarsonemus granarius etc. for example; The Acarina mite that belongs to Raphignathidae section is Raphignathus domesticus etc. for example; The Acarina mite that belongs to fowl thorn mite section (Macronyssidae) is ornithonyssus bacoti (Omithonyssusbacoti) etc. for example; The Acarina mite that belongs to Sarcoptidae (Sarcoptidae) is itch mite (SarcoptesScabiei) etc. for example; The Acarina mite that belongs to Trombidiidae (Trombiculidae) is fiber Leptotrombidium globus pallidus (Leptotrombidium pallidum), Leptotrombidium scutellare (Leptotrombidium scutellare) etc. for example; The Acarina mite that belongs to Tetranychidae (Tetranychidae) is Tetranychus Ludeni, Tetranychus urticae (Tetranychus urticae), Shi Shi beginning tetranychid (Eotelranychus smithi) etc. for example; Belong to walk haltingly Acarina mite grape brevipalpus (Brevipalpus lewisi) etc. for example of section (Tenuipalpidae) of pseudo-leaf; The Acarina mite that belongs to Eriophyidae (Eriophyidae) is Calepitrimerus vitis, Colomerus vitis etc. for example; The Acarina mite that belongs to Carpoglyphidae section is Carpoglyphuslactis or the like for example.
Embodiment
At length explain the present invention with reference to the following example, but the present invention is not limited to these embodiment.
Reference example 1: the mensuration of farnesyl acetone concentration in the air
Farnesyl acetone (1mL) is placed in the 50mL sample bottle, and the big magnetic stirring bar of energy rotary air is also placed in wherein.Bottle is placed in 130 ℃ the oil bath of rotation, dark to bottleneck, heated 1 hour, with the inside of farnesyl acetone vapo(u)rous sample bottle.After this, with gas 5mL in the confined gas syringe sampling product bottle, use the concentration of the gas-chromatography of band fid detector with absolute Calibrating Method mensuration farnesyl acetone.The result learns that the farnesyl acetone of 20,000 μ g/L is included in this 5mL gas.The gas of this sampling comprises white mist a little, has tang, causes cough when a large amount of suction, makes the people produce uncomfortable feeling.
Farnesyl acetone (1mL) is placed in the 50mL sample bottle, and the big magnetic stirring bar of energy rotary air is also placed in wherein.Bottle is placed in 60 ℃ the water-bath of rotation, dark to bottleneck, heated 1 hour, with the inside of farnesyl acetone steam filling sample bottle.After this, with gas 5mL in the confined gas syringe sampling product bottle, use the concentration of the gas-chromatography of band fid detector with absolute Calibrating Method mensuration farnesyl acetone.The result learns that the farnesyl acetone of 20 μ g/L is included in this 5mL gas.Almost side by side, gas (5mL) in the sample thief bottle again, a screw is placed in the 10L beaker, this gas is joined in the beaker of sealing, with air in the propeller agitation beaker 10 minutes to dilute this gas 2,000 times, obtain comprising the gas of the farnesyl acetone of 0.01 μ g/L thus.Be somebody's turn to do the gas (200mL) of dilution with syringe sampling, a screw is placed in the 2L flask, this gas is joined in the flask of sealing, air in the beaker with 10 times of this gases of further dilution, obtains comprising the gas of the farnesyl acetone of 0.001 μ g/L with propeller agitation 10 minutes thus.The gas of this sampling has the people hardly can detected smell.
Embodiment 1
Revise " the glass tube method " of one of the expulsion test of known fiber as Acarina mite expellant processing, be used for the expulsion test.
Fig. 1 represents the sectional view of testing equipment.As shown in Figure 1, the glass tube of 20mm diameter is bent into the L type and uses, and the absorbent cotton of 0.5g is filled in the B part of Fig. 1, and thickness is 25mm, and the fresh powder feed (0.1g) of luring Acarina mite to use that is soaked with the water of about 20wt% is placed on the C part.Glass tube the inside in the D part is fixed on filter paper in the L type glass tube of test region with the two sides adhesive tape, places test specimen (absorbing the filter paper of farnesyl acetone (0.1g)), air-tightness parafilm (PARAFILM) sealing of the glass mouth of pipe of D side.Then, the medium that will comprise 10,000 Acarina mites alive (dermatophagoides pteronyssinus, Dermatophagoides pteronyssinus) is placed on the A part of L type glass tube, when keeping air permeability, the glass end of A side is with preventing that the high-density fabric that Acarina mite passes through from sealing.This testing equipment left standstill 48 hours in maintaining 37 ± 1 ℃, the container of 75 ± 5%Rh.After 48 hours on-tests, the syringe needle of the confined gas syringe of 5mL penetrates the film of the D side of sealing L type test glass tube, the gas (2mL) of sampling the inside.Farnesyl acetone concentration with gas in the gas Chromatographic Determination D part.This concentration is considered to 5 μ g/L.
Then, take out luring of C part and use charging, go out to invade the Acarina mite number of luring with following method number with in the charging.That is, luring with charging of taking out is placed in the conical flask of 50mL, dropwise adds two and be diluted to the neutral cleaners that 0.5% plate is used, to wherein pouring saturated salt solution into to the flask mouth, flask left standstill 10 minutes.Number goes out to float on the Acarina mite number on upper strata.For the contrast part, similarly test simultaneously, wherein there is not test specimen to be placed on the D part of L type pipe.The expulsion ratio of test specimen by following formula is determined learn to be 98%.
Expulsion ratio (%)=(1-invades the Acarina mite number of luring the usefulness charging with the Acarina mite number/intrusion check plot of charging of luring of test region) * 100
Embodiment 2
Modification prevents the intrusion method, expels test.
Fig. 2 represents testing equipment, and wherein (A) is vertical view, (B) is its sectional view.
As shown in Figure 2, glass plate (long 13cm, wide 6cm, thick 1.3mm) as substrate (1), 2 glass sheets (long 13cm, wide 5mm, thick 1.3mm) spacer of making (2,2 ') adhere to two long limits of substrate 1,2 glass sheets (long 5cm, wide 5mm, thick 1.3mm) spacer of making (3,3 ') adhere to two minor faces of substrate, all use the quick-drying gelatin stick, obtain a test box (the shallow box of long 12cm, wide 5cm, dark 1.3mm).Prepare the lid (4,4 ') of two glass plates (long 5.5cm, wide 6cm, thick 1.3mm) as this box of lid.
With the ethanolic solution of farnesyl acetone (1%, 100mg) be coated on the surface of (test region side) in two lids that cover test box, air-dry 10 minutes of ethanol.Then, lure sample (50mg) to be placed on the two ends of the longitudinally of test box each Acarina mite, place the above-mentioned lid (4 ') that is coated with farnesyl acetone individually, make to be coated with the inside of the surface of farnesyl acetone towards box.This box is placed on the test region side that was full of test box in 37 ℃ the incubator in 60 minutes up to farnesyl acetone steam.Put another lid thereon, make the center of test box that the slit of 2cm be arranged, discharge 50,000 dust mites (Dermatophagoides farinae), test box is placed in the incubator that maintains 25 ℃ 1 day by it.After this take out test chamber, calculate the Acarina mite number (be respectively 50 and 1100, all the other Acarina mites are fled from) of the charging of invading test region side and check plot side.Determine the expulsion ratio by following formula, learn to be 95%.Same way as mensuration with reference example 1 spreads in 37 ℃ airborne farnesyl acetone concentration, thinks 5 μ g/L.Expulsion ratio (%)=(1-invades the Acarina mite number of the Acarina mite number/intrusion check plot of test region) * 100
Under these experimental conditions, farnesyl acetone is not coated on the base plate of test box, means the farnesyl acetone steam that exists in the channel space of Acarina mite away from the abundant height that may avoid the physics contact at the Acarina mite health.
Embodiment 3
Be equipped with a Teflon pipe (internal diameter 2mm) that is used for discharging the gas that contains farnesyl acetone and use measuring pump with the 2L flask of the gas that accommodates the farnesyl acetone that contains 0.001 μ g/L of the same way as of reference example 1 preparation water is added to Teflon pipe in the container, emit the equipment that (supply) contains the gas of farnesyl acetone with 1mL/min thereby make thus by in flask, introducing water with 1mL/min.Transform the testing equipment that the glass plate that uses among the embodiment 2 is made: the entry needle that adding is contained the gas of farnesyl acetone is placed on the deepest part of test region side, and with this entry needle be connected to from the Teflon pipe of equipment to supply the above-mentioned gas that contains farnesyl acetone.In addition, place the entry needle that an adding does not contain the air of farnesyl acetone, introduce fresh air with 1mL/min in the deepest part of check plot side.
Then testing equipment is placed in the room of 37 ± 1 ℃, the steady temperature of 75 ± 5%Rh and humidity, operate this equipment 3 hours and be full of the test region with farnesyl acetone with above-mentioned concentration, then, insert the Acarina mite medium that comprises 10000 Acarina mites alive from the slit of lid, left standstill 4 hours.Calculate luring in each the C part that invades test region and check plot then with the Acarina mite number in the charging.That is, take out to lure and use charging, be placed in the conical flask of 50mL, dropwise add two and be diluted to the neutral cleaners that 0.5% plate is used, to wherein pouring saturated brine into to the flask mouth, flask left standstill 10 minutes.Calculating swims in the Acarina mite number on upper strata.The expulsion ratio by following formula is determined learn to be 80%.
Expulsion ratio (%)=(1-invades the Acarina mite number of the Acarina mite number/intrusion check plot of test region) * 100
The gas that comprises 0.001 μ g/L farnesyl acetone produces smell hardly to the people, but Acarina mite is had the expulsion effect.
Test example 1
(prevent the intrusion method: " Processing Technique " by the expulsion test method, the 33rd volume, No.2,153-155 page or leaf (1998), " titled:Acarina repellent-processedproduct repellence test basic manual " (Apareru Seihin-tou Hinshitsu SeinouTaisaku Kyougikai)) determine that the isomer of farnesyl acetone and phytone are at 1.0g/m
2Condition under to the expulsion ratio of a class dermatophagoides pteronyssinus.The result is illustrated in the following table 1.
Table 1
| Sample | Observe fate | ||
| After 1 day (Acarina mite) | After 2 days (Acarina mite) | After 3 days (Acarina mite) | |
| (control group) is untreated | 65 | 132 | 140 |
| Enrichment is suitable-suitable farnesyl acetone ++ | 5(92.3 +) | 15(88.6 +) | 29(79.3 +) |
| Instead-anti-farnesyl acetone | 8(87.7 +) | 13(90.2 +) | 24(82.9 +) |
| Phytone | 7(89.2 +) | 12(90.9 +) | 23(83.6 +) |
+: { 1-(the Acarina mite number of the Acarina mite number/control zone of treatment region) } * 100 (%)
++: farnesyl acetone, wherein (5-is suitable, 9-along form): (5-is suitable, 9-anti-form and 5-is anti-, 9-is along the mixture of form) is 6: 4.
The commercially available candle of fusion, farnesyl acetone (10g) are dissolved in the wax (90g) that obtains (storage device) equably.The wax that comprises farnesyl acetone sticks to around the wick, experimental field makes the candle of enshrining and worship candle that is used for the Buddhism sacrificial altar thus.Sweep with the observation by microscope Cyclonic vacuum cleaner and to light the dust that the room of enshrining and worship candle (heater) obtains every day.The result lights in the dust that the room of enshrining and worship candle obtains in every day and does not find Acarina mite, comprises 10 Acarina mites but clean the dust that other room obtains in its 0.5g.Enshrining and worship after candle extinguishes, gaseous state farnesyl acetone concentration is 60 μ g/L in the room.
Embodiment 5
Farnesyl acetone (10g) and soft propene acid resin powder (100g, name of product ParapetSA-N are produced by KURARAY CO.LTD.) at room temperature mixed 15 minutes.This mixture 125 ℃ of following melt kneading 1 minute in two roller kneaders are at 135 ℃, 50kg/cm
2Following extrusion modling made the thick soft rubber sheet of 1mm (storage device and disengagement area expanding unit) in 1 minute.This sheet is placed on below a part of carpet, after 2 weeks of normally living, and dust that microscopic examination contrast obtains from this sheet upper part that comprises farnesyl acetone with Cyclonic vacuum cleaner and the dust that obtains from part away from the sheet that comprises farnesyl acetone.The result does not find Acarina mite the dust that the sheet upper part that comprises farnesyl acetone from this obtains, but comprises 7 Acarina mites at the dust that the part away from this sheet obtains in its 0.5g.Air in the blanket of placement soft propene acid sheet is driven out of, measured farnesyl acetone concentration, learn to be 1 μ g/L.
Embodiment 6
Mix by dissolving farnesyl acetone (2g) and poly-acetate (10g in carrene (100mL), produce by Cargill Dow LLC, number mean molecule quantity 87,000, weight average molecular weight 163,300, D/L is than 8/92) disperse phase that obtains and the continuous phase (10.4g) be made up of 4% polyvinyl alcohol water solution (1400mL) and surfactant (Q12S), stirred 30 minutes with the speed of propeller blades with 100rpm down at 30 ℃.Raise the step by step level of the pressure that reduces in the reaction vessel, this mixture stirs 6 hours evaporation carrene under the decompression that aspirator is created.The suspension that obtains washes product with water several times by glass filter, and freeze-drying made the microcapsules that comprise farnesyl acetone in one day.The microcapsules that obtain are the about spheric granules with 0.4mm mean particle size, show the dry flow property of similar sand grain.
Embodiment 7
By expelling test method (preventing the intrusion method: see test example 1) to determine dermatophagoides pteronyssinus (Dermatophagoides pteronyssinus) the expulsion ratio of the microcapsules that embodiment 6 obtains, be defined as 99%.According to this method, 60% or above expulsion ratio be considered to effective.In addition, the microcapsules that embodiment 6 obtains are placed on the container that does not have lid, at room temperature static 2 months or 6 months, similarly test.As a result, rear-guard was to be 81% after 99%, 6 month by ratio in 2 months, and this proves that this effect can keep for a long time.
Embodiment 8
Microcapsules that mix embodiment 6 obtains (30g) and soft propene acid resin powder (100g, name of product Parapet SA-N are produced by KURARAY CO.LTD.), 155 ℃ of following melt kneading are 1 minute in two roller kneaders, at 160 ℃, 50kg/cm
2Following extrusion modling 1 minute, cooling makes a slice.Microcapsules are evenly dispersed in this sheet, but the cigarette that for example in forming process, do not note abnormalities etc.
Embodiment 9
The monodisperse silica particle that has the mean particle size of 0.045 μ m to dilute with water (is produced by Nissan Chemical Industries Ltd., Snowtex OL) adds dissolve polyvinyl alcohol (2g in the slurry (600g) that obtains as adhesive with solids content of 17%, KURARAYCO.LTD. water (20g) PVA117 of Sheng Chaning) mixes this mixture up hill and dale.The slurry that obtains makes the flocculated particle of the particle size with about 20 μ m with spray dryer (L-8, by Ohkawarakakouki Co., Ltd. produces) atomized drying.This particle is calcined down at 450 ℃ and was removed adhesive in 1 hour, obtains the porous agglutinating particle (95g) that silica is formed thus.The solution of phytone (20g) and ethanol (80mL) is placed in the pyriform flask, adds above-mentioned porous agglutinator (80g).The pyriform flask is fixed on the rotary evaporator, and normal pressure rotated 5 minutes down.When the level of the pressure that little by little raise to reduce and temperature, evaporation is removed ethanol and is made the silica dioxide granule that resembles sand that keeps phytone.
Embodiment 10
Polyvinyl acetate (5g) and farnesyl acetone (10g) are dissolved in the methyl alcohol (300mL), and (100g) joins in this solution with the porous silica powder.Remove methyl alcohol with rotary evaporator, methyl alcohol flow out stop after, the operation rotary evaporator is 1 hour under 40 ℃, 20mmHg, thus preparation the inside and the aggegation silica solid that is coated with polyvinyl acetate that comprises farnesyl acetone on its surface.Collect and pulverize this condensation product, a spot of mica is adhered to its surface, make the silica dioxide granule of reservation farnesyl acetone with the particle size that is not higher than 1mm.
Test example 2
Determine the dermatophagoides pteronyssinus expulsion ratio of the silica dioxide granule of embodiment 9 and 10 preparations by expulsion test method (preventing the intrusion method: see test example 1).The result is illustrated in the table 2.
Table 2
| Sample | Observe fate | ||
| After 1 day | After 2 days | After 4 days | |
| The silica dioxide granule of embodiment 9 | 78％ | 83％ | 73％ |
| The silica dioxide granule of embodiment 10 | 100％ | 100％ | 100％ |
Embodiment 11
An equipment, comprise internal diameter 8cm, high 5cm also comprises the syrindrical storage area (storage device) of farnesyl acetone and is fixed on the glass cloth (disengagement area expanding unit) that the farnesyl acetone that is included in storage area is oozed out enlarge the disengagement area of farnesyl acetone, wherein use heater strip (heater) and bimetal leaf (temperature control equipment) that bottom and wall are heated to 90 ℃, use small fan (air blowing equipment) to blow with 5L/min facing to the bottom from the top of container, this equipment is fixed on the room of 3 airtight tatami mats, operation.
Industrial applicability
The method according to this invention, the concentration of keeping compound (I) in the space of plan expulsion Acarina mite is in specific concentration range, and Acarina mite can be controlled effectively. And reagent of the present invention can provide the Acarina mite control action to various article.
This application is based on the patent application of submitting in Japan the 31409/2002nd and No. 34625/2002, and their content is merged in the present invention as a reference all thus.
Claims (2)
1. an Acarina mite controlling agent comprises that phytone is as active component.
2. phytone is used to control the purposes of Acarina mite.
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| CN101928709B (en) * | 2009-06-24 | 2012-05-23 | 中国农业科学院上海兽医研究所 | Gene sequence, recombinant expression and application of hyalomma asiaticum histamine binding protein HaHBP |
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| CN104969997A (en) * | 2015-06-05 | 2015-10-14 | 陈东霖 | Disinfestation mat and applications thereof |
| CN108143763A (en) * | 2017-12-26 | 2018-06-12 | 重庆医学检验试剂研究所 | A kind of preparation that Dragonfly nymph is inhibited to sprout wings and method |
| CN109258578B (en) * | 2018-11-21 | 2023-12-05 | 北京阔野田园生物技术有限公司 | Indoor industrial breeding method for ladybug larvae |
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| CN101928709B (en) * | 2009-06-24 | 2012-05-23 | 中国农业科学院上海兽医研究所 | Gene sequence, recombinant expression and application of hyalomma asiaticum histamine binding protein HaHBP |
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