CN106702734A

CN106702734A - Impregnated textile containing pesticide and/or insecticide

Info

Publication number: CN106702734A
Application number: CN201611024120.0A
Authority: CN
Inventors: 过冬
Original assignee: Individual
Current assignee: Individual
Priority date: 2016-11-17
Filing date: 2016-11-17
Publication date: 2017-05-24

Abstract

The invention relates to an impregnated textile containing a pesticide and/or an insecticide. The textile contains at least 65% of pesticide which exists in the textile in a solid particle mod, wherein the particle size of at least 82% solid particles in the textile is 0.1-25 micrometers, and the solid particles contain pesticide and/or insecticide microcrystal particles. The surface of the textile still contains the pesticide and/or the insecticide after the impregnated textile is washed several times, and the textile evaporates sufficient pesticide and can kill insects 20 cm away from the textile.

Description

A kind of impregnating woven product comprising insecticide and/or pest repellant

Technical field

The present invention relates to a kind of impregnating woven product comprising insecticide and/or pest repellant having improved properties, it is several Insecticide and/or pest repellant are still included after secondary washing on textile surface.

Background technology

Insect and Arachnoidea mesh include biting because of it, attack behavior and final propagation have virus, bacterium or parasitic special The disease levied and the family being harmful to human and animal.Such include Diptera (mosquito, buffalo gnat, sand fly, tsetse fly and other flies of sucking blood), Semiptera (bedbug), hidden wing mesh (flea, louse and tick).Many these insects can impose on surface as wall or window by contact Insecticide on curtain is prevented and treated, or is prevented and treated by aerosol spray.Recently, several works with textile development Tool, as mosquito net, treatment blanket, tarpaulin and tent.The advantage of these methods is, compared with being sprayed on wall, its treatment is only needed Will smaller surface and effect can keep for a long time, and aerosol spray can not keep for a long time.The material is generally carried out periodically Washing, therefore, the solution based on water without addition for the insecticide of the special additive for keeping will be readily removed. Experience have shown that, the treatment for allowing people to re-establish textile has difficulties and is expensive, thus, composition is improved to be, by this A little products are paid together with wash resistant technology and are given people.The technology can be dipping in coating or fiber.Insecticide only resists to be washed It is inadequate to wash, and it can must also just be utilized after protecting effect is re-established on textile surface.

Many prior art literatures describe " wash resistant " textile comprising insecticide.The common ground of all prior arts It is：Focus is manufacture " wash resistant " product, and wherein insecticide will not be washed off in the washing process for limiting, and with respective amount Still there is bioactivity on textile surface.Reason for this is that：The strategy of prior art be by with textile surface On insecticide contact and kill insect.

This is illustrated by following：Above-mentioned representative testing experiment of the prior art be based on insect (such as mosquito) with comprising The surface directly contact of the textile of insecticide.

In order to manufacture " wash resistant " textile comprising insecticide, above-mentioned representative prior art provides many different Technical scheme, for example：In the course of the polymerization process desinsection is captured in aqueous emulsion using acryloyl group or carbamates monomer Agent, is allowed to form coating (US2005/0132500A1)；There is hydrophobic copolymer adhesive (when net is knitted using to insecticide Product do not discharge when being dried) and there is smaller hydrophobic dispersant to insecticide, with order to work as mesh in such as Normal Wash During produce limited insecticide to discharge (WO03/034823) when drenching；Wherein polyurethanes, polyacrylic, poly- isocyanide Esters of gallic acid and polylactic acid-based polymer backbone are used for the insecticide for film being formed on fiber yarn and being dissolved and is emulsified at this The method (WO0137662) being captured on film；Insecticide is kept by wash cycle several times using polyvinylacetate adhesive The insecticidal effect (EP731208A2) of Permethrin；Use the sustained release preparation (WO95/ of the starch encapsulated of insect repellent DEET 17091)；Fabric is impregnated with polymer adhesive [polyvinyl acetate (PVA)] and/or crosslinking agent (carbamate resins), Wherein insecticide is added in the emulsion containing thickener (EP787851A1)；And based on the net using cyclodextrin microencapsulation Fabric (US6896892).

Above-mentioned representativeness another common technology main points of the prior art are：The insecticide in textile is incorporated into each Molecule exists with " aggregation " with lesser amt molecule.This is for example realized in the following way：Insecticide is molten Solution obtains the textile of insecticide dipping in enough solvents, adding it to textile afterwards.Example description to this In WO0137662A1, wherein working Examples describe the preparation containing desinsection agent emulsion, and the emulsion for example by that will kill first Worm agent is dissolved into solvent (such as acetone), then (is such as washed with emulsifying agent in suitable oil (such as silicone oil and/or polypropylene glycol) Agent) it is mixed together, finally mix in water, water-in-oil emulsion is formed, wherein the insecticide is present in water with dissolved form In oil droplet in.For dipping, the emulsion comprising insecticide is applied to textile.

In other words, by using the dipping method of prior art, it is impossible to obtain wherein insecticide or pest repellant with " solid The textile that form " particulate (such as comprising the solia particle of the insecticide microcrystal grain for for example being coated with resin) is present.

The content of the invention

To sum up, the problem to be solved in the present invention can be having improved properties comprising insecticide and/or pest repellant by providing Impregnating woven product be achieved.

A scheme of the invention is to be based on：Present inventor have demonstrated that the new dipping of some prior arts, unwashed Textile (such as mosquito net) comprising insecticide can be before first time washs, apart from textile certain distance (at least up to 50cm) Interior kill insect (such as mosquito).In other words, insect " kill " effect can spatially extend, and it is not limited only to contact action, i.e. Insect contacts with the insecticide being present on textile (such as mesh) surface.This certainly advantage, because insect can be with Below textile (mosquito net) or the back side is kept away from crowd, and just it is killed when room is entered, such as rests on wall attached Closely.But the present inventors have additionally discovered that, " kill " effect that this spatially extends is in identical prior art comprising insecticide Textile washing is once just substantially disappeared afterwards.In other words, after washed once, weaving of the prior art comprising insecticide Product can only kill the insect for directly being contacted with textile.

It is not only restricted to theory, it is believed that before first time washs, enough insecticides are evaporated (due to multi-fiber from textile surface Dimension structure, bigger than what naked eyes were seen) with apart from textile certain distance (about 50cm) kill insect.However, first After secondary washing, the insecticide of " excessive " is washed off, and the insecticide of only correlative is present on textile surface, i.e. insecticide Will not " evaporation " be walked from textile with correlative.

As discussed above, the strategy of prior art is had sought to when insect contacts with the insecticide on textile surface " kill " insect.

The present inventor this be found to be developed for prepare the impregnating woven product (such as mosquito net) comprising insecticide open Yishanmen.Therefore, as described herein, the present inventor has been developed for a kind of new impregnating woven product comprising insecticide, The textile wash resistant (after washing several times, the insecticide comprising correlative on textile surface), and the textile with Textile of the prior art comprising insecticide is compared, or even can be apart from the spacing of textile one after several times in the textile washing Insect (such as mosquito) is killed from (at least up to 20cm).

For example, as described in this paper working Examples 2 or 3, a kind of mode for manufacturing new textile is that insecticide is soaked Stain composition is made and being suitably modified (e.g., the different change ratios of resin and polymer).However, once being disclosed based on the present invention Content (or even after textile washing, textile should also be as can be in certain distance those skilled in the art will know that the purpose Kill insect), then belonging to the knowledge of those skilled in the art is：Prepare many different suitable insecticide dipping combinations Thing, to obtain functional objective as herein described.

Therefore, the first aspect of the present invention be related to it is a kind of after washing several times on textile surface still comprising desinsection The impregnating woven product comprising insecticide of agent, (are tested after being washed 10 minutes in the suds of 0.2-0.5% by WHO standard (WHOPES2005/11) for described in mesh sample in), its enough insecticide of evaporation is deposited with killing apart from textile 20cm Insect (according to the testing experiment of embodiment hereof 1).

" WHOPES2005/11 " decantation test that foregoing is directed to is found in " Guidelines for Laboratory And Field Testing of Long Lasting Insecticidal Mosquito Nets, WHO/CDS/WHOPES/ CDPP/2005.11”。

WHO experiments are the code tests for washing mesh sample.However, the standard wash experiment of the foundation can be usual According to requiring as described herein for washing textile or mesh of interest.

" dipping comprising insecticide of insecticide is still included on textile surface after washing several times on statement " washing several times " in textile " is it should be understood that be according to above-mentioned " wash resistant " comprising insecticide dipping known in the art The requirement of textile.It is (more preferably big that " washing several times " can carry out about 10 washings according to the WHO washings standard procedure set up About 20 washings).

The second aspect of the present invention is related to the impregnating woven product comprising insecticide of first aspect to be used to kill the use of insect On the way.

Corresponding to first and second aspect of the invention, the third aspect of the present invention is related to a kind of experiment comprising insecticide The method whether impregnating woven product can kill the insect existed apart from textile 20cm after it washed once, it includes following step Suddenly：

I () will still include the impregnating woven comprising insecticide of insecticide after washing several times on textile surface Product are washed；

(ii) test whether the washed textile evaporates enough insecticides to kill apart from textile at least The insect that 20cm is present, and test the textile and whether can kill afterwards apart from textile at least 20cm washed once The insect of presence.

Obviously, one kind carries out the mode of the washing of step (i) can wash according to the WHO mentioned on first aspect present invention Wash standard.However, it will be obvious to a person skilled in the art that washing as the purpose of washing step (i) is work, is somebody's turn to do Washing represents the example of the washing that normal person is carried out during normal life in the context of the present invention.Therefore, in this hair In bright context, " washing " of the step (i) in third aspect present invention should be understood to：With corresponding to the WHO for setting up The washing of the washing " characteristic " of washing standard (such as WHO washs standard " WHOPES2005/11 ").

Also, it should be apparent that the mode that one kind carries out test procedure (ii) can be surveyed according to the testing experiment of embodiment hereof 1 Fixed experiment.However, it is obvious to a person skilled in the art that the purpose of test procedure (ii) can be entered in another way Go and realize same purpose.In brief, pilot system should be simply such system, within the system, related Insect exists apart from textile at least 20cm, and combination is used to analyze whether the insect existed apart from textile at least 20cm is killed Dead method.

There is the problem of the impregnating woven product comprising insecticide and/or pest repellant for improving performance, the present invention on providing Another scheme be to be based on：Present inventor have demonstrated that when insecticide and/or pest repellant in solid form particulate (such as comprising example The solia particle of the insecticide microcrystal grain for such as being coated with resin) in the presence of, insecticide and/or expelling parasite are can obtain in textile Agent to more controlled (as continue) of textile surface release.And, it has already been proven that, if the size of solia particle is more than 25 μm, then can not obtain advantageous effects related herein.

This is different from background art discussed above, because by using the dipping method of prior art, it is impossible to obtain this The textile of sample, particulate is present in solid form for insecticide or pest repellant in the textile.

Therefore, the 4th independent aspects of the invention are related to a kind of still being included on textile surface after washing several times to kill Worm agent and/or the impregnating woven product comprising insecticide and/or pest repellant of pest repellant, at least 65% insecticide and/or expelling parasite Particulate is present in textile in solid form for agent, and at least 82% solid form particulate in the textile is particle chi The very little solid form particulate for 0.1-25 μm.

Term " washing several times " should be understood to identical with the explanation of first aspect present invention.

Be not only restricted to theory, it is believed that insecticide and/or pest repellant solid form particle be considered as provide insecticide and/or The low-solubility " depot " of pest repellant.During this period, insecticide and/or pest repellant are slowly dissolved in the coating around for example In, textile surface is thus discharged into lasting controlled way.

The fifth aspect of the present invention is related to used for textiles in killing comprising insecticide and/or pest repellant comprising fourth aspect Purposes that is dead and/or driving away insect.

It is foregoing micro- comprising insecticide and/or pest repellant solid form that the sixth aspect of the present invention is related to one kind to prepare The method of the textile of grain, wherein the method comprises the steps：

(A) the suitable dip composition of the insecticide and/or pest repellant existed comprising particulate in solid form is prepared；

(B) said composition impregnating woven product are used.

Textile such as fabric (such as mesh) generally wants set not shrink after washing.This can be by by mesh or knitting Thing is heated to the temperature (for example, yarn is melted together) of slight melting or must be later the chemistry of washing stabilization by coating Coating and obtain.Dipping chemistry is coated in than for being carried out under thermal fixation lower temperature.In the prior art, so far can't Two techniques that will be specified below are merged：A be impregnated into textile for insecticide and/or pest repellant by (), and (b) weaving The set of product.A reason to this is：Coating Chemicals (such as wrapping halogen-containing polymer) for prior art can be with work Property insecticide and/or pest repellant reaction, and be polymerized these chemicals needed for temperature under they are destroyed.Correspondingly, this is asked Topic is addressed by hereafter the 7th independent aspects of the invention, and this aspect is related to a kind of method, in the method, can will be upper Two techniques that face is mentioned be merged into for not only carry out the dipping of (a) textile but also carry out (b) textile chemical set one Footwork.The one-step method can provide suitable technique saving.

Therefore, the 7th independent aspects of the invention are related to a kind of impregnating woven prepared comprising insecticide and/or pest repellant The method of product, two techniques (a) that will be specified below and (b) are integrated into a technique：A () soaks insecticide and/or pest repellant Stain in textile, and (b) textile set, wherein methods described comprises the steps：

(I) as an integrated technique, insecticide and/or pest repellant are impregnated into weaving at a temperature of 70-200 DEG C On product and make the textile set, wherein the temperature keeps stabilization (± 10 DEG C) in an integrated technical process, And wherein

A () described impregnation technology is can to carry out polycondensation or polymerization (solidification) to obtain at the temperatures used based on use Obtain coating and polycondensation or polymerization can be carried out without the monomer for forming ion (such as halogen ion) or free radical or short-term polymerization Thing (short termed polymer), and wherein

B () described set technique is based on using set additive (chemical set), wherein the set additive can Carry out set at the temperatures used, or wherein described set technique is based on irradiation (such as infrared, ULV or ultrasound), the irradiation Exclusive use or and set additive combination provide textile set；

(II) optionally, superfluous composition is removed by extruding textile or mesh；

(III) it is passively or actively at a temperature of 20-200 DEG C and dries textile；And

(IV) optionally, textile is solidified at a suitable temperature.

Compared with prior art, the present invention at least has the advantages that：

By using impregnating woven product of the invention, it still includes insecticide after washing several times on textile surface And/or pest repellant, and its enough insecticide of evaporation can kill the insect existed apart from textile 20cm.

Specific embodiment

For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation Example is only to aid in understanding the present invention, is not construed as to concrete restriction of the invention.

Definition：

Before detailed embodiment of the invention is discussed, there is provided be related to determining for the particular term of the main aspect of the present invention Justice.

Typically, the definition of all relational languages should be understood to that those skilled in the art will be with current techniques context Implication understands them.

" solidification " represents the process after finishing agent is added in textile fabric, wherein being entered using suitable condition Row chemical reaction (as being polymerized).The heat treatment of a few minutes has been standardization, but it is also possible to during using temperature end (snap cure) When long with low temperature.

" drying " is generally carried out under than solidification lower temperature, and this is because drying is not directed to for carrying out in itself The condition of chemical reaction (as being polymerized).Can be dried for many reasons, such as in order to remove excessive solvent.

" fabric " represents the flexible artificial material being made up of the network of natural or staple fibre (filament or yarn), the fibre Dimension is for example formed by woven, knitting or being pressed into felt.The example of fabric is cloth, mesh (such as mosquito net), tent etc..

" felt " represents the fabric (non-weaving cloth) being made without weaving, and it is made up of paving, concentration and compressed fibre.

" fiber " represents long into the natural, artificial of silk or the material of manufacture.Natural plant fibre is generally by cellulose group Into example includes cotton, flax and hemp.Natural animal fibres include spider silk, tendon, hair and wool.Staple fibre is people That work is made those (often cellulosics) but for being made up of natural material.Example includes glass fibre, artificial silk, vinegar Ester fiber, cuprammonium rayon and the Lyocell of exploitation of more coming in.

Synthetic fibers include nylon fiber, acrylic fiber, polyester fiber, polyethylene fiber peacekeeping graphite fibre.

On " dipping " in the impregnating woven product comprising insecticide and/or pest repellant, it represents insecticide and/or expelling parasite Agent is applied (being such as covered with insecticide and/or pest repellant by painting) to the textile above it.

" dipping " represents the method being administered to insecticide and/or pest repellant on textile, such as by coating and/or admittedly Change/dry to obtain impregnating woven product.

" insecticide " represents the chemical substance or acaricide for killing insect.

" pest repellant " represents the active component in the product with insect (such as flea and tick) ability of expeling.Pest repellant Itself can not kill insect.

" textile " represents any kind of woven, braiding, knotting, tufting or supatex fabric.Textile also refers to can be with Spinning, woven, tufting, knotting and other yarn, silk thread and wools for manufacturing plant.

Embodiments of the invention are only described by following embodiments.

Textile comprising insecticide --- kill the insect existed apart from textile 20cm

As described above, the first aspect of the present invention is related to one kind still to be included on textile surface after washing several times The impregnating woven product comprising insecticide of insecticide, (are tried after being washed 10 minutes in the suds of 0.2-0.5% by WHO standard Test in (WHOPES2005/11) for described in mesh sample), it evaporates enough insecticides to kill apart from textile 20cm The insect (according to the experimental test of embodiment hereof 1) of presence.

The first aspect of the present invention is related to a kind of technology being attached to insecticide on textile, its adhering mode to allow it Quick diffusion, for example washing eliminated or reduce on the surface it is bioavailable and available for what is evaporated Quickly coating is diffused through after the amount of insecticide.

Therefore, in preferred embodiments, the impregnating woven product comprising insecticide of first aspect are characterised by that it steams The insect that the insecticide for sending out enough apart from textile 30cm, more preferably exists to kill apart from textile 40cm, even more preferably It evaporates enough insecticides to kill the insect existed apart from textile 50cm.

In a period of time, textile (such as fabric, such as mesh) thus enough insecticide or expelling parasites can be evaporated The combination of agent and insecticide from room driving away insect --- when it hang, and even kill stop or plant room in Insect.After the washing of certain number of times, the concentration of insecticide will be too weak and can not provide drive away at a distance or kill effect Really, but remain to drive away and kill susceptible insect during contact.

Therefore, in preferred embodiments, the impregnating woven product comprising insecticide of first aspect are characterised by：Twice After washing (after more preferably 3 times washings, after even more preferably 5 times washings, after most preferably 10 times washings), it evaporates enough desinsections Agent with kill apart from textile 20cm exist insect.

Insecticide is impregnated on textile to have with acquisition and (that is, is being washed on the functional character mentioned by first aspect Can be killed after washing once apart from textile 20cm exist insect) textile one kind it is preferable that：It is being present in spinning Prepares coating around insecticide on fabric (generally on textile fiber).

Dipping carrying out preferably so that, insecticide with the coating around insecticide have low-solubility in the form of deposit .The effect of the coating be allow insecticide less dissolving in the coating, and when dissolving in the coating when, insecticide by because This " trying to leave " coating, or in other words, move to surface.It is possibly realized, enough insecticides are moved in a controlled manner Surface is moved on to, to evaporate enough insecticides, so as to kill the insect existed apart from textile 20cm.

The detailed description of common knowledge and this paper based on those skilled in the art, to those skilled in the art, The coating can in several ways be prepared (such as by using suitable polymer and adhesive).

Suitable example includes fluorinated hydrocarbon polymer.Fluorinated hydrocarbon polymer is suitable oil-repellent agent, hence allows to insecticide Rarely dissolve (low-solubility of insecticide) in the coating.Preferred fluorinated hydrocarbon polymer is the fluoro polymerized hydrocarbon being selected from the group Thing, the very big part of the molecule of the group only fluorinated hydrocarbon polymer of fraction as resin.Resin is used as storage, Fluorohydrocarbon gives washing protection.Suitable commercially available example is (deriving from Rudolf Chemie, Germany).

Other preferred polymer include polyurethanes, polyacrylic, Polyisocyanate esters and polylactic acid-based.

In preferred embodiments, short-term polymer is used.It is preferred that short-term polymer used has more than 1000 Monomer length and most of linearly aligned longer chain, so that less contact point and less polymerization additive.This Imply that polycondensation needs less energy, can such as carry out at a lower temperature, and the lower temperature for destruction insecticide and/or The risk of pest repellant is lower.Suitably having can be purchased in market from Rhodia more than 10000 polymer of the long-chain of monomer.

It is further preferred that being made " two-layer " coating.Ground floor exists on textile fiber around insecticide.This In one layer, insecticide should have relatively low dissolubility.The second layer sets up face on the first layer, with the dissolubility in ground floor Compare, second layer reply insecticide preferably has much lower dissolubility.The effect of " two-layer " coating system is：First Coating as insecticide " depots ".However, due in the ground floor insecticide there is low-solubility, therefore insecticide is worked as " will try to exit from " and move to second coating when being dissolved in the coating.There is lower dissolubility in second coating,

Therefore insecticide is by quickly in bloom to evaporate enough insecticides, so as to kill apart from textile 20cm The insect of presence.

Example for the suitable material of first coating is resin, and such as synthetic resin is (as being based on polyacrylate or poly- second Alkenyl class).Preferably, first coating is made up of thicker resin bed, to cause that first coating has larger storage storage capacity Amount.

Example for the suitable material of second coating is fluorinated hydrocarbon polymer (for preferred fluoro polymerized hydrocarbon on Described in thing).

In highly preferred embodiment, the impregnating woven product and this paper comprising insecticide of first aspect present invention Described corresponding embodiment is further characterized by：At least 65% insecticide is according to a fourth aspect of the present invention and such as this Particle is present in solid form in the textile of the related embodiment described in text.Details is for example, see below with respect to desinsection That part of agent solid form particle.

Textile comprising insecticide and/or pest repellant-contain solid form particulate

As described above, the 4th independent aspects of the invention are related to one kind still to be wrapped on textile surface after washing several times The impregnating woven product comprising insecticide and/or pest repellant containing insecticide and/or pest repellant, it is characterised in that：At least 65% Particulate is present in textile in solid form for insecticide and/or pest repellant, and in the textile at least 82% solid The particle size of form particulate is 0.1-25 μm.

Measurement whether at least 65% insecticide and/or the pest repellant particulate in solid form in specific textile of interest Exist it is preferable that based on using electron microscope (EM) photo method.

In order to measure whether at least 65% insecticide and/or pest repellant particulate is present in textile in solid form, The EM photos of the representative number of textile of interest (such as fabric, such as mesh) can be made.The EM photos of representative number Refer to the suitable quantity of the appropriate samples of textile of interest (such as fabric, such as mesh), with order to have from of interest The EM photos of the diverse location of textile, from terms of technical standpoint viewpoint, it is of interest that these photos can be described as " covering " (representative) The whole surface of textile (such as fabric, such as mesh).Determine that what can be the representative number of specific textile of interest The EM photos of amount are the common knowledges of those skilled in the art.As example, for typical commercial related mosquito net, represent The EM photos of property quantity can be 10 EM photos from mesh diverse location with the whole surface of " covering " textile. Based on these EM photos, can calculate this paper being present in textile it is relevant comprising insecticide and/or pest repellant solid shape Decline the quantity and size of grain.Generally know that specific textile of interest is the (painting how to prepare due to those skilled in the art Cover material etc.) and know the amount of application of coating material, therefore those skilled in the art can routinely calculate such as coating material The amount of (such as around insecticide and/or pest repellant), the coating material of the amount by it is objective be fifty-fifty present in it is related herein The solid form particulate comprising insecticide and/or pest repellant in.Thus, those skilled in the art can routinely calculate objective flat Insecticide and/or the amount of pest repellant that particulate is present in solid form, can objectively calculate micro- in solid form accordingly Grain is present in the total amount of the insecticide and/or pest repellant in specific textile of interest.Because those skilled in the art know Through for impregnating the insecticide of specific textile of interest and/or the total amount of pest repellant, therefore those skilled in the art know institute Textile is stated to amount to comprising how many insecticide and/or pest repellant.

In a word, due to those skilled in the art can routinely objective computation in solid form particulate be present in it is of interest specific The total amount of insecticide and/or pest repellant in textile and the textile totally include how many insecticide and/or pest repellant, Thus those skilled in the art can routinely determine whether at least 65% insecticide and/or pest repellant particulate is deposited in solid form In being specific textile of interest.

Therefore, in preferred embodiments, particulate is present in solid form at least 60% insecticide and/or pest repellant In textile, more preferably at least 82%, even more desirably at least 90%, most preferably at least 95% insecticide and/or pest repellant Particulate is present in textile in solid form.

Therefore, the preferred embodiments of the invention be related to fourth aspect present invention and related embodiment comprising desinsection Agent and/or the impregnating woven product of pest repellant, wherein the solid form particulate is the crystallite comprising insecticide and/or pest repellant The solid form particulate of grain.

Therefore, in preferred embodiments, solid form particulate is the microcrystal grain comprising insecticide and/or pest repellant Solid form particulate, wherein the microcrystal grain suitable material (such as resin) of the insecticide and/or pest repellant is coated.

Therefore, in preferred embodiments, the solid form particulate of at least 82% in textile is that particle size is 0.1-20 μm, more preferably particle size is 0.25-15 μm, even more preferably particle size is for 0.25-5 μm of solid form is micro- Grain, at least 82% solid form particulate most preferably in textile is that particle size is 0.25-3 μm of solid form particulate.

Solid form particulate is the solid form particulate comprising the insecticide microcrystal grain coated with resin.Accordingly, herein The particle size of the related solid form particulate comprising insecticide and/or pest repellant is related in textile as each particle The solid form particulate comprising insecticide and/or pest repellant being physically present with itself.It is described comprising insecticide and/or expelling parasite The solid form particulate of agent may include suitable coating material, such as around insecticide and/or the coating material of pest repellant.

During the example of preferred insecticide and/or pest repellant is described below.Especially with respect to preparing insecticide and/or drive Worm agent crystallite (as described herein), it is preferred that insecticide allows for forming crystallite or formation in solvent or aqueous mixtures The other forms of micro-solid form particulate.

As described above, the sixth aspect of the present invention is related to prepare the solid form particulate comprising insecticide and/or pest repellant Textile method, wherein methods described comprises the steps：

(B) said composition impregnating woven product are used.

Alternatively express, the 6th aspect is considered as being related to according to a fourth aspect of the present invention and its embodiment The fourth aspect present invention of the textile comprising insecticide and/or pest repellant solid form particulate and its preferred reality of embodiment Scheme is applied, wherein the textile can be obtained by the method for comprising the steps：

(B) said composition impregnating woven product are used.

This paper for preparing the suitable dip composition comprising insecticide and/or pest repellant in microcrystal grain is preferred Technology is considered as based on " standard " for preparing the microcrystal grain of compound of interest generally known to those skilled in the art Technology.During most preferably technology is described below herein.

The suitable dipping combination of insecticide and/or pest repellant that the preparation of step (A) exists comprising particulate in solid form A kind of method for optimizing of thing is the method for comprising the steps：

(1) by insecticide and/or pest repellant it is as far as possible dense be dissolved completely in and have for the insecticide and/or pest repellant (insecticide and/or pest repellant of higher concentration are for example obtained by heating) in compared with the organic solvent (such as acetone) of highly dissoluble；

(2) gained mixture is mixed into (preferably at a high speed) has relatively low deliquescent another solvent to the insecticide In (such as water), microcrystal grain (" precipitation ") is consequently formed, to obtain comprising the microcrystal grain containing insecticide and/or pest repellant The dip composition (such as solution or dispersion) of solid form particulate.

In preferred embodiments, the organic solvent of step (1) is the appropriate solvent to insecticide with highly dissoluble.Have The suitable example of machine solvent is selected from following organic solvent：Acetone, hexane, heptane, ligroin and petroleum ether；Aromatic hydrocarbon solvent (such as benzene, toluene and dimethylbenzene)；Halogenated hydrocarbon solvent (such as chloroform, carbon tetrachloride, dichloroethanes, chlorobenzene and dichloro-benzenes)；Ether solvents (such as ether, Di Iso Propyl Ether, dioxs, tetrahydrofuran and glycol dimethyl ether)；Ester solvent (such as ethyl acetate and acetic acid fourth Ester)；Nitro compound (such as nitroethane and nitrobenzene)；And dimethylformamide.Also their mixture can be used.

The solution further can be diluted with increment solvent, to provide the smaller composition of toxicity in more volume, or Person provides evaporating temperature higher.The boiling point for temperature being remained and being only only below the component with minimum boiling point is may also require that, To prevent insecticide from precipitating.

In preferred embodiments, the solvent with low-solubility in step (2) is colder, with " stimulation " microcrystal grain Produce.And it is also preferred that the solvent with low-solubility in step (2) includes emulsifying agent (preferably detergent), with breast Solid form particulate produced by changing (e.g., produced microdeposit particle is not gathered into too big precipitation).

Particle size can be reduced by heating the first stage (step (1)) and cooling second stage (step (2)).

Preferred steps (2) be blended in it is high speed homogenizing under carry out, but even hand operated mixing can also obtain good knot Really.

The solvent with low-solubility in step (2) can be water.In this case, by insecticide and/or pest repellant Be dissolved in them has compared with (step (1)) in the solvent of highly dissoluble wherein.Insecticide can be added to have wherein relatively low molten Solution property increment solvent, but concentration of the increment solvent in whole solvent phase have to be lower than insecticide occurs in the solution sink The concentration in shallow lake.The concentration can be increased by heating the mixture of increment solvent or heating insecticide, solvent and increment solvent.Will The solution is mixed into water phase (step (2)).In the mixed process, insecticide forms crystallite immediately, and mixture becomes desinsection Dispersion of the agent crystallite in water phase.Preferably, solvent is mutually entered into water phase mixing is high speed homogenizing to be carried out, low to ensure Particle size, while avoiding formation of foam using very low-level detergent.

The solvent with low-solubility in step (2) can be organic or inorganic solvent.In this case, by insecticide And/or pest repellant is dissolved in compared with (step (1)) in the solvent of highly dissoluble, then by it in preferred high-speed stirred, homogenizing Or the insecticide and/or pest repellant are mixed under ultrasonication wherein with (step in relatively low deliquescent second solvent (2)).Then, insecticide will in the mixture with little particle or crystal settling.Particle size can be by heating the first stage (step Suddenly (1)) and cooling second stage (step (2)) and reduce.Then it is preferably, by means of being primarily adapted for the suitable of increment solvent Emulsifying agent is by the emulsifying mixture to water.

The dipping of the textile of step (B) can be applied by by the dip composition comprising solid form particulate of step (A) Use on textile, optionally remove excessive solvent, and then appropriate coating insecticide and/or pest repellant are carried out.This is herein In may also be referred to as two-step method (that is, solid form particulate being applied on textile first, be then coated with them).

However, in preferred embodiments, this can be carried out with being referred herein as the method for one-step method, and the method feature exists In：The dip composition comprising solid form particulate of step (A) before the textile dipping for step (B), is wrapped Containing related additive material to be used to prepare (the short-term polymerization coated as being used to be polymerized of the related other materials of coating textile Thing monomer；For the stabilisation that these are coated, optional thickener to prevent crystallization dispersion from depositing, optional UV stabilizer Deng).Part or all of in these additives can mix according to step (2) with insecticide or expelling parasite agent solution or dispersion After or before add.

The dipping of the textile according to above-mentioned steps (B) is preferably carried out by following manner：

A) at a temperature of less than the boiling point of each solvent, textile (such as fabric, such as mesh) is passed through step (A) In the insecticide and/or the dip composition of pest repellant that exist comprising particulate in solid form, or by the dipping group of step (A) Compound is sprayed on textile；

B) optionally, superfluous insecticide and/or pest repellant is removed for example, by extruding, centrifugation or vacuum absorption；

C) by drying textile so that insecticide is precipitated on textile (such as fabric, such as mesh), and preferably open The dynamic coating for being polymerized and forming protectiveness chemicals；With

D) optionally, solidification and/or set textile.

In order to prevent the precipitation of insecticide, optional crystal is melted, and the temperature of the drying, solidification and set must The melting temperature of insecticide used must be preferably shorter than.

Alternatively, solvent mutually includes insecticide, at least two solvents and one or more emulsifying agents.By the insecticide Be dissolved in the first solvent, mix with the second solvent, its hybrid mode to cause to obtain solid form particulate as described above, so Afterwards by the suspended substance water emulsification, the O/W emulsions for impregnating are formed.By sticking agent, UV protective agents, technique protective agent etc. with Solvent is added in water phase before or after mixing.

Preferably, in all cases, the solvent evaporates in drying stage at relatively elevated temperature.In the party In method, the insecticide and/or pest repellant solid form particle deposition on the fiber surface or are deposited near fiber surface, and Coating chemicals is deposited on around these particulates.The drying process preferably should long enough, with cause coating chemicals extremely Small part is polymerized and ideally all polymerizations.

According to step (B), one kind that insecticide and/or pest repellant are impregnated on textile it is preferable that being present in Coating is produced around insecticide on textile (generally on textile fiber).

The carrying out of the dipping should preferably so that：Insecticide has low-solubility in the coating.The effect of the coating It is to allow insecticide rarely to dissolve in the coating, and therefore " will tries to exit from " being somebody's turn to do when insecticide is dissolved in the coating Coating, or in other words, move on surface.Enough insecticides is moved in a controlled manner turns on the surface of textile May.

The detailed description of common knowledge and this paper based on those skilled in the art, those skilled in the art can also be with several The mode of kind carries out the coating (such as by using appropriate polymer and adhesive).

The example of suitable polymer includes fluorinated hydrocarbon polymer.Fluorinated hydrocarbon polymer is suitable oil pest repellant, thus is permitted Perhaps insecticide rarely dissolves (low-solubility of insecticide) in the coating.Preferred fluorinated hydrocarbon polymer is the fluorine being selected from the group For hydrocarbon polymer, the group is characterized by more than 1000, preferably greater than 5000 monomers it is very long almost linear Resin (carbamate or acrylic resin).Other preferred polymer include the polyurethanes without side chain, poly- third Olefin(e) acid class, Polyisocyanate esters and polylactic acid-based.

It is further preferred that being made " two-layer " coating.Ground floor around insecticide is present on textile fiber.At this In ground floor, the insecticide should have relatively low dissolubility.The second layer is set up above ground floor, and in ground floor Dissolubility compare, the second layer reply insecticide preferably have much lower dissolubility.The work of " two-layer " coating system With being, first coating as insecticide " depots ".However, due to having relatively low dissolubility in ground floor, therefore kill Worm agent " will be tried to exit from " when being dissolved in coating and move to second coating.There is much lower dissolving in the second layer Property, therefore insecticide will the relatively rapidly frosting on textile surface.

Example for the suitable material of first coating is resin, and such as synthetic resin is (as based on polyacrylate or poly- It is vinyl-based).Preferably, first coating is made up of thicker resin bed, to cause that first coating has larger depots Capacity.

Example for the suitable material of second coating is that fluorinated hydrocarbon polymer (is seen above on preferred fluoro polymerized hydrocarbon Described in thing).As described above, fluoro hydrocarbon layers are used as insecticide to be maintained at two regions (or at first coating (such as resin) In " depots " or on textile surface) in barrier.Surface insecticide is supplemented after evaporating or washing off.

In preferred embodiments, short-term polymer is used.Preferably, short-term polymer used has longer chain (preferably its chain has 1000-20,000 monomer), so that less contact point and less polymerization additive.This is dark Show, polymerization/polycondensation (solidification) can be carried out at a lower temperature, and the lower temperature is for destruction insecticide and/or pest repellant Risk it is lower.

Fourth aspect present invention and its embodiment comprising insecticide and at least 65% insecticide in solid form Particulate is present in the preferred embodiment of the impregnating woven product on textile, further characterized in that, it is the present invention The impregnating woven product comprising insecticide of first aspect and its embodiment are (that is, on the surface of textile after washing several times On still comprising insecticide the impregnating woven product comprising insecticide), it is characterised in that：Washed in the suds of 0.2-0.5% After washing 10 minutes (as described in WHO standard experiment (WHOPES2005/11) for mesh sample), it evaporates enough desinsections Agent with kill apart from textile 20cm exist insect (according to the experiment of embodiment hereof 1).

An integrated technique --- the dipping of textile and set

As described above, the 7th independent aspects of the invention are related to a kind of dipping prepared comprising insecticide and/or pest repellant The method of textile, it is characterised in that two techniques (a) and (b) that will be specified below are integrated into a technique：A () is by desinsection Agent and/or pest repellant are impregnated into textile, and (b) textile set, wherein methods described comprises the steps：

A () described impregnation technology is can to carry out polycondensation or polymerization (solidification) to obtain at the temperatures used based on use Obtain polymer coating and polycondensation or polymerization can be carried out without forming the monomer or short of ion (such as halogen ion) or free radical Phase polymer, and wherein

(II) optionally, superfluous composition is removed by extruded fabric or mesh；With

(III) the drying fabric is passively or actively at a temperature of 20-200 DEG C.

The technological temperature of step (I) temperature wanted generally more commonly required than simple coating is higher, but ratio is generally used for thermosetting The temperature is lower.Typically, the temperature is 120-180 DEG C, but there is the set addition that set can be provided at about 80 DEG C Agent.

Preferably, the set additive is selected from following additive：Condensation polyurethanes and polyacrylate (such as Rhodopass, derive from Rhodia), the anionic stabilizer for such as being used in colour stabilizer system (such as Ciba P and Cibafast4595), as be mixed with prevent the kicker of 120 DEG C of pre-polymerization blocked isocyanate be polymerized poly- ammonia Esters (such as in Rucoguard).Cation kicker generally can not be used, because the water of the ester bond of their meeting acceleration of killing agent Solution (wherein these esters are the esters as pyrethroid, organophosphorus ester and carbamate).The aqueous emulsion of additive is preferred It is weakly acidic, and is never alkalescence, because most of insecticides tested can be destroyed in alkalescence, especially in elevated temperature Lower destruction is faster.

In all of technological temperature, may only be walked using the catalyst or accelerator that are not based on being formed free radical Suddenly the polymerization of (I) (a).One example is the isocyanates based on closing.And, when desinsection of the use with halogen reactive center During agent, it is impossible to use the polymerization interacted based on halogen ion.

Preferably, the polymer coating for being obtained in step (I) (a) is selected from fluorinated hydrocarbon polymer, polyurethanes, gathers Acrylic compounds, Polyisocyanate esters and polylactic acid-based polymer.Preferred fluorinated hydrocarbon polymer is the fluorohydrocarbon being selected from the group Polymer, the very big part of the molecule of the group only fluorinated hydrocarbon polymer of fraction as resin.Resin is used as storage Zang Ku, fluorohydrocarbon gives washing protection.

In preferred embodiments, short chain polymer is used in step (I) (a).Preferably, it is used short-term poly- Compound is (preferably greater than 1000 monomers long and most of linear array) more long, so that less contact point and less Polymerization additive.This implies that polymerization/polycondensation destroys insecticide and/or the risk of pest repellant is lower.

The example of the monomer or short-term polymer that are not suitable for step (I) (a) be in order to be polymerized using polymerization from By base polymerization and halogen reaction or hydrolysis of ester bonds with cationic catalyst those.

In preferred embodiments, according to a seventh aspect of the present invention and its related embodiment, for the dipping of textile It is following method with the integrated one-step method of set, the method is obtained：

- according to a first aspect of the present invention and its related embodiment the impregnating woven product containing insecticide, the textile steam The insecticide for sending out enough, to kill the insect existed apart from textile 20cm；And/or

- according to a fourth aspect of the present invention and its related embodiment several times wash after on textile surface still The dip composition comprising insecticide and/or pest repellant comprising insecticide and/or pest repellant, it is characterised in that：At least 65% Insecticide and/or pest repellant particulate is present in textile in solid form, and at least 82% consolidating in the textile The bodily form grain that declines is that particle size is 0.1-25 μm of solid form particulate.

The preferred embodiment related to all aspects of invention as described herein：

Insecticide

For all aspects and embodiment herein, insecticide is preferably with rapid paralysis or the effect for killing insect simultaneously Insecticide with extremely low mammalian toxicity.

Preferred insecticide is belonging to one group of insecticide of Pesticidal compound as described in US2005/0132500A1.

Central, the insecticide with low water-soluble is best suitable for the method, especially when washability is important.

In preferred embodiments, insecticide is pyrethroid, such as decis (deltamethrin), ethofenprox (etofenprox), alpha cypermethrin (alfacypermethrin), lambda-cyhalothrin (lambdacyhalothrin) or fluorine Cypermethrin (cyfluthrin).The more new pesticides with relatively low mammalian toxicity are that more people is interested under dosage Substitute, this is especially because the insect that carries disease germs (vector insect) seldom develops the resistance to the action of a drug to these insecticides.Institute The novel pesticide stated is pyramidialmine (pyramine phenylate (Pyrimidifen)), pyrazoles (Frontline (Fipronil) With fenpyroximate (Fenproxiamte)), pyroles (clofenapyr) and imidacloprid (imidacloprid).

When mesh is used for large-scale activity, it is alternatively that or the insecticide of supplement can also be with bactericidal effect Insecticide, thus the next generation that is sterilized and avoiding mosquito is carried out to mosquito.Described insecticide can be benzoyl area kind (such as 1- (α- 4- (chloro- α-cyclopropyl benzylideneamino-epoxide)-p-methylphenyl) -3- (2,6- difluoro benzoyl) urea)；TH-6040 (Diflubenzuron)：N- (((3,5- bis- chloro- 4- (1,1,2,2- tetrafluoro ethyoxyl) phenyl amino) carbonyls 2,6- difluorobenzene first Acid amides；Desinsection is grand (Triflumuron)：The chloro- N- of 2- (((4- (trifluoromethoxy) phenyl)-amino -) carbonyl)-benzamide, Or triazine (such as N- cyclopropyl -1,3,5-triazines -2,4,6- triamines, or there are other insecticides of bactericidal effect to adult mosquito.

Pest repellant

For all aspects and embodiment herein, pest repellant is preferably belonging to a group described in US2005/0132500A1 The pest repellant of Pesticidal compound.

The preferred embodiment of suitable pest repellant is the pest repellant being selected from the group：N, N- Diethyl-m-toluamide (DEET) And N, N- diethylbenzene acetamide (DEPA) and the pyrethroid registered as pest repellant, such as Dtrans allethrin (esbiothrin) (amyl- 2- (+) the trans-chrysanthemate ester (chrysantemate) of 3- pi-allyl -2- methyl -4- oxo rings).

Preferred textile-fabric

In preferred embodiments, textile is fabric.Preferred fabric is the fabric being selected from the group：Mesh is (preferably Mosquito net), bedding, blanket, curtain and clothes (such as socks, trousers or shirt).

The fiber of preferably textile product is that, by synthetic fibers, such as nylon, acrylic acid, polyester, polypropylene and/or polyethylene is made Fiber.Blanket is made up of cotton or cotton-polyester mixture in preferred embodiments.

Dark dipping fabric can be used as catching mosquito agent.In this case, insecticide should preferably not be pest repellant, because should Effect is not based on making insect away from being conversely to allow them to hide and be retained in fabric.Insect (such as mosquito) is hidden on daytime In dark place, so that finding the dipping fabric hidden insecticide or killed by insecticide.Dipping fabric can also be wrapped Containing the remote insecticide or pest repellant driven away or kill insect, thus supplement or replacement such as dipping net.Can also be suspended on sleeping In room, thus effect of the increase in the bed net in same room even when being not impregnated with.Can be used for clothing or carpet, as long as insecticide It is hypotoxicity and no skin irritation effect, such as false pyrethroid, ethofenprox.

Dipping-be typically dried/cured

For all aspects and embodiment herein, preferred impregnation technology is described below, Gu including it is preferred dry/ Change.

Typically, the dipping of textile is preferably carried out by following manner：

A) textile (such as fabric, such as mesh) is passed through in the dip composition comprising insecticide and/or pest repellant, Or spray on textile dip composition；

D) optionally, solidification and/or set textile.

Fabric (such as mesh) is preferably for example, by being passed through air stream, passing through under infrared lamp or by ultrasound or simple Ground is dried in an oven.Fabric and especially mesh preferably must in the process keep set without changing shape. The temperature used in drying process must be preferably lower than the boiling point of insecticide, so as to avoid causing insecticide in preparation process Loss, and the loss is likely to result in environment and worker-safety issues.Change between insecticide and crosslinking agent or polymerizable molecular It is temperature dependency to learn cross-linking reaction, has to consider it thus for optimal process.The polymerization for forming free radical preferably must Need avoid, the catalyst of hydrolysis of ester bonds with can potentially destroy many insecticides containing ester bond.

Overflow dyeing machine that impregnation technology can also be used in such as industrial textile is carried out in rinsing maching.These methods it is excellent Point is that they can be after cutting out and sewing for textile applies coating or dipping.Thus the place of insecticide treated material is reduced Reason, and material is dry in drying tumbler, or make size set when needing and being stretched in drying process It is dried in machine.

Fabric can also be made to pass through such roller, in roller segment ground immersion dip composition solution or emulsion, and should Solution or emulsion are taken out of on that side of mesh or fabric contact roller.

Mesh or fabric after arrangement can be with dip composition dispersion, solution or emulsions by mesh or fabric Upper spray stream body phase is impregnated, such as impregnated in improved washing machine or in transmission belt.Then, can be by after arrangement Mesh or fabric are for example dried with air, or are dried in drying tumbler or in baking oven, or through infrared light or super Sound is dried.

As is described in greater detail herein, the dip composition solution or emulsion can further include one kind or many Plant and be selected from following composition：Detergent, stabilizer, UV protective agents, solvent, spreading agent, migration inhibitor, preservative, formation of foam Agent and anti-fouling agent.

Other auxiliary agents that will be used are antistatic additive, anti-grey agent and anti-roll agent.And, the present composition can also be mixed To in the detergent mixture of clothes washing, or it is incorporated into the conditioner (fabric softener) of rinsing fabric.Should examine Consider, most fabric softener is that based on cationic detergent, and the latter may degrade insecticide.In this aspect There should be particular formulations to consider.

Preferably carried out at a temperature of less than 200 DEG C with the dipping of insecticide, preferably less than with the molten of minimum boiling point Carried out under the boiling point of agent or insecticide, to reduce volatilization in the process.

The administration of insecticide and/or steeping liq can also be by forming the foam of emulsion with the composition, and should Foam is applied on mesh or fabric and carries out.The amount of application of liquid is this method reduce, thus is reduced in subsequent drying Energy ezpenditure in technique.

Dipping can be by using as described in the simple sprayer administration for agriculturally or in mosquito-proof room spray using Emulsion is carried out.The method is a kind of alternative method, and impregnate poor before extremely can be used for impregnating again or Mesh or fabric that person is not impregnated into.During administration of spraying, it is necessary to operate to avoid suction comprising insecticide with caution Other mixtures.Additionally, preferably being recycled by evaporating the solvent for removing in plant processes.

In subsequent drying process, temperature is preferably shorter than 200 DEG C, and desinsection is removed to avoid such as rapid solvent evaporation Agent.Vapour pressure higher for extension in wherein particular formulations and wherein insecticide preparation also higher, relatively low drying It is sufficient that temperature, requires relatively low drying temperature.In dry and solidification/set technique, the temperature with transformation temperature Distribution can be used to obtain the optimum performance of coating.

When fabric is fine and close and thick, the room temperature in the technique can be higher than said temperature, as long as the temperature in the fabric does not surpass Cross these limit.Solidification can also include operations described below or is made up of operations described below：Make fabric or mesh by being pressurized Heating surface, such as flatiron or hot-rolling.In drying process and solidification process, fabric or mesh by mechanically set, To prevent them from deforming.

According to the present invention, impregnation technology can also be carried out with very simple equipment.Fabric or mesh immersion are included Required insecticide/pest repellant and protective agent (make it easy to soak and stablize the emulsion/solution of concentration with needed for Suitable detergents) aqueous emulsion or the aqueous solution in.Superfluous water is removed by being extruded manually or by simple roller, will be described Fabric, clothes or mesh horizontal positioned are simultaneously dried, and are preferably dried in the shade.Solidification can be pressed by a temperature of less than 200 DEG C It is improved.

In other embodiments of the present invention, impregnation technology as herein described can also be spun into fiber, it is woven or Carried out before braiding.Fiber according to present invention dipping is related to be formed the single structure of clothes.However, the dipping can also be direct Carried out to clothes or to final fabric (such as mosquito net).In an example, it is by 20- according to currently preferred mesh The net that 72 spun yarns for being spun into fiber are made, by the fibrage into net or machine woven into fabric.Used according to the invention is poly- Compound can substantially coat the filament or spinning fiber in fabric, so as to cause excellent resistant to wash-off ability, while making activity Composition is discharged with being enough to show the amount of insect killing or expeling effect.

Common protectiveness (such as coating) material

All aspects and embodiment for this paper, describe preferred protectiveness (such as coating) material below.

Forming the component of coating can include the polyurethanes, the polypropylene that mix with poly- fluorohydrocarbon or polyorganosiloxane ramification Acids, Polyisocyanate esters and polylactic acid-based, or it simply can be made up of polymer formative fender, the fender by Shorter polymer or monomer is formed.

The consumption of insecticide and/or pest repellant in fabric

All aspects and embodiment for this paper, describe insecticide and/or pest repellant preferred in fabric below (typical case) consumption.

Obviously, textile (such as fabric) as described herein can include insecticide and pest repellant.And it can include two kinds Or more plant different insecticides and/or pest repellant.In useful embodiment, by more than one insecticide according to the present invention It is administered.Therefore, a part of fabric (such as mesh) for example can be impregnated with a kind of insecticide, and another part can use another kind Insecticide impregnates, so as to prevent anti-insecticide, or when anti-insecticide be already present in them it is a kind of when prevented Control effect.Two kinds of insecticides should preferably belong to wherein cross-resistance can not possibly play the group of Main Function.

The typical amounts of insecticide and/or pest repellant are that the 0.001-10% of fabric (such as mesh) (dry) weight is (dry Weight), this depends on the insecticidal power of such as insecticide and/or pest repellant.Preferred consumption is 0.05-1%, is specifically dependent upon Insecticide and/or pest repellant.For the pyrethroid of such as decis or alpha cypermethrin etc, preferred consumption is The 0.05-0.3% of fabric weight.For such as Permethrin or the pyrethroid of ether polyester, preferred consumption is 0.1-6%.

The consumption of protectant consumption and insecticide depends on many factors.The dosage of insecticide must be enough to kill elder brother Worm, perhaps kills the insect (being technically to remove the Resistant Individuals of heterozygosis to postpone resistance appearance) of even slight resistance. Preferably, dosage excessive enough must then be selected as stock (preferably crystal form), it is bioavailable from the stock Insecticide can (be ideally several years) in a period of extension draw, although cyclic washing is also such.Once Determine so, coating just must be preferably sufficiently thick or be crosslinked to be enough to resistance to migration, so as to it be protected with required minimum Hold.External coating preferably must have low-solubility for insecticide, so as to be not configured to the storage that insecticide is easy to remove therefrom Zang Ku.

For protecting (coating) with the fluorohydrocarbon including specific fluorohydrocarbon for increasing resin bed, its typical amounts is 0.1- 10%, preferably 0.5-3%.For polyurethanes, polyacrylic, Polyisocyanate esters and polylactic acid-based, typical amounts are 0.01-10%, preferably 0.2-5%.

Based on protectant amount, crosslinking agent and bridging agent and the typical adding proportion of catalyst are less than 1:1.These should It is preferred that not being the type that insecticide can be destroyed as most of free radical and peroxide.Most interested is that can provide net The chemical set of fabric or fabric and simultaneously contribute to protection insecticide without destroying its combination of polymers.

The typical amounts of the pest repellant for being used with insecticide composition or being used alone are the 0.1-10% of solvent or aqueous emulsion, So as to produce the 0.001-1% contents of dipping mesh or fabric, based on dry weight.

Depending on the purposes of final products, UV filtering agents can be added to prevent or reduce sunlight to insecticide and/or expelling parasite The passivation of agent.UV filtering agents should be selected to be absorbed with the UV of insecticide and matched certainly.And, it should not play the solvent of insecticide Effect, and thus reduce crystal formation and increase coating in rate travel.

In other embodiments, impregnating woven product (such as fabric) of the invention can also be selected from comprising one or more Following component：Water, solvent, preservative, detergent, stabilizer, UV protective agents, spreading agent, migration inhibitor, preservative, water resistant Solution agent or antioxidant, and pickup reduce agent.Pickup reduces agent and is preferably selected from fluorinated hydrocarbon, and it is also film forming agent of the invention. Therefore, fluorinated hydrocarbon can be added into when other film forming agents are applied, and dye and reduction wash-out are dirt to reduce infusion product.

Embodiment

Embodiment 1：Test the experiment of the remote effect of insecticide

In order to test the remote effect of dipping mosquito net, the mosquito net is suspended on the room of 2.5m × 2.5m × 2m (height) It is interior.The cylinder mould of 10cm × 10cm × 10cm is suspended on apart from the space of mosquito net 50cm.By 10 female malarial mosquitos of susceptible strain (3 day age and do not feed blood, but use feeding sugar solution) is incorporated into cylinder mould for 6 points in the afternoon.In 7 points and 24 hours of the next morning Afterwards, survival rate is determined, and is compared with similar room but using the result that mosquito net obtains is not impregnated with.Measurement is shown in the following table Go out.

Mesh is tested in this experiment.However, the principle of the experiment can be used to test any textile of interest (such as fabric).And, the experiment can be used for test, and (cylinder mould is simply suspended on the sky apart from mosquito net 20cm at such as 20cm Between) effect.

The first two contrasted in washing for the first time contains the mesh of insecticide, and one of which is made coating, another Plant and be made through dipping in fiber.Both meshes represent the WHO of the day only commercially available acquisition in present patent application proposition Long-acting (" the wash resistant ") mesh recommended.

Embodiment 2：The contrast after wash of two kinds of meshes, a kind of evaporation without insecticide after washing, and it is another A kind of evaporation for having an insecticide.

Each data represent the average value that washing mesh is followed by even 4 days.For using decis mesh, at a distance The evaporation effect of mosquito eradication is not rebuild, and for the mesh using alpha cypermethrin, the evaporation effect part of remote mosquito eradication Rebuild.Alpha cypermethrin mesh is prepared according to the present invention, and aforementioned differences are due to because being evaporated caused by formula variation Speed, alpha cypermethrin mesh is based on permeable polyurethane coating prepared in accordance with the present invention.After only 24 hours 35% death rate is significantly different with the reference death rate of untreated mesh.

Use the formula of alpha cypermethrin：There are 0.3 gram of alpha cypermethrin, 1 gram of dimethylbenzene, emulsifying agent in 100mL 0.05 gram, 3 grams of polyurethane, 0.2 gram of UV filtering agents, the acquisition rate 70% in mesh.Polyurethane evaporates after allowing washing, lays equal stress on Build remote effect.

Embodiment 3：Fabric with remote effect

The embodiment is related to mesh of the invention, and by using the experiment of embodiment 1, the mesh has good remote Distance kills insect effect.

Per 100ml：3 grams of Permethrin (Permethrin), 1 gram of dimethylbenzene, 0.1 gram of emulsifying agent, 10 grams of polyurethane, UV filterings 3 grams of agent, acquisition rate 75%.Immersion fluid is emulsion, and the emulsion is the O/W emulsions of the insecticide oil droplet.UV filtering agents can be made Be single emulsion addition, or with insecticide emulsify after add.When drying, water evaporation, oil is drawn into polyurethane coating.

Applicant states that the present invention illustrates detailed process equipment of the invention and technological process by above-described embodiment, But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, Addition, the selection of concrete mode to the equivalence replacement and auxiliary element of each raw material of product of the present invention etc., all fall within of the invention Within the scope of protection domain and disclosure.

Claims

1. a kind of impregnating woven product comprising insecticide and/or pest repellant, it is characterised in that at least 65% insecticide is with solid Form particulate is present in textile, and at least 82% solid form particulate in the textile is that particle size is 0.1-25 μm of solid form particulate, and wherein described solid form particulate is the crystallite comprising insecticide and/or pest repellant The solid form particulate of particle.

2. the impregnating woven product of insecticide and/or pest repellant are included as claimed in claim 1, it is characterised in that the crystallite Particle is selected from as the insecticide and/or pest repellant microcrystal grain coated with resin.

3. the impregnating woven product of insecticide and/or pest repellant are included as claimed in claim 1 or 2, it is characterised in that the leaching The carrying out of stain should cause that insecticide exists in the form of having low-solubility in the coating around insecticide, and the painting Layer effect be it allow insecticide rarely dissolve in the coating, and when insecticide is dissolved in the coating will therefore from The coating is opened, or is in other words moved on surface.

4. impregnating woven product comprising insecticide and/or pest repellant as described in one of claim 1-3, it is characterised in that its At least 82% solid form particulate in middle textile is that particle size is 0.25-3 μm of solid form particulate.

5. impregnating woven product comprising insecticide and/or pest repellant as described in one of claim 1-4, it is characterised in that its In the textile include insecticide, and it be after washing several times on textile surface still including comprising insecticide The impregnating woven product of insecticide；

After being washed 10 minutes in the suds of 0.2-0.5%, it evaporates enough insecticides to kill apart from textile 20cm The insect of presence.

6. impregnating woven product comprising insecticide and/or pest repellant as described in one of claim 1-5, it is characterised in that its In be made two layers of coatings, wherein ground floor exists on textile fiber around insecticide, and in the ground floor, desinsection Agent has relatively low dissolubility；And the second layer sets up face on the first layer, and compared with the dissolubility in ground floor, should Second layer reply insecticide has much lower dissolubility, wherein be resin for the material of first coating, such as synthetic resin, and And preferably the first coating is made up of thicker resin bed, to cause that there are larger reservoir capacities, and wherein it is used for the The material of two coatings is selected from fluorinated hydrocarbon polymer, polyurethanes, polyacrylic, Polyisocyanate esters and polylactic acid-based poly- Compound.

7. impregnating woven product comprising insecticide and/or pest repellant as described in one of claim 1-6, it is characterised in that its In the textile pass through the method that comprises the steps and obtain：(A) insecticide comprising the presence of particulate in solid form is prepared Suitable dip composition；(B) said composition impregnating woven product are used；

The method of the dip composition of the insecticide that the preparation of wherein step (A) exists comprising particulate in solid form is under including The method for stating step：

(1) insecticide is dissolved completely in for the insecticide with the organic solvent compared with highly dissoluble；

(2) gained mixture is mixed into the insecticide during there is relatively low deliquescent another solvent, is consequently formed micro- Brilliant particle, to obtain the dip composition of the solid form particulate comprising the microcrystal grain containing insecticide.

8. impregnating woven product comprising insecticide and/or pest repellant as claimed in claim 7, it is characterised in that wherein step (1) with the organic solvent compared with highly dissoluble be acetone, hexane, heptane, ligroin, petroleum ether, benzene,toluene,xylene, chlorine Imitative, carbon tetrachloride, dichloroethanes, chlorobenzene, dichloro-benzenes, ether, Di Iso Propyl Ether, dioxs, tetrahydrofuran, glycol dinitrate Any one in ether, ethyl acetate, butyl acetate, nitroethane, nitrobenzene or dimethylformamide；And wherein step (2) solvent with low-solubility in is water.

9. the impregnating woven product of insecticide and/or pest repellant are included as claimed in claim 7 or 8, it is characterised in that wherein walked Suddenly the dipping of the textile of (B) is carried out by following manner：A) at a temperature of less than the boiling point of each solvent, textile is passed through In the dip composition of the insecticide existed comprising particulate in solid form of step (A), or the dipping of step (A) is combined Thing is sprayed on textile；B) optionally, superfluous insecticide is removed by extruding, centrifugation or vacuum absorption；C) by textile Dry so that insecticide is precipitated on the textile, and preferably starts the coating for being polymerized and being formed protectiveness chemicals；And d) appoint Selection of land, solidification and/or set textile.

10. impregnating woven product comprising insecticide and/or pest repellant as described in one of claim 1-9, it is characterised in that its Described in insecticide be decis, ethofenprox, alpha cypermethrin, lambda-cyhalothrin or cyfloxylate in any one Or at least two mixture；And wherein the consumption of insecticide is the 0.001-10% of the dry weight of fabric；

Wherein the textile is fabric, and preferably the fabric is the fabric being selected from the group：Mesh, bedding, blanket, curtain and Clothes.