CN104838060B - The method for preparing the fabric comprising insecticide - Google Patents
The method for preparing the fabric comprising insecticide Download PDFInfo
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- CN104838060B CN104838060B CN201380063511.1A CN201380063511A CN104838060B CN 104838060 B CN104838060 B CN 104838060B CN 201380063511 A CN201380063511 A CN 201380063511A CN 104838060 B CN104838060 B CN 104838060B
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- Prior art keywords
- acid
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- detergent
- water
- polymer
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
Abstract
The present invention relates to a kind of improved method for preparing the fabric comprising insecticide, the fabric includes the active component of the alkaline-sensitive of the desinsection at least one embedded polymer substrate.The invention further relates to the method in the life-span (including store and use) for extending the fabric for including alkaline-sensitive insecticide.
Description
The present invention relates to a kind of improved method for preparing the fabric comprising insecticide, the fabric is comprising at least one embedded
The active component of the alkaline-sensitive of desinsection in polymeric matrices.The invention further relates to extend the fabric for including alkaline-sensitive insecticide
Life-span (including store and use) method.
It is effective to reducing Mosquito population and Incidence Rate of Malaria to have proven to long-acting lasting insecticidal net (LLIN).It is various not
Sold with LLIN (or needing), it uses polymeric material (such as polyethylene, polypropylene and polyester) and insecticide (such as bromine
Cyano chrysanthemate (Deltamethrin), α-cypermethrin (Alpha-Cypermethrin) and permethrin (Permethrin)) (ginseng
See the LLIN that WHO recommends：http：//www.who.int/whopes/Long_lasting_insecticidal_nets_Jul_
2012.pdf).Some insecticides for being used for LLIN be described as pH it is sensitive and for how to be kept away during LLIN is prepared
The unfavorable degraded for exempting from the insecticide (such as decis and permethrin) of alkaline-sensitive gives suggestion (WO2011/
124227A1).Specifically, it is proposed that in process of production mix the insecticide and thermoplastic polymer of a kind of acid and alkaline-sensitive
Close so that the acid turns into the LLIN finally prepared part.However, the scheme proposed in WO2011/124227A1 may
The mechanical stability of fabric can be caused to be reduced due to sour addition in solid particulate form.In addition, produced by the acid added
Acidity can cause to the undesirable toxicity of user, for example, in use to have skin due to the acid in yam surface
Corrosivity.
In view of prior art, it is an object of the invention to solve to be used for LLIN alkali during production (and use)
Property sensitive insecticide degraded/racemization the problem of, so as to avoid the generation of the LLIN with potential unfavorable feature.Especially
It is, it is contemplated that the R- αisomers for reducing the inactive isomers such as decis of the desinsection of decis are (following to be also referred to as
For R- αisomers) forming amount, and be intended to keep high content desinsection active decis isomers (S- αisomers).It is existing
It has been found that the present invention can solve this problem by a kind of method for preparing polymer fabrics, wherein by polymer and more than one
The active insecticidal components of alkaline-sensitive melt or be respectively melted together at a temperature of between 120 and 250 DEG C, make melt composition
Sewing thread (spun thread), and using spinning oil during spinning, the sewing thread being cooled into, and pass through
Tensioning system, is stretched and weaves to form fabric, then carries out thermal finalization operation to fabric, it is characterised in that in thermal finalization operation
Polymer fabrics are washed before：
- the acid water with pH value less than 5, or
- the detergent being less than with water and pH value under 5 acid condition, or
- use includes alkylaryl sulfonates (one or more), fatty acid ethoxylates (one or more) and/or fat
The detergent of alcohol b-oxide (one or more)
And/or
Acid spinning oil is applied on line in spinning process and (carries out purge step in the Optional of thermal finalization operation
Suddenly).
The method of the manufacture fabric of washing step and the use note of spinning oil are carried out before being included in thermal finalization operation
It is loaded in WO2011/141260A1.However, optimal wash conditions are not discussed in WO2011/141260A1 and in manufacturing process
It is middle to use acid spinning oil.The use of acidic cleaning groove or acid spinning oil is not also recorded in WO2011/124227A1.
Existing method for preparing polymer fabrics, usable thermoplastic polymer such as TPO is (polyethylene, poly-
Propylene etc.), polyesters (polyethylene terephthalate (polyethylenterephthalates) etc.) and it is polyamide-based with
And the composition of the fabric manufactured by different polymer.It is however preferred to use TPO, particularly polypropylene and polypropylene
Copolymer.More preferably use polypropylene.Polyacrylic diversity is well known in the prior art.Polypropylene in principle can basis
Their synthesis mode is distinguished.Polyacrylic major part in the presence of Ziegler-Natta catalyst with suspension method or
More particularly prepared with so-called vapor phase method (referring to Kaiser " Kunststoffchemie f ü r Ingenieure ", the 246th
Page is to page 254).Specific catalyst such as metallocene can also be used in vapor phase method.The polymer prepared using metallocene catalyst
It is particularly useful as the polymeric matrices of the present invention polymeric material comprising insecticide to be used.Prepared using metallocene catalyst
Polyacrylic fusing point be generally significantly lower than those that conventional heterogeneous catalysis system can be used to obtain.The present invention's includes desinsection
The polymeric material of agent prepares long filament, fiber and the polypropylene of spinning building preferably by melt-spinning process is intended for.It is special
Do not preferably use polypropylene be used for prepare have 50 to 150 fiber numbers low line density multifilament (multifilament).These are
Polymer for example with following trade names：With(coming from LyondellBasell, Holland),(Reliance Industries Limited, India),(SK corporation, Korea S),(LG Chemical, Korea S),WithGrades (Total Petrochemicals, than
When sharp) and(ExxonMobile Chemical Company, the U.S.).Poly- the third of particularly preferred metallocene catalysis
Alkene, for exampleHM562S, 145 DEG C of fusion temperature (come from LyondellBasell, Holland) and
3845 (ExxonMobile Chemical Company, the U.S.).
Additive can be added when preparing used polymeric material, the additive is mixed into polymer, with
Stabilization improves its working properties.Suitable additive is single phenol, the Alkvlthiomethvlphenols of such as alkylation
(alkylthiomethylphenol), quinhydrones, tocopherol, hydroxylated thiodiphenyl ethers, alkylidene bisphenol, O-, N- and S- benzyl
Based compound, Hvdroxvbenzvlated malonates, Aromatic hydroxybenzyl compound, triaizine compounds, acylamino- phenol, β-(3,5- bis-
Tert-butyl-hydroxy phenyl) propionic acid and monohydric alcohol or polyalcohol ester, β-(5- tertiary butyl-4-hydroxy -3- aminomethyl phenyls) propionic acid
Ester, β with monohydric alcohol or polyalcohol-(3,5- dicyclohexyl -4- hydroxy phenyls) propionic acid and unitary or ester, 3, the 5- bis- of polyalcohol
Tert-butyl-hydroxy phenyl acetic acid and monohydric alcohol or ester, the acyl of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid of polyalcohol
Amine, ascorbic acid (vitamin C) and amino antioxidant (aminic antioxidants).Can also use thiosynergistic,
Secondary antioxidants, phosphite ester and phosphonous acid diester.
Polymeric material used can also be prepared by using following material：Metal deactivators, peroxide are removed
Agent, the co-stabilizer of alkalescence, nucleator, plasticiser, lubricant, emulsifying agent, pigment, viscosity improver, catalyst, flow control
Agent, Optical Bleaching Agent, fireproof agent, antistatic additive and foaming agent, benzofuranone and indolone, fluorescence plasticizer, releasing agent, UV
Stabilizer, flame-retardant additive, antistatic additive such as sulfonate, pigment and organic and inorganic dyestuff and include cycloalkyl groups
Or the compound of anhydride group.
, first, will be poly- at a temperature of between 120-250 DEG C (preferably 150-230 DEG C) in order to prepare the fabric of the present invention
Compound material (preferably polypropylene), the active insecticidal components of alkaline-sensitive and optionally (it is preferred that) UV stabilizer and optionally
Other insecticides or additive melt or are respectively melted together, then cooling and solidification polymer mixture, and the latter is thin
It is divided into pellet.
In addition to insecticide, can optionally (and preferably) using UV stabilizer, (i.e. UV absorbents and/or light are steady
Determine agent), consumption is 0.01 weight % to 15 weight %, and preferably 0.03 weight % is to 8 weight %, based on the polymerization comprising insecticide
The gross weight meter of the composition of thing material.For implement the UV absorbents and/or light stabilizer of methods described for such as 2- (2 '-
Hydroxy phenyl) BTA, 2- dihydroxy benaophenonels, substitution and unsubstituted benzoic acid ester, acrylate, nickel chemical combination
Thing, sterically hindered amines, oxamides, 2- (2- hydroxyphenyls) -1,3,5-triazines and its mixture.It is preferred that without using the non-steric hindrance in space
Amine as UV stabilizer, and use 2- (2 '-hydroxy phenyl) BTA, 2- dihydroxy benaophenonels, substitution and it is unsubstituted
Ester, acrylate, nickel compound, oxamides, 2- (2- hydroxy phenyls) -1,3,5-triazines and its mixture of benzoic acid.It is special
Not preferred triaizine compounds and butrimezole.The very special preferred phenol of phenol, side chain and straight chain 2- (2H- BTAs-
2- yls) -6- dodecyl -4- methyl-phenols (CAS 125304-04-3) and 2- (the chloro- 2H- BTAs -2- bases of 5-) -6-
(1,1- dimethyl ethyl) -4- cresols (CAS 3896-11-5).
Polymeric material to be used is in such as single screw extrusion machine, double screw extruder, multi-screw extruder or pinches altogether
Melted in conjunction machine.Workable single screw extrusion machine can be for example smooth or with groove cartridge type extruder (smooth or
Grooved barrel extruder) or transmission blender (Transfermix).It is preferred that the cartridge type extruder of with groove.Double spiral shells
Bar extruder can be rotating Vortex or reverse rotation.In addition, double screw extruder can be (the close- tightly engaged
Meshing it is) or non-intermeshing (non-intermeshing).It is preferred that the rotating Vortex configuration tightly engaged.Multiscrew is squeezed
Going out machine has at least three screw rod, preferably 4 to 12.The screw rod can each be tightly engaged arrangement in pairs, in the situation
Under, the screw rod is to tangent and inverting each other rotatably arrange.In addition, the screw rod of multi-screw extruder can all rotating Vortex cloth
Put, in this case, each screw rod intermeshes with 2 adjacent screws.A kind of concrete form of multi-screw extruder is planet
Roll extruder, wherein the planet axis that driving central shaft driving is rotated freely, the planet axis is circulated in fixed housing again.
There is gear to intermesh for central shaft, planet axis and housing.The manufacture method of the present invention is same particularly preferably using what is tightly engaged
Carried out to rotating twin-screw extruder.The construction of extruder screw is adapted to respective application scenario.
In a preferred embodiment, insecticide, the optional UV at room temperature for the alkaline-sensitive of solid are stable
The feed zone of agent and other additives metered extruder together with starting polymer pellet.In another preferred embodiment party
In case, fusing is insecticide, UV stabilizer and other additives of the alkaline-sensitive of solid at room temperature and counted in liquid form
Amount is added.It it is 4 to 250 DEG C by the temperature adjustment of extruder housing.Preferably cooled down in the extruder shell of the feed zone of extruder
To 4 to 50 DEG C.The control of other extruder housing preferable temperatures is 100 to 250 DEG C and more preferably 140 to 250 DEG C.In extruder
In, melt and insecticide and UV stabilizer depending on mixed polymer and visual fusion point.The mixture is extruded through casement simultaneously
It is granulated.The additive may also comprise other inorganic or organic fillers, such as organic pigment, titanium dioxide, carbon black or cunning
Stone flour.The residence time in fusing and mixed process when polymer is liquid is preferably 5 and 120 seconds between 3 and 300 seconds
Between and more preferably between 8 and 30 seconds.Insecticide, optionally UV stabilizer and other additives are mixed with the polymer of fusing
Conjunction can be carried out in the same equipment with melt polymer, or be carried out in other equipment.All above-mentioned extruders are all suitable for
In mixing.Further possibility is that, lethane and (if appropriate) additive and polymer in static mixer.It is preferred that
Mixed with static mixer.If adding insecticide or additive in liquid form, generally melted, and intermediate storage
In initial charge device, then from initial charge device is transferred into mixing apparatus.For example by pump or pass through increased entrance
Pressure, it is possible to achieve the transport.The temperature of initial charge device is selected so that insecticide is the sticky enough of stable and insecticide
It is small to ensure good pumpability.Heating initial charge device, pump and all pipelines are favourable in the case.Set to mixing
Metering in standby is preferably carried out by needle-valve.Preferably, it is by suitable mass flow gauge table, such as former according to Coriolis
Reason or the amount according to the insecticide added by hot line principle, measuring, and adjusted by pump or valve come closed loop to small deviation.
By needle-valve, by be at room temperature liquid alkaline-sensitive insecticide add in extruder processing district melted it is poly-
In compound.Therefore, according to the viscosity and fusing point of the insecticide of alkaline-sensitive, to the insecticide of alkaline-sensitive, UV stabilizer and its
His additive or their mixture are heated.After blending, a preferred embodiment includes carrying out the polymerization
The cooling and solidification of thing material, and it is subdivided into pellet.This can be implemented as described below：For example using common extruder grain method
(strand pelletization process), one of mould above extrudes continuous strip (strand), then
With strip described in air or water cooling to solidify, desired size is then crushed in comminutor.Granulation underwater is another
Method, melt is sprayed by mould under water, the blade cutting circulated there, is then cooled down, is sieved afterwards in water
And drying.Another method is water ring granulation (water ring pelletization), wherein cutting is in molten in atmosphere
The polymer of body liquid condition, then by centrifugal force in the water ring of rotation whiz to cool down.Particularly preferably make under water
Grain method and extruder grain method.
In an embodiment of the method for the present invention, the polymeric material feedstock only prepared by married operation to
In process operation afterwards.The scope of the amount of the insecticide of alkaline-sensitive in simple married operation is 0.05 weight % to 15
Weight %, preferred scope be 0.2 weight % to 10 weight % and more preferably scope be 0.4 weight % to 8 weight %, based on total
Quality meter.
In another embodiment, the polymeric material of the active insecticidal components with high concentration (institute in the form of pellets
The masterbatch of meaning) prepare, and with feeding in the form of the mixture of untreated polymer to subsequent process operation.In the situation
Under, the insecticide concentration of the alkaline-sensitive in the masterbatch polymer material of the present invention is increased, is preferably increased to 3-20
Weight % concentration, particularly preferred 5-15 weight % concentration, based on gross mass meter.
Another embodiment includes, the first step, and hereafter the polymeric material of the invention of preparation, passes through as masterbatch
Melt and with the mixing of untreated polymer and other possible additives, the polymeric material that further processing cost is invented
Material, the polymeric material is produced in the form of pellet.
Subsequent process operation can include：For example, in a procedure of processing, by obtained polymeric material of the invention
The pellet of material has been processed into the polymeric material of type part, such as the insecticide comprising alkaline-sensitive, and in subsequent spinning operation
In to form fiber, yarn, long filament or preferred line.
Discussed in WO2011/124227A1 some be used for the present invention fabric suitable desinsection alkaline-sensitive work
Property composition and be preferably selected from Abamectin (Abamectin), orthene (Acephate), acequinocyl (acequinocyl),
Acetamiprid (Acetamiprid), neem tree (Azadirachtin), Ficam (Bendiocarb), Beta-Cycfluthrin,
Bifenazate (Bifenazate), Biphenthrin (Bifenthrin), Buprofezin (Buprofezin), chlorfenapyr
(Chlorphenapyr), chlopyrifos (Chlorpyrifos), clofentezine (Clofentezine), clothianidin
(Clothianidin), cyfloxylate (Cyfluthrin), Cyromazine (Cyromazine), decis
(Deltamethrin), MTI-446 (Dinotefuran), difluorobenzene grand (Diflubenzuron), ethiprole (Ethiprol),
Etoxazole (Etoxazole), Fenpropathrin (Fenpropathrin), fenpyroximate (Fenpyroximate), ethiprole
(Fipronil), flonicamid (Flonicamid), taufluvalinate (Fluvalinate), imidacloprid
(Imidacloprid), mercaptodimethur (Methiocarb), novaluron (Novaluron), permethrin (Permethrin), mosquitos and flies
Ether (Pyriproxyfen), pymetrozine (Pymetrozine), pyridaben (Pyridaben), Rynoxapyr, pleocidin
(Spinosad), Spiromesifen (Spiromesifen), thiacloprid (Thiacloprid), Diacloden (Thiamethoxan) and
Transfluthrin (Transfluthrin).
The insecticide mentioned can be used alone or use as a mixture.
It is preferred that alkaline-sensitive insecticide be decis and transfluthrin and its mixture.The alkaline-sensitive used
Insecticide be most preferably decis.
The concentration of the active component of the alkaline-sensitive of desinsection in polymeric material can become in relatively wide concentration range
Change, such as 0.05 weight % to 15 weight %, preferably 0.2 weight % to 10 weight %, more preferably 0.4 weight % to 8 weight %.
The concentration should be selected according to application field, so as to meet the requirement on insecticidal power, durability and toxicity.Can be with
The adjustment of the performance of material is completed by following manner：By the material containing different insecticides of the blending present invention by desinsection
Agent is mixed into polymeric material；Or it is made in combination with one another by using the material containing different insecticides of the present invention
Use, such as chimeric net (mosaic net), to realize the adjustment of material property.The material of weaving cotton cloth of customization is obtained with this
Material.
In the preparation process of long filament, fiber, line and yarn, first by the polymeric material melts comprising insecticide, formed
Sewing thread is simultaneously cooled down, and being spinned what is obtained through tensioning system and being stretched, then optionally carries out long filament, fiber, line and yarn
Sizing.
After the mixing operation, by melt spinning come production line or long filament, for example, it is recorded in DE-A 41 36 694 (
The 27-38 rows of page 2, the 45th row of page 5 to the 23rd row of page 6) or DE-A 10 2,005 054 653 ([0002]) in.In the party
In method, the desinsection polymer of preparation is melted in single screw extrusion machine, and is suppressed by means of gear pump by draw ring
(die plate).There is filter pack (filter pack) before the draw ring.To the polymer strip come out from draw ring
High-speed stretch, spin finishing (spin finishing) are carried out, and is wound.Melt-spin processes comprise the steps：Prepare spinning
Melt, melt spinning (melt spinning), cooling, spin finishing, stretching and post processing.
Fiber is prepared by the polymeric material of the fusing of the present invention by known melt-spin processes.It is preferred for preparing
Monfil, multifilament fiber, fibrous nonwoven web, doughnut, chopped fiber, the microfibre of multicomponent fibre and embedded matrix
Method.The preparation of particularly preferred multifilament fiber.Term " line " and term " fiber " are used as synonymous in this whole patent application
Word.
In step (1), the polymeric material comprising insecticide prepared by married operation is less than decomposition temperature extremely
Melted at a temperature of few 10 DEG C temperature and at least 5 DEG C of the fusing point higher than polymeric material, be then sent to spray without cooling
Silk head die assembly.Polymeric material melts and spinning, more preferably less than 235 DEG C preferably at a temperature of less than 250 DEG C.Pass through
By polymeric material, direct feeding, to carry out spinning operation, can carry out fiber system in a step in molten form after the mixing
It is standby.Two-step method can be implemented in the same way, wherein being made before being melted in conveying extruder or in heatable flask
The standby pellet being made up of above-mentioned polymeric material, and transport to filament spinning component.In a preferred embodiment, it will include
The polymeric material of the insecticide of alkaline-sensitive after the mixing in molten form direct feeding to carry out spinning operation.It is especially excellent
Selection of land, will have increased insecticide concentration, the insecticide containing alkaline-sensitive masterbatch polymer material according to the present invention
Material is mixed in spinning operations with pure polymeric material.It may be realized in various forms mixing.In an embodiment party
In case, the polymeric material comprising insecticide and other polymers material are fed to screw rod by two independent metering accessories
In extruder, the melt material described in the screw extruder.In another embodiment, two kinds of polymer material is adding
Enter to before screw extruder first mixing and then extruder is supplied in the form of pre-composition.In another embodiment, two
Melted in individual independent extruder the polymer containing insecticide and without loading insecticide polymeric material, then by this two
Individual melt flow is mixed with each other.The spinning head die assembly is by known contexture.The spinning head die assembly can have 1
Thousand to thousands of nozzle bores, the nozzle bore, which has, is used for the conventional bore dia that fiber is produced.Spinning head die assembly it
Afterwards, spin through cooling zone, carry out spin finish, and wind or be stored in tank.The cooling medium used is liquid or gas.
If liquid, then using water.According to the present invention, the water of the acidifying of cooling can be used.The form of shock chamber is taken in dry cooling zone,
Wherein spin and cooled down with cold air, nitrogen or carbon dioxide as cooling gas.
Spinning oil is applied on fiber during spinning operation.Spinning oil is generally with 1-50 weight % distribution
The form of spinning oil solution in water is applied as the aqueous solution.The administration of spinning oil changes the surface nature of fiber simultaneously
It will be remained in after spinning in yam surface until yarn is woven into fabric.Spinning oil reduce inter alia metal and line
Between and the friction between line and line, decrease antistatic charged (the antistatic charging) of fiber.In order to enter
Row melt-spinning operation, the administration of spinning oil is necessary.If without appropriate spinning oil, the winding of filament yarn
It is impossible with unwinding and further processing.The those of ordinary skill of this technology knows how to adjust spinning for this purpose
Finish.Spinning oil is also known for those skilled in the art.Spun it was unexpectedly determined that having now found that by mugineic acid
Silk oiling agent can minimize the degraded of the insecticide of alkaline-sensitive.By using such acid spinning oil, particularly show
Going out the R- α isomerization of decis can minimize.In addition, it has now been found that by using acid spinning oil, (thermal finalization is operated
Washing step discussed below can be optional before).However, in a preferred embodiment in accordance with this invention, can both make
Acid spinning oil is used, washing step can also be implemented.As acid spinning oil, workable spinning oil preferably has
PH value be less than 5, more preferably pH value be less than 5, even more preferably pH most less than 4, and most preferably pH most be less than 4.Therefore,
This commercially available spinning oil can be used or can be diluted in demineralized water between the weight % of concentration 5 and 20 as absolute oil with shape
Into emulsion, the emulsion is applied on yarn in spinning process.The pH value of solution to be administered (can preferably have by adding acid
Machine acid) adjust such as lactic acid, acetic acid, citric acid, formic acid, the hydrochloric acid.Commercially available spinning oil is known, trade name：
Limanol, Silastol (Schill＆Seilacher, Germany), Fasavin (Zschimmer＆Schwarz, Germany), Duron
(Breitlich GmbH), Afilan, Appretan (Clariant AG, Switzerland), Stantex Standapol Katax
Resista(Pulcra Chemicals)。
The scope of the amount of the non-aqueous composition for the spinning oil applied is 0.1 weight % to 3.0 weight % and preferred model
Enclose for 0.5 weight % to 1.5 weight %, the gross mass meter based on fiber.Spinning oil can fiberline, up- coiler/
Hauling machine, the outlet of rewinding machine and/or shock chamber or porch are applied.Spinning oil --- or more accurately spinning oil and
The mixture of water --- it can be applied in a variety of ways on fiber.In general, it can be applied by spraying, dip-coating, roller coat, bar
Applied with rod painting.Spinning oil can one, two or more stages it is metered.Then it can make winding or storage
Spin through stretching device, stretch and be wound into flat filaments, or optionally curl, be molded or cut into chopped fiber.Preferably,
Spinning and stretched operation are carried out in a system, and centre does not wind non-stretched long filament.Suitable tensioning system is for flat
It is drawtwister or stretching and winding machine for multifilament, is compact monofilament spin-draw system for monofilament, for
It is stretching production line and compact spin-drawing system for chopped fiber.The tensioning system can be furnished with heatable or part
Not heatable godet or draw roll and deflector roll (guide roller), in addition equipped with steam lead, hot air duct and
Infrared catheters, apparatus for coating (coating device), curl unit, drier, cutter device and other units.Stretched operation
Any of arrangement measure, such as the administration of coating can be carried out afterwards.Generally after stretching step on these systems
Carry out the sizing of long filament or fiber.Spun multifilament can stretching-weaving on the machine for become known for this purpose at high speeds
(draw-textured), and can equally weave the multifilament of stretching.Had according to currently preferred multifilament 1 to 100 long
Silk, more preferably 5 to 75 long filaments and most preferably 10 to 60 long filaments.According to the present invention, the line density of the fiber used is 1000
To 10 fiber numbers, more preferably preferably 500 to 20 fiber numbers and 200 to 50 fiber numbers.Thus line, yarn, fiber or the long filament prepared is subsequent
It can be reworked as any target product such as such as yarn fabric.It is preferred that for example woven fabric, knitting, braid, felt or
The textile of non-thermoplastic.Particularly preferred network polymers fabric, such as mosquito net/sleep net (sleeping net).
Woven fabric (woven) and knotwork are realized by the two-wire system (warp and weft) crossed at right angles to each other
(braid) preparation.(single line braid (knit)) can be made up or according to warp thread technology by 2 in the fabric of braiding of 1 line
Or more root line constitute (warp knitting thing).Circle forms preparation on machine or coil stretching-machine to these fabrics of the present invention online.
Short-term or the end of a thread can be used to prepare felt or non-woven fabric.
To be prepared the reticulated of the present invention by means of coil formation process and coil drawing process, it is necessary to which it is so-called to prepare
Warp beam (warp beam).The line of polymer with equal length close wind on reel, i.e., in so-called warp beam.
To make the line of polymerization more lubricate and firmer during the polymer fabrics that processing cost is invented, generally to institute
Line starching is stated, i.e., is coated with the diaphragm of starch or synthesis slurries.Reeling finish (winding oil) starching, institute can be used
Lip river silk oiling agent is stated to apply in warp beam production process, to improve the winding property in warp beam production process, and reduce line with
Friction between the friction of line and metal and line.It is important to reduce for friction is produced not only for warp beam, and for
It is also important for subsequent coil formation operation.
Before further processing (such as bleach and dye), preferably wash the polymer being made up of the fiber prepared and knit
Thing, because the fiber prepared includes a small amount of additive at fiber surface.These additives more particularly include above-mentioned spinning
Finish, but other additives are also removed in this process, the sizing material that may such as apply (size).The washing operation can be with
Those of ordinary skill in the art generally known various ways are carried out.In certain methods, agitator treating liquid, in other method
In, polymer fabrics move across the washing lotion of standing.Possible method is：Pulsed washer, jet washer, in rotating cylinder
Washing, padder and vacuum method on sieve.The preferred continuity method of commercial scale.
In the case of polypropylene and polyethylene fibre, the operation is not implemented with art methods, because containing
The polymer fabrics for having these polymer can not be dyed with dye bath.More particularly for reticulated such as mosquito net particularly such as
This, because in this case, polymer fabrics are without any other finishing operation in addition to thermal finalization.
However, in WO2011/141260A1, unexpectedly it is now discovered that, water and washing are used before heat setting step
Agent to including polypropylene respectively, the reticulated of polyethylene fibre is washed in the process washed according to WHOPES criterions
The loss of middle insecticide plays the role of positive.All washing methods (i.e. pulsed washer, injecting type washings described above
Device, washing, padder and vacuum method on drum sieve) it all can be used for this washing operation.For the present invention, it has been shown that
With following substances laundering of textile fabrics for removing spinning oil and minimizing the R- α isomerization of decis before thermal finalization operation
Solution than proposing in WO2011/141260A1 has even preferably effect：With acid water (being free of any detergent)；Or use
Detergent under water and acid condition；Or with including alkylaryl sulfonates (one or more), fatty acid ethoxylates (one kind
Or it is a variety of) and/or aliphatic alcohol ethyl oxide (one or more) detergent, preferably include at least fatty acid ethoxylates and
More preferably alkylaryl sulfonates and fatty acid ethoxylates.In addition, it has also been found that when the spinning in spinning process using acidity
During silk oiling agent, to minimize the R- α isomerization of decis, the washing step before thermal finalization operation only needs optional progress.
However, in a preferred embodiment in accordance with this invention, the administration of acid spinning oil and following during spinning
Both administrations of material carry out not having Detrimental characteristics (such as due to the highly acidity on polymer fabrics surface in order to produce
Low skin-tolerant/compatibility for causing or the lower mechanical stability caused due to the solid contents in thread material)
Polymer fabrics：PH value is less than 5 acid water；Acid waters (be free of any detergent) of the pH less than 5；Water and pH value are less than 5
Acid condition under detergent；Or it is (a kind of or many including alkylaryl sulfonates (one or more), fatty acid ethoxylates
Kind) and/or aliphatic alcohol ethyl oxide (one or more) detergent.
In a preferred embodiment in accordance with this invention, washing step (during polymer fabrics are prepared) is 20
DEG C carried out to preferred (preferably at a temperature of 30 DEG C to 60 DEG C) at a temperature of between 80 DEG C less than 5 minutes, more preferably less than 1
The time of minute.In another embodiment, it is less than 5 for the pH value that the acid water of washing has, more preferably pH value is less than 4
And even more preferably pH value is less than 4.According to the acid water of the present invention can by by sour (preferably organic acid) such as lactic acid, acetic acid,
Citric acid, formic acid, hydrochloric acid etc. (acid preferably is selected from acetic acid and citric acid) addition is obtained into softened water with adjusting pH value.If
Except water also uses detergent (it is a preferred embodiment of the invention) in washing step, such combination has
Preferably smaller than 5 pH value, preferably less than 4 pH value and even more preferably less than 4 pH value.Such acid condition can also lead to
Cross and add acid discussed above into cleaning solution to adjust.Washing also can use include alkylaryl sulfonates (one kind or it is many
Kind), the detergent of fatty acid ethoxylates (one or more) and/or aliphatic alcohol ethyl oxide (one or more) carry out,
Preferably at least fatty acid ethoxylates and more preferably alkylaryl sulfonates and fatty acid ethoxylates.Including such component
Detergent is learnt for example to state trade name below：Rucogen FWK (coming from Rudolf Chemie), Rucogen DFL 200
(come from RudolfChemie), Rucogen SFW (coming from RudolfChemie), Lavonyl LGC (coming from Impocolor),
Lavonyl JN (coming from Impocolor), Lavonyl NBA (coming from Impocolor).If having used such detergent,
Washing step can even be carried out at higher ph values.However, in a preferred embodiment, such detergent exists
Used under less than 7 pH, preferably less than 5 pH value and even more preferably less than 4 pH value.
The polymer fabrics of preparation generally have very elastic property, rather than form stable.In such form,
It is particularly unsuited for preparing netted polymer fabrics such as mosquito net, because the purposes is being determined according to DIN EN ISO 5077
There is particular/special requirement in terms of degree of shrinkage.It is therefore preferable that carrying out thermal finalization operation.Thermal finalization can use hot water, saturated vapor or heat
Air is carried out, or is carried out in atmosphere is dried.Preferably, thermal finalization is carried out in normal atmosphere, without adding water or steam.It is excellent
Choosing carries out thermal finalization using continuity method, wherein polymer fabrics are fixed on stenter, and guides by the baking on stenter
Case.The baking oven is preferably divided into two or more heating zones, and the heating zone can individually carry out temperature control.In heat treatment
During, polymer fabrics can be applied with different degrees of mechanical load by stretching simultaneously.This is implemented as described below：Make in sizing
The both sides counter motion of stenter in baking oven, needed for reaching the knitting to form coil (formed-loop knit)
Width.The temperature selection of the polymer fabrics of the thermal finalization present invention is preferably low 10 DEG C to be lower than the fusion temperature of polymer 20 DEG C.
The fabric of the insecticide comprising alkaline-sensitive of the present invention can be successfully used to kill harmful or disagreeable section
Main drive thing, more specifically, spider animal and insect.The polymer fabrics of the present invention are preferred for the mosquito of production defence mosquito
Account.
Spider animal includes：Mite (such as Sarcoptes scabiei hominis (Sarcoptes scabiei), dermatophagoides pteronyssinus
(Dermatophagoides pteronys-sinus), dust mite (Dermatophagoides farinae), Dermanyssus gallinae
(Dermanyssus gallinae), Acarus siro (Acarus siro)) and the tick (hard tick (Ixodes of such as double-edged fine-toothed comb
Ricinus), the hard tick of scapulet (Ixodes scapularis), the auspicious edge tick of dove (Argas reflexus), tampan tick
(Ornithodorus moubata), Boophilius microplus, amblyomma hebraeum (Amblyomma hebraeum),
Brown dog tick (Rhipicephalus sanguineus)).
Suction sobs insect and consists essentially of mosquito (such as Aedes aegypti (Aedes aegypti), aedes albopictus (Aedes
Albopictus), Aedes vexans (Aedes vexans), Culex quinquefasciatus (Culex quinquefasciatus), culex tarsalis
(Culex tarsalis), anopheles costalis (Anopheles gambiae), anopheles albimanus (Anopheles albimanus),
Anopheles maculipalpis (Anopheles stephensi), Mansonia titillans), sand fly (sand flies) (such as Ba Pubai
Sandfly (Phlebotomus papatasii)), midge (gnats) (such as Mao Kumeng (Culicoides furens)), black fly
(black flies) (for example disliking buffalo gnat (Simulium damnosum)), bite housefly (biting houseflies) (such as matting
Chela fly (Sto-moxys calcitrans)), tsetse fly (Tsetse flies) (such as glossina morsitans (Glossina
Morsitans morsitans)), horse botfly (horseflies) (such as Taba-nus nigrovittatus, Haematopota
Pluvialis, Chrysops caecutiens), house fly (common houseflies) (such as housefly (Musca
Domestica), autumn fly (Musca autumnalis), Musca vetustissima, Fannia canicularis (Fannia
Canicularis), flesh fly (flesh flies) (such as Sarcophaga carnaria (Sarcophaga carnaria)), cause fly maggot
Fly (myiasis-causing flies) (such as lucilia cuprina (Lucilia cuprina), the Chrysomyia chloro- of disease
Pyga, bomb fly (Hypoderma bovis), heel fly (Hypoderma lineatum), human botfly (Dermatobia
Hominis), people torsalo (Oestrus ovis), Gaste-rophilus intestinalis, cochliomyia bominovorax
(Cochliomyia hominivorax), bedbug are (for example, bed bug (Cimex lectularius), phodnius prolixus
(Rhodnius prolixus), invade and harass triatomid (Triatoma infestans), lice (such as Pediculus humanis,
Haematopinus suis (Haematopinus suis), D amalina ovis)), flea (for example disturb flea (Pulex irritans), xanthopsylla
(Xenopsylla cheopis), ctenocephalides canis (Ctenocephalides canis), ctenocephalides felis (Ctenocephali-
Des felis) and sand hopper (sand fleas) (chigo (Tunga penetrans)).
Biting insects mainly include：Blattaria (cockroaches) (such as Groton bug (Blattella germanica),
American cockroach (Periplaneta americana), oriental cockroach (Blatta orientalis), brown belt blattaria (Supella
Longipalpa)), beetle (such as Sitiophilus granarius, tenebrio molitor (Tenebrio molitor), lader beetle
Moth-eaten (Dermestes lardarius), Anthrenus verbasci (Stegobium paniceum), furniture death watch beetle (Anobium
Punctatum), house longhorn beetle (Hylotrupes bajulus)), termite (termites) (such as European reticulitermes flavipe
(Reticulitermes lucifugus)), ant (such as black ant (Lasius niger), little red ant (Monomorium
Pharaonis)), larva (the larvae of of wasp (the yellow lake honeybee (Vespula germanica) of such as Germany) and moth
Moths) (such as tobacco powder sp (Ephestia elutella), meal moth (Ephestia cautella), India rain moth
(Plodia interpunctella), brown knit moth (Hofmannophila pseudospretella), Tineolabisselliella (Tineola
Bisselliella), bag rain moth (Tinea pellionella), Trichophaga tapetzella (Trichophaga tapetzella)).
The material of the present invention is preferred for resisting insect, particularly Diptera (order Diptera), and even more excellent
Choosing confrontation Nematocera (suborder Nematocera).
Constituted (or at least including) present invention also offers the polymer fabrics by being prepared according to method described above
Net, mosquito net, woven fabric, knitting, braid, felt, the non-woven fabric of sleep.(these terms exist net/mosquito net of sleep
It is used as synonym in this patent application) it is preferred.
23 minimum complete bore/cm are preferably had according to the reticulated of the present invention2And it is averaged 23 and 29 completely
Hole/cm2。
Another embodiment of the present invention is related to a kind of isomerization for the R- α for making to be embedded in the decis in polymeric material
The method of minimum, including：
- acid spinning oil coated polymeric material is used during polymeric material is prepared, and/or
- used in the washing of polymeric material：PH value is less than 5 acid water；Water and pH are less than under 5 acid condition
Detergent or including alkylaryl sulfonates (one or more), fatty acid ethoxylates (one or more) and/or fatty alcohol
The detergent of b-oxide (one or more).
According to the present invention, the R- α isomerization minimums of decis are made to mean that the R- α for particularly minimizing decis are different
Structure body：
1.In preparation process in contrast to：
- be used to prepare polymer fabrics using alkaline spinning oil, the alkaline spinning oil preferably has greater than 5 pH
Value, preferably greater than 7,
- thermal finalization operation before in the basic conditions (in pH value more than 7) respectively with addition to following detergent
Detergent washing copolymer fabric：It is (a kind of or many including alkylaryl sulfonates (one or more), fatty acid ethoxylates
Kind) and/or aliphatic alcohol ethyl oxide (one or more), more preferably and preferably at least fatty acid ethoxylates, alkylaryl
The detergent of sulfonate and fatty acid ethoxylates.
2.In the use of polymer fabrics in contrast to：The cleaning method advised according to WHOPES criterions.
The minimum of the R- αisomers of decis in polymer fabrics causes life-time dilatation, and the life-span prolongs
Length includes the longer storage of such material and used, and this is substantially very useful to need the consumer of such product.
According to the method for the R- αisomers for minimizing decis, term " polymer " material " refer to being used for above-mentioned
The similar material of polymer fabrics, such as polyolefin (polyethylene, polypropylene etc.), polyester (polyethylene terephthalate etc.) and
Polyamide.According to the method, polymeric material can be above-described fiber, yarn, long filament, line, polymer fabrics (preferred net
The polymer fabrics of shape), sleep net/mosquito net, woven fabric, knitting, braid, felt, non-woven fabric.
The preferred embodiment of the present invention, which is related to, makes to be embedded in the R- α isomerization of the decis in polymer fabrics
The method of minimum, the preferred network polymers fabric of polymer fabrics, more preferably mosquito net, including：
- acid spinning is used during polymer fabrics (preferably netted polymer fabrics, more preferably mosquito net) are prepared
Finish coating sewing thread (referring to above description), and/or
- (grasped in the washing process of polymer fabrics during final polymer fabrics are prepared and in thermal finalization
Before work and/or when the polymer fabrics of cleaning manufacture, to extend mosquito net during use preferably in the form of mosquito net
Life-span) using pH value be less than 5 acid water；Water and pH are less than detergent under 5 acid condition or including alkylaryl sulphur
Hydrochlorate (one or more), fatty acid ethoxylates (one or more) and/or aliphatic alcohol ethyl oxide (one or more)
Detergent.
With the above-mentioned method for preparing polymer fabrics also, it is preferred that embodiment for reduce decis R- α isomeries
The method of body is in preferred polymer, manufacturing step, pH value, detergent preferably, wash conditions, preferred spinning oil etc.
It is effective.
Another embodiment of the present invention is related to a kind of method that R- α isomerization for making decis is minimized, wherein on
State polymer fabrics (preferably netted polymer fabrics, most preferably mosquito net) according to WHOPES criterions with alkaline soap (preferably
Savon de Marseille) and it is less than 5 with pH value after being washed with alkaline soap (preferably Savon de Marseille)
Acid water rinses at least 10 seconds (preferably at least 30 seconds).With it is above-mentioned for other method also, it is preferred that embodiment also can quilt
For " acid water " for the method.
The effect directly produced after washing is for controlling the polymer fabrics of (vector control) for vector
It is very important.For example, such as being learnt from WO 2008/032844A2, the fabric containing polyethylene experienced its effect of some days
The rear wash cycle loss (so-called recovery time) of power, so certain time must be placed again at high temperature to recover effect.
The method is inconvenient for user and always under cover this step does not carry out and therefore makes polymer fabrics in protectiveness
The risk of decay can be gone up.What the recovery time less than two hours was desirable to.This regeneration can accelerate in aforementioned manners.
According to the present invention, " WHOPES criterions " is understood to mean that criterion " is used for the long-acting pesticidal mosquito net at laboratory and scene
Guide (the Guidelines for laboratory and field testing of long-lasting of experiment
insecticidal mosquito nets)”(2005).This criterion can be obtained in following network address：http：// www.who.int/whopes/gnidelines/en/。
According to WHOPES criterions, " washing " is defined as follows：Reticulated (25cm x 25cm) is introduced into comprising 0.5 liter
Deionized water and 2g/l " in 1 liter of beaker of Savon de Marseille " soap (pH10-11), the soap is only in net
Add and be dissolved completely in deionized water before shape fabric.After addition reticulated, beaker is introduced into 30 DEG C immediately
Under tepidarium in and with 155 times motion/it is per minute vibration 10 minutes.Then reticulated is taken out and as above from beaker
State under the oscillating condition of identical with clean deionized water rinsing twice, 10 minutes every time.Then, by reticulated in room temperature
Lower drying is simultaneously kept in dark place at 30 DEG C between washings.
Embodiment
Sample preparation：
The double screw extruder tightly engaged using rotating Vortex come generate the present invention polymeric material, the extruder
The shell length of screw diameter and 1200mm with 34mm.In all steps, extruder case temperature is 200 DEG C, and is squeezed
Go out machine speed for 160rpm.It is water-cooled the feed zone of extruder.So-called masterbatch, the masterbatch tool are generated in the extruder
There is high decis concentration.Therefore, mixing 10 weight % technical grade decis (BCS AG, Monheim in an extruder
DE), 2 weight %326FL (BASF (Ciba), Ludwigshafen, Germany) and 88 weight % polypropylene (HM562S, LyondellBasell, Rotterdam, Holland) (TK10).All material is supplied in solid form
To the feed zone of extruder.The mixture leaves extruder in the form of strip, and cools down the strip in a water bath.Then
The strip is crushed by being granulated.The pellet contains about 9.2 weight % bromine cyanogen polyester.
The production line in second step, wherein with 98.9 weight % pure polypropylene (HM562S) dilute about
The pellet containing bromine cyanogen polyester of 1.1 weight % production as described above.Therefore, in each case, pellet is metered
In the feed zone of single screw extrusion machine, and melt, then merge and mix this 2 melt flows., will about 1 in spinning process
Weight %'s6051 spinning oils (Pulcra Chemicals GmbH, D ü sseldorf, Germany) are applied to fibre
In dimension.With fiber described in after-drawing and on reel.Fiber thickness is 210 dtexs, and the fiber is by 25 long filament groups
Into.In second step, the fiber is stretched to the thickness of 110 dtexs.Fiber is stretched using 3 pairs of godets.The seal wire
The temperature of roller pair is 60,80 and 120 DEG C.The average tenacities of the fiber are 4.3cN/ dtexs, the permanent elongation of the fiber
(residual extension) is 51%.
Then generated using the polypropylene fibre being spun into (i.e. netted to knit according to the braid of formation coil of the invention
Thing) it is used to further test.Therefore, the first step is, by by the polypropylene fibre close wind from each bobbin in reel
On, i.e., in so-called warp beam, to prepare warp beam.These warp beams are used subsequently in warp-braider, and coil is formed for producing
Braid.
Then with laboratory scale, thermal finalization operation is carried out to a part of untreated braid for forming coil.For this
Use the laboratory steam generators of Mathis DHe 61599.Before thermal finalization, a part is formed to the braid piece of coil
Washing 1 time.In each case by the braid of 2g untreated formation coil at 60 DEG C 10ml hot bath post
Washed 30 seconds in son, the hot bath is by the demineralized water of the pH (pH3, pH5, pH7) with change and adding for following change
Plus agent is made：Commercial detergent (detergent-free, Lavonyl LGC (coming from Impocolor), 2g/l Savon de
Marseille, 3g/l Radopal GX/2000 (come from Baur), 2g/l Rucogen FWK (come from Rudolf
Chemie), 1g/l Rucogen DFL 200 (coming from Rudolf Chemie), 5g/l Rucogen SFW (come from Rudolf
Chemie), 2g/l Lavonyl LGC (coming from Impocolor), 2g/l Lavonyl JN (coming from Impocolor), 0.4g/l
Lavonyl NBA (coming from Impocolor), 4g/l Invatex MD (coming from Huntsman), 1.5g/L Invatex CS/
4g/l Ultravon PRE (come from Huntsman).The pH of washing bath is by adding proper amount of citric acid needed for reaching
PH value adjust.Mesh sheet is rolled, then hangs at room temperature at least 1 hour and carrys out drying.Then heat is carried out at 140 DEG C fixed
Type is operated 30 seconds.Then sample is stored to 2 weeks (2w/54 DEG C) in an oven at 54 DEG C and decis is analyzed after storage
Content and its R- αisomers.
The analysis of decis and R- αisomers in different polypropylene specimens
Part A- sample preparations：
The material (yarn, fabric or pellet) of about 1g representative samples is put into 250ml flasks；Then about 30ml is added
Dimethylbenzene (PA grades).Then, in backflow (water cooling post, 20cm) and stir under (125 revs/min, magnetic stirrer and stirring rod),
In 190 DEG C of oil baths, specimen material is accurately dissolved 3 minutes.Oil bath is removed, and adds about 10ml isopropanols (PA grades), will
Flask is cooled down about 5 minutes in room temperature, to be settled out polymer.Hereafter, extract is made with 30ml acetonitriles.
Then, sample is filtered out under suction (analysis filter, 5cm diameters), filtrate is passed through collapsible filtering
Device (MN 715,240mm).In every case, washed by using 10-20ml solvent (acetonitrile), complete 2 filterings.
Finally, filtrate is quantitatively transferred into 100ml measuring bottles, and calibration mark is complemented to acetonitrile.
Part B- is with HPLC relative to the quantitative determination that outer standard items are carried out：
By HPLC methods in polypropylene extract sample on the instruments of Agilent 1100 for be equipped with double pump system
Decis carries out quantitative analysis.Decis and R- αisomers are the target molecules of analysis.Use the analysis mark by verification
Quasi- product are used as tester.In 40 DEG C of column temperature on the posts of Merck Lichrosorb SI 60 (5 μ particles, size 250x 4mm)
Under separated under the conditions of positive.
Volume injected is 10 microlitres (preparation of samples is referring to part above A).By normal heptane and methyl tertiary butyl ether(MTBE)
Solvent mixture (950+50, HPLC grades) realizes separation under 1ml/min flow velocity.Elution time under these conditions is 10
Minute.
Under 230nm wavelength ultraviolet detection is carried out using PDAD.Conventional reservation under the described conditions
Time is：It is about 6.3 minutes for R- αisomers, is 7.0 minutes for decis.
In Fig. 1, R- αisomers content (X_R- α) is used in decis (c_DLT) in storage net after storage
Concentration and concentration (c_R- α) from R- αisomers are simultaneously calculated with following formula：X_R- α=c_R- α/c_DLT.CDLT etc.
In c (DLT R- αisomers and S- αisomers).Acid water as can be seen from Figure 1；Detergent or bag under water and acid condition
Include alkylaryl sulfonates (one or more), fatty acid ethoxylates (one or more) and/or aliphatic alcohol ethyl oxide (one
Kind or it is a variety of) detergent (such as Lavonyl NBA, Lavonyl LGC) cause decis have lower isomerization.
Fig. 2 shows the R- αisomer contents of following samples：Savon de are used before thermal finalization as described above
The sample of Marseille (such as according to the recommendation of WHOPES criterions) washings (being carried out 30 seconds at a temperature of 60 DEG C)；And use
Savon de Marseille washings (at a temperature of 60 DEG C carry out 30 seconds) and then with containing citric acid (citron acid)
Water (adjusting to pH=3) rinses the sample of 10 seconds at 60 DEG C.Rinsed with the water containing citric acid and significantly reduce decis
Isomerization (about 10 times).With this contrast, the data with the Lavonyl NBA samples washed under pH 5 and pH3 are also shown for, its
Also significantly reduce the isomerization of decis.Sample (2w/ in heat setting step and after storing 2 weeks in 54 DEG C of baking box
54 DEG C) directly analyzed as described above with HPLC methods.
Fig. 2：
The influence of the acidity of spinning oil
By weigh 0.1g decis and add spinning oil solution to total amount be 10g come prepare pure spinning oil and
The mixture of decis.Use two kinds of different spinning oils：A kind of conventional spinning oil Dakolub L1863TW, come
From Dako AG, it is the weaving oil solution of the 1 weight % in 342ppm water, and pH is 6.43；And a kind of Dakolub
L1863TW acid version, it is the weaving oil solution of the 1 weight % in 342ppm water, and pH is 4.43.
Spinning oil is added into 0.1g decis to the total amount for obtaining 10g.Sample is stirred at room temperature 2 hours simultaneously
It is divided into two parts upon mixing.Sample is stored 2 weeks at 54 DEG C, is then analyzed after storage.Use HPLC as described above
Analyze and the content of decis and S- αisomers is measured.
Fig. 3 shows storage or the storage in acid Dakolub L1863TW in spinning oil Dakolub L1863TW
The S- αisomer contents for the sample deposited.The decis contacted compared to the spinning oil with same small acidity, decis
Contact with acid spinning oil significantly reduces the isomerization of decis.
Fig. 3：
Claims (11)
1. a kind of method for preparing polymer fabrics, wherein by polymer and more than one selected from Beta-Cyfluthrin, connection
Benzene chrysanthemum ester, cyfloxylate, decis, Fenpropathrin, taufluvalinate, the alkaline-sensitive of permethrin and transfluthrin
Active insecticidal components melt or be respectively melted together at a temperature of between 120 DEG C and 250 DEG C, make melt composition sewing thread,
And use spinning oil during spinning, the sewing thread being cooled into, and pass through tensioning system, stretch and weave with
Polymer fabrics are formed, thermal finalization operation then is carried out to polymer fabrics, it is characterised in that to poly- before thermal finalization operation
Compound fabric is washed：
- the acid water with pH value less than 5, or
- the detergent being less than with water and pH value under 5 acid condition, or
- use includes the detergent of alkylaryl sulfonates, fatty acid ethoxylates and/or aliphatic alcohol ethyl oxide
And/or
PH value is applied on line for less than 5 acid spinning oil in spinning process.
2. according to the method described in claim 1, it is characterised in that the active insecticidal components of alkaline-sensitive are decis.
3. method according to claim 1 or 2, it is characterised in that polymer fabrics are washed before thermal finalization operation
Wash：
- the acid water with pH value less than 5, or
- the detergent being less than with water and pH value under 5 acid condition, or
- use includes the detergent of alkylaryl sulfonates, fatty acid ethoxylates and/or aliphatic alcohol ethyl oxide
And be applied to pH value on line for less than 5 acid spinning oil during spinning.
4. method according to claim 1 or 2, it is characterised in that prepare netted polymer fabrics.
5. method according to claim 1 or 2, it is characterised in that the temperature selection of thermal finalization operation is to gather than to be used
The fusion temperature of compound is low 20 DEG C.
6. method according to claim 1 or 2, it is characterised in that washed before thermal finalization operation：
- the acid water with pH value less than 5, or
- the detergent being less than with water and pH value under 5 acid condition, wherein the detergent includes alkylaryl sulfonates, fat
Fat acid b-oxide and/or aliphatic alcohol ethyl oxide.
7. a kind of method that R- α isomerization for making to be embedded in the decis in polymeric material is minimized, including
- the acid spinning oil coated polymeric material that pH value is less than 5 is used during polymeric material is prepared, and/or
- used in the washing of polymeric material：PH value is less than 5 acid water；Water and pH are less than the washing under 5 acid condition
Agent or the detergent for including alkylaryl sulfonates, fatty acid ethoxylates and/or aliphatic alcohol ethyl oxide.
8. the method according to claim 2 or 7, it is characterised in that polymer is polypropylene.
9. method according to claim 8, wherein polymeric material are netted polymer fabrics.
10. method according to claim 9, wherein according to WHOPES criterions with alkaline soap washing copolymer fabric and
The acid water for being less than 5 with pH value after being washed with alkaline soap rinses polymer fabrics at least 10 seconds.
11. method according to claim 10, it is characterised in that the detergent includes alkylaryl sulfonates and fat
Sour b-oxide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12195368.1 | 2012-12-04 | ||
| EP12195368 | 2012-12-04 | ||
| PCT/EP2013/075034 WO2014086666A1 (en) | 2012-12-04 | 2013-11-29 | Method to produce an insecticide-containing fabric |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104838060A CN104838060A (en) | 2015-08-12 |
| CN104838060B true CN104838060B (en) | 2017-08-25 |
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ID=47290722
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380063511.1A Expired - Fee Related CN104838060B (en) | 2012-12-04 | 2013-11-29 | The method for preparing the fabric comprising insecticide |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2016507659A (en) |
| KR (1) | KR20150091335A (en) |
| CN (1) | CN104838060B (en) |
| WO (1) | WO2014086666A1 (en) |
| ZA (1) | ZA201504810B (en) |
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| CN108048931A (en) * | 2017-12-09 | 2018-05-18 | 中国农业科学院植物保护研究所 | A kind of isotropic nanofiber preparation of Xestia c nigrum |
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|---|---|---|---|---|
| CN1693553A (en) * | 2005-05-13 | 2005-11-09 | 武汉农翔生物技术有限公司 | Konjaku high hygroscopicity fibre and its preparation method |
| CN101516197A (en) * | 2006-09-11 | 2009-08-26 | 住友化学株式会社 | Insect-repellent fiber |
| WO2009121580A2 (en) * | 2008-04-04 | 2009-10-08 | Bayer Cropscience Aktiengesellschaft | Materials having embedded insecticides and additives |
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| JP3864011B2 (en) * | 1999-03-02 | 2006-12-27 | 株式会社クラレ | Insect repellent and textile products |
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| JP2008013508A (en) * | 2006-07-07 | 2008-01-24 | Sumitomo Chemical Co Ltd | Insect pest control material |
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| CN102883611B (en) * | 2010-05-19 | 2015-01-21 | 住友化学株式会社 | Pest control material |
| JP5969977B2 (en) * | 2011-03-15 | 2016-08-17 | フマキラー株式会社 | Insect repellent fiber manufacturing method and insect repellent fiber manufactured by the method |
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2013
- 2013-11-29 JP JP2015545746A patent/JP2016507659A/en not_active Ceased
- 2013-11-29 CN CN201380063511.1A patent/CN104838060B/en not_active Expired - Fee Related
- 2013-11-29 WO PCT/EP2013/075034 patent/WO2014086666A1/en active Application Filing
- 2013-11-29 KR KR1020157016433A patent/KR20150091335A/en not_active Application Discontinuation
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2015
- 2015-07-03 ZA ZA2015/04810A patent/ZA201504810B/en unknown
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| CN1693553A (en) * | 2005-05-13 | 2005-11-09 | 武汉农翔生物技术有限公司 | Konjaku high hygroscopicity fibre and its preparation method |
| CN101516197A (en) * | 2006-09-11 | 2009-08-26 | 住友化学株式会社 | Insect-repellent fiber |
| CN101652426A (en) * | 2007-03-29 | 2010-02-17 | 因温斯特技术公司 | Wash resistant synthetic polymer compositions containing active compounds |
| WO2009121580A2 (en) * | 2008-04-04 | 2009-10-08 | Bayer Cropscience Aktiengesellschaft | Materials having embedded insecticides and additives |
| CN102362019A (en) * | 2009-04-06 | 2012-02-22 | 智能昆虫控制公司 | Textile product (e.g. an insecticide net) |
| WO2011128380A1 (en) * | 2010-04-15 | 2011-10-20 | Bayer Cropscience Ag | Insecticide-comprising polymer material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104838060A (en) | 2015-08-12 |
| ZA201504810B (en) | 2017-08-30 |
| KR20150091335A (en) | 2015-08-10 |
| WO2014086666A1 (en) | 2014-06-12 |
| JP2016507659A (en) | 2016-03-10 |
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