WO2012149933A1 - Procédé de régulation de la migration d'un insecticide ou d'un acaricide dans une fibre polymère impliquant un étirage de ladite fibre - Google Patents

Procédé de régulation de la migration d'un insecticide ou d'un acaricide dans une fibre polymère impliquant un étirage de ladite fibre Download PDF

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Publication number
WO2012149933A1
WO2012149933A1 PCT/DK2011/050148 DK2011050148W WO2012149933A1 WO 2012149933 A1 WO2012149933 A1 WO 2012149933A1 DK 2011050148 W DK2011050148 W DK 2011050148W WO 2012149933 A1 WO2012149933 A1 WO 2012149933A1
Authority
WO
WIPO (PCT)
Prior art keywords
denier
filament
draw ratio
polymer
insecticide
Prior art date
Application number
PCT/DK2011/050148
Other languages
English (en)
Inventor
Mikkel Vestergaard Frandsen
Sebastien Gouin
Huyen Thanh HOANG
Matthieu Zellweger
Original Assignee
Vestergaard Frandsen Sa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Vestergaard Frandsen Sa filed Critical Vestergaard Frandsen Sa
Priority to PCT/DK2011/050148 priority Critical patent/WO2012149933A1/fr
Publication of WO2012149933A1 publication Critical patent/WO2012149933A1/fr

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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
    • A01N25/08—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 containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
    • 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
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins

Definitions

  • the present invention relates to regulation of the migration of insecticides or acaricides in a polymer fibre by stretching. Especially, it relates to a method for regulating the migration of insecticide or acaricide in a polymer filament that also contains Carbon Black.
  • Stretching of polymers is a well known measure for adjusting the physical properties, especially for fibres. Different draw ratios are disclosed in US patent applications and patents US2007/134305, US7291669, US3418200, US429720, US4369156, US4245001, US6444312, US6465095, US6743506, and US7560159.
  • WO2008/032842 by Sumitomo discloses advantages of an elongation percentage of 25% to 40% in a matrix of high density polyethylene (HDPE) and linear low density polyethylene (LLDPE) containing porous particles with insecticide.
  • the advantage of the elongation percentage is a reduction of the tendency to crease.
  • the elongation in this interval of 25-40% is achieved with a draw ratio of 7-9.
  • WO2008/032844 by Sumitomo discloses an insect-repellent fiber comprising a mixture of LLDPE and HDPE with a preferable weight ratio of 5-30:70-95 and a pyrethroid. Furthermore, the insect-repellent fiber may comprise a UV absorber, antistatic agent, lubricant, anti-blocking agent, pigment, nucleator, metal soap. A draw ratio of 8 is mentioned in example 1.
  • WO2009/75373 by Sumitomo discloses a 270 deniers 24-filament yarn extruded from a mixture of a polypropylene (PP) and PP-l-butene copolymer as a permethrin matrix and drawn by a factor of 3 to a 90 deniers yarn. No other examples are given for draw ratios. Preferred mass per length for fibres are 50-500 deniers (page 21 line 4).
  • WO2008/047604 by Sumitomo discloses a polymer fibres containing a pesticide on a pesticide support. A stretching rate ratio of 5 or more is disclosed.
  • US6770356 by Procter & Gamble discloses fibres, for example with insecticide (col. 20 line 2), in which the draw ratio is less than 4 (col. 7 line 62), preferably between 1.2- 2.5 for poly(lactic acid) in order to obtain soft fibres with low degree of shrinkage.
  • US4935232 by Interface Research Corporation discloses a biocidal polymeric composition.
  • XV microbiocidal fiber composed for example of polyethylene and combined with biocidally effective amount of a phosphate ester is disclosed.
  • a draw ratio of 3 is mentioned in relation to tensile properties.
  • Examples of fibre mass per lengths are given for PP as 179 deniers and as 280 deniers for nylon yarn.
  • WO2008/004711 by Sumitomo concerns mainly the bleed coefficient caused by and a powdery carrier material for the insecticide, for example with fine powdery carriers of carbon. Further, the migration rate is determined by a large number of factors including the draw ratio. It discloses a draw ratio of 8 for a monofilament of HDPE and LLDPE containing permethrin.
  • the preferred fibres are made of HDPE/LDPE with a mass per length of 100-350 deniers but rather 130-230 denier.
  • the patent applications Wo2010/015256 and Wo2010/015257 by Vestergaard Frand- sen refer to draw ratios between 5 and 11 for proper migration rate and physical prop- erties of a matrix containing HDPE/LDPE at a ratio of 8 to 10.
  • the preferred fibre mass per length is 50-100 denier.
  • Carbon Black in addition to the use of Carbon Black to regulate the migration, it is known to apply various draw ratios to polyethylene fibres and sheets. However, the interplay between the content of Carbon Black and the draw ratio has not been explicitly discussed. As Carbon Black is desired in fibres, especially insecticidal nets, for its UV protection of the insecticide, it would be desirable to find suitable draw ratios for insecticidal or acaricidal fibres in dependence of their thickess and content of Carbon Black.
  • filament is restricted to monofilaments and does not include multifilaments.
  • polymer is used for polymer or the blend of polymers without insecti- cide/acaricide, Carbon Black and further additives.
  • matrix is used for the blend of polymers and the additives, including Carbon Black and insecticide/acaricide, and optionally synergists and other additives.
  • insect or acari has to be read as “insect or acari or both”.
  • insec- ticide'V'acaricide is not meant as only one single insecticide/acaricide and does not exclude the insecticide/acaricide being part of a group of insecticides/acaricide. It should also be pointed out that many specific insecticides are also acaricides, as they act against insects as well as acari; thus, the expression “an insecticide or an acaricide” is not meant as one of them excluding the other.
  • filaments for mosquito nets are fully drawn at a draw ratio of around 8. This appears from
  • the filaments are polyolefms, especially polyethylene (PE) and polypropylene (PP).
  • PE polyethylene
  • PP polypropylene
  • the term polyethylene comprises the different types of PE, including high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE).
  • the filament has at least 150 denier or at least 250 or at least 350 denier.
  • the polymer matrix contains at least 75% or at least 90% of PE or PP.
  • a non limiting example of polymer matrices for which the above stated values are considered advantageous is a polyethylene polymer that contains a mixture including HDPE and LDPE or HDPE and LLDPE or HDPE and LDPE and LLDPE.
  • An advantageous polymer for the above draw ratios contains more HDPE than LDPE or LLDPE, for example, at least 50% HDPE and at least 20% LDPE or LLDPE.
  • the polymer contains at least 50% HDPE and at least twice as much HDPE than LDPE or LLDPE.
  • insecticide/acaricide a large variety of migrating insecticide/acaricides can be used.
  • the filament may also contain synergists, for example piperonyl butoxide (PBO).
  • PBO piperonyl butoxide
  • the filament contains DM and PBO.
  • the insecticide/acaricide and the synergist may be provided in the same polymer matrix of the filament.
  • filaments with DM and filaments with PBO may be combined to a multifilament yarn.
  • the migration and surface concentration of the DM and the migration and surface concentration of the PBO can be better controlled, as it is described in International patent applications WO2009/003468 by Vestergaard Frandsen and WO2010 046348 by Intelligent Insect Control.
  • a further alternative is a yarn, which is co-extruded to comprise in a single yarn a first polymer with a specific insecticide/acaricide but not PBO and a second polymer with PBO and not the specific insecticide/acaricide, for example as disclosed in Wo2009/003468 by Vestergaard Frandsen, where a side-by-side configuration is disclosed with one half of the yarn being made of the first polymer and the other half by the second, or where the yarn has two quarters of the first polymer and two quarters of the second polymer.
  • a further alternative is this respect is a yarn with a core having a polymer with the one agent and a sheath around the cores having a polymer with the other agent.
  • the filaments are useful for a variety of fabrics. Special attention have filaments for nets, for example bed nets, greenhouse nets, nets for crop coverage, or fences surrounding at least partly an agricultural open air area for preventing low flying insects to enter the area. The latter is explained in more detail in the International patent application WO2003003827 by Vestergaard Frandsen. Insect nets, typically, have a mesh size of 1-5 mm, for example 1.5-2.5 mm. Yarns for nets advantageously have a thickness of 75-900 denier. Useful examples for greenhouse nets are yarns with 150-600 denier. For fencing, typically, thicker yarns are used, for example 500-900 denier yarns.
  • pesticidal films or textiles including sacks, bags, and nets can successfully be used to enclose the harvested crops.
  • pesticidal textiles can be used to surround crops, such as banana, while still connected to the plant itself.
  • An advantageous concentration for insecticide/acaricide, for example DM, in products, especially, fabrics, including nets is between 10 and 500 mg/m 2 or between 20 and 250 mg/m 2 or between 50 and 150 mg/m 2 of the fabric.
  • the concentration is of the insecticide/acaricide is 2-10 g/kg of the polymer or 3-4g/kg of the polymer.
  • Non exclusive applications include curtains, window screens and door screens in livestock, horse blankets, wrapping sacks, paper, construction materials, and leathers.
  • beneficial ingredients for a product according to the above include biocides, acaricides, repellents, and additives of various kinds, for example synergists, bactericides, bacteriostatics, herbicides, UV protecting agents, preservatives, anti-hydrolysis agents, detergents, fillers, impact modifiers, anti-fogging agents, blowing agents, clari- fiers, nucleating agents, coupling agents, conductivity-enhancing agents to prevent static electricity, stabilizers such as anti-oxidants, carbon and oxygen radical scavengers and peroxide decomposing agents, flame retardants, mould release agents, optical brighteners, spreading agents, antiblocking agents, other anti-migrating agents, migration promoters, foam-forming agents, anti-soiling agents, antifouling agents, thicken- ers, wetting agents, plasticizers adhesive or anti-adhesive agents, fragrance, pigments, dyestuffs, and oils and waxes, for example polymer oil and polymer waxes.
  • the end points are included or, optionally, excluded.
  • the effect of the draw ratio was investigated for polyethylene monofilament yarn experimentally.
  • the yarn was a monofilament comprising about 60% HDPE and 25-35% LLDPE and containing 0.5% w/w DM and varying loads of Carbon Black.
  • the stretching targeted a 325 denier yarn.
  • Bioefficacies against mosquitoes were measured after 4 and 8 weeks. Results are shown in the table below.
  • the draw ratio is advantageously
  • the following yarn has turned out to be beneficial.
  • It is a thermoplastic polymer filament, for example PE or PP filament, with 150 to 350 denier containing 2-10% Carbon Black, for example 3-8% Carbon Black, and having been stretched with a draw ratio of between 4 and 6.5.
  • it may comprise at least 50% HDPE and at least 20% LDPE or LLDPE.
  • the polymer comprises 0.2-1 % by weight DM.
  • the optimum draw ratio does not change much any more and should be below 4.5.
  • the draw ratio should be higher than [7.1-0.011 » D] for filaments having a mass per length of between 100 and 350 denier.
  • the two formulae also express implicitly the low-denier limit corresponding to a full drawing, which is typically around 8 or slightly higher. With increasing mass per length, the draw ratio should decrease in order to achieve proper migration properties for the insecticide/ acaricide .
  • thermoplastic matrices can be made even more precise in dependence on the material and the amount of Carbon Black.
  • the above approximation for the upper limit of [8.7- 0.011 » D] for filaments having a mass per length of between 100 and 350 denier is valid for a thermo- plastic matrix containing a restricted concentration of 2-5% Carbon Black and at least 50% HDPE and more than 25% LLDPE.
  • the lower limit of the draw ratio in this case may be restricted to higher than [7.6- 0.011 » D] for filaments having a mass per length of between 100 and 350 denier and higher than 3.5 for filaments having a mass per length higher than 350 denier.
  • the draw ratio should be lower.
  • the upper limit for the draw ratio may be expressed by the simple formulae [8.2- 0,011 D].
  • the same formula applies for a thermoplastic matrix with a relatively high content of more than 75% HDPE, optionally with at least 10% LLDPE or LDPE.
  • the draw ratio should be higher than [7.1- 0.011 » D] for filaments having a mass per length of between 100 and 350 denier and higher than 3.5 for filaments heavier than 350 denier.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Textile Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Mechanical Engineering (AREA)
  • Plant Pathology (AREA)
  • Toxicology (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Abstract

La présente invention concerne un procédé de régulation de la migration d'un insecticide ou d'un acaricide dans une fibre polymère impliquant un étirage de ladite fibre. L'invention concerne également un procédé de production d'un filament polymère insecticide ou acaricide, dans lequel l'effet de rétention exercé par le noir de carbone sur la migration de l'insecticide/acaricide est compensé par un rapport d'étirage faible. Ledit procédé comprend les étapes consistant à mélanger un insecticide/acaricide et du noir de carbone à un polymère thermoplastique à l'état fondu, à extruder ledit polymère insecticide ou acaricide comportant l'insecticide/acaricide et le noir de carbone afin d'obtenir un filament, à étirer ledit filament selon un rapport d'étirage de 3 à 7,7 afin d'obtenir un filament étiré de 10 à 1 000 deniers.
PCT/DK2011/050148 2011-05-02 2011-05-02 Procédé de régulation de la migration d'un insecticide ou d'un acaricide dans une fibre polymère impliquant un étirage de ladite fibre WO2012149933A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/DK2011/050148 WO2012149933A1 (fr) 2011-05-02 2011-05-02 Procédé de régulation de la migration d'un insecticide ou d'un acaricide dans une fibre polymère impliquant un étirage de ladite fibre

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/DK2011/050148 WO2012149933A1 (fr) 2011-05-02 2011-05-02 Procédé de régulation de la migration d'un insecticide ou d'un acaricide dans une fibre polymère impliquant un étirage de ladite fibre

Publications (1)

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WO2012149933A1 true WO2012149933A1 (fr) 2012-11-08

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5856271A (en) * 1995-06-07 1999-01-05 Battelle Memorial Institute Method of making controlled released devices

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5856271A (en) * 1995-06-07 1999-01-05 Battelle Memorial Institute Method of making controlled released devices

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