WO2010067902A1 - Composition de résine pour filaments - Google Patents

Composition de résine pour filaments Download PDF

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Publication number
WO2010067902A1
WO2010067902A1 PCT/JP2009/071072 JP2009071072W WO2010067902A1 WO 2010067902 A1 WO2010067902 A1 WO 2010067902A1 JP 2009071072 W JP2009071072 W JP 2009071072W WO 2010067902 A1 WO2010067902 A1 WO 2010067902A1
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WO
WIPO (PCT)
Prior art keywords
insect
weight
resin composition
controlling agent
density polyethylene
Prior art date
Application number
PCT/JP2009/071072
Other languages
English (en)
Inventor
Susumu Ejiri
Original Assignee
Sumitomo Chemical Company, Limited
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 Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Priority to CN2009801496548A priority Critical patent/CN102245817B/zh
Priority to AP2011005775A priority patent/AP3393A/xx
Publication of WO2010067902A1 publication Critical patent/WO2010067902A1/fr

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Classifications

    • 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
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene

Definitions

  • the present invention relates to a resin composition for filaments, and filaments formed of the same resin composition.
  • Resin compositions which comprise polyolefin resins such as polypropylene and polyethylene, and insect- controlling agents are formed into a variety of molded articles for use as materials for preventing bugs such as ticks, lice, mosquitoes and flies.
  • Patent Publication 1 discloses a composition comprising a polypropylene resin and an insect-controlling agent, and a filament obtained by melt-spinning the same composition.
  • Patent Publication 2 discloses a composition comprising a linear low-density polyethylene and an insect-controlling agent, and a collar made of the same composition.
  • Patent Publication 3 discloses a resin composition for filaments, which comprises an ethylene- ⁇ -olefin copolymer and an insect-proofing agent.
  • Patent Publication 4 discloses a resin composition for filaments, which comprises an ethylene homopolymer and an insect-proofing agent.
  • Patent Publication 5 discloses a polymer composition comprising an olefin-based polymer, an insect-proofing agent and an insect-proofing agent carrier, and textiles made of such a polymer composition.
  • Patent Publication 1 JP-A-4-65509 Patent Publication 2: JP-A-6-315332 Patent Publication 3: JP-A-2008-031431 Patent Publication 4: JP-A-2008-031619 Patent Publication 5: JP-A-2008-106232 Disclosure of Invention
  • filaments made of the conventional resin compositions which comprise polyolefin resins and insect- controlling agents are demanded to be further improved in bleeding performance of the insect-controlling agents in the initial stage of use thereof.
  • objects of the present invention are to provide a resin composition capable of providing a filament excellent in bleeding performance of an insect-controlling agent in the initial stage of use thereof, and to provide a filament made of the same resin composition.
  • the present invention makes it possible to provide a resin composition for filaments, which contains a high- density polyethylene, an insect-controlling agent and synthetic silica, and which can provide filaments excellent in bleeding performance of the insect-controlling agent in the initial stage of use thereof, and filaments made of the same resin composition.
  • the present invention firstly relates to a resin composition for filaments, which comprises a high-density polyethylene, an insect-controlling agent and synthetic silica, wherein the density of the high-density polyethylene is from 935 to 965 kg/m 3 , and the MFR thereof, from 0.1 to 6 g/10 mins; wherein the average pore radius of the synthetic silica is from 0.040 to 0.105 ⁇ m; and wherein the resin composition contains 100 parts by weight of the high-density polyethylene, and 0.1 to 10 parts by weight of the insect-controlling agent and 0.1 to 10 parts by weight of the synthetic silica per 100 parts by weight of the high-density polyethylene.
  • the present invention secondly relates to a filament formed of the above-described resin composition. Best Mode for Carrying Out the Invention
  • the resin composition for filaments, of the present invention contains a high-density polyethylene, an insect- controlling agent and synthetic silica, and this resin composition specifically contains 100 parts by weight of the high-density polyethylene, and 0.1 to 10 parts by weight of the insect-controlling agent and 0.1 to 10 parts by weight of the synthetic silica per 100 parts by weight of the high-density polyethylene.
  • the content of the insect-controlling agent is from 0.1 to 10 parts by weight per 100 parts by weight of the high-density polyethylene.
  • the content of the insect-controlling agent is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, from the viewpoint of inhibition of stickiness of the resin composition before use in molding for filaments; and this content is preferably 0.5 part by weight or more, more preferably 1 part by weight or more, from the viewpoint of improvement on insect-proofing performance of the resin composition.
  • the content of the synthetic silica in the resin composition of the present invention is from 0.1 to 10 parts by weight per 100 parts by weight of the high-density polyethylene .
  • the content of the synthetic silica is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, from the viewpoint of prevention of cutting of a filament, and this content is preferably 0.5 part by weight or more, more preferably 1 part by weight or more, from the viewpoint of inhibition of stickiness of the resin composition before use in molding for filaments.
  • the high-density polyethylene to be used in the present invention is an ethylene homopolymer or an ethylene- ⁇ -olefin copolymer.
  • the high-density polyethylene is an ethylene- ⁇ -olefin copolymer from the viewpoint of improvement on the strength of the resultant filament.
  • the ⁇ -olefin include propylene, 1- butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl- 1-pentene, 4-methyl-l-hexene, etc. Any of these monomers may be used alone, or at least two selected therefrom may be used in combination.
  • the density of the high-density polyethylene is measured according to the procedure regulated in the method A out of the methods of JIS K7112- 1980, using a test piece which is annealed in accordance with the method for low-density polyethylene regulated in JIS K6760-1995.
  • the content of an ethylene-based monomer unit in the high-density polyethylene is usually from 90 to 100% by weight, based on the total weight (100% by weight) of the high-density polyethylene.
  • the content of an ⁇ -olefin- based monomer unit in the high-density polyethylene is usually from 0.1 to 10% by weight, based on the total weight (100% by weight) of the high-density polyethylene.
  • the high-density polyethylene examples include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1- octene copolymer, an ethylene-1-butene-l-hexene copolymer, etc., among which an ethylene-propylene copolymer, an ethylene-1-butene copolymer and an ethylene-1-hexene copolymer are preferred.
  • the melt flow rate (MFR) of the high-density polyethylene is from 0.1 to 6 g/10 mins.
  • the MFR is preferably 0.3 g/10 mins. or more, more preferably 0.6 g/10 mins.
  • the MFR is preferably 4 g/10 mins. or less, more preferably 2 g/10 mins. or less, from the viewpoint of improvement on drawability under heating and mechanical strength.
  • the MFR is measured at a temperature of 190°C under a load of 21.18 N, according to the method regulated in JIS K7210-1995.
  • the melt flow rate ratio (MFRR) of the high-density polyethylene is preferably 50 or less, more preferably 45 or less, still more preferably 40 or less, from the viewpoint of improvement on melt-spinning performance.
  • the MFRR is preferably 10 or more, more preferably 15 or more, still more preferably 20 or more, from the viewpoint of improvement on melt extrudability.
  • the MFRR is a quotient found by the following division: that is, a melt flow rate (MFR-H, g/10 mins.
  • the density of the high-density polyethylene is from 935 to 965 kg/m 3 . This density is preferably 960 kg/m 3 or less, more preferably 955 kg/m 3 or less, still more preferably 950 kg/m 3 or less, from the viewpoint of improvement on drawability under heating.
  • This density is preferably 940 kg/m 3 or more, more preferably 945 kg/m 3 or more, from the viewpoint of improvement on drawability under heating.
  • the density of the high-density polyethylene is measured according to the procedure regulated in the method A out of the methods of JIS K7112- 1980, using a test piece which is annealed in accordance with the method for low-density polyethylene regulated in JIS K6760-1995.
  • the method for producing the high-density polyethylene there is employed any of the known methods such as solution polymerization, slurry polymerization, vapor phase polymerization, high-pressure ionic polymerization or the like, in the presence of any of the known catalysts for polymerization of olefin, such as a Ziegler-Natta catalyst, a chromium-based catalyst, a metallocene-based catalyst or the like.
  • the polymerization may be either of batch process or continuous process, or otherwise may be of two- or multi-stage polymerization process .
  • catalysts (1) and (2) there are exemplified the following catalysts (1) and (2) : (1) a catalyst which comprises an organometal compound as a co-catalyst and a component which is obtained by carrying, on a magnesium compound-based carrier, at least one selected from the group consisting of titanium trichloride, vanadium trichloride, titanium tetrachloride and titanium halo-alcoholate; and
  • a catalyst which comprises a co-precipitate or an eutectic crystal of a magnesium compound and a titanium compound, and an organometal compound as a co-catalyst.
  • the chromium-based catalyst there is exemplified a catalyst which comprises a component having a chromium compound carried on synthetic silica or synthetic silica alumina, and an organometal compound as a co-catalyst.
  • a catalyst which comprises a component containing a transition metal compound having a group with a cyclopentadiene skeleton, and a component containing an almoxane compound; (2) a catalyst which comprises the above-described component containing a transition metal compound, and a component containing an ionic compound such as trityl borate, anilium borate or the like;
  • a catalyst which comprises the above-described component containing a transition metal compound, the above-described component containing an ionic compound, and a component containing an organoaluminum compound; and (4) a catalyst obtained by carrying any of the above- described components on an inorganic particle-like carrier such as SiO 2/ AI2O3 or the like, or a particle-like polymer carrier of a polymer of an olefin such as ethylene, styrene or the like, or by impregnating the above-described carrier with any of the above-described components.
  • an inorganic particle-like carrier such as SiO 2/ AI2O3 or the like, or a particle-like polymer carrier of a polymer of an olefin such as ethylene, styrene or the like, or by impregnating the above-described carrier with any of the above-described components.
  • a production method using a Ziegler-Natta-based catalyst or a metallocene-based catalyst is preferable as the production method for the high-density polyethylene.
  • a shorter residence time distribution during polymerization is preferable from the viewpoint of improvement on melt- spinning performance.
  • To shorten the residence time distribution a single-step polymerization, or a polymerization in association with parallel operation of a plurality of reactors in a process with the use of the plurality of reactors is preferable.
  • insect-controlling agent to be used in the present invention there are exemplified compounds having insect-proofing activities, such as insecticides, insect growth-controlling agents and insect-repelling agents.
  • insecticides include pyrethroid-based compounds, organophosphorus-based compounds, carbamate- based compounds, phenyl pyrazole-based compounds, etc.
  • pyrethroid-based compounds include permethrin, allethrin, d-allethrin, dd-allethrin, d- tetramethrin, prallethrin, d-phenothrin, d-resmethrin, empenthrin, fenvalerate, esfenvalerate, fenpropathrin, cyhalothrin, etofenprox, tralomethrin, esbiothrin, benfluthrin, terallethrin, deltamethrin, phenothrin, tefluthrin, bifenthrin, cyfluthrin, cypermethrin, ⁇ - cypermethrin,
  • organophosphorus-based compounds examples include fenitrothion, dichlorovos, naled, fenthion, cyanophos, chlorpyrifos, diazinon, carcrofos, salithion, diazinon, etc.
  • carbamate-based compounds examples include methoxydiazon, propoxur, fenobucarb, carbaryl, etc.
  • phenyl pyrazole-based compound include fipronyl, etc.
  • insect growth-controlling agent examples include pyriproxfen, methoprene, hydroprene, diflubenzuron, cyromazine, phenoxycarb, lufenuron (CGA 184599), etc.
  • insect-repelling agent examples include diethyl toluamide, dibutyl phthalate, etc. Any of these insect-controlling agents may be used alone, or two or more thereof may be used as a mixture. Otherwise, a compound which acts to enhance an insect- proofing activity may be used in combination with the insect-controlling agent. As such a compound, there are exemplified piperonyl butoxide, MGK264, octachlorodipropyl- ether, etc .
  • an insecticide is preferable, and a pyrethroid-based compound is more preferable.
  • a pyrethroid-based compound which shows a vapor pressure lower than 1 X 10 ⁇ 6 mmHg at
  • pyrethroid-based compound there are exemplified pyriproxfen, resmethrin, permethrin, etc.
  • silica synthesized by the precipitation method or the gel method is exemplified. Examples thereof include powdered silicic acid, fine powdered silicic acid, white carbon, etc.
  • synthetic silica amorphous synthetic silica is preferable.
  • the average pore radius of the synthetic silica to be used in the present invention is from 0.040 to 0.105 ⁇ m.
  • the upper limit of the average pore radius of the synthetic silica is preferably 0.090 ⁇ m or less, more preferably 0.080 ⁇ m or less, still more preferably 0.070 ⁇ m or less, from the viewpoint of improvement on bleeding performance of the insect-controlling agent in the initial stage of use thereof.
  • the lower limit of the average pore radius of the synthetic silica is preferably 0.050 ⁇ m or more, more preferably 0.060 ⁇ m or more.
  • the average pore radius is measured by the mercury intrusion technique.
  • the specific surface area of the synthetic silica to be used in the present invention is preferably 240 m 2 /g or less, more preferably 210 m 2 /g or less, from the viewpoint of improvement on bleeding performance of the insect- controlling agent in the initial stage of use thereof. Again, it is preferably 50 m 2 /g or more, more preferably 80 m 2 /g or more, still more preferably 110 m 2 /g or more, from the viewpoint of improvement on bleeding performance of the insect-controlling agent in the initial stage of use thereof.
  • the specific surface area is measured by the nitrogen adsorption BET method.
  • the oil absorption weight W (g/100 g) as the weight of the insect-controlling agent retained per 100 g of the synthetic silica is preferably 1,000 g/100 g or less, more preferably 500 g/100 g or less, still more preferably 350 g/100 g or less, from the viewpoint of improvement on bleeding performance of the insect-controlling agent in the initial stage of use thereof. Again, it is preferably 30 g/100 g or more, more preferably 60 g/100 g or more, still more preferably 120 g/100 g or more, from the viewpoint of improvement on retention of the insect-controlling agent.
  • the content of the insect-controlling agent in the resin composition of the present invention is preferably (5 X W) parts by weight or less, more preferably (3 X W) parts by weight or less, still more preferably (W) parts by weight or less, per 100 parts by weight of the synthetic silica, with the proviso that the oil absorption weight of the insect-controlling agent to the synthetic silica is W (g/100 g) .
  • the resin composition of the present invention optionally may contain additives such as an antioxidant, an anti-blocking agent, a filler, a lubricant, an anti-static agent, a weathering agent, a pigment, a processability- improving agent and a metal soap; and a polymer component other than the high-density polyethylene. Two or more selected from the above additives and the above polymer component may be used in combination.
  • the resin composition of the present invention can be prepared by melting and kneading the high-density polyethylene, the insect-controlling agent and the synthetic silica, and optionally other components, according to a known method.
  • the high-density polyethylene, the insect-controlling agent and the synthetic silica are mixed in advance, and the resulting mixture is molten and kneaded, using an extruder, a roll molding machine, a kneader or the like;
  • the high-density polyethylene, the insect-controlling agent and the synthetic silica are separately fed to an extruder, a roll molding machine or a kneader and then are molten and mixed;
  • a mixture of the synthetic silica and the insect- controlling agent prepared in advance and the high-density polyethylene are fed to an extruder, a roll molding machine or a kneader and then are molten and mixed; and a mixture of the high-density polyethylene and the synthetic
  • the insect-controlling agent in the production of the resin composition, it is preferable to use the insect-controlling agent as an insect-controlling agent retainer which is prepared by retaining, carrying or incorporating the insect-controlling agent in the synthetic silica, or by infiltrating or injecting the insect-controlling agent in the synthetic silica, or by allowing the synthetic silica to adsorb or absorb the insect-controlling agent.
  • a master batch may be prepared by adding, to a resin, the insect-controlling agent or the silica, or the insect- controlling agent and the silica, or the above-described insect-controlling agent retainer, and the master batch thus obtained may be melted and kneaded with the high- density polyethylene, to obtain the resin composition of the present invention.
  • a master batch prepared by adding the insect-controlling agent retainer to the resin is used.
  • the resin as the base of the master batch examples include olefin-based resins such as ethylene-based resins, propylene-based resins, butene-based resins, 4-methyl-l- pentene-based resins, and modified, saponified and hydrogenated products of these resins, etc.
  • olefin-based resins such as ethylene-based resins, propylene-based resins, butene-based resins, 4-methyl-l- pentene-based resins, and modified, saponified and hydrogenated products of these resins, etc.
  • ethylene-based resins such as a high-density polyethylene, a linear low-density polyethylene, a linear very low-density polyethylene, a linear ultralow-density polyethylene, a high-pressure-processed low density polyethylene, an ethylene-vinyl acetate copolymer, etc.
  • hydrogenated products of butadiene-based polymers examples include olefin-based resins such as
  • the amount of the master batch to be added is usually less than 50 parts by weight, per 100 parts by weight of the high-density polyethylene contained in the resin composition of the present invention. This amount is preferably 20 parts ' by weight or less, more preferably 10 parts by weight or less, from the viewpoint of the cost-effectiveness.
  • the resin composition of the present invention is formed into filaments such as multifilaments, monofilaments, etc., because of its superior melt-spinning performance and melt-extrudability .
  • this resin composition is formed into monofilaments.
  • the filaments formed of this resin composition are superior in heat drawability and sufficient in mechanical strength.
  • the method of producing filaments from this resin composition is superior in cost performance, since it is possible to extrude and spin the resin composition at a high discharge rate and is possible to highly draw the resulting strands by a single-step drawing operation.
  • the method for forming the resin composition of the present invention into filaments there are given the known molding methods such as a melt-spinning method, a (direct) spinning/drawing method, etc.
  • the resin composition is molten with an extruder or the like; the resulting melt is extruded from a die/nozzle via a gear pump to form a strand-like melt; the extruded strand-like melt of the resin composition is spun and is cooled with a cooling medium such as water, an air or the like; and then, if needed, the resulting strand is drawn under heating, treated by heating, coated with an oil, and is then taken up as a filament.
  • a cooling medium such as water, an air or the like
  • the sectional shape of the filament is circular, elliptic, triangular, rectangular, hexagonal or star-shaped.
  • the fineness of the filament is usually from 50 to 500 denier, preferably from 100 to 350 denier, more preferably from 150 to 250 denier.
  • the filaments formed of the resin composition of the present invention are used' as monofilaments, such monofilaments are used to manufacture nets such as mosquito nets, wind screens, insect proof nets; ropes; yarns; and filters.
  • the filaments formed of the resin composition of the present invention are used as multifilaments, such multifilaments are used to manufacture ropes, nets, carpets, non-woven cloths, filter, shoes, clothes, etc.
  • the filaments of the present invention are preferably used for products which are required to have insect-proofing performance, such as wind screens, insect proof nets, mosquito nets, filters, carpets, shoes and clothes .
  • insects as objects to be controlled by the filaments formed of the resin composition of the present invention are Arthropoda such as spiders, ticks and insects.
  • Arthropoda such as spiders, ticks and insects.
  • insects belonging to Polydesmoidea, in Chilopoda.
  • the insects the following are given: Ctenolepisma villosa Escherich, etc. belonging to Thysanura; cave cricket, mole cricket, Teleogryllus emma, locusta migratoria, Schistocerca gregaria, locust, etc. belonging to Orthoptera; earwig, etc. belonging to Dermaptera; Blattella germanica, Periplaneta fuliginosa, Periplaneta Japonica, Periplaneta americana, etc. belonging to Blattaria; Japanese subterranean termite, Formosan subterranean termite, Incisitermes minor HAGEN, etc.
  • melt flow rate was measured at 190 0 C under a load of 21.18 N according to the method regulated in JIS K7210-1995.
  • MFRR Melt Flow Rate Ratio
  • a MFRR is a quotient found by the following division: that is, a melt flow rate (MFR-H, g/10 mins. in unit) measured at 190°C under a load 211.83 N according to the method regulated in JIS K7210-1995 is divided by a melt flow rate (MFR) measured at 190°C under a load 21.18 N according to the method regulated in JIS K7210-1995.
  • MFR-H melt flow rate
  • a density was measured according to the procedure regulated in the method A among the methods described in JIS K7112-1980.
  • a test piece to be measured was annealed according to the method for low-density polyethylene, regulated in JIS K6760-1995.
  • Synthetic silica was dried at 12O 0 C for 4 hours, and a pore distribution of pores with radii of from about 0.0018 to 100 ⁇ m was measured, using AutoPore III 9420 manufactured by MICROMERITICS .
  • An average pore radius was defined as a pore radius at which the infiltration ratio of mercury became 50% of the entire infiltration amount of mercury.
  • Synthetic silica to be measured was previously deaerated in vacuum at 120° for 8 hours.
  • BELSORP-mini manufactured by BEL JAPAN, INC. was used to measure an adsorption/desorption constant temperature line, using nitrogen as an adsorbate, by the constant volume method, at an adsorption temperature of 77K, provided that the sectional area of the adsorbate was 0.162 nm 2 .
  • the specific area of the synthetic silica was calculated by the BET multipoint method.
  • Example 1 An insect-controlling agent (5 cm 3 ) was poured into a glass container, and synthetic silica heated to 5O 0 C was added little by little thereto under stirring, until any ball-like agent localized on the synthetic silica disappeared. At a point of time when any ball-like agent had disappeared, it was judged that the insect-controlling agent had been retained in the synthetic silica.
  • the oil absorption weight of the insect-controlling agent per 100 g of the synthetic silica was calculated from the weight of the synthetic silica added and the weight of the insect- controlling agent.
  • Example 1 1.
  • the filament cleansed at its surface was put into a glass bottle, and the bottle was capped and was left to stand still in an oven at 60°C for one day. Then, the filament was removed from the oven, and ethanol (50 cm 3 ) was added to the filament. Then, the filament was agitated with an agitator for 10 minutes to cleans off the insect- controlling agent bled out of the surface of the filament.
  • the resulting cleansing liquid was measured with respect to its permethrin concentration, using a spectrophotometer for ultraviolet and visible region.
  • the filament wiped at its surface was put in a glass bottle, and the glass bottle was capped and was again left to stand still in an oven at 60°C for 6 days.
  • the filament was removed from the oven, and ethanol (50 cm 3 ) was added, and the glass bottle was agitated with an agitator for 10 minutes to cleans off the insect-controlling agent bled out to the surface of the filament.
  • the resulting cleansing liquid was measured with respect to its insect-controlling agent concentration, using a spectrophotometer for ultraviolet and visible region.
  • the surface-cleansing liquid was measured with a spectrophotometer V-650 for ultraviolet and visible region, manufactured by JASCO Corporation, under the following conditions; and the absorbances of the peaks of the permethrin within a range of 200 ⁇ 1 nm were measured.
  • Measuring conditions for the spectrophotometer cell length: 10 nm band width: 2.0 nm scanning speed: 400 nm/min. wavelength at start: 340 nm wavelength at end: 190 nm data-loading interval: 1.0 nm
  • the amount of permethrin in the surface-cleansing liquid was determined from this calibration curve.
  • the amount of permethrin bled from the surface of the filament found one day after was defined as a quotient calculated as follows: the amount of permethrin in the cleansing liquid found one day after was divided by the measured weight of the filament.
  • the amount of permethrin bled from the surface of the filament found 7 days after was defined as a quotient calculated as follows: the amount of permethrin in the cleansing liquid found 6 days after the one day after, i.e., 7 days after, was divided by the measured weight of the filament.
  • the sum of the amount of permethrin bled from the surface of the filament found one day after and the amount of permethrin bled from the surface of the filament found 7 days after was defined as a cumulative amount of permethrin bled from the surface of the filament 7 days after, which was used to evaluate the amount of permethrin bled out of the surface of the filament in the initial stage of use.
  • Example 2 Example 1 was repeated, except that Finesil CM-F manufactured by Tokuyama Corp. (hereinafter referred to as Silica 2, of which the physical properties are shown in Table 1) was used as the synthetic silica. No stickiness was felt in this resin composition. The cumulative amount of permethrin bled out of the surface of this filament 7 days after was 2.23 mg/g.
  • Silica 2 Finesil CM-F manufactured by Tokuyama Corp.
  • Example 1 was repeated, except that Finesil B manufactured by Tokuyama Corp. (hereinafter referred to as Silica 3, of which the physical properties are shown in Table 1) was used as the synthetic silica. No stickiness was felt in this resin composition.
  • Silica 3 of which the physical properties are shown in Table 1.
  • Example 1 was repeated, except that Finesil T-32 manufactured by Tokuyama Corp. (hereinafter referred to as
  • Table 1 was used as the synthetic silica. No stickiness was felt in this resin composition.
  • Example 1 was repeated, except that Carplex FPS-5 manufactured by EVONIC INDUSTRIES (hereinafter referred to as Silica 5, of which the physical properties are shown in
  • Table 1 was used as the synthetic silica. No stickiness was felt in this resin composition.
  • Example 1 was repeated, except that Tokusil GU manufactured by Tokuyama Corp. (hereinafter referred to as
  • the cumulative amount of permethrin bled out of the surface of this filament 7 days after was 1.23 mg/g.
  • Example 1 Comparative Example 1 Example 1 was repeated, except that Finesil X-32 manufactured by Tokuyama Corp. (hereinafter referred to as
  • Table 1 The cumulative amount of permethrin bled out of the surface of this filament 7 days after was 0.81 mg/g.
  • Example 1 was repeated, except that Mizukasil P-707 manufactured by MIZUSAWA INDUSTRIAL CHEMICALS, LTD. (hereinafter referred to as Silica 8, of which the physical properties are shown in Table 1) was used as the synthetic silica. No stickiness was felt in this resin composition. The cumulative amount of permethrin bled out of the surface of this filament 7 days after was 0.54 mg/g. Comparative Example 3
  • Example 1 was repeated, except that Carplex BS-308N manufactured by EVONIK INDUSTRIES (hereinafter referred to as Silica 9, of which the physical properties are shown in
  • Example 1 was repeated, except that Sipernat 880 manufactured by EVONIK INDUSTRIES (hereinafter referred to as Silica 10, of which the physical properties are shown in
  • Table 1 was used as the synthetic silica. No stickiness was felt in this resin composition.
  • Example 1 was repeated, except that Nipsil E-743 manufactured by TOSOH SILICA CORPORATION (hereinafter referred to as Silica 11, of which the physical properties are shown in Table 1) was used as the synthetic silica. No stickiness was felt in this resin composition.
  • Silica 11 manufactured by TOSOH SILICA CORPORATION
  • Example 7 The cumulative amount of permethrin bled out of the surface of this filament 7 days after was 0.40 mg/g.
  • an insect-controlling agent retainer B which contained the insect-controlling agent
  • Insect-Controlling Agent Retainer Permethrin (64.9 parts by weight) as the insect- controlling agent was admixed with butylhydroxytoluene (1.9 parts by weight) as the antioxidant, and the mixture was stirred and dissolved.
  • Carplex 8OD manufactured by EVONIC INDUSTRIES (hereinafter referred to as silica 13, of which the physical properties are shown in Table 1) (33.2 parts by weight) was added to the resulting solution, and the mixture was stirred and mixed.
  • silica 13 Carplex 8OD manufactured by EVONIC INDUSTRIES
  • a high-density polyethylene, HI-ZEX 440M, (100 parts by weight) and the master batch of the insect-controlling agent retainer (11.8 parts by weight) were kneaded, using a Banbury mixer, to obtain a resin composition for filaments. No stickiness was felt in this resin composition. 3. Production of Filament, and

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

Abstract

L'invention concerne une composition de résine capable de fournir des filaments ayant une performance de dégorgement supérieure d'un agent anti-insectes dans la phase initiale d'utilisation de celui-ci. La présente invention concerne une composition de résine pour filaments, comprenant un polyéthylène haute densité, un agent anti-insectes et une silice synthétique. La densité du polyéthylène haute densité est comprise entre 935 et 965 kg/m3, et son MFR est compris entre 0,1 et 6 g/10 min. Le rayon de pore moyen de la silice synthétique est compris entre 0,040 à 0,105 m et ladite composition de résine contenant 100 parties en poids du polyéthylène haute densité et 0,1 à 10 parties en poids de l'agent anti-insectes et 0,1 à 10 parties en poids de la silice synthétique pour 100 parties en poids du polyéthylène haute densité.
PCT/JP2009/071072 2008-12-12 2009-12-11 Composition de résine pour filaments WO2010067902A1 (fr)

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CN2009801496548A CN102245817B (zh) 2008-12-12 2009-12-11 用于长丝的树脂组合物
AP2011005775A AP3393A (en) 2008-12-12 2009-12-11 Resin composition for filaments

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Cited By (4)

* Cited by examiner, † Cited by third party
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WO2011121509A1 (fr) * 2010-03-30 2011-10-06 Pascal Martinet Composition d'un matériau constitutif d'une barrière physico-chimique servant à protéger les batiments contre les termites.
FR2958499A1 (fr) * 2010-04-09 2011-10-14 Pascal Martinet Composition d'un materiau constitutif d'une barriere physico-chimique servant a proteger les batiments contre les termites
WO2012070778A2 (fr) * 2010-11-23 2012-05-31 Kwon Young-Tak Procédé pour la fabrication d'un monofilament insecticide utilisant un lot-maître d'insecticide
WO2012164080A1 (fr) * 2011-06-03 2012-12-06 Intelligent Insect Control Fibre, fils ou produits textiles en polyéthylène insecticide présentant des profils de migration et une résistance au lavage améliorés

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KR101235255B1 (ko) 2010-12-06 2013-02-20 주식회사 삼양사 나노 실리카 입자가 포함된 고강도 폴리에틸렌 멀티필라멘트 연신사의 제조방법
WO2018181309A1 (fr) * 2017-03-29 2018-10-04 東洋紡株式会社 Fibres de polyéthylène, et article mettant en œuvre celles-ci
EP3479692A1 (fr) * 2017-11-03 2019-05-08 Clariant Plastics & Coatings Ltd Compositions polymères insectifuges
JP7070667B2 (ja) * 2018-03-27 2022-05-18 東洋紡株式会社 ポリエチレン繊維、およびそれを用いた製品
CN110438582B (zh) * 2019-07-30 2022-03-01 青岛信泰科技有限公司 一种吸油超高分子量聚乙烯纤维的制备方法
KR102564030B1 (ko) * 2021-03-12 2023-08-04 도레이첨단소재 주식회사 부직포용 방충제 마스터배치의 제조방법, 부직포용 방충제 마스터배치, 부직포 및 물품

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011121509A1 (fr) * 2010-03-30 2011-10-06 Pascal Martinet Composition d'un matériau constitutif d'une barrière physico-chimique servant à protéger les batiments contre les termites.
FR2958117A1 (fr) * 2010-03-30 2011-10-07 Pascal Martinet Composition d'un materiau constitutif d'une barriere physico-chimique servant a proteger les batiments contre les termites.
FR2958499A1 (fr) * 2010-04-09 2011-10-14 Pascal Martinet Composition d'un materiau constitutif d'une barriere physico-chimique servant a proteger les batiments contre les termites
WO2012070778A2 (fr) * 2010-11-23 2012-05-31 Kwon Young-Tak Procédé pour la fabrication d'un monofilament insecticide utilisant un lot-maître d'insecticide
WO2012070778A3 (fr) * 2010-11-23 2012-09-27 Kwon Young-Tak Procédé pour la fabrication d'un monofilament insecticide utilisant un lot-maître d'insecticide
WO2012164080A1 (fr) * 2011-06-03 2012-12-06 Intelligent Insect Control Fibre, fils ou produits textiles en polyéthylène insecticide présentant des profils de migration et une résistance au lavage améliorés
CN103649390A (zh) * 2011-06-03 2014-03-19 Vegro有限责任公司 具有改善的迁移特征和洗涤抗性的杀虫的聚乙烯纤维、纱线或纺织产品

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CN102245817B (zh) 2013-11-06
JP2010159403A (ja) 2010-07-22
CN102245817A (zh) 2011-11-16
AP3393A (en) 2015-08-31
JP5720093B2 (ja) 2015-05-20
AP2011005775A0 (en) 2011-06-30

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