CN102245817A - Resin composition for filaments - Google Patents
Resin composition for filaments Download PDFInfo
- Publication number
- CN102245817A CN102245817A CN2009801496548A CN200980149654A CN102245817A CN 102245817 A CN102245817 A CN 102245817A CN 2009801496548 A CN2009801496548 A CN 2009801496548A CN 200980149654 A CN200980149654 A CN 200980149654A CN 102245817 A CN102245817 A CN 102245817A
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- China
- Prior art keywords
- insect
- controlling agent
- density polyethylene
- resin combination
- synthetic silica
- Prior art date
- Legal status (The legal status 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 status listed.)
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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
Abstract
A resin composition capable of providing filaments superior in bleeding performance of an insect-controlling agent in the initial stage of use thereof is disclosed. The present invention relates to a resin composition for filaments, comprising 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 [mu]m; and wherein said 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.
Description
Technical field
The present invention relates to be used for the resin combination of long filament and the long filament that forms by this resin combination.
Background technology
Comprise vistanex for example the resin combination of polypropylene and polyethylene and insect-controlling agent be formed various mechanographs, as preventing for example material of tick (ticks), louse (lice), mosquito and fly of insect.For example, patent disclosure 1 discloses a kind of composition and long filament by the said composition melt spinning is obtained that comprises acrylic resin and insect-controlling agent.Patent disclosure 2 discloses a kind of circle (collar) that comprises the composition of linear low density polyethylene (LLDPE) and insect-controlling agent and made by said composition.Patent disclosure 3 discloses a kind of resin combination that is used for long filament, and it comprises ethene-alpha-olefin copolymer and protection against insect agent.Patent disclosure 4 discloses a kind of resin combination that is used for long filament, and it comprises Alathon and protection against insect agent.Patent disclosure 5 discloses a kind of polymer composition of olefin-based polymer, protection against insect agent and protection against insect agent carrier and fabric of being made by this polymer composition of comprising.
Patent disclosure 1:JP-A-4-65509
Patent disclosure 2:JP-A-6-315332
Patent disclosure 3:JP-A-2008-031431
Patent disclosure 4:JP-A-2008-031619
Patent disclosure 5:JP-A-2008-106232.
Summary of the invention
Yet the long filament of being made by the conventional resins composition that comprises vistanex and insect-controlling agent need ooze out performance (bleeding performance) what its initial stage operational phase was further improved insect-controlling agent.
In this case, the purpose of this invention is to provide resin combination, this resin combination can be provided at the long filament that oozes out function admirable of its initial stage operational phase insect-controlling agent and the long filament of being made by this resin combination is provided.
The invention enables resin combination that can be provided for long filament and the long filament of making by this resin combination, described composition comprises high density polyethylene (HDPE), insect-controlling agent and synthetic silica, and described composition can be provided at the long filament that oozes out function admirable of its initial stage operational phase insect-controlling agent.
The present invention at first relates to the resin combination that is used for long filament, and it comprises high density polyethylene (HDPE), insect-controlling agent and synthetic silica, and wherein the density of high density polyethylene (HDPE) is 935-965 kg/m
3And its MFR is 0.1-6 g/10 min; Wherein the average pore radius of synthetic silica is 0.040-0.105 μ m; Comprise 100 weight portion high density polyethylene (HDPE)s and per 100 weight portion high density polyethylene (HDPE) 0.1-10 weight portion insect-controlling agents and 0.1-10 weight portion synthetic silica with wherein said resin combination.
Secondly the present invention relates to the long filament that is formed by above-mentioned resin combination.
The specific embodiment
The resin combination that is used for long filament of the present invention comprises high density polyethylene (HDPE), insect-controlling agent and synthetic silica, and this resin combination comprises 100 weight portion high density polyethylene (HDPE)s and per 100 weight portion high density polyethylene (HDPE) 0.1-10 weight portion insect-controlling agents and 0.1-10 weight portion synthetic silica especially.
The content of insect-controlling agent is the 0.1-10 weight portion, per 100 weight portion high density polyethylene (HDPE)s.
From being used for suppressing before the long filament molding viewpoint of the viscosity of resin combination, the content of insect-controlling agent is preferably 5 weight portions or still less, more preferably 3 weight portions or still less; And from improving the protection against insect performance standpoint of resin combination, this content is preferably 0.5 weight portion or more, more preferably 1 weight portion or more.
In the resin combination of the present invention, the content of synthetic silica is the 0.1-10 weight portion, per 100 weight portion high density polyethylene (HDPE)s.
From preventing the viewpoint of long filament cutting, the content of synthetic silica is preferably 5 weight portions or still less, more preferably 3 weight portions or still less, and from being used for the viewpoint that the long filament molding suppresses the viscosity of resin combination before, this content is preferably 0.5 weight portion or more, more preferably 1 weight portion or more.
To be used for high density polyethylene (HDPE) of the present invention is Alathon or ethene-alpha-olefin copolymer.Preferably, from the viewpoint of the intensity of improving the gained long filament, described high density polyethylene (HDPE) is an ethene-alpha-olefin copolymer.The example of alpha-olefin comprises propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene etc.Any these monomers can use separately, perhaps can be used in combination from least two kinds of wherein selecting.The density of high density polyethylene (HDPE) uses test piece to measure according to the process of stipulating among the method A in the JIS K7112-1980 method, and described test piece is according to the method annealing that is used for low density polyethylene (LDPE) of stipulating in JIS K6760-1995.
Based on the gross weight (100 weight %) of high density polyethylene (HDPE), the content based on the monomeric unit of ethene in the high density polyethylene (HDPE) is generally 90-100 weight %.Based on the gross weight (100 weight %) of high density polyethylene (HDPE), the content based on the monomeric unit of alpha-olefin in the high density polyethylene (HDPE) is generally 0.1-10 weight %.
The example of high density polyethylene (HDPE) comprises ethylene-propylene copolymer, ethene-butene-1 copolymer, ethene-1-hexene copolymer, ethene-1-octene copolymer, ethene-1-butene-1-hexene copolymer etc., wherein optimal ethylene-propylene copolymer, ethene-butene-1 copolymer and ethene-1-hexene copolymer.
The melt flow rate (MFR) of described high density polyethylene (HDPE) (MFR) is 0.1-6 g/10 min.From improving the viewpoint of melt extrudability, this MFR is preferably 0.3 g/10 min or more, more preferably 0.6 g/10 min or more.In addition, from improving the viewpoint of the tensility under mechanical strength and the heating, this MFR is preferably 4 g/10 min or still less, more preferably 2 g/10 min or still less.This MFR measures under 21.18 N load 190 ℃ of temperature according to the method for stipulating among the JIS K7210-1995.
From improving the viewpoint of melt spinning performance, the melt flow rate (MFR) of high density polyethylene (HDPE) is preferably 50 or littler than (MFRR), and more preferably 45 or littler, still more preferably 40 or littler.In addition, from improving the viewpoint of melt extrudability, MFRR is preferably 10 or bigger, and more preferably 15 or bigger, still more preferably 20 or bigger.MFRR is the quotient that obtains by following division: promptly, according to the method for stipulating among the JIS K7210-1995 190 ℃ of temperature in the melt flow rate (MFR) of measuring under the 211.83 N load (MFR-H, the g/10 min of unit) divided by the melt flow rate (MFR) of measuring under 21.18 N load 190 ℃ of temperature according to the method for stipulating among the JIS K7210-1995 (MFR).
The density of high density polyethylene (HDPE) is 935-965 kg/m
3From improving the viewpoint of the tensility under the heating, this density is preferably 960 kg/m
3Or still less, more preferably 955 kg/m
3Or still less, more preferably 950 kg/m still
3Or still less.From improving the viewpoint of the tensility under the heating, this density is preferably 940 kg/m
3Or more, more preferably 945 kg/m
3Or it is more.The density of high density polyethylene (HDPE) uses test piece to measure according to the process of stipulating among the method A in JIS K7112-1980 method, and described test piece is according to the method annealing that is used for low density polyethylene (LDPE) of stipulating in JIS K6760-1995.
As the method for preparing high density polyethylene (HDPE), use any known method, for example polymerisation in solution, slurry polymerization, gas-phase polymerization, high-pressure ion polymerization (high-pressure ionic polymerization) etc., any known catalysts that is used for olefinic polymerization for example Ziegler-Natta catalyst, chromium-based catalysts, Metallocenyl catalyst etc. in the presence of.Described polymerization can be batch technology or continuous processing, perhaps can be two-stage or more multistage polymerization technique.
As Ziegler-Natta catalyst, exemplify following catalyst (1) and (2):
(1) catalyst, it comprises as the organo-metallic compound of co-catalyst with by support at least a component that obtains that is selected from titanium trichloride, vanadium trichloride, titanium tetrachloride and titanium halogenated alcoholate (titanium halo-alcoholate) on the carrier based on magnesium compound; With
(2) catalyst, it comprises the coprecipitate of magnesium compound and titanium compound or eutectic and as the organo-metallic compound of co-catalyst.
As chromium-based catalysts, exemplify and comprise following catalyst: have the component that is supported on the chromium compound on synthetic silica or the synthetic silica aluminium oxide and as the organo-metallic compound of co-catalyst.
As the Metallocenyl catalyst, exemplify following catalyst (1)-(4):
(1) catalyst, it comprises: comprise the group with cyclopentadienyl skeleton transistion metal compound component and comprise the component of aluminium alkoxide compound;
(2) catalyst, it comprises: above-mentionedly comprise the component of transistion metal compound and comprise for example component of trityl borate (trityl borate), boric acid aniline salt (anilium borate) etc. of ionic compound;
(3) catalyst, it comprises: the above-mentioned component of transistion metal compound, the above-mentioned component that comprises the component of ionic compound and include machine aluminium compound of comprising; With
(4) catalyst, it obtains in the following manner: make any said components be supported on for example SiO of inorganic particulate carrier
2, Al
2O
3Deng, perhaps alkene is for example on the granulated polymer carrier of the polymer of ethene, styrene etc., perhaps by flooding above-mentioned carrier with any said components.
Use the catalyst based or Metallocenyl Preparation of catalysts method of Ziegler-Natta preferably as the preparation method of high density polyethylene (HDPE).From improving the melt spinning performance standpoint, the time of staying short during the preferred polymeric distributes.Distribute in order to shorten the time of staying, preferred single step polymerization, perhaps with the technology of using a plurality of reactors in the relevant polymerization of a plurality of reactor multiple operations.
As being used for insect-controlling agent of the present invention (insect-controlling agent), exemplify compound, for example pesticide, insect growth controlling agent and pest repellant (insect-repelling agents) with protection against insect activity.
The example of pesticide comprises pyrethroid ester group compound (pyrethroid-based compounds), organophosphor based compound, carbamate based compound (carbamate-based compounds), Phenylpyrazole based compound etc.The example of pyrethroid ester group compound comprises permethrin, allethrin, the d-allethrin, the dd-allethrin, the d-tetramethrin, the alkynes third chrysanthemum ester, the d-phenothrin, the d-resmethrin, the alkynes valerate, fenvalerate, efficient fenvalerate (esfenvalerate), Fenpropathrin, three lambda-cyhalothrins (cyhalothrin), ether chrysanthemum ester, tralomethrin, ES EXTHIN (esbiothrin), transfluthrin, terallethrin, decis, phenothrin, Tefluthrin, Biphenthrin, cyfloxylate (cyfluthrin), cypermethrin, α-cypermethrin etc.The example of organophosphor based compound comprises Folithion, DDVP, 2-dichloroethylk dimethyl phosphate, Entex, cynock, chlopyrifos, basudin, carcrofos, salithion, basudin etc.The example bag of carbamate based compound is drawn together Evil worm ketone (methoxydiazon), arprocarb, Bassa, sevin etc.The example of Phenylpyrazole based compound comprises fluorine worm nitrile etc.
The example of insect growth controlling agent comprises pyrrole propyl ether, methoprene (methoprene), increases fibroin (hydroprene), diflubenzuron, fly eradication amine, ABG-6215, Acarus tritici urea (CGA 184599) etc.
The example of pest repellant comprises DEET, dibutyl phthalate etc.
Any of these insect-controlling agent can use separately, perhaps its two or more can be used as mixture and use.In addition, the compound that is used to strengthen the protection against insect activity can be used in combination with insect-controlling agent.As this compounds, exemplify Butacide, MGK264, eight chlorine dipropyl ethers etc.
As insect-controlling agent, preferred pesticide, and more preferably pyrethroid ester group compound.Especially, still more preferably show and be lower than 1 X 10 at 25 ℃
-6The pyrethroid ester group compound of the vapour pressure of mmHg.As this class pyrethroid based compound, exemplify pyrrole propyl ether (pyriproxfen), resmethrin (resmethrin), permethrin (permethrin) etc.
As being used for synthetic silica of the present invention, exemplify by the precipitation method or the synthetic silica of gel method.Its example comprises powdered silicate, fine-powdered silicic acid, white carbon etc.As synthetic silica, preferred amorphous synthetic silica.
The average pore radius (average pore radius) that will be used for synthetic silica of the present invention is 0.040-0.105 μ m.From improving the viewpoint of oozing out performance at its initial stage operational phase insect-controlling agent, the upper limit of the average pore radius of synthetic silica is preferably 0.090 μ m or littler, more preferably 0.080 μ m or littler, still more preferably 0.070 μ m or littler.The lower limit of the average pore radius of synthetic silica is preferably 0.050 μ m or more, more preferably 0.060 μ m or more.The average pore radius is measured by mercury injection method (mercury intrusion technique).
From improving the viewpoint of oozing out performance at its initial stage operational phase insect-controlling agent, the specific area that will be used for synthetic silica of the present invention is preferably 240 m
2/ g or littler, more preferably 210 m
2/ g or littler.In addition, from improving the viewpoint of oozing out performance at its initial stage operational phase insect-controlling agent, it is preferably 50 m
2/ g or bigger, more preferably 80 m
2/ g or bigger, still more preferably 110 m
2/ g or bigger.Specific area is measured by nitrogen absorption BET method.
From improving the viewpoint of oozing out performance at its initial stage operational phase insect-controlling agent, the weight of the insect-controlling agent that keeps as every 100g synthetic silica, oil absorbs weight W (g/100 g) and is preferably 1,000 g/100 g or still less, more preferably 500 g/100 g or still less, still more preferably 350 g/100 g or still less.In addition, from the viewpoint of the reservation that improves insect-controlling agent, 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.
In resin combination of the present invention, the content of insect-controlling agent is preferably (5 X W) weight portion or still less, more preferably (3 X W) weight portion or still less, still more preferably (W) weight portion or still less, to be insect-controlling agent absorb weight to the oil of synthetic silica is W (g/100 g) for per 100 weight portion synthetic silicas, condition.
Resin combination of the present invention randomly can comprise additive, for example antioxidant, anti-blocking agent, filler, lubricant, antistatic additive, anti-climate-aging agent, pigment, working ability improver and metallic soap; With the polymers compositions that is different from described high density polyethylene (HDPE).Two or more that are selected from above-mentioned additive and above-mentioned polymers compositions can be used in combination.
Resin combination of the present invention can be according to known method by with high density polyethylene (HDPE), insect-controlling agent and synthetic silica, and other optional component melts and kneading and prepare.For example, high density polyethylene (HDPE), insect-controlling agent and synthetic silica are pre-mixed, and use extruder, roller die molding machine (roll molding machine), kneader etc. fusion of gained mixture and kneading; High density polyethylene (HDPE), insect-controlling agent and synthetic silica are sent into extruder, roller die molding machine or kneader and fusion and mixing then separately; The mixture of high density polyethylene (HDPE) and previously prepared synthetic silica and insect-controlling agent is sent into extruder, roller die molding machine or kneader and fusion and mixing then; With the mixture of insect-controlling agent and previously prepared high density polyethylene (HDPE) and synthetic silica is sent into extruder, roller die molding machine or kneader and fusion and kneading then separately.By using extruder to carry out under the situation of melt kneading, use side extruder (side extruder) or feeder mixture can be added in the middle of extruder.
In the preparation of resin combination, preferably use insect-controlling agent as insect-controlling agent preservative (insect-controlling agent retainer), described insect-controlling agent preservative is by keeping insect-controlling agent, support or be combined in the synthetic silica, or, perhaps prepare by making synthetic silica absorption or absorbing insect-controlling agent by with insect-controlling agent infiltration or injection synthetic silica.
Can pass through insect-controlling agent or silica, perhaps insect-controlling agent and silica, perhaps above-mentioned insect-controlling agent preservative adds in the resin and prepares masterbatch (master batch), and can make the masterbatch and high density polyethylene (HDPE) fusion and the kneading that obtain thus, to obtain resin combination of the present invention.Preferably, use by the insect-controlling agent preservative being added the masterbatch for preparing in the resin.
Example as the resin of masterbatch matrix comprises the alkylene resin, for example based on the resin of ethene, based on the resin of propylene, based on the resin of butylene, based on the modification of the resin of 4-methyl-1-pentene and these resins, saponification and product hydrogenation, etc.The preferred resin that is based on ethene that uses is the low density polyethylene (LDPE), vinyl-vinyl acetate copolymer etc. of high density polyethylene (HDPE), linear low density polyethylene (LLDPE), linear extra-low density polyethylene, line style ultra-low density polyethylene, high pressure processing for example; With hydrogenated products based on the polymer of butadiene.
When masterbatch is used to prepare resin combination, the amount of the masterbatch that adds is generally is less than 50 weight portions, per 100 weight portions are contained in the high density polyethylene (HDPE) in the resin combination of the present invention.From cost-efficient viewpoint, this amount is preferably 20 weight portions or still less, more preferably 10 weight portions or still less.
Because its excellent melt spinning performance and melt extrudability, resin combination of the present invention is formed long filament (filaments) for example multifilament (multifilaments), monofilament (monofilaments) etc.Preferably, this resin combination is formed monofilament.The hot tensility of the long filament that is formed by this resin combination is good and have enough mechanical strengths.The cost-performance of method that is prepared long filament by this resin combination is good, because can extrude and the spinning resin combination at high discharge rate, and can operate the tow of high elongation gained by single stage drawing.
As the method that resin combination of the present invention is formed long filament, provide known molding methods for example melt spinning process, (directly) spinning/extension etc.For example, make the resin combination fusion with extruder etc.; The melt of extruding gained by gear pump from die head/nozzle is to form tow shape melt; With the tow shape melt spinning of the resin combination extruded and with for example cooling such as water, air of cooling medium; And then, if desired, the gained tow stretches under heating, handles, covers with oil by heating, and rolls as long filament then.
The cross sectional shape of long filament is circle, ellipse, triangle, rectangle, hexagon or star.
The fineness of long filament is generally the 50-500 DENIER, preferred 100-350 DENIER, more preferably 150-250 DENIER.
When the long filament that is formed by resin combination of the present invention was used as monofilament, this monofilament was used to make net for example mosquito net, wind screen (wind screens), insect guard net; Rope; Yarn; And filter.When the long filament that is formed by resin combination of the present invention was used as multifilament, this multifilament was used to make rope, net, carpet, non-weaving cloth, filter, footwear, clothes etc.Especially, long filament of the present invention is preferred for having the product of insect guard performance, for example wind screen, insect guard net, mosquito net, filter, carpet, footwear and clothes.
Example as the insect of the target of long filament control that will be by being formed by resin combination of the present invention is for example spider, tick and an insect of arthropod.Below be its example: belong to Ormithonyssus sylviarum, tangerine Panonychus citri, tyrophagus putrescentiae of Acarina (Acarina) etc.; With the Atypus karshi that belongs to the Araneida in the Arachnoidea, Pholcus phalangioides etc.; Belong to common house centipede dragonfly purpose common house centipede dragonfly etc.; With thick back of the body stone centipede that belongs to the Lithobiomorpha in the Chcilopoda etc.; With band julid purpose axidus gracilis, the Nedyopus tambanus etc. that belong in the Chcilopoda.
As insect, provide following these: the moth that belongs to Thysanoptera (Thysanura); Belong to cave cricket, mole cricket, field cricket, Asiatic migrotory locust, desert locust, locust of Orthoptera etc.; Belong to the ground centipede of Dermaptera etc.; The Groton bug, Peroplaneta fluligginosa, Japanese Lian, the American cockroach etc. greatly that belong to Blattaria; Belong to Japanese subteranean termites, coptotermes formosanus of taiwan, little principal columns of a hall termite HAGEN of Isoptera etc.; Belong to psocopteran Liposcelis entomophilus Enderlein, l.bostrychophila etc.; Belong to dog hair lice, Felicola subrostratus of Mallophaga etc.; Belong to body louse, pediculus humanus capitis, humanlice of Anoplura etc.; Belong to brown paddy plant hopper, rice green leafhopper, greenhouse white fly, black peach aphid, Cimex lectularius Linnaeus, tea wing stinkbug of Semiptera etc.; Belong to khapra beetle beetle, aulacophora femoralis, sitophilus zea-mais, Lyctus brunmeus, Ptinus japonicus, Japanese beetle of coleoptera etc.; Belong to cat flea, dog flea, Pulex irritans of Siphonaptera etc.; Belong to dipterous Culex pipiens pallens couguillett, Aedes aegypti, anopheles, Simulidae, Chironomous, Moth files, housefly, glossina palpalis, horsefly, wasp fly subfamily etc.; Belong to hymenopteran Vespa, Polistes, Nesodiprion japonicus Marlatt, chestnut cynipid, the swollen leg honeybee of Japanese sclerderm, little red ant etc.; Or the like.
Embodiment
Hereinafter, will the present invention be described by embodiment and comparative example.In embodiment and comparative example, measure physical property according to following method.
(1) melt flow rate (MFR) (MFR, the g/10 min of unit)
Melt flow rate (MFR) is measured under 21.18 N load at 190 ℃ according to the method for stipulating among the JIS K7210-1995.
(2) melt flow rate (MFR) is than (MFRR)
MFRR is the merchant who obtains by following division: promptly, according to the method for stipulating among the JIS K7210-1995 190 ℃ the melt flow rate (MFR)s of measuring under the 211.83 N load (MFR-H, the g/10 min of unit) divided by according to the method for stipulating among the JIS K7210-1995 190 ℃ of melt flow rate (MFR)s (MFR) of under 21.18 N load, measuring.
(3) density (units/m
3)
Density is according to the process measurement of stipulating among the method A in the middle of the method that is described among the JIS K7112-1980.Test piece to be measured is according to the method annealing that is used for low density polyethylene (LDPE) of stipulating in JIS K6760-1995.
(4) average pore radius (the μ m of unit)
120 ℃ of dryings 4 hours, and use the AutoPore III 9420 that produces by MICROMERITICS to measure the distribution of pores of hole synthetic silica with about 0.0018-100 μ m radius.The infiltration ratio that the average pore radius is defined in this pore radius mercury becomes 50% pore radius of whole infiltration capacities of mercury.
(5) specific area (m of unit
2/ g)
Synthetic silica to be measured was outgased 8 hours in advance at 120 ℃ in a vacuum.Use is by BEL JAPAN, and the BELSORP-mini that INC. produces uses nitrogen to measure adsorption/desorption attached thermoisopleth by the constant volume method at the 77K adsorption temp as absorbate, and condition is that the sectional area of this absorbate is 0.162 nm
2The specific area of synthetic silica is calculated by the BET multipoint method.
(6) oil absorbs weight (the g/100 g of unit)
With insect-controlling agent (5 cm
3) pour glass container into, and under agitation to the synthetic silica that wherein is heated to 50 ℃ gradually, disappear up to any spherical reagent (ball-like agent) that is positioned on the synthetic silica.At the time point that any spherical reagent has disappeared, judge that insect-controlling agent is retained in the synthetic silica.The insect-controlling agent oil that is calculated every 100g synthetic silica by the weight of the weight of the synthetic silica that adds and insect-controlling agent absorbs weight.
Embodiment 1
1. the preparation of insect-controlling agent preservative
Will as the permethrin of insect-controlling agent (by Sumitomo Chemical Company, the Eksmin that Limited produces
Density: 1.21 g/cm
3) (51 weight portion) mix with butylated hydroxytoluene (1.5 weight portion) as antioxidant, and under agitation the gained mixture is dissolved.Subsequently, adding (hereinafter is called silica 1 by the SOLEX CM that Tokuyama Corp. produces as synthetic silica, its physical property is shown in table 1) (47.5 weight portion), and stir the protection against insect agent preservative (hereinafter be called the preservative A that comprise protection against insect agent) of gained mixture to obtain comprising the protection against insect agent.Subsequently, with the low density polyethylene (LDPE) of high pressure processing (by Sumitomo Chemical Company, the Sumikathene that Limited produces
G803-1; MFR=20 g/10 min; Density=918 kg/m
3) (60.3 weight portion), the preservative A (34.2 weight portion) that comprises the protection against insect agent and zinc stearate (5.5 weight portion) be in the Banbury mixer, 150 ℃ temperature is set and mediated 5 minutes at 300rpm.Obtain the masterbatch of insect-controlling agent preservative thus.
2. be used for the preparation of the resin combination of long filament
With high density polyethylene (HDPE) (HI-ZEX
440M, promptly ethylene-propylene copolymer is produced by PRIME POLYMER; MFR=0.9 g/10 min; Density=948 kg/m
3MFRR=35) masterbatch of (100 weight portion) and insect-controlling agent preservative (14.5 weight portion) is mediated in the Banbury mixer.Preparation is used for the resin combination of long filament thus.In this resin combination, do not feel viscosity.
3. the preparation of long filament
Use has 20 mm φ extruders of the die head with 6 1.0 mm φ holes, by being arranged on 200 ℃ die head and with the discharge rate of 0.9kg/hr, extruding the resin combination that is used for long filament.The resin combination tow of gained is sent in the linear velocity of 14m/min, and made it, and send in the speed of 112m/min then by hot bath.Obtain having the monofilament of 200 DENIER fineness thus.
4. ooze out performance evaluation
(500 mg) puts into vial with long filament, and will leave standstill in 60 ℃ baking oven 2 hours on the bottle cap and then.Afterwards, with acetone (450 cm
3) add in the bottle, and bottle was stirred 30 minutes, clean filament surface thus.The long filament that its surface obtains cleaning is put into vial, and will leave standstill 1 day on the bottle cap and in 60 ℃ baking oven.Then, from baking oven, take out long filament, and with ethanol (50 cm
3) the adding long filament.Then, stir the insect-controlling agent that long filament oozed out from filament surface with cleaning in 10 minutes with mixer.Use is used for the permethrin concentration of cleaning solution of the spectrophotometer measurement gained of ultraviolet and visibility region.The long filament that the surface is obtained wiping is put into vial, and will leave standstill in 60 ℃ baking oven 6 days on the glass cap and once more.From baking oven, take out long filament, and add ethanol (50 cm
3), and be exuded to the insect-controlling agent of filament surface in 10 minutes with cleaning with mixer stirred glass bottle.Use is used for the insect-controlling agent concentration of cleaning solution of the spectrophotometer measurement gained of ultraviolet and visibility region.
Use is used for spectrophotometer measurement permethrin (permethrin) concentration of ultraviolet and visibility region
Adopt the spectrophotometer V-650 that is used for ultraviolet and visibility region that produces by JASCO Corporation to measure surperficial cleaning solution under the following conditions; And measure the absorbance at the peak of permethrin in 200 ± 1 nm scopes.
Spectrophotometric measuring condition:
Cell length (cell length): 10 nm
Bandwidth: 2.0 nm
Sweep speed: 400 nm/min
Initial wavelength: 340 nm
Stop wavelength: 190 nm
Data load at interval: 1.0 nm
Use above-mentioned spectrophotometer to have the ethanolic solution of 8 kinds of different permethrins of 0.632-15.8 mg/L concentration in advance, obtain the calibration curve of the absorbance and the permethrin concentration of permethrin in 200 ± 1 nm scopes by measurement.
Determine the amount of permethrin in the cleaning surfaces liquid by this calibration curve.
The amount of the permethrin that oozes out from filament surface that obtains after 1 day is defined as the merchant of following calculating: with the amount of permethrin the cleaning solution that obtains after 1 day divided by the long filament weight of measuring.The amount of the permethrin that oozes out from filament surface that obtains after 7 days is defined as the merchant of following calculating: after 6 days after described 1 day, the amount of permethrin is divided by the long filament weight of measuring in the cleaning solution that obtains after promptly 7 days.The summation of the amount of the amount of the permethrin that oozes out from filament surface that obtains after 1 day and the permethrin that oozes out from filament surface that obtains after 7 days is defined as after 7 days the cumulant of the permethrin that oozes out from filament surface, and it is used to estimate the amount of the permethrin that operational phase in the early stage oozes out from filament surface.
The cumulant of oozing out the permethrin of filament surface after 7 days is 2.23 mg/g.
Embodiment 2
Repeat embodiment 1, except using the Finesil CM-F (hereinafter be called silica 2, its physical property is shown in table 1) that produces by Tokuyama Corp. as synthetic silica.In this resin combination, do not feel viscosity.
The cumulant of oozing out the permethrin of this filament surface after 7 days is 2.23 mg/g.
Embodiment 3
Repeat embodiment 1, except using the Finesil B (hereinafter be called silica 3, its physical property is shown in table 1) that produces by Tokuyama Corp. as synthetic silica.In this resin combination, do not feel viscosity.
The cumulant of oozing out the permethrin of this filament surface after 7 days is 2.70 mg/g.
Embodiment 4
Repeat embodiment 1, except using the Finesil T-32 (hereinafter be called silica 4, its physical property is shown in table 1) that produces by Tokuyama Corp. as synthetic silica.In this resin combination, do not feel viscosity.
The cumulant of oozing out the permethrin of this filament surface after 7 days is 2.53 mg/g.
Embodiment 5
Repeat embodiment 1, except using the Carplex FPS-5 (hereinafter be called silica 5, its physical property is shown in table 1) that produces by EVONIC INDUSTRIES as synthetic silica.In this resin combination, do not feel viscosity.
The cumulant of oozing out the permethrin of this filament surface after 7 days is 1.73 mg/g.
Embodiment 6
Repeat embodiment 1, except using the Tokusil GU (hereinafter be called silica 6, its physical property is shown in table 1) that produces by Tokuyama Corp. as synthetic silica.In this resin combination, do not feel viscosity.
The cumulant of oozing out the permethrin of this filament surface after 7 days is 1.23 mg/g.
Comparative example 1
Repeat embodiment 1, except using the Finesil X-32 (hereinafter be called silica 7, its physical property is shown in table 1) that produces by Tokuyama Corp. as synthetic silica.In this resin combination, do not feel viscosity.
The cumulant of oozing out the permethrin of this filament surface after 7 days is 0.81 mg/g.
Comparative example 2
Repeat embodiment 1, except using by MIZUSAWA INDUSTRIAL CHEMICALS, the Mizukasil P-707 (hereinafter be called silica 8, its physical property is shown in table 1) that LTD. produces is as synthetic silica.In this resin combination, do not feel viscosity.
The cumulant of oozing out the permethrin of this filament surface after 7 days is 0.54 mg/g.
Comparative example 3
Repeat embodiment 1, except using the Carplex BS-308N (hereinafter be called silica 9, its physical property is shown in table 1) that produces by EVONIK INDUSTRIES as synthetic silica.In this resin combination, do not feel viscosity.
The cumulant of oozing out the permethrin of this filament surface after 7 days is 0.89 mg/g.
Comparative example 4
Repeat embodiment 1, except using the Sipernat 880 (hereinafter be called silica 10, its physical property is shown in table 1) that produces by EVONIK INDUSTRIES as synthetic silica.In this resin combination, do not feel viscosity.
The cumulant of oozing out the permethrin of this filament surface after 7 days is 0.70 mg/g.
Comparative example 5
Repeat embodiment 1, except using the Nipsil E-743 (hereinafter be called silica 11, its physical property is shown in table 1) that produces by TOSOH SILICA CORPORATION as synthetic silica.In this resin combination, do not feel viscosity.
The cumulant of oozing out the permethrin of this filament surface after 7 days is 0.40 mg/g.
Embodiment 7
1. the preparation of insect-controlling agent preservative
To mix with butylated hydroxytoluene (1.9 weight portion) as the permethrin (64.9 weight portion) of insect-controlling agent, and mixture will be stirred and dissolving as antioxidant.Subsequently, will add gained solution as synthetic silica (hereinafter be called silica 12, its physical property is shown in table 1) (33.2 weight portion) by the Carplex 80 that EVONIC INDUSTRIES produces, and mixture will be stirred and mixing.Obtain comprising the insect-controlling agent preservative (hereinafter being called insect-controlling agent preservative B) of insect-controlling agent thus.
Subsequently, use the Banbury mixer with low density polyethylene (LDPE) Sumikathene G803-1 (64.9 weight portion), the insect-controlling agent preservative B (29.0 weight portion) of high pressure processing and zinc stearate (5.9 weight portion) 150 ℃ temperature is set and 300rpm kneading 5 minutes.Obtain the masterbatch of insect-controlling agent preservative thus.
2. be used for the preparation of the resin combination of long filament
Use the Banbury mixer that the masterbatch (11.8 weight portion) of high density polyethylene (HDPE) HI-ZEX 440M (100 weight portion) and insect-controlling agent preservative is mediated, to obtain being used for the resin combination of long filament.In this resin combination, do not feel viscosity.
3. the preparation of long filament and ooze out the evaluation of performance
With with embodiment 1 in identical mode carry out the preparation of long filament and it oozes out the evaluation of performance.The accumulation seepage discharge of this long filament is 2.06 mg/g after 7 days.
Embodiment 8
1. the preparation of insect-controlling agent preservative
To mix with butylated hydroxytoluene (1.9 weight portion) as the permethrin (64.9 weight portion) of insect-controlling agent, and mixture will be stirred and dissolving as antioxidant.Subsequently, will add gained solution by the Carplex 80D (hereinafter be called silica 13, its physical property is shown in table 1) (33.2 weight portion) that EVONIC INDUSTRIES produces, and mixture will be stirred and mixing.Obtain comprising the insect-controlling agent preservative (hereinafter being called insect-controlling agent preservative C) of insect-controlling agent thus.
Subsequently, use the Banbury mixer with low density polyethylene (LDPE) Sumikathene G803-1 (64.9 weight portion), the insect-controlling agent preservative C (29.0 weight portion) of high pressure processing and zinc stearate (5.9 weight portion) 150 ℃ temperature is set and 300rpm kneading 5 minutes.Obtain the masterbatch of insect-controlling agent preservative thus.
2. be used for the preparation of the resin combination of long filament
Use the Banbury mixer that the masterbatch (11.8 weight portion) of high density polyethylene (HDPE) HI-ZEX 440M (100 weight portion) and insect-controlling agent preservative is mediated, to obtain being used for the resin combination of long filament.In this resin combination, do not feel viscosity.
3. the preparation of long filament and ooze out the evaluation of performance
With with embodiment 1 in identical mode carry out the preparation of long filament and it oozes out the evaluation of performance.The accumulation seepage discharge of this long filament is 1.47 mg/g after 7 days.
Table 1
Claims (2)
1. the resin combination that is used for long filament comprises high density polyethylene (HDPE), insect-controlling agent and synthetic silica, wherein
The density of this high density polyethylene (HDPE) is 935-965 kg/m
3And its MFR is 0.1-6 g/10 min;
The average pore radius of this synthetic silica is 0.040-0.105 μ m; With
Described resin combination comprises this high density polyethylene (HDPE) of 100 weight portions and per this high density polyethylene (HDPE) of 100 weight portions 0.1-10 this insect-controlling agent of weight portion and this synthetic silica of 0.1-10 weight portion.
2. the long filament that forms by the resin combination of claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008316758 | 2008-12-12 | ||
| JP2008-316758 | 2008-12-12 | ||
| PCT/JP2009/071072 WO2010067902A1 (en) | 2008-12-12 | 2009-12-11 | Resin composition for filaments |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102245817A true CN102245817A (en) | 2011-11-16 |
| CN102245817B CN102245817B (en) | 2013-11-06 |
Family
ID=42242883
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801496548A Expired - Fee Related CN102245817B (en) | 2008-12-12 | 2009-12-11 | Resin composition for filaments |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5720093B2 (en) |
| CN (1) | CN102245817B (en) |
| AP (1) | AP3393A (en) |
| WO (1) | WO2010067902A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110438582A (en) * | 2019-07-30 | 2019-11-12 | 青岛信泰科技有限公司 | A kind of preparation method of oil suction ultra high molecular weight polyethylene fiber |
| CN111278282A (en) * | 2017-11-03 | 2020-06-12 | 科莱恩塑料和涂料有限公司 | Pest repellent polymer composition |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2958117B1 (en) * | 2010-03-30 | 2012-08-03 | Pascal Martinet | COMPOSITION OF A MATERIAL COMPRISING A PHYSICO-CHEMICAL BARRIER FOR PROTECTING BUILDINGS AGAINST TERMITES |
| FR2958499B1 (en) * | 2010-04-09 | 2015-02-13 | Pascal Martinet | COMPOSITION OF A MATERIAL COMPRISING A PHYSICO-CHEMICAL BARRIER FOR PROTECTING BUILDINGS AGAINST TERMITES |
| KR101052300B1 (en) * | 2010-11-23 | 2011-07-27 | 권영탁 | Manufacturing method of containing insecticidal in monofilament |
| KR101235255B1 (en) | 2010-12-06 | 2013-02-20 | 주식회사 삼양사 | Manufacturing method of high strength polyethylene multifilament drawn fibers containing nano silica particles |
| WO2012164080A1 (en) * | 2011-06-03 | 2012-12-06 | Intelligent Insect Control | Insecticidal polyethylene fiber, yarn or textile products with improved migration profiles and washing resistance |
| JP6996555B2 (en) * | 2017-03-29 | 2022-01-17 | 東洋紡株式会社 | Polyethylene fiber and products using it |
| WO2019186696A1 (en) * | 2018-03-27 | 2019-10-03 | 東洋紡株式会社 | Polyethylene fiber, and product using same |
| KR102564030B1 (en) * | 2021-03-12 | 2023-08-04 | 도레이첨단소재 주식회사 | Method of preparing insect repellent materbatch for non-woven fabric, insect repellent materbatch for non-woven fabric made according to the method, non-woven fabric including the materbatch, and article including the non-woven fabric |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0249707A (en) * | 1988-05-31 | 1990-02-20 | Asahi Glass Co Ltd | Insecticide |
| JPH0284595A (en) * | 1988-09-20 | 1990-03-26 | Tokyo Houraishiya:Kk | Mark material having insecticide emitting function |
| JPH03246202A (en) * | 1990-02-20 | 1991-11-01 | Showa Electric Wire & Cable Co Ltd | Molded article of rubber-plastic |
| JPH03249270A (en) * | 1990-02-22 | 1991-11-07 | Showa Electric Wire & Cable Co Ltd | Harmful organism-repelling fiber product |
| JP2537690B2 (en) * | 1990-03-16 | 1996-09-25 | 豊田合成株式会社 | Ethylene propylene rubber compound |
| JPH08239600A (en) * | 1995-03-06 | 1996-09-17 | Hazama Gumi Ltd | Coating material composition |
| JP3610301B2 (en) * | 2000-12-06 | 2005-01-12 | 株式会社タイキ | Fine resin particles for makeup |
| JP2004203971A (en) * | 2002-12-24 | 2004-07-22 | Rifure:Kk | Delayedly releasing resinous supporting material and its use |
| ATE520742T1 (en) * | 2003-04-15 | 2011-09-15 | Innogel Ag | POLYMER NETWORKS |
| WO2007011728A2 (en) * | 2005-07-19 | 2007-01-25 | Dow Global Technologies Inc. | Frothed thermoplastic foam and its uses in sanitary applications |
| JP2008013508A (en) * | 2006-07-07 | 2008-01-24 | Sumitomo Chemical Co Ltd | Insect pest control material |
| JP5157221B2 (en) * | 2007-03-30 | 2013-03-06 | 住友化学株式会社 | Resin composition and filament |
| JP2008248091A (en) * | 2007-03-30 | 2008-10-16 | Sumitomo Chemical Co Ltd | Resin composition and filament |
-
2009
- 2009-12-04 JP JP2009276382A patent/JP5720093B2/en active Active
- 2009-12-11 CN CN2009801496548A patent/CN102245817B/en not_active Expired - Fee Related
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111278282A (en) * | 2017-11-03 | 2020-06-12 | 科莱恩塑料和涂料有限公司 | Pest repellent polymer composition |
| CN110438582A (en) * | 2019-07-30 | 2019-11-12 | 青岛信泰科技有限公司 | A kind of preparation method of oil suction ultra high molecular weight polyethylene fiber |
| CN110438582B (en) * | 2019-07-30 | 2022-03-01 | 青岛信泰科技有限公司 | Preparation method of oil-absorbing ultra-high molecular weight polyethylene fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5720093B2 (en) | 2015-05-20 |
| AP3393A (en) | 2015-08-31 |
| JP2010159403A (en) | 2010-07-22 |
| WO2010067902A1 (en) | 2010-06-17 |
| AP2011005775A0 (en) | 2011-06-30 |
| CN102245817B (en) | 2013-11-06 |
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