CN101466780B - Resin composition for filament, filament, and method for producing the filament - Google Patents

Resin composition for filament, filament, and method for producing the filament Download PDF

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Publication number
CN101466780B
CN101466780B CN2007800216907A CN200780021690A CN101466780B CN 101466780 B CN101466780 B CN 101466780B CN 2007800216907 A CN2007800216907 A CN 2007800216907A CN 200780021690 A CN200780021690 A CN 200780021690A CN 101466780 B CN101466780 B CN 101466780B
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flow rate
melt flow
mfr
long filament
jis
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CN101466780A (en
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江尻晋
永松龙弘
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • 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
    • 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
    • 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
    • D01F1/103—Agents inhibiting growth of microorganisms
    • 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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • 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
    • 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
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

A resin composition for a filament, which comprises an ethylene-a-olefin copolymer having a density of 935 to 965 kg/m3, and a pesticide of 0.1 to 10 parts by weight per 100 parts by weight of the ethylene-a-olefin copolymer, wherein the copolymer is a copolymer of ethylene and an a-olefin having 4 to 8 carbon atoms, and the composition has a melt flow rate of 0.3 to 7 g/10 minutes and a melt flow rate ratio of 10 to 50 and a density of 935 to 980 kg/cm3.

Description

Be applicable to the method for resin combination, long filament and the production long filament of long filament
Background of invention
Description of Related Art
Advance that the sterilant resultant composition has been processed to various moulded partss and as the prevention insect, like the material of tick, louse, mosquito, fly and so on through compound in alkene-Ji resin such as Vestolen PP 7052, Vilaterm etc.For example, JP-A-04-065509 discloses by melt-spun acrylic resin and the resulting long filament of insecticide composition.Further, the JP-A-06-315332 neck ring that discloses linear low density of polyethylene and insecticide composition and processed by said composition.In addition, the JP08-A-302080 expanded film that discloses high density polyethylene(HDPE), new LDPE (film grade) and insecticide composition and processed by said composition.
But when being moulded long filament to the conventional resins composite mold of polyolefin resin and sterilant, melt-spun property and thermal stretch property are all satisfied inadequately.
Invention field
The present invention relates to be applicable to the resin combination of long filament, by this resin combination long filament of processing and the method for producing long filament.
DISCLOSURE OF INVENTION
In this case, the purpose of this invention is to provide the polyolefin-containing resin and the resin combination of sterilant that can make long filament have good thermal stretch property and good melt-spun property, the long filament of processing by said composition and with the method for said composition production long filament.
That is, first inventive point of the present invention relates to the resin combination that is applicable to long filament: it comprises density is 935～965kg/m 3Alathon and per 100 parts by weight of ethylene homopolymer in the sterilant of 0.1～10 weight part of proportioning; The melt flow rate(MFR) of wherein said compsn (MFR) is 0.3～7g/10min, melt flow rate(MFR) than (MFRR) be 10～50 with density be 935～980kg/m 3
Further, second inventive point of the present invention relates to the resin combination that is applicable to long filament: it comprises density is 935～965kg/m 3Ethylene-propylene copolymer and per 100 parts by weight of ethylene-propylene copolymer in the sterilant of 0.1～10 weight part of proportioning; Wherein the melt flow rate(MFR) of compsn (MFR) is 0.3～7g/10min, melt flow rate(MFR) than (MFRR) be 10～50 with density be 935～980kg/m 3
Further, the 3rd inventive point of the present invention relates to the long filament of being processed by above-mentioned resin combination.
Again further, the 4th inventive point of the present invention relates to the method for producing long filament, and this method comprises and is configured as wire to the resin combination melt extrusion, discharges the wire compsn, and the wire compsn that thermal stretch is discharged under 70～120 ℃ of heating.
Detailed Description Of The Invention
It is 935～965kg/m that the resin combination of the present invention's first inventive point contains density 3Alathon and sterilant.The content of sterilant is 0.1～10 part of sterilant of per 100 parts by weight of ethylene homopolymer proportionings.It is 935～965kg/m that the resin combination of second inventive point contains density 3Ethylene-propylene copolymer and sterilant.The content of sterilant is per 100 parts by weight of ethylene-0.1～10 part of sterilant of propylene copolymer proportioning.
The content of sterilant is seen from antiseized viewpoint, 5 weight parts or still less preferably, and more preferably 3 weight parts or still less on the contrary, are seen preferred 0.5 weight part or more, more preferably 1 weight part or more from the viewpoint that improves pesticidal.
The melt flow rate(MFR) of the resin combination in first and second inventive points (MFR) is 0.3～7g/10min.As MFR during less than 0.3g/10min, melt-extrudability can variation, because the load of extruding during the long filament moulding becomes too high.MFR is preferably 0.5g/10min or bigger, more preferably 0.7g/10min or bigger.
On the contrary, when MFR surpassed 7g/10min, thermal stretch property and mechanical strength can variation.And MFR is preferably 5g/10min or littler, more preferably 3g/10min or littler.MFR uses the method according to JIS K7210-1955, under the temperature of the load of 21.18N and 190 ℃, measures.
The melt flow rate(MFR) of resin combination is 10～50 than (MFRR) in first and second inventive points.When MFRR surpassed 50, the melt-spun ability can variation.MFRR is preferably 45 or littler, and more preferably 40 or littler.
Further, when MFRR less than 10 the time, melt-extrudability can variation.And MFRR is preferably 15 or bigger, more preferably 20 or bigger.MFRR be according to JIS K7210-1995 190 ℃ with 211.83N load under the MFR value (MFR-H, the unit: that record g/10min) divided by the resulting value of melt flow rate value that under 190 ℃ and 21.18N load, records according to JIS K7210-1995.
The density of the resin combination in the present invention's first and second inventive points is 935～980kg/m 3When density surpasses 980kg/m 3The time, thermal stretch property can variation.Density is preferably 975kg/m 3Or lower, more preferably 970kg/m 3Or lower, more preferably 966kg/m again 3Or it is lower.On the other hand, be lower than 935kg/m when density 3The time, thermal stretch property can variation.Density is preferably 940kg/m 3Or higher, more preferably 945kg/m 3Or it is higher.The density of compsn, after annealing according to the method for the new LDPE (film grade) described in the JIS K6760-1995, the A-method of pressing among the JIS K7112-1980 is measured.
See that from the viewpoint that improves thermal stretch property swelling of the resin combination in the present invention's first and second inventive points is preferably 1.40 or littler than (SR), more preferably 1.30 or littler, again more preferably 1.25 or littler.On the other hand, see that from the viewpoint that improves melt-extrudability SR is preferably 1.10 or bigger, more preferably 1.13 or bigger, again more preferably 1.16 or bigger.
Mensuration is D from diameter according to JIS K7210-1995 under 21.18N load and 190 ℃ 0Aperture in the diameter of the material bar extruded, and be defined as material bar diameter (D) and hole diameter (D than (SR) swelling 0) ratio (D/D 0).
Resin combination of the present invention contains Alathon or ethylene-propylene copolymer.After this, this base polymer can be called " ethene-based polyalcohol ".
See that from the viewpoint that improves thermal stretch property the density of Alathon is 965kg/m 3Or lower, preferred 960kg/m 3Or lower, more preferably 955kg/m 3Or it is lower.On the other hand, see that density is 935kg/m from the viewpoint of thermal stretch property 3Or higher, preferred 950kg/m 3Or higher, more preferably 952kg/m 3Or higher, more preferably 954kg/m again 3Or it is higher.Density will be measured according to the A-method among the JISK7112-1980 after annealing by the method for the described new LDPE (film grade) of JISK6760-1995.
See that from the viewpoint that improves thermal stretch property the density of ethylene-propylene copolymer is 965kg/m 3Or lower, preferred 960kg/m 3Or lower, more preferably 955kg/m again 3Or it is lower.On the other hand, see that density is 935kg/m from the viewpoint of thermal stretch property 3Or higher, preferred 940kg/m 3Or higher, more preferably 945kg/m 3Or it is higher.Density will be measured according to the A-method among the JIS K7112-1980 after annealing by the method for the described new LDPE (film grade) of JIS K6760-1995.
Often be the 90wt% of ethylene-propylene copolymer gross weight (100wt%) or more based on the content of the monomeric unit of ethene in the ethylene-propylene copolymer.Often be the 10wt% of multipolymer gross weight (100wt%) or still less based on the content of the monomeric unit of propylene in the multipolymer.
See that from the viewpoint that improves melt-extrudability the MFR of ethene-based polyalcohol is preferably 0.1 or bigger, more preferably 0.3g/10min, more preferably 0.6g/10min or bigger again.
Further, see that from the viewpoint that improves thermal stretch property and mechanical strength MFR is preferably 6g/10min or littler, more preferably 4g/10min or littler, more preferably 2g/10min or littler again.
MFR presses the method for JIS K7210-1995, under the temperature of the load of 21.18N and 190 ℃, measures.
See that from the viewpoint that improves melt-spun property the melt flow rate(MFR) of ethene-based polyalcohol is preferably 50 or littler than (MFRR), more preferably 45 or littler, most preferably 40 or littler.On the other hand, see that from the viewpoint that improves melt-extrudability MFRR is preferably 10 or bigger, more preferably 15 or bigger, most preferably 20 or bigger.MFRR be according to JIS K7210-1995 190 ℃ with 211.83N load under record melt flow rate value (MFR-H, unit: g/10min) divided by according to JIS K7210-1995 190 ℃ with 21.18N load under the resulting value of MFR value that records.
See that from the viewpoint that improves melt-spun property the maximum of ethene-based polyalcohol is received silk speed (MTV) preferably 70m/min or bigger, more preferably 100m/min or bigger, most preferably 130m/min.On the other hand, see that from the viewpoint that improves mechanical strength MTV is preferably 500m/min or littler, more preferably 400m/min or littler, most preferably 300m/min.
MTV is meant that it is under the condition of 5.5m/min with piston rotation perdurability that the melt resin that ought be contained in the 9.5mm φ barrel is 190 ℃ in temperature; From diameter is that 2.09mm and length are to extrude the aperture of 8mm; And use the wind up roll of diameter as 150mm; When receiving silk speed coiling, make the melt resin disruptive receive silk speed with the rising of 40rpm.
Working method about ethene-based polyalcohol; Can enumerate known polymerization; Like solution polymerization process, slurry polymerization process, gaseous polymerization with use known polymerizing catalyst, like Zieglar-Natta catalyzer, chromium-catalyst based or metallocene catalyst, the high-pressure ion polymerization.
And polymerization method can be batchwise polymerization method or continuous polymerization, further can also adopt the multistep polymerization method.
Above-mentioned Zieglar-Natta catalyzer comprises, for example, and following catalyzer (1) and (2):
(1) by the combination through be loaded at least a halogenated alcoholate that is selected from titanous chloride, vanadium trichloride, titanium tetrachloride, titanium component made on magnesium compound-base carrier and the resulting catalyzer of organometallic compound promotor and
(2) by the co-precipitation or cocrystallization product and the resulting catalyzer of organometallic compound promotor that make up magnesium compound and titanium compound carrier.
Chromium-catalyst based comprising, for example, by making up through being loaded in chromium cpd component made on silicon-dioxide or the silica-alumina and the resulting catalyzer of organometallic compound promotor.
Metallocene catalyst comprises, for example, and following catalyzer (1)～(4)
(1) by combination contain band contain cyclopentadienyl skeleton group transistion metal compound component with contain the resulting catalyzer of component of aluminium alkoxide compound,
(2) contain the component of transistion metal compound and contain ionic compound by combination is above-mentioned, like the resulting catalyzer of component of tolyl borate or boric acid aniline salt,
(3) by above-mentioned component and above-mentioned component and the resulting catalyzer of organo-aluminium compound that contains ionic compound that contains transistion metal compound of combination,
(4) through being held in inorganic granule carriers to above-mentioned each group of branches, like SiO 2Or Al 2O 3Or on polymer beads carrier such as alkene (like ethene, the vinylbenzene) polymkeric substance or be immersed in wherein resulting catalyzer.
About the working method of ethene-based polyalcohol, preferably use Zieglar-Natta catalyzer or metallocene catalyst method as polymerizing catalyst.
Further, see, preferably shorten the residence time that generates polymkeric substance between polymerization period and distribute from the viewpoint that improves melt-spun property; And for the shortening residence time distributes, preferred one-step polymerization, further; In method, preferably with parallelly connected reaction vessel operation polymerization with a plurality of reaction vessels.
Be used for sterilant of the present invention and comprise the compound that contains insecticidal activity, like sterilant, insect growth control agent, wormer etc.
Sterilant comprises pyrethroid compound, organo phosphorous compounds, carbamate compounds, phenyl pyrazole compounds or the like.Pyrethroid compound comprises WL 43479; Esbiothrin; The d-esbiothrin; The dd-esbiothrin; The d-Tetramethrin 97; The alkynes third chrysanthemum ester; The d-phenothrin; The d-resmethrin; Empenthrin; Fenvalerate; Esfenvalerate; Fenvalerate; Cyhalothrin; Ether chrysanthemum ester; Tralomethrin; The chrysanthemum ester; Fenfluthrin; Terallethrin; Deltamethrin; Phenothrin; Tefluthrin; Bifenthrin; FCR-1272; Cyphenothrin; PP-383 and α-PP-383.The instance of organo phosphorous compounds comprises phenitrothion, dichlorobos, SD-1750, RE-4355, Tiguvon, cynock, clo Pyrrho good fortune, diazinon, calcholphos and dioxabenzofos.
The instance of carbamate compounds comprises the methoxyl group sulfoxone sodium, massacres, fenobucarb and carbaryl.The instance of phenyl pyrazole compounds comprises fluorine worm nitrile.
The instance of insect growth control agent comprises pyrrole propyl ether, methoprene, hydroprene, diflubenzuron, fly eradication amine, ABG-6215 and Acarus tritici urea (CGA184599).
The instance of wormer comprises diethylammonium para toluene sulfonamide (diethyltolamide) and Witcizer 300.
These sterilants can use separately or use with 2 kinds or multiple mixture.The combination of the sterilant that 2 kinds or multiple mechanism differ from one another makes with the resistance of infective insect insecticide beyond expression of words.As sterilant, preferred sterilant (insecticide), more preferably pyrethroid compound, more preferably 25 ℃ of following vapour pressures are less than 1 * 10 -6The pyrethroid compound of mmHg.25 ℃ of following vapour pressures are less than 1 * 10 -6The instance of the pyrethroid compound of mmHg comprises resmethrin and d-WL 43479.
But compounding has the compound that improves the insect protected active function in resin combination of the present invention.Said examples for compounds comprises piperonyl butoxide, MGK264 and eight chlorine propyl ether.
Further, in resin combination of the present invention, can add the solid support material that keeps sterilant.As solid support material, use the material that can keep, support, absorb, adsorb, flood, permeate or inject sterilant, and the example comprises silicon-dioxide-based compound, zirconium white, clay material, MOX, mica, hydrotalcite and organic carrier.That the instance of silicon-dioxide-based compound comprises is non--brilliant (amorphous) silicon-dioxide and crystalline silica, for example, powdered silicate, finely powdered silicic acid, acidic white earth, zeyssatite, quartz and hard charcoal.Zirconic instance comprises A-type zirconium white and mordenite.The instance of clay material comprises polynite, saponite, beidellite, wilkinite, kaolinite, halloysite, nakrite, dickite, anauxite, illite and sericite.The instance of MOX comprises zinc oxide, Natural manganese dioxide, aluminum oxide, red stone, cupric oxide and titanium oxide.The micaceous instance comprises mica and vermiculite.The instance of hydrotalcite comprises hydrotalcite and smectite.As organic carrier; (for example can enumerate coal; Coke, peat, glass peat), polymeric beads (for example, thin crystal fiber element, polystyrene bead, polyacrylic ester-Ji pearl, Rohm tech inc-Ji pearl, Vilaterm ol-yl pearl) and their cross-linked polymer pearl.Further can enumerate perlite, gypsum, pottery and volcanics.
As insecticide carrier, preferably non--brilliant inorganic carrier, more preferably soft silica.
When using insecticide carrier, the content of insecticide carrier in resin combination often is per 100 parts by weight of ethylene-based polyalcohol proportioning 0.1～20 weight part sterilant.See preferred 10 weight parts or still less, more preferably 5 weight parts or still less from the viewpoint that improves mechanical strength.On the contrary, see preferred 0.5 weight part or more, more preferably 1 weight part or still less from improving the controlled viewpoint of insect.
In resin combination of the present invention, can add additive of oxidation inhibitor, anti, filler, lubricant, static inhibitor, protective agent, pigment, processing aid and metallic soap and so on and the polymeric constituent beyond alkene-based polyalcohol.
2 kinds or multiple additives and polymeric constituent can be added respectively.
Resin combination of the present invention can be through obtaining with the known method melt-ethene-based polyalcohol of kneading, sterilant and other optional component.For example, a kind of typical method is, first mixed ethylene-based polyalcohol and sterilant are then with the knead mixture of gained of forcing machine, rolling mould molding machine, kneading machine or similar devices melt; Also have a kind of method to be, feed forcing machine or similar devices ethene-based polyalcohol and sterilant respectively, then melt-knead it.Carrying out melt with forcing machine when kneading, sterilant can lean on feeding device from the forcing machine stage casing, like side forcing machine or feeding machine, feeds.
In the production of resin combination; Sterilant can be at sterilant through handling; As keep, support, soak, permeate, inject, adsorb be absorbed on the carrier or in the carrier after use, further also can through the sterilant of above-mentioned processing or the sterilant that is untreated through adding resin to sterilant and using with masterbatch.
Instance as the basic resin of masterbatch comprises alkene-Ji resin, like modified product, saponification resultant and the hydrogenated products of ethene-Ji resin, allyl resin, butylene-Ji resin, 4-methyl-1-pentene-Ji resin and these resins.As preferred resin, can enumerate ethene-Ji resin, like high density polyethylene(HDPE), linear low density of polyethylene, linear VLDPE, linear ultra-low density polyethylene, high-pressure process new LDPE (film grade) and ethylene-vinyl acetate copolymer; And the hydrogenated products of divinyl-based polyalcohol.
When using masterbatch in the production at resin combination, the consumption of masterbatch often is less than the 50wt% of resin combination weight (100wt%), and sees from the viewpoint of increasing economic efficiency, preferred 20wt% or still less, more preferably 10wt% or still less.
Because resin combination of the present invention has good melt-spun property and good melt-extrudability, so be molded as long filament, like multifilament or long filament, and uses it.And the long filament of being processed by this resin combination has good thermal stretch property and good mechanical intensity.In addition, the method for producing long filament with this resin combination has the cost advantage, thereby carries out spinning and this long filament of high elongation because might discharge resin combination from the extruder nozzle high speed with the once step stretching operation.
About being molded as resin combination of the present invention the method for long filament, can enumerate the melt-spun method and spin (silk)-La (stretching) method, as the method that comprises the following steps (1) molten resin compsn also being discharged compsn with wire through toothed gear pump and so on from mouth mould/nozzle with (directly); (2) then, the wire melt of this discharge that stretches, then spinning; Use heat-eliminating medium such as water or air cooling tow simultaneously, handle (3), like thermal stretch, thermal treatment, last wet goods; If necessary, winding filaments.
In obtaining the method for long filament, the molding that in spinning, obtains for thermal stretch is to process long filament, and the thermal stretch temperature is preferably 70～120 ℃; And see from the viewpoint that improves thermal stretch property; More preferably 75～115 ℃, more preferably 80～110 ℃ again, most preferably 90～105 ℃.
The cross-sectional shape of long filament comprises circle, ellipse, trilateral, square, sexangle, star etc.
The purposes of the long filament of being processed by resin combination of the present invention comprises as long filament, reticulattion, like mosquito net, window screening or door yarn, fly net; Rope; Yarn; Strainer or the like, and as multifilament, rope; Reticulattion, carpet; Non-woven fabrics; Strainer; Footwear are carried out; Clothing etc.Needing to be particularly useful for the articles for use of insect protected, for example, window screening or door yarn, fly net, mosquito net, strainer, carpet, footwear shoe, clothing etc.
Intend the insect of controlling with the long filament of resin combination of the present invention and comprise the sufficient animal of joint, like spider, mite class and insect.Do below further to detail.
The spider guiding principle comprises, for example, educates female spider (like the perverse mite of woods fowl, the perverse mite of capsule fowl, red spider, tyrophagus putrescentiae); And Araneida (for example, Ka Shi ground spider, tongue ghost spider).Chilopoda comprises, for example, and common house centipede order (for example, spending the common house centipede); And Lithobiomorpha (for example Bothropolys rugosus).Diplopoda comprises, for example, and polydesmoidea (for example, Oxidus gracilis, Nedyopus tambanus).
In addition, the instance of Insecta comprises Thysanura (for example, moth); Orthoptera (for example, Japanese house cricket found in a kitchen, Japanese rhizoma atractylodis, Asiatic migrotory locust, African desert locust, rice grasshopper); Skin wing order (for example, European earwig); Blattodea (blatta germanica, Peroplaneta fluligginosa, the big Lian of Japan, periplaneta americana); Isoptera (for example, reticulitermes flavipe, coptotermes formosanus of taiwan, little principal columns of a hall termite); Corrodentia (having a liking for worm booklice, l.bostrychophila); Mallophaga (for example, Trichodectes latus, cat nibble a mao lice); Anoplura (clothing lice, crab louse, body louse); Hemiptera (for example, brown paddy plant hopper, rice green leafhopper, greenhouse whitefly, cigarette aphid, bed bug, tea wing stinkbug); Beetle order (for example, black japan khapra beetle, roundlet khapra beetle, aulacophora femoralis, sitophilus zea-mais, Lyctus brunneus Stephens, plan globose spider beetle (gibbium aequinoctiale), Japanese strain first, Japanese beetle); Siphonaptera (for example, cat flea, dog flea, people flea); Diptera (for example, culex pipiens pollens, Aedes Aegypti, to anopheles, maringouin, midge, moth fly, housefly, Fannia canicularis, horsefly, allograpta iavana); And Hymenoptera (Japanese hornet, Asia-africa hornet, Japanese loose greenery honeybee, chestnut cynipid, the swollen leg honeybee of the lucky fourth of Japanese Chinese wax, MonomoriumMayr).
Embodiment
The present invention describes with following embodiment and comparative example.
Physicals among embodiment and the comparative example is measured with following method:
(1) melt flow rate(MFR) (MFR, unit: g/10min)
Press JIS K7210-1995, under 190 ℃ of conditions with 21.18N load, measure.
(2) melt flow rate(MFR) is than (MFRR)
Melt flow rate(MFR) than (MFRR) be by JIS K7210-1995 in the melt flow rate value that records under 190 ℃ and 211.83N (21.60kg) load divided by the resulting value of melt flow rate value that under 190 ℃ and 21.18N (2.16kg) load, records.
(3) density (unit: kg/m 3)
The density of resin combination, after annealing by the method for the described new LDPE (film grade) of JIS K6760-1995, the A method of pressing among the JIS K7112-1980 is measured.
(4) swell than (SR)
Press JIS K7210-1995 when 21.18N load and 190 ℃ are measured melt flow rate(MFR) down, measuring the diameter of the material bar of extruding from aperture, and material bar diameter (D) and hole diameter (D 0) ratio be defined as the SR value.
(5) maximum silk speed (MTV, the unit: m/min) received
Melt tension tester with Toyo Seiki Seisaku-sho Ltd. manufacturing; The melt resin that is contained in the 9.5mm φ barrel, under 190 ℃, be that 2.09mm and length are the aperture of 8mm from diameter; Lowering speed with 5.5m/min is extruded; Use the wind up roll of diameter then, rise with 40rpm and receive the melt resin that silk speed is reeled and extruded, and measure the receipts silk speed that makes melt resin that fracture take place as 150mm.When this value was big, expression melt-spun property was better.
(6) the thermal stretch property of long filament
The thermal stretch of long filament is so that (i)～(method is v) carried out and measured the length that stretches between the mark line of back, calculates the elongation of length between the mark line then.When this elongation was big, expression thermal stretch property was better.
(i) the long long filament of cutting 70cm and mark along its length that spacing is 2 lines of 40mm.
(ii) fix an end of made long filament in (i).
Hot air heater (iii) is installed, and making the distance between heater outlet and the long filament is 50mm, with long filament 15s or the 30s between 2 mark lines of hot air heater heating.Long filament temperature behind heating 15s and the 30s is respectively 85 ℃ and 98 ℃.
After (iv) heating, a loose end on the speed elongate filaments with 100m/min.
(after v) stretching, the length between the measuring mark line (mm), and be calculated as follows the elongation of the length between the mark line.In addition, when during long filament is stretching, being broken, measure the length between each broken filament mark line and the breaking point, and be defined as the length between the mark line to total length.
The elongation of length between the mark line=(length before the length-stretching after stretching between the mark line between the mark line)/(length before stretching between the mark line) * 100 (%)
Length=40mm before stretching between the mark line.
(7) mechanical strength of long filament
In the chuck spacing is that 20mm and draw speed are under the condition of 500mm/min, and long filament is carried out tension test, to measure tensile break strength (unit: MPa) with normalization method tension fracture strain (unit: %).These values are big more, and then mechanical strength is good more.
Embodiment 1
(1) preparation of resin combination
Mix 51 weight part WL 43479s (Sumitomo Chemical Co. with paddling process; Ltd. make; Trade(brand)name:
Figure GSB00000508895500101
), (Fuji Silysia Chemical Ltd. makes 47.5 weight part soft silicas; Trade(brand)name:
Figure GSB00000508895500102
) and 1.5 weight part oxidation inhibitor (butylhydroxy toluene), to process insecticide carrier.Being 160 ℃ with Labo Plastmill (Toyo Seiki Seisaku-sho Ltd. manufacturing) in temperature is under the condition of 60rpm with rotating speed, 60.3 weight part linear low density of polyethylene pellets [Sumitomo Chemical Co., Ltd. manufacturing, trade(brand)name:
Figure GSB00000508895500103
-LGA807 (MFR:25g/10min, density: 913kg/m 3), ethene-butene-1 copolymer], 34.2 weight part insecticide carriers and 5.5 weight part Zinic stearass, the melt-10min that kneads is to obtain the sterilant masterbatch.Then; Being 160 ℃ with Labo Plastmill (Toyo Seiki Seisaku-sho Ltd. manufacturing) in temperature is under the condition of 60rpm with rotating speed; 100 weight part pellets of high density polyethylene [GF7750M2 (after this be referred to as " HD-1 ", the physicals of HD-1 is shown in table 1), Basell Polyolefin Co.; Ltd. make], 14.7 weight part sterilant masterbatch and the 0.8 weight part Zinic stearas melt-10min that kneads, to obtain resin combination (after this being referred to as " compsn-1 ").The evaluation result of the physicals of resulting composition-1 is shown in table 2.
(2) manufacturing of long filament
With Toyo Seiki Seisaku-sho, Capirograph and type hole (L/D:40/1mm, flow angle: 90 °) that Ltd. makes; Being 190 ℃ in temperature is under the condition of 10mm/min with piston rotation perdurability, and melt-extrusion compositions-1 is to form wire; With Capirograph with receipts silk equipment; With the speed of about 3m/min, rolling melt-extrude line, to obtain the long filament that diameter is 450 μ m.The evaluation result of the physicals of gained long filament is shown in table 2.
Embodiment 2
With with embodiment 1 in identical method; But with high density polyethylene(HDPE) (
Figure GSB00000508895500104
5000S; Prime Polymer Co.; Ltd. make) (after this be referred to as " HD-2 ", the physicals of HD-2 is shown in table 1) replacement HD-1, make resin combination and long filament.The evaluation result of the physicals of resulting composition and long filament is shown in table 2.
Embodiment 3
With with embodiment 1 in identical method; But with high density polyethylene(HDPE) (
Figure GSB00000508895500105
3300F; Prime Polymer Co.; Ltd. make) (after this be referred to as " HD-3 ", the physicals of HD-3 is shown in table 1) replacement HD-1, make resin combination and long filament.The evaluation result of the physicals of resulting composition and long filament is shown in table 2.
Embodiment 4
With with embodiment 1 in identical method; But with high density polyethylene(HDPE) (
Figure GSB00000508895500111
455M; Prime Polymer Co.; Ltd. make) (after this be referred to as " HD-4 ", the physicals of HD-4 is shown in table 1) replacement HD-1, make resin combination and long filament.The evaluation result of the physicals of resulting composition and long filament is shown in table 2.
The comparative example 1
(1) preparation of resin combination
With Labo Plastmill (Toyo Seiki Seisaku-sho Ltd. manufacturing); Being 160 ℃ in temperature is under the condition of 60rpm with rotating speed; 100 weight part pellets of high density polyethylene [HYA-800; Exxon-MobilCo.; Ltd. make) and (after this be referred to as " HD-5 ", the physicals of HD-5 is shown in table 1) and 2.6 weight part WL 43479s (Sumitomo Chemical Co., Ltd. makes; Trade(brand)name:
Figure GSB00000508895500112
)] melt-10min that kneads is to obtain resin combination (after this being referred to as " compsn-5 ").The evaluation result of the physicals of resulting composition-5 is shown in table 3.
(2) manufacturing of long filament
Use and identical method during embodiment 1 long filament is made, be molded as the long filament that diameter is 450 μ m to resin combination-5.The evaluation result of the physicals of gained long filament is shown in table 3.
The comparative example 2
(1) preparation of resin combination
Mix 48 weight part WL 43479s (Sumitomo Chemical Co. with paddling process; Ltd. make; Trade(brand)name:
Figure GSB00000508895500113
) and 52 weight part soft silicas (Fuji Silysia Chemical; Co.; Ltd. make; Trade(brand)name:
Figure GSB00000508895500114
530), to process insecticide carrier.Then; With LaboPlastmill (Toyo Seiki Seisaku-sho Ltd. manufacturing); Being 160 ℃ in temperature is under the condition of 60rpm with rotating speed; 100 weight part HD-5 pellets and the 4.9 weight part insecticide carrier melt-10min that knead, to obtain resin combination (after this being referred to as " compsn-6 ").The evaluation result of the physicals of resulting composition-6 is shown in table 3.
(2) manufacturing of long filament
Use and identical method during embodiment 1 long filament is made, be molded as the long filament that diameter is 450 μ m to resin combination-6.The evaluation result of the physicals of gained long filament is shown in table 3.
The comparative example 3
With with embodiment 1 in identical method, but change HD-1 into HD-5, make resin combination and long filament.The evaluation result of the physicals of gained resin combination and long filament is shown in table 3.
The comparative example 4
With with embodiment 1 in identical method, but change HD-1 into high density polyethylene(HDPE) GC7260 (Basell Polyolefin Co., Ltd. make) (after this be referred to as " HD-6 ", the physicals of HD-6 is shown in table 1), make resin combination and long filament.The evaluation result of the physicals of gained resin combination and long filament is shown in table 3.
Figure GSB00000508895500151
According to the present invention the resin combination that makes long filament have good thermal stretch property and have good melt-spun property that contains ethene-Ji resin and sterilant can be provided, long filament of processing by said composition and the method for producing long filament with said composition.Further, the resin combination that contains sterilant has good extrudability, and the long filament of being processed by this resin combination has good mechanical intensity, and has the cost meliority with the method for this resin combination production long filament.

Claims (6)

1. be applicable to the resin combination of long filament, it is 935～965kg/m that said composition comprises density 3Alathon and per 100 parts by weight of ethylene homopolymer in the sterilant of 0.1～10 weight part of proportioning, wherein the melt flow rate(MFR) of compsn is 0.3～7g/10min, the melt flow rate(MFR) ratio be 10～50 with density be 935～980kg/m 3,
Melt flow rate(MFR) is the method for using according to JIS K7210-1955, under the temperature of the load of 21.18N and 190 ℃, measures,
Melt flow rate(MFR) than be according to JIS K7210-1995 190 ℃ with 211.83N load under the melt flow rate value that records divided by according to JIS K7210-1995 190 ℃ with 21.18N load under the resulting value of melt flow rate value that records.
2. according to the resin combination of claim 1, the melt flow rate(MFR) of therein ethylene homopolymer is that 0.1～6g/10min and melt flow rate(MFR) ratio are 10～50,
Melt flow rate(MFR) is the method for using according to JIS K7210-1955, under the temperature of the load of 21.18N and 190 ℃, measures,
Melt flow rate(MFR) than be according to JIS K7210-1995 190 ℃ with 211.83N load under the melt flow rate value that records divided by according to JIS K7210-1995 190 ℃ with 21.18N load under the resulting value of melt flow rate value that records.
3. be applicable to the resin combination of long filament, it is 935～965kg/m that said composition comprises density 3Ethylene-propylene copolymer and per 100 parts by weight of ethylene-propylene copolymer in the sterilant of 0.1～10 weight part of proportioning, wherein the melt flow rate(MFR) of compsn is 0.3～7g/10min, the melt flow rate(MFR) ratio be 10～50 with density be 935～980kg/m 3,
Melt flow rate(MFR) is the method for using according to JIS K7210-1955, under the temperature of the load of 21.18N and 190 ℃, measures,
Melt flow rate(MFR) than be according to JIS K7210-1995 190 ℃ with 211.83N load under the melt flow rate value that records divided by according to JIS K7210-1995 190 ℃ with 21.18N load under the resulting value of melt flow rate value that records.
4. according to the resin combination of claim 3, the melt flow rate(MFR) of therein ethylene-propylene copolymer is that 0.1～6g/10min and melt flow rate(MFR) ratio are 10～50,
Melt flow rate(MFR) is the method for using according to JIS K7210-1955, under the temperature of the load of 21.18N and 190 ℃, measures,
Melt flow rate(MFR) than be according to JIS K7210-1995 190 ℃ with 211.83N load under the melt flow rate value that records divided by according to JIS K7210-1995 190 ℃ with 21.18N load under the resulting value of melt flow rate value that records.
5. the long filament that obtains by the resin combination of any one in the claim 1～4.
6. produce the method for long filament, comprise and be configured as wire to the resin combination melt extrusion of any one in the claim 1～4,
Discharge the wire compsn and
The wire compsn that thermal stretch is discharged under 70～120 ℃ of heating conditions.
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