CN101516986B - Polymer composition, process for producing fiber and the fiber - Google Patents
Polymer composition, process for producing fiber and the fiber Download PDFInfo
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- CN101516986B CN101516986B CN2007800354061A CN200780035406A CN101516986B CN 101516986 B CN101516986 B CN 101516986B CN 2007800354061 A CN2007800354061 A CN 2007800354061A CN 200780035406 A CN200780035406 A CN 200780035406A CN 101516986 B CN101516986 B CN 101516986B
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- 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
-
- 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
- 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
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
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- Biodiversity & Conservation Biology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A polymer composition which comprises an olefin-based polymer, a pesticide of 0.1 to 10 parts by weight per 100 parts by weight of the olefin-based polymer and a support for retaining the pesticide of 0.1 to 20 parts by weight per 100 parts by weight of the olefin-based polymer, wherein a moisture content of the polymer composition is 30 to 1500 ppm by weight, a process for producing a fiber from the composition and a fiber obtainable by the process.
Description
Background of invention
Description of related art
The agricultural chemicals and the compsn that makes that is mixed based on the polymkeric substance (for example Vestolen PP 7052, Vilaterm etc.) of alkene are processed into various mo(u)lded items, and with acting on the material that prevents insect (for example flat lice, louse, mosquito, fly etc.).For example JP-A-04-065509 discloses a kind of fiber that makes through the compsn of melt-spun acrylic resin and agricultural chemicals.In addition, the JP-A-06-315332 circle (collar) that discloses the compsn of a kind of linear low density polyethylene and agricultural chemicals and processed by said compsn.
But; In the moulded parts that the polymer compsn moulding through the preparation that will be mixed based on the polymkeric substance of alkene and agricultural chemicals and farm chemical carrier makes, particularly in fiber, its tensile fracture elongation or fracture tensile strength maybe deteriorations; Therefore, this goods are not very satisfactory.
Invention field
The present invention relates to a kind of polymer compsn that comprises polymkeric substance, agricultural chemicals and farm chemical carrier, by the method for said polymer compsn producd fibers and the fiber that makes by said method.
Disclosure of the Invention
In this case; A target of the present invention be a kind of polymer compsn that comprises polymkeric substance, agricultural chemicals and carrier based on alkene is provided, through with the method for said compsn moulding producd fibers and the fiber that makes by said method, said polymer compsn can make fiber have excellent tensile fracture elongation and fracture tensile strength.
That is to say; First aspect of the present invention relates to a kind of polymer compsn; Said polymer compsn comprises polymkeric substance, 0.1-10 weight part agricultural chemicals/100 weight parts said polymkeric substance and the said polymkeric substance based on alkene of 0.1-20 weight part carrier/100 weight parts based on alkene based on alkene, and the moisture content of wherein said polymer compsn is a 30-1500ppm weight.
In addition, second aspect of the present invention relates to a kind of method of producd fibers, and said method comprises and melt extrudes above-mentioned polymer compsn to form the fusion wire rod and with 5 or the higher stretch ratio said fusion wire rod that stretches.
Further again, the third aspect of the invention relates to a kind of fiber that is made by aforesaid method.
Detailed Description Of The Invention
Said polymkeric substance based on alkene for example comprises polymkeric substance based on ethene, based on the polymkeric substance of propylene, based on the polymkeric substance of butylene with based on polymkeric substance and modification, saponification or the hydrogenated products of 4-methyl-1-pentene.
Said polymkeric substance based on ethene comprises the polymkeric substance [that is to say, be included as 50% weight of said total polymer weight (100% weight) or the monomeric unit of higher derived from ethylene] of the monomeric unit that mainly comprises derived from ethylene, for example Alathon; Ethene-alpha-olefin copolymer (for example ethene-butene-1 copolymer, ethene-1-hexene copolymer, ethene-1-octene copolymer and ethene-1-butylene-1-hexene copolymer); Vinyl-vinyl acetate copolymer; Ethylene-acrylic acid copolymer; Ethylene-acrylate copolymer (for example ethylene-methyl acrylate multipolymer); Ethylene-methacrylic acid copolymer; Ethylene-methyl acrylate multipolymer (for example ethylene-methyl methacrylate methyl terpolymer); Ethene-cyclic olefine copolymer.In addition, the terminal olefin in ethene-alpha-olefin copolymer comprises the terminal olefin (for example propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene) with 3-20 carbon atom.
Said polymkeric substance based on propylene comprises that the polymkeric substance of the monomeric unit that mainly comprises derived from propylene [that is to say; Be included as 50% weight of said total polymer weight (100% weight) or the monomeric unit of higher derived from propylene], for example alfon, propylene-alpha-olefin copolymers (for example propylene-ethylene copolymers, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer) and propylene-cyclic olefine copolymer.
Among this paper, the terminal olefin in the propylene-alpha-olefin copolymers comprises the terminal olefin with 2-20 carbon atom (for example ethene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene) except that propylene.
Said multipolymer based on alkene is preferably the polymkeric substance based on ethene, more preferably Alathon and ethene-alpha-olefin copolymer.In addition, said ethene-alpha-olefin copolymer is preferably ethene-butene-1 copolymer, ethene-1-hexene copolymer, ethene-1-octene copolymer and ethene-1-butylene-1-hexene copolymer.
From the angle of the exterior quality that improves the moulding bodies that makes through extrusion molding, the melt flow rate(MFR) of the olefin polymer of use (MFR) is preferably 0.1g/10 minute or higher, more preferably 0.3g/10 minute or higher, also is preferably 0.5g/10 minute or higher.On the other hand, from improving the angle of moulding bodies physical strength, the MFR of the olefin polymer of use is preferably 20g/10 minute or lower, more preferably 10g/10 minute or lower, also is preferably 5g/10 minute or lower.
Method according to JIS K7210-1995 is measured MFR; Measure under 230 ℃, 21.18N load based on the polymkeric substance of propylene, remove based on the polymkeric substance the polymkeric substance of propylene (for example based on the polymkeric substance of ethene, based on the polymkeric substance of butylene) measurement under 190 ℃, 21.18N load based on alkene.
From improving the angle of insecticidal properties, the density of said polymkeric substance based on ethene is preferably 980kg/m
3Or lower, 970kg/m more preferably
3Or lower, also be preferably 960kg/m
3Or it is lower.On the other hand, from improving the inflexible angle, said density is preferably 900kg/m
3Or higher, 920kg/m more preferably
3Or higher, also be preferably 940kg/m
3Or it is higher.After described method annealing, according to the method A measuring density of JIS K7112-1980 according to JIS K6760-1995.
As working method based on the polymkeric substance of alkene; The illustrational known polymerization that the known polymerizing catalyst of use (for example Ziegler-Natta catalyst, chromium-based catalysts, metalloscene catalyst or catalysts for radical polymerization) is arranged, for example solution polymerization process, slurry polymerization process, gaseous polymerization and method for high pressure polymerization.
Above-mentioned Ziegler-Natta catalyst for example comprises following catalyzer (1) and (2):
(1) through at least a material that is selected from the halogenated alcoholate (haloalcolate) of titanous chloride, vanadium trichloride, titanium tetrachloride and titanium is loaded on catalyzer that the component for preparing on the carrier based on magnesium compound and organometallic compound (for example triethyl aluminum) combination as promotor make and
(2) catalyzer through the coprecipitate of magnesium compound and titanium compound or cocrystallization product and organometallic compound (for example triethyl aluminum) combination as promotor are made.
Said chromium-based catalysts for example comprises through chromium cpd being loaded on the catalyzer that the component for preparing on silicon-dioxide or the silica-alumina and organometallic compound combination as promotor make.
Said metalloscene catalyst for example comprises following catalyzer (1)-(4):
(1) catalyzer that makes through component that will comprise transistion metal compound and the combination of components that comprises aikyiaiurnirsoxan beta (alumoxane) compound with the group that contains cyclopentadienyl skeleton,
(2) catalyzer through above-mentioned component that comprises transistion metal compound and component (for example boric acid mesitylene ester or the boric acid puratized agricultural spray salt) combination that comprises ionic compound are made,
(3) through the above-mentioned component that comprises transistion metal compound and above-mentioned is comprised the component of ionic compound and catalyzer that the organo-aluminium compound combination makes and
(4) through at granular inorganic carrier (SiO for example
2Or Al
2O
3) or the granular carrier of polymkeric substance (for example alkene (for example ethene, vinylbenzene) polymkeric substance) go up load or flood the catalyzer that above-mentioned respective components makes.
Above-mentioned organometallic compound for example comprises butyllithium and triethyl aluminum.
Said catalysts for radical polymerization (initiator) for example comprises organo-peroxide (for example ditertiary butyl peroxide, t-butyl peroxy hydrogen, the peroxide 2 ethyl hexanoic acid tert-butyl ester, dicumyl peroxide, the peroxy isopropyl base carbonic acid tert-butyl ester, t-butyl per(oxy)benzoate, two t-amyl peroxy things, cumene hydroperoxide, t-butylperoxy pivarate; And oxygen.
As working method, preferably use the working method of Ziegler-Natta catalyst, metalloscene catalyst or catalysts for radical polymerization based on the polymkeric substance of alkene.
Be used for agricultural chemicals of the present invention and comprise compound, for example agricultural chemicals, insect growth control agent, exterminator etc. with insecticidal activity.
Said agricultural chemicals comprises pyrethroid compound, organo phosphorous compounds, carbamate compounds, phenyl pyrazole compounds etc.The instance of said pyrethroid compound comprises permethrin; Allethrin; The d-allethrin; The dd-allethrin; D-tetramethyl chrysanthemum ester; D-prallethrin; The d-phenothrin; The d-resmethrin; Prallethrin; Fenvalerate; Esfenvalerate; Fenvalerate; (RS)-cyhalothrin; Ether chrysanthemum ester; Tralomethrin; The ES EXTHIN; Five Flumethrins (benfulthrin); Terallethrin; Deltamethrin; Phenothrin; Tefluthrin; Bifenthrin; FCR-1272; Cyphenothrin; PP-383 and α-PP-383.The instance of said organo phosphorous compounds comprises phenitrothion, dichlorobos, SD-1750, RE-4355, Tiguvon, cynock, Chlorpyrifos 94, diazinon, cynock (calchlophos) and dioxabenzofos.
The instance of said carbamate compounds comprises methoxydiazon, Propoxur 97, fenobucarb and carbaryl.The instance of said phenyl pyrazole compounds comprises fluorine worm nitrile.
The instance of said insect growth control agent comprises SK 591, methoprene, illiteracy 512, diflubenzuron, cyromazine, ABG-6215 (phenoxycarb) and octafluoro urea (CGA184599).
The instance of said insect repellants comprises mosquito repellent amine and Witcizer 300.
These agricultural chemicals can use separately or use with two kinds or more kinds of form of mixtures.As agricultural chemicals, preferred sterilant, more preferably pyrethroid compound, and also be preferable over the pyrethroid compound of 25 ℃ of following vapour pressures less than 1 * 10-6mmHg.Comprise resmethrin and permethrin in 25 ℃ of following vapour pressures less than the instance of the pyrethroid compound of 1 * 10-6mmHg.
As being used for farm chemical carrier of the present invention; Use can keep (retain), load, absorption, absorption, dipping, infiltration or inject the material of said agricultural chemicals, and the example comprises compound, zeolite, clay mineral, MOX, mica, hydrotalcite and organic carrier based on silicon-dioxide.Said examples for compounds based on silicon-dioxide comprises noncrystalline silicon-dioxide and crystalline silica, for example powdered silicate, finely powdered silicic acid, acid white clay, zeyssatite, quartz and WHITE CARBON BLACK.The instance of said zeolite comprises A type zeolite and mordenite.The instance of said clay mineral comprises smectite, saponite, beidellite, wilkinite, kaolin, halloysite, nakrite, dickite, anauxite, illite and sericite.The instance of said MOX comprises oxide compound, cupric oxide and the titanium oxide of zinc oxide, Natural manganese dioxide, aluminum oxide, iron.Said micaceous instance comprises mica and vermiculite.The instance of said hydrotalcite comprises hydrotalcite and terre verte.As organic carrier, that lists has coal (for example charcoal, mud coal, glass mud coal), polymer beads (for example Microcrystalline Cellulose, polystyrene bead, based on the bead of polyacrylic ester, based on the bead of Rohm tech inc, based on the bead of Z 150PH) and a cross-linked polymer bead thereof.That also lists in addition, has perlite, gypsum, pottery and a volcanics.
As farm chemical carrier, preferred noncrystalline inorganic carrier, and more preferably noncrystalline silicon-dioxide.
Can the polymeric constituent of various additives (for example inhibitor, anti-hard caking agent, filler, lubricant, static inhibitor, protective agent, pigment, modifier for processing and metallic soap) and non-polymkeric substance based on alkene be added in the polymer compsn of the present invention.
Can add two kinds or more kinds of additive and polymeric constituent respectively.
The content of the agricultural chemicals in polymer compsn of the present invention is the said polymkeric substance based on alkene of 0.1-10 weight part/100 weight parts.From the angle of the viscosity that causes of prevention agricultural chemicals, the content of agricultural chemicals is preferably 5 weight parts or lower, more preferably 3 weight parts or lower.In contrast, from strengthening the angle of insect control performance, the content of agricultural chemicals is preferably 0.5 weight part or higher, more preferably 1 weight part or lower.
The content of the farm chemical carrier in polymer compsn of the present invention is the said polymkeric substance based on alkene of 0.1-20 weight part/100 weight parts.From improving the angle of tensile fracture elongation and the outward appearance of improving the moulded parts that makes through extrusion molding, the content of farm chemical carrier is preferably 10 weight parts or lower, more preferably 5 weight parts or lower.In contrast, from strengthening the angle of insect control performance, the content of farm chemical carrier is preferably 0.5 weight part or higher, more preferably 1 weight part or higher.
Moisture content in polymer compsn of the present invention is a 30-1500ppm weight.When moisture content surpassed 1500ppm weight, tensile fracture elongation and fracture tensile strength maybe deteriorations.Moisture content is preferably 1000ppm weight or lower, more preferably 800ppm weight or lower.On the other hand, when moisture content was lower than 30ppm weight, the processing of polymer compsn operation possibly become complicated.Moisture content is preferably 50ppm or higher, more preferably 100ppm weight or higher.In addition; Moisture content is the value based on the polymer compsn of 1000000ppm weight; And using Ka Er-Fischer device for measuring moisture, is that 200 ℃, nitrogen flow are that 100ml/ minute and example weight are to measure under the condition of 0.5g at the moisture gasification temperature.
Polymer compsn of the present invention can pass through known method, through making based on polymkeric substance, agricultural chemicals, farm chemical carrier and other optional component melt-kneadings of alkene.For example exemplary a kind of method is for will mix with agricultural chemicals based on the polymkeric substance of alkene in advance, the mixture that uses melt-kneadings such as forcing machine, rolling forging die molding machine (roll molding machine), kneader to make so subsequently; Another kind method is will be based on polymkeric substance, agricultural chemicals and farm chemical carrier separate charging to the forcing machine etc. of alkene, subsequently with they melt-kneadings.
In the production of said polymer compsn, can agricultural chemicals and farm chemical carrier be mixed in advance, melt-kneaded further can be used as at least a masterbatch that comprises in them and is used for melt-kneading subsequently.In addition, when carrying out melt-kneading through forcing machine, can use adding set (for example side forcing machine or side feeder) to inject agricultural chemicals and/or farm chemical carrier from the middle part of forcing machine.
As base resin; When agricultural chemicals and/or farm chemical carrier during as masterbatch, exemplary base resin has polymkeric substance based on ethene, based on the polymkeric substance of propylene, based on polymkeric substance and 4-methyl-1-pentene polymkeric substance and modification, saponification or the hydrogenated products of butylene.In addition; The amount of being mixed of masterbatch that is used to produce said polymer compsn is usually less than 50% weight of said polymer compsn (100% weight); And from improving the angle of economical efficiency, the amount of being mixed of masterbatch is preferably 20% weight or lower, more preferably 10% weight or lower.
Through known molding methods [for example extrusion molding, injection moulding, powder moulding (slush moulding, rotational molding etc.), compression moulding] polymer compsn of the present invention is molded as various moulded partss.In these methods; The suitable extrusion molding that uses for example is coated with extrusion molding, flexible pipe extrusion molding (tube extrusionmolding), tubular type extrusion molding (pipe extrusion molding), flexible pipe extrusion molding, blow moulding, T-die head casting, blowing-extrusion molding, monofilament extrusion molding and multifilament extrusion molding.
In addition, also enumerated the molding methods of any and foam-formed combination in these methods.
Through the moulded products that makes based on the compsn moulding of alkene of the present invention is used for various application; For example with product (for example kennel, mat, sheet material, circle, label), and these goods are used for the insect protected product of people, pet (for example dog, cat, bird) and domestic animal (for example ox, pig, sheep) with line, rope, filter, shoes, luggage, electronic component, electron device, domestic electronic utensil part, office machine part, vehicle parts, transportation machine parts, the material (for example container, box), household product or the part that are used for dispense articles and pet for film, sheet material, wallpaper, curtain, flooring material, wrapping material, flexible pipe, adhesive tape, pipe (tubes), pipeline (pipes), bag, tent, turf, shop curtain, window shutter, electric wire, cable, sheath, fibril, fiber, mesh screen (for example mosquito net, screen window, insect catch net), weaving.
The insect of controlling through the mo(u)lded item of polymer compsn of the present invention comprises various arthropodss, for example spider, mite and insect.Below these insects further are detailed.
Spider for example comprises mite class (for example northern fowl mite (Ornithonyssus sylviarum), citrus red mite (crm) (Panonychus citri), tyrophagus putrescentiae (Tyrophaugus putrescentiae)); And Araneida (Araneae) (for example Ka Shi ground spider (Atypus karschi), indoor ghost spider (Pholcusphalangioides)).Centipede for example comprises common house centipede (Scutigeromorpha) (for example wart rope common house centipede (Thereuonema tuberculate)); With stone sky pinales (Lithobiomorpha) (for example rough cave stone centipede (Bothropolys rugosus)).Diplopoda for example comprises the confused noctuid of dark line (Polydesmoidea) (for example Artline acid band julid (Oxidus gracilis) is with julid (Nedyopus tambanus) for fat).
In addition, the instance of Insecta comprises Thysanura (for example silverfish (Ctenolepisma)); Orthoptera (for example house cricket found in a kitchen Xi (Diestrammena japonica), atractylodes japonica (Atractylodesjaponica), Asia migratory locusts (Locusta migratoria), desert locust (Schitocercagregarta), brachypterism oryza chinensis (Oxya yezoensis); Dermaptera (for example DIWUGONG (Forficulaauricularia)); Cockroach order (Blattaria) (for example bllatella germanica, Peroplaneta fluligginosa (periplaneta fuliginosa), the big Lian (periplaneta japonica) of Japan, periplaneta americana (Periplaneta Americana)); Isoptera (for example termite (Reticulitermes), coptotermes formosanus of taiwan (Coptptermes formosanus), little principal columns of a hall termite (Incistermes minor)); Corrodentia (for example having a liking for worm booklice (Liposcelis entomophilus), l.bostrychophila (Lipocescelisbostrychophilus)); Mallophaga (is for example pinched peristome lice (Trichodectes canis); Cat bird lice (Felicola subrostratus)); Anoplura (for example head louse (Pediculus corporis), crab louse (Pthirus pubis), body louse (Pediculus humanus)); Hemiptera (for example brown paddy plant hopper (nilaparvata lugens), rice green leafhopper (Nephotettix cincticeps), greenhouse whitefly (Trialeurodes vaporariorum), cigarette aphid (Myzus persicae), the yellow hair of willow sawfly (Cimexlectularius), tea wing stinkbug (Halyomorpha mista)); Coleoptera (for example black wool skinworm worm (Attagenus japonicus), Authrenus verbasci, aulacophora femoralis (Aulacophorafemoralis), sitophilus zea-mais (Sitophilus zeamais), Lyctus brunneus Stephens (Lyctus brunneus), intend globose spider beetle (Gibbium aequinoctiale), Ptinus japonicus (Ptinus japonicus), Japanese beetle (Popillia japonica); Siphonaptera (for example cat flea (Ctenocephalides felis), ctenocephalides canis (Ctenocephalides canis), Pulex irritans (Pulex irritans)); Diptera (for example Culexpipienspallens, Aedes aegypti (Aedes aegypti), Anopheles (Anoheles spp.), Maringouin, midge (Chironomus yoshimatsui), moth fly (Clogmiaalbipunctatus), housefly (Musca domestica), Fannia canicularis (Fannia canicularis), triangle horsefly (Tabanus trigonus), Allograpta iavana); And Hymenoptera (for example Vespamandarinia japonica, Asia-africa hornet (Polistes hebraeus), loose greenery honeybee (Nesodiprion japonicus), chestnut cynipid (Dryocosmum kuriphilus), Sclerodermus nipponicus, single waistband worm (Monomorium nipponensis)).
Compsn based on alkene of the present invention is used for above-mentioned application; Be preferred for extrusion moulding product; For example film, sheet material, wallpaper, flexible pipe, adhesive tape, pipe (tubes), pipeline (pipes), electric wire, cable, fibril and fiber are preferably used as fiber and the product that uses fiber (for example wallpaper, curtain, mat, tent, turf, shop curtain, window shutter, clothes, bag, mesh screen (for example mosquito net, screen window, insect catch net), rope) especially.
As method by the composition production fiber based on alkene of the present invention; Example a kind of melt-spun method; This method comprises uses forcing machine to melt extrude said polymer compsn to form the fusion wire rod by die head, stretches and the cooling wire rod fiber of reeling and making so subsequently.LV at the die head exit of the fusion wire rod that melt extrudes is preferably 0.2 meter/minute or higher, more preferably 0.8 meter/minute or higher.On the other hand, LV is preferably 5 meters/minute or lower, more preferably 2 meters/minute or lower.The volume of the compsn that the unit time is extruded by a hole of die head is confirmed the LV at die head exit divided by the port area in this hole.
Draw speed compares (take-off) speed of drawing and the ratio of the fusion wire rod of being extruded by die head in the LV of die head exit for the fusion wire rod of extruding from die head; The angle of the fracture tensile strength of the fiber that makes from raising; The draw speed ratio is preferably 5 or higher; More preferably 7 or higher, also be preferably 10 or higher.On the other hand, the angle of the tensile fracture elongation of the fiber that makes from raising, the draw speed ratio is preferably 70 or lower, and more preferably 25 or lower, also be preferably 18 or lower.
Embodiment
Through following each embodiment and comparative example the present invention is described.
Measure the physical properties among each embodiment and the comparative example through following method.
(1) melt flow rate(MFR) (MFR, unit: g/10 minute)
According to the method for JIS K7210-1995, under 190 ℃ of conditions with the 21.18N load, measure melt flow rate(MFR).
(2) density (unit: kg/m
3)
Measure the density of polymer compsn according to the method A of JIS K7112-1980.In addition, also use according to the test block after the method described in the JIS K6760-1995 annealing and be used for measuring.
(3) moisture content (unit: ppm weight)
Using Ka Er-Fischer device for measuring moisture, is that 200 ℃, nitrogen flow are that 100ml/ minute and example weight are to measure under the condition of 0.5g at the moisture gasification temperature.
(4) Elongation test of fiber
Using stretching testing machine, is that 1000mm/ minute and gauge length (chuchdistance) carry out Elongation test under the condition of 200mm at draw speed.Confirm tensile fracture elongation and fracture tensile strength through following equation.
Tensile elongation (%)=length of fracture (mm)/20 (mm) * 100
The cross-sectional area of fracture tensile strength (MPa)=breaking weight (N)/fiber
Embodiment 1
(1) comprises the preparation of the carrier masterbatch of agricultural chemicals
1.5 weight parts are added to 51 weight part permethrins as the BHT (3,5-di-t-butyl-4-hydroxytoluene) of inhibitor, and (by Sumitomo Chemical Co., Ltd. makes; Trade(brand)name:
) in; Through the stirring and dissolving inhibitor, subsequently, with the noncrystalline silicon-dioxide of 47.5 weight parts (by Suzuki Yushi; Co.; Ltd. make, trade(brand)name: Porous Silica hereinafter is called " carrier S ") add in the resulting mixture; Mix and stirring, obtain comprising the farm chemical carrier (hereinafter being called " carrier A that comprises agricultural chemicals ") of agricultural chemicals.Then, use twin screw extruder with 59.48 parts by weight of ethylene-butene-1 copolymer [by Sumitomo Chemical Co., Ltd. makes, trade(brand)name:
CE5502 (MFR:20g/10 minute, density: 917kg/m
3)], 31.0 weight parts comprise carrier A, 5 weight part Zinic stearass and 4.52 weight part blue colorant (by Sumika Color Co., the Ltd make) melt-kneading under 200 ℃ design temperature of agricultural chemicals, obtain comprising the masterbatch of the carrier A of agricultural chemicals.
(2) preparation of polymer compsn
With 100 weight part high density polyethylene(HDPE)s (by Prime Polymer Co., Ltd. makes, trade(brand)name:
440M, MFR:0.9g/10 minute, density: 947kg/m
3) mix with masterbatch and 0.7 weight part Zinic stearas that 16.4 weight parts comprise the carrier A of agricultural chemicals, use single screw rod granulator granulation of diameter 65mm subsequently, obtain polymer compsn (hereinafter being called " sample-1 ").
(3) preparation of fiber
With the pellet of sample-1 in 80 ℃ baking oven dry 6 hours.After the drying, the moisture content of pellet is a 570ppm weight.Using forcing machine (by Musashino Kikai, Ltd makes, the forcing machine of diameter 20mm), is that (the die head exit LV was 9.6 * 10 in 130g/ hour with load under 200 ℃ of temperature
-1Rice/minute) under, the circular hole die head of pellet by diameter 1mm melt extruded, with draw speed (the draw speed ratio: 15) draw, and cool off, obtain fiber of the wire rod that melt extrudes like this with 1.4 * 10 meters/minute.The tensile fracture elongation of the fiber that makes like this is 2121%, and fracture tensile strength is 58.1MPa.
Embodiment 2
Adopt the mode molding fiber identical with embodiment 2, difference is the speed of drawing to become 2.0 * 10 meters/minute, and (draw speed compares: 21).The tensile fracture elongation of the fiber that makes is 1863%, and fracture tensile strength is 62.0MPa.
Embodiment 3
Adopt the mode producd fibers identical with embodiment 2, difference is the speed of drawing to become 8.0 meters/minute, and (draw speed compares: 8).The tensile fracture elongation of the fiber that makes is 2454%, and fracture tensile strength is 52.4MPa.
Embodiment 4
Is that 60 ℃ and humidity are to keep 22 hours in 50% the thermostatic constant wet chamber with the pellet of sample-1 in temperature.After the maintenance, the moisture content of pellet is a 1330ppm weight.Adopt the mode producd fibers identical with embodiment 1.The tensile fracture elongation of the fiber that makes is 2050%, and fracture tensile strength is 56.9MPa.
The comparative example 1
Is that 50 ℃ and humidity are to keep 36 hours in 90% the thermostatic constant wet chamber with the pellet of sample-1 in temperature.After the maintenance, the moisture content of pellet is a 1970ppm weight.Adopt and pellet is molded as fiber with embodiment 1 identical mode.The tensile fracture elongation of the fiber that makes is 1588%, and fracture tensile strength is 46.3MPa.
Industrial usability
The invention provides a kind of polymer compsn of polymkeric substance, agricultural chemicals and farm chemical carrier based on alkene, the method for producd fibers and fiber that is made by said method of comprising, said compsn makes fiber have excellent tensile fracture elongation and fracture tensile strength.
Claims (4)
1. polymer compsn; Said polymer compsn comprises polymkeric substance, 0.1-10 weight part agricultural chemicals/100 weight parts said polymkeric substance and the said polymkeric substance based on alkene of 0.1-20 weight part farm chemical carrier/100 weight parts based on alkene based on alkene, and the moisture content of wherein said polymer compsn is a 100-1500ppm weight.
2. the method for a producd fibers; Said method comprises by die head and melt extrudes polymer compsn to form the fusion wire rod; With with 5 or the higher stretch ratio said fusion wire rod that stretches; Said polymer compsn comprises polymkeric substance, 0.1-10 weight part agricultural chemicals/100 weight parts said polymkeric substance and the said polymkeric substance based on alkene of 0.1-20 weight part farm chemical carrier/100 weight parts based on alkene based on alkene, and the moisture content of wherein said polymer compsn is a 100-1500ppm weight.
3. the method for claim 2 wherein melt extrudes said polymer compsn with 0.2 meter/minute or higher LV at die head exit.
4. fiber, said fiber makes through the method for claim 2 or 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006267186 | 2006-09-29 | ||
| JP267186/2006 | 2006-09-29 | ||
| PCT/JP2007/069408 WO2008047604A1 (en) | 2006-09-29 | 2007-09-27 | Polymer composition, process for producing fiber and the fiber |
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| Publication Number | Publication Date |
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| CN101516986A CN101516986A (en) | 2009-08-26 |
| CN101516986B true CN101516986B (en) | 2012-06-20 |
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| CN2007800354061A Expired - Fee Related CN101516986B (en) | 2006-09-29 | 2007-09-27 | Polymer composition, process for producing fiber and the fiber |
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| WO (1) | WO2008047604A1 (en) |
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| CN102226301B (en) * | 2011-04-28 | 2012-11-14 | 东北林业大学 | Preparation method of pesticide supported superfine fiber |
| TWI563915B (en) * | 2011-12-27 | 2017-01-01 | 大日本除蟲菊股份有限公司 | Volatile chemicalcontaining structure |
| CN104871888B (en) * | 2015-04-23 | 2018-06-05 | 安徽海义源进出口有限公司 | A kind of desinsection farm network and preparation method thereof |
| CN105646974A (en) * | 2016-04-12 | 2016-06-08 | 苏州科茂电子材料科技有限公司 | Preparation method of insect-resistant high-temperature-resistant flame-retardant cable |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4504432A (en) * | 1981-09-04 | 1985-03-12 | Showa Denko Kabushiki Kaisha | Process for producing a monofilament having high tenacity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57128212A (en) * | 1981-01-26 | 1982-08-09 | Showa Denko Kk | High-density and high-tenacity polyethylene yarn |
| JPH08113828A (en) * | 1994-10-13 | 1996-05-07 | Nippon Ester Co Ltd | Insect repellent core-sheath type conjugated fiber |
| JPH10168686A (en) * | 1996-12-04 | 1998-06-23 | Mitsubishi Rayon Co Ltd | Acaricidal polyolefin crimped yarn, its production and acaricidal carpet using the polyolefin crimped yarn |
| JPH11140719A (en) * | 1997-11-12 | 1999-05-25 | Nippon Polychem Kk | Ultrafine polypropylene fiber |
| JP3348043B2 (en) * | 1999-06-15 | 2002-11-20 | 田村駒株式会社 | Catechin-containing polypropylene fiber and method for producing the same |
| JP3934061B2 (en) * | 2002-01-10 | 2007-06-20 | 宇部日東化成株式会社 | Method for producing polyolefin-based drawn fiber |
| JP4649104B2 (en) * | 2003-11-07 | 2011-03-09 | 住化カラー株式会社 | Two-layer olefin resin pellets for insect repellent resin composition |
-
2007
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4504432A (en) * | 1981-09-04 | 1985-03-12 | Showa Denko Kabushiki Kaisha | Process for producing a monofilament having high tenacity |
Non-Patent Citations (4)
| Title |
|---|
| JP特开2000-355827A 2000.12.26 |
| JP特开2003-268622A 2003.09.25 |
| JP特开2005-139329A 2005.06.02 |
| JP特开平9-30911A 1997.02.04 |
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| CN101516986A (en) | 2009-08-26 |
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