CN104870700A - Polyolefin yarns and method for manufacturing - Google Patents
Polyolefin yarns and method for manufacturing Download PDFInfo
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- CN104870700A CN104870700A CN201380066406.3A CN201380066406A CN104870700A CN 104870700 A CN104870700 A CN 104870700A CN 201380066406 A CN201380066406 A CN 201380066406A CN 104870700 A CN104870700 A CN 104870700A
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- Prior art keywords
- yarn
- silk thread
- dtex
- silk
- fabric
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/442—Cut or abrasion resistant yarns or threads
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
- D10B2321/021—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene
- D10B2321/0211—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene high-strength or high-molecular-weight polyethylene, e.g. ultra-high molecular weight polyethylene [UHMWPE]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
- Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]
Abstract
The invention relates to a multifilament yarn having a tenacity of at least 30 cN/dtex, and comprising a plurality of spun ultrahigh molecular weight polyolefin filaments characterized in that the titer of any one of said spun filaments is at least 10 dtex.
Description
The present invention relates to multifilament ultra-high molecular weight polyethylene (UHMWPE) yarn and manufacture method thereof with high strength.The invention still further relates to the multiple product comprising described yarn, the invention particularly relates to the purposes of described yarn in the application expecting cutting resistance, described application examples is as clothing item or rugged outerwear goods such as gloves, apron, legging, trousers, boots, leisure tread shoes, shirt, jacket, overcoat, socks, footwear, underwear, vest, waterproof boots, cap, protective gloves etc.The invention still further relates to the monofilament be included in described polyfilament yarn.
Multifilament UHMWPE yarn is such as known by WO 2005/066401, it is disclosed that high performance multifilament polyethylene yarn, and described yarn has extraordinary mechanical performance and physical property, such as high tenacity, high-modulus, high abrasion and high creep resistance.In addition, even if when the yarn of WO 2005/066401 comprises a large amount of silk thread (filament), it also keeps their superperformance, thus making them be suitable for very much in multiple semi-finished product or finished product, the example comprises rope, rope yarn, fishing net, sports equipment, medical implant and ballistic composite.
In above-mentioned semi-finished product and finished product, form special classification for making wearer from the clothing item hurt or rugged outerwear goods.Such as, for specific industry, when such as treatment and processing food, the gloves of individual dress and the cutting resistance of other protective garment need there is competency for operation higher than certain level at least to make article.Obvious example comprises meat industry, and wherein protectiveness goods need for wearer provides the cutting resistance level of raising, and flexibility and tactile sensativity.
Therefore, observe: although the known multifilament yarns of WO 2005/066401 demonstrates many extraordinary performances, they can have not good enough performance in some application (especially cut resistant application).Therefore, require further improvement known yarn, to provide best cutting resistance to the product comprising it.Especially, need more general cut resistant fabric, can enough fabrics in wider range of application, their cutting resistance is primary in the application.
Therefore, the invention provides and there is high tenacity (such as, the preferably toughness of at least 30cN/dtex) and comprise the polyfilament yarn of many spinning ultra-high molecular weight polyethylene silk threads, it is characterized in that: the fiber number of any described spinning silk thread is at least 10dtex.
Observe: the damage of yarn of the present invention (yarn of the present invention hereinafter) high resistance and chemical resistance, and provide cutting resistance and/or the comfortableness of raising for the product comprising it.Especially, observe: it is very good that the product comprising the fabric containing yarn of the present invention shows during process oiliness or moist goods, because they resist the fluid accumulation on fabric face in the best way.
" silk thread " is understood to slender bodies in this article, its length dimension much larger than its lateral dimension, the size of such as diameter or width and thickness.Typically, the lateral dimension of silk thread make the ratio of the full-size of described cross section and its minimum dimension at the most 5, preferably at the most 3.Assemble with multi-filament line the aggregation forming monofilament-like product to be formed and contrast, silk thread (being also referred to as monofilament) should be understood to: the single slender bodies obtained through single spinning hole by spinning process.Term " silk thread " also comprises fiber embodiment, and it can have rule or irregular cross section.Silk thread typically has continuous length, but in order to some application, they can be processed into so-called staple fiber, that is, usually by the silk thread with discontinuous length cut or crush cutting silk thread obtains.In order to realize object of the present invention, yarn is the slender bodies comprising many independent silk threads.
Preferably, the fiber number of the silk thread of yarn of the present invention is at least 12dtex, more preferably at least 14dtex, even more preferably at least 16dtex, more preferably at least 18dtex, most preferably at least 22dtex.
Preferably, the toughness of yarn of the present invention is at least 35cN/dtex, more preferably at least 40cN/dtex, most preferably at least 45cN/dtex.Observe: this high toughness yarn is except being highly suitable for cut resistant protective garment, and they are also suitable for the clothes being designed to resistance to ballisticimpact.
Preferably, the fiber number of yarn of the present invention is at least 50dtex, more preferably at least 100dtex, most preferably at least 400dtex.Due to actual cause, preferably, the fiber number of yarn of the present invention is 5000dtex, more preferably 4000dtex, most preferably 3000dtex at the most at the most at the most.Preferably, the silk thread number of yarn of the present invention is at least 5, more preferably at least 24, most preferably at least 80.Observe: (conservative) technique utilizing fund and energy requirement to guard can manufacture the higher yarn of the present invention of fiber number.
In a preferred embodiment, the toughness of yarn of the present invention is at least 30cN/dtex, and the fiber number of silk thread is at least 12dtex, more preferably at least 15dtex, most preferably at least 20dtex.Observe: this yarn provides the cutting resistance of raising for the product comprising it.
On the other hand, the invention provides polyfilament yarn, it has high tenacity (such as, the preferably toughness of at least 35cN/dtex) and comprise many spinning ultra-high molecular weight polyethylene silk threads, it is characterized in that: the fiber number of any described spinning silk thread is at least 10dtex, more preferably at least 12dtex, most preferably at least 15dtex.Observe: this yarn provides resistance to ballistic impact resistance for the product comprising it.
In another embodiment, yarn of the present invention comprises the silk thread containing hard filler." hard filler " is understood to that Mohs' hardness is the filler of at least 2.5, more preferably at least 4, most preferably at least 6 in this article.The good example of suitable hard filler comprises glass filler, mineral filler or metallic packing.Filler can have any shape, such as graininess, thin slice, needle-like, threadiness.In one preferred embodiment, hard filler has fibrous shape, and average diameter be 20 microns at the most, more preferably at the most 15 microns, most preferably at the most 10 microns.Preferably, the average aspect ratio of hard fibre shape filler is at least 3, more preferably at least 6, even more preferably at least 10, and wherein said draw ratio is length and the diameter ratio of hard fibre shape filler.By the diameter and the draw ratio that use scanning electronic microscope (SEM) photo easily can measure hard fibre shape filler.For diameter, SEM photo that hard fibre self extends along surface can be obtained and at the position measurement diameter of 100 Stochastic choice, then calculate the average of 100 values obtained like this.For draw ratio, the SEM photo of one or more bat wools can be obtained and measure the length of hard fibre.Preferably, backscattered electron is utilized to obtain SEM photo.Preferably, spinning technique is utilized to manufacture hard fibre shape filler.The advantage of this filler is: its diameter has value constant in fact, and this can be the excellent performance that yarn of the present invention is provided in cut resistant product.
The invention still further relates to polyfilament yarn, it has high tenacity (such as, the preferably toughness of at least 12cN/dtex, more preferably at least 15cN/dtex, most preferably at least 17cN/dtex) and comprise many spinning ultra-high molecular weight polyethylene silk threads, it is characterized in that: the fiber number of any described spinning silk thread is at least 10dtex, and wherein said silk thread comprises hard filler.Disclosed above the preferred embodiment of hard filler.Preferably, the dtex of described multifilament is at least 12, more preferably at least 14, even more preferably at least 16, most preferably at least 18.
Yarn of the present invention also can comprise the silk thread be made up of the synthetic material being different from UHMWPE and the silk thread be made up of natural material, and described yarn preferably has discontinuous length, i.e. natural staple fiber.The example of natural staple fiber includes but not limited to the fiber of cellulose, cotton, fiber crops, wool, silk, jute, sisal hemp, coconut and flax etc., and wherein cotton is preferred.The example of natural silk thread comprises wire, glass wire etc.Observe: the yarn comprising cotton and silk thread of the present invention demonstrates extraordinary comfortableness.The example of synthetic polymer silk thread includes but not limited to by those of following manufacture: such as polyamide and Nomex, such as poly-(to phenylene-terephthalamide) (is called as
); Poly-(tetrafluoroethylene) (PTFE); Poly-{ 2,6-diimidazole is pyridine-Isosorbide-5-Nitrae (2,5-dihydroxy) penylene also-[4,5b-4 ', 5 ' e] } (being called as M5); Poly-(p-penylene-2,6-Ben Bing bis-oxazole) (PBO) (is called as
); Poly-(hexamethylene adipamide) (being called as nylon 6,6); Poly-(4-Aminobutanoicacid) (being called as nylon 6); Polyester, such as poly-(ethylene glycol terephthalate), poly-(mutual-phenenyl two acid bromide two alcohol ester) and poly-(terephthalic acid (TPA) Isosorbide-5-Nitrae-cyclohexylenedimethanol ester); Polyvinyl alcohol.The preferred embodiment of synthetic thread comprises the polyester and/or polyamide silk thread with continuous and/or discontinuous length.
The invention still further relates to the fabric comprising yarn of the present invention.
Fabric of the present invention (fabric of the present invention hereinafter) can have any structure known in the art, such as weave, knitting, inverted pleat (plaited), braiding or nonwoven or its combination.Textile fabric can comprise plain weave fabric, rib fabric, seat woven fabric and oblique woven fabric etc.Knit goods can be the fabric (such as single jersey or double jersey) of weft knitting or the fabric through compiling.The example of bondedfibre fabric is felt." Handbook of Technical Textiles ", ISBN 978-1-59124-651-0 the 4th, 5, describe weaving, other example of knitting or bondedfibre fabric and manufacture method thereof in 6 chapters, its disclosure is merged in herein as a reference.The Chapter 11 (more specifically in 11.4.1 section) of identical handbook describes kind and the example of braided fabric, and its disclosure is merged in herein by reference.
Preferably, fabric of the present invention is knit goods, is more preferably textile fabric, and even more preferably, the weight that textile fabric is configured to per unit length and total cross section diameter is very little.Observe: with have compared with mutually isostructural known fabrics, this fabric per unit surface coverage area demonstrate that low weight and degree improve suppleness and flexibility, there is the cutting resistance of improvement simultaneously.
The invention still further relates to goods, be specifically related to the clothing item or the rugged outerwear goods that comprise fabric of the present invention.The example of such goods includes but not limited to gloves, apron, legging, trousers, boots, leisure tread shoes (gator), shirt, jacket, overcoat, socks, footwear, underwear, vest, waterproof boots, cap, protective gloves etc.
The invention still further relates to the purposes of fabric of the present invention in clothing item or rugged outerwear goods, be specifically related to purposes in the above-described example.
Particularly, the present invention relates to the gloves comprising fabric of the present invention.Observe: gloves of the present invention can demonstrate good comfortableness and gas permeability.Preferably, the fabric that gloves of the present invention comprise is that knit goods is to improve well-formedness and the pliability of gloves.
Observe: yarn of the present invention has the performance of the useful material that can become for rope, rigging etc., preferably rope designed to be used the heavy operation of such as ocean, industry and operation on the sea.Heavy operation can include but not limited to the anchoring etc. of anchor process, anchoring for the supporting platform of maritime renewable energy generating, offshore petroleum drilling equipment and production platform.
Yarn of the present invention is also suitable as fastening element such as flexible pipe, pipeline, cable and the optical cable of reinforcing product very much, is used as the fastening element of the reinforcing product used in deepwater environment especially.Therefore, the invention still further relates to the reinforcing product comprising fastening element, wherein said fastening element comprises yarn of the present invention.
The invention still further relates to the Medical Devices comprising yarn of the present invention.In a preferred embodiment, Medical Devices are preferably used for hawser in implant or suture.Other example comprises reticulated, annular products (endless loop product), bag-shaped or balloon-like product, and other weaving and/or knit product.The good example of hawser comprises that wound fixes hawser, breastbone close line, preventative or prosthetic hawser, long bone fracture fixes hawser, fracture of ossiculum fixes hawser.In addition, tubular products such as ligament replacement thing is suitable for being made up of yarn of the present invention.This by the thread product of yarn of the present invention demonstrate their load surface and they be exposed to human body or animal body surface between ratio efficiently.Also observe: yarn of the present invention can be not easily contaminated, and easier bactericide also can be allowed to rinse.
The invention still further relates to the composite product comprising yarn of the present invention.Preferably, composite product according to the present invention comprises multiple layer, and wherein each described layer comprises yarn of the present invention, and wherein said yarn is preferably arranged as parallel array, is also referred to as unidirectional (UD) layer.
The composite product of multilayer shows in trajectory application (such as bulletproof jacket, the helmet, hard and soft scuta, plate etc. for vehicular armor) very useful.Therefore, the invention still further relates to ballistic-resistant article, because those enumerating comprise yarn of the present invention above.
Also observe: yarn of the present invention is also suitable for other application, such as setline and fishing net, earth mat, goods net and curtain, kite string, dental floss, tennis racket line, canvas (such as tent canvas), the fabric of nonwoven fabric and other type, webbing, battery separators, capacitor, pressure vessel, flexible pipe, (sea) umbilical cable, electrical equipment, optical fiber and signal cable, automotive fittings, power transmission belt, building materials, cut resistant and resistance toly jab goods and resistance toly to cut product, protective gloves, composite motion device is ski such as, the helmet, canoe, dugout canoe, bicycle and barnacle and mast, loudspeaker cone, high-performance electronic insulant, antenna house, sail, geotextile etc.Therefore, the invention still further relates to the enumerated application comprising yarn of the present invention above.
The invention still further relates to the telecontrol equipment comprising yarn of the present invention, comprise setline, kite string and yacht line.The invention still further relates to the cargo container with the wall comprising yarn of the present invention.
In another aspect of this invention, polyfilament yarn comprises gel spinning UHMWPE monofilament, described monofilament has the high tenacity toughness of at least 30cN/dtex, more preferably at least 35cN/dtex (such as, preferably) and fiber number is at least 10dtex, more preferably at least 12dtex, most preferably at least 15dtex.Also observe: use monofilament of the present invention especially in food service industry, to demonstrate good advantage as the cutting equipment of cutting element, such as, for cutting the egg or cheese product that boil.Especially, observe: the cleanliness of cutting equipment is best.
Therefore, the invention still further relates to gel spinning UHMWPE monofilament and the cutting equipment comprising cutting element (being namely used to the element of production sharing smaller portions to be cut), described cutting element comprises any one yarn of the present invention, and preferably described cutting element comprises inventive gel spun monofilaments.
In one embodiment of the invention, gel spinning UHMWPE monofilament has the intensity of every silk thread at least 4.0N, preferably at least 4.5N, more preferably at least 5.0N, even more preferably at least 6.0N, most preferably at least 7N.Observe: comprise monofilament of the present invention and especially in sewing fabric (such as, multicolour cloth) or as setline, demonstrate advantage as the yarn of strength members.Especially, observe: monofilament according to the present invention provides human eye visible seam hardly by means of their fineness and transparency.Preferably, be at least 20cN/dtex, more preferably 25cN/dtex, most preferably 30cN/dtex according to the toughness of the monofilament of this embodiment of the present invention.Observe: the monofilament that toughness is higher provides the seam with the human eye visibility reduced further.Therefore, the present invention goes back providing package containing at least one according to the yarn of monofilament of the present invention, and preferably yarn is made up of monofilament according to the present invention in fact.
The invention still further relates to the method manufacturing the yarn comprising many UHMWPE spinning silk threads, described method comprises the step according to following order:
A. the UHMWPE solution in suitable solvent, preferably decahydronaphthalenes is provided in;
B. make described solution by comprising the mould of multiple spinneret orifice (aperture), wherein said spinneret orifice is discharged described solution with First Speed thus is formed the silk thread that many comprise described solution; Each spinneret orifice has outlet diameter
outlet; Described in every root that the outlet of described capillary is measured, the diameter of silk thread is D
silk;
C. the silk thread containing described solution is immersed in cooling bath, preferably cold bath; And the described silk thread immersed is rolled onto with on the work beam of second speed rotation; With
D. from described bath, take out described silk thread thus form spinning silk thread; The described solvent of at least part of extraction; And before, during and/or after described extraction, stretch described spinning silk thread at least one stretching step;
Wherein at drawdown (draw-down) (DD
operation) be resonance drawdown DD
resonance20%-90% between lower operating procedure b), wherein DD
operationbe defined as the ratio of second speed and First Speed;
Wherein DD
resonancebe defined as: D
silkin maximum
and minimum of a value
between percentage fluctuation with at least 25% per minute time second speed and First Speed ratio; Formula 1 is wherein utilized to calculate described percentage
formula 1
Wherein,
the D calculated by least 10 measured values recorded 1 minute period
silkmean value.
Observe: the inventive method is highly stable, wherein the minimizing of fracture of wire amount and/or all silk threads for yarn, allow similar stretch mode.In addition, the inventive method allows to produce the yarn with the best of breed of intensity and silk thread fiber number.
According to the inventive method, in step b) in, each spinneret orifice discharges solution with First Speed, and described First Speed is calculated as the volume flow of the solution of each spinneret orifice and the area of this spinneret orifice
ratio.By by the volume flow of solution before entering mould divided by the number of spinneret orifice, easily can measure the volume flow of the solution of each spinneret orifice.By the volume flow of solution before using spinning pump or extruder easily to arrange to enter mould.Preferably, all spinneret orifices are substantially identical, if use the spinneret orifice with different-diameter, then above-mentioned value is understood to mean value in this article.
In step c) in, the silk thread immersed is rolled onto with on the work beam of second speed rotation." speed " is understood to the superficial velocity of described roller at this.The drive motors of described roller is driven can easily to regulate described speed by utilizing.
According to the inventive method, by analyzing D per minute
silkfluctuation measures DD
resonance.By the photo calibrated or by using the video camera of calibration easily can measure D
silk.D
silkexpress with mm.In the present invention,
for at least 25%, more preferably at least 30%, even more preferably at least 40%, most preferably at least 50%.Observe: measure DD by selecting higher thresholds
resonance, the advantage of the inventive method is more remarkable.Especially, DD is worked as
operationat DD
resonance40%-90% between, more preferably DD
resonance50%-90% between, more preferably DD
resonance60%-90% between time, the inventive method is run with its optimum state.
By can easily arrange the step b carrying out the inventive method as follows) time drawdown (DD
operation): such as, first improve drawdown to reach drawdown as above resonance, then drawdown is reduced to desirable value, such as DD
resonanceat the most 90%.Preferably, DD
operationfor such as DD
resonanceat the most 85%, more preferably at the most 80%, most preferably at the most 75%.Observe: when reducing drawdown, the stability of the inventive method increases.In addition, DD
operationfor DD
resonanceat least 20%, preferably at least 40%, most preferably at least 60%.Such DD
operationvalue is new and has run counter to the common recognition of this area, because be used in DD for the manufacture of the existing textile technology of UHMWPO silk thread
resonance5% scope at the most in DD
operationvalue.Cause using so away from DD
resonancedD
operationthe broad idea of value is: technique is more stable, and improves DD
operationto only introduce unstability and wire broken rate.But the present inventor demonstrates reverse side and achieves the high stability of the inventive method.
Preferably, each spinneret orifice
be at least 1.5mm, more preferably at least 2mm, most preferably at least 3mm.Preferably, described in
for 5mm at the most, more preferably 4mm, most preferably 3.5mm at the most at the most.Observe: even if for this major diameter spinneret orifice, even if use closer to DD
resonancedD
operationtime, the inventive method is also highly stable.Preferably, each spinneret orifice comprises diameter capillary constant in fact, and described diameter is at least 1.5mm, more preferably at least 2mm, most preferably at least 3mm, and the diameter of wherein said capillary is equal to
preferably, described diameter is 5mm, more preferably 4mm, most preferably 3.5mm at the most at the most at the most.Observe: when the diameter of capillary between 2mm-4mm, most preferably between 2.5mm-3.5mm, most preferably about 3mm time, the inventive method provides extraordinary result.Preferably, described capillary
ratio is at least 1.5, more preferably at least 2.0, most preferably at least 2.5; Wherein L is the length of capillary.Preferably, described in
than at the most 10, more preferably at the most 7.5, most preferably at the most 5.
Spinneret orifice also can comprise so-called constriction zone, that is: diameter is from D
0be decreased to gradually
region.The angle of constriction zone is preferably within the scope of 8-75 °.Preferably, spinneret orifice also comprises the capillary as directly limited above, and in this case, constriction zone is preferably located in the upstream of capillary.
Step b in the inventive method) in, make UHMWPE solution with the spinneret orifice of the first flow velocity by mould, described first flow velocity is preferably at least 1.4 gram/minute/spinneret orifice, more preferably at least 2.0 gram/minute/spinneret orifice, even more preferably at least 2.4 gram/minute/spinneret orifice.Preferably, described first flow velocity is between 2.0 gram/minute/spinneret orifice and 8.0 gram/minute/spinneret orifice, more preferably between 2.4 gram/minute/spinneret orifice and 7.7 gram/minute/spinneret orifice.
The inventive method as herein described can allow production polyfilament yarn of the present invention and both monofilament of the present invention.As described herein the silk thread extruded can be processed into yarn beam or in any stage of technique, the silk thread extruded can be divided into one or more monofilament and the optional polyfilament yarn residue be made up of monofilament residue.
Preferably, the step b in the inventive method) in, make to flow in air gap (air-gap) containing solution filaments (being hereafter also referred to as fluid filament).Preferably, adopt preferably at least 8, more preferably at least 12, even more preferably at least 14, still even more preferably the draw ratio of at least 16, most preferably at least 18 stretches described fluid filament in air gap.Preferably, the length of air gap between 1mm and 20mm, more preferably between 2mm and 15mm, even more preferably between 2mm and 10mm, most preferably between 2mm and 5mm.Observe: so preferred gas length can allow to reduce the draw ratio in air gap, does not affect tenacity of yarn in fact simultaneously.
In the alternative, the draw ratio between 3-12, more preferably between 4-10, most preferably between 4-8 is adopted to stretch in air gap fluid filament.Draw wire in so preferred air gap produces than being specially adapted to monofilament and the yarn that every rhizoid line has high strength, wherein as described in experiment on yarn or independent silk thread measured intensity.
Although be called as air gap, this gap can be filled by any gas or admixture of gas (such as, air, nitrogen or other inert gas)." air gap " is understood in this article: the distance between mould and cooling bath.At the temperature (such as, about room temperature) lower than weaving temperature, cooling bath can be for bathing containing liquid (such as, water).If cooling bath is liquid cools bath, then the minimum of a value of air gap is preferably selected to contact die surface to avoid any liquid surface wave.
Any being suitable for can be used to spin the known solvent of UHMWPE as solvent to prepare described solution, such as solid paraffin, paraffin oil or mineral oil, kerosene, decahydronaphthalenes, tetrahydronaphthalene or its mixture.Find: this method is especially of value to more volatile solvent, preferred boiling point is under atmospheric conditions lower than 275 DEG C, solvent more preferably less than 250 DEG C or 225 DEG C.Suitable example comprises: decahydronaphthalenes, tetrahydronaphthalene and several kerosene grade.Known method can be utilized to prepare solution; Preferably, apply double screw extruder and prepare uniform solution by the UHMWPE slurry in described solution.Preferably, utilize constant displacement pump with constant flow rate by solution feed to mould (be also referred to as spinning plate).The concentration of solution preferably between 3-25 quality %, wherein polyolefin or poly molal weight higher time, low concentration is preferred.Preferably, for intrinsic viscosity (IV) UHMWPE within the scope of 15-25dl/g, concentration is between 3-15 quality %.Preferably, at solvent boiling point 90 DEG C at the most, temperature more preferably at the most in 70 DEG C, UHMWPE solution is formed.
Preferably, the intrinsic viscosity of UHMWPE (IV measures based on the solution in decahydronaphthalenes at 135 DEG C) about between 8dl/g and 40dl/g, preferably between 10dl/g and 30dl/g, more preferably between 12dl/g and 28dl/g, most preferably between 15dl/g and 25dl/g.Intrinsic viscosity is the measurement about molal weight (being also referred to as molecular weight), its comparable actual molar mass parameters (such as M
nand M
w) be easier to measure.IV and M
wbetween there are some empirical relations, but such relational dependence is in molar mass distribution.Based on equation M
w=5.37*10
4[IV]
1.37(see EP0504954A1), IV be 4 or 8dl/g will be equal to M respectively
wfor about 360 or 930kg/mol.
Preferably, UHMWPE is that every 100 carbon atoms have and are less than 1 branch, preferably every 300 carbon atoms and have the Hi-fax being less than 1 branch; Branch or side chain or chain component comprise at least 10 carbon atoms usually.Hi-fax also can comprise one or more comonomers of maximum 5 % by mole, such as alkene such as propylene, butylene, amylene, 4-methylpentene or octene.
The UHMWPE used in the inventive method also can comprise on a small quantity, be usually less than 5 quality %, be preferably less than 3 % by weight usual additive, such as antioxidant, heat stabilizer, colouring agent, flow improver additive etc.UHMWPE can be single polymer grade, but also can be the mixture of two or more different polymer grades (such as, the type of IV or molar mass distribution and/or comonomer or side base is different with number).
According to the present invention, from bath take out silk thread thus obtain spinning silk thread after, make described spinning silk thread stand extraction step, in this step, from described silk thread, remove the solvent be present in wherein at least partly.Removal of solvents can have been come by known method, such as, by evaporating (if using more volatile solvent such as decahydronaphthalenes), passing through to use extract or the combination by these two kinds of methods.
The inventive method also comprises at least one stretching step, wherein preferably adopts the draw ratio of at least 4 at least one stage stretching yarn silk thread.Preferably, at least 2 stages, and preferably stretch having under the different temperatures increasing progressively curve.Stretch and preferably occur between about 120 DEG C of-Yue 155 DEG C.It is most preferred that the 3-stage stretches, wherein total drawing ratio DR
always=DR
stage 1* DR
stage 2* DR
stage 3for at least 10, more preferably at least 20, most preferably at least 40.
In one preferred embodiment, the inventive method produces yarn of the present invention, wherein use with
for the mould of at least spinneret orifice of 2mm; Use the solution of the UHMWPE containing at least 5 % by weight total solution weight; Use DD
resonanceat least 20% DD
operation; And adopt total drawing ratio be at least 20 the 3-stage stretch.Preferably,
for at least 3mm, more preferably between 2.5mm and 3.5mm.Preferably, UHMWPE solution has at least 6 % by weight, and more preferably at least 8 % by weight, most preferably at least 9 % by weight.Preferably, solvent is decahydronaphthalenes.Preferably, DD
operationdD
resonanceat least 40%, most preferably at least 60%.
The present invention will be explained further by following embodiment and contrast experiment, but first show the method for measuring the various parameters used above.
.
dtex: the fiber number being measured yarn or silk thread by weigh respectively 100 meters of yarns or silk thread.By weight (expressing with mg) to be calculated the dtex of yarn or silk thread divided by 10;
.
iV: measure intrinsic viscosity according to method ASTM D1601 (2004), test condition is: at 135 DEG C, in decahydronaphthalenes, dissolution time is 16 hours, use amount be the BHT (butylated hydroxytoluene) of 2g/l solution as antioxidant, wherein the viscosity measured under variable concentrations extrapolation is obtained the viscosity under zero-dose.
.
the tensile property of fiber: as described in ASTM D885M, the fiber that use nominal gauge length is 500mm, the crosshead speed of 50%/min and " Fibre Grip D5618C " type Instron2714 fixture define and measure TENSILE STRENGTH (or intensity) and the stretch modulus (or modulus) of polyfilament yarn.Based on measured load-deformation curve, with the slope determination modulus between 0.3%-1% strain.In order to calculate modulus and intensity, by surveyed tensile force divided by fiber number (as measured by 10 meters of fibers of weighing); Assumed density is 0.97g/cm
3calculate GPa value.
by measuring every root as follows the intensity of monofilament: the toughness in order to the polyfilament yarn of cN/dtex meter is multiplied by the dtex of every one thread silk thread.
Embodiment 1-4
The UHMWPE being about 20dl/g by IV in decahydronaphthalenes prepares slurry and is fed in co-rotating twin screw extruder so that slurry is converted into solution.Heated extruder and spinneret at the temperature of 185 DEG C.Solution is made to be about the speed of 7.7g/min (for embodiment 1 and 2) and 3.8g/min (for embodiment 3 and 4) by having the mould of 24 spinneret orifices with each spinneret orifice.
Spinneret orifice exists
for 3mm and the capillary upstream that length is about 8mm comprises the territory, conical contraction zone that angle is 15 °.
The fluid filament of discharging from spinneret orifice enters air gap and rolled-up with the speed applying draw ratio as shown in Table 1 below air gap.Operate DD during this process
operationidentical with the draw ratio in air gap, and be resonance drawdown DD in all cases
resonanceabout 90%.
Subsequently, fluid filament enters water-bath, and they are cooled wherein and are rolled on work beam.Subsequently, they enter in the first baking oven, they be stretched wherein 8 times simultaneously decahydronaphthalenes evaporated.
Silk thread enters the second baking oven from the first baking oven, in the second baking oven, adopts various draw ratio as shown in Table 1 below and silk thread described in the Properties Tensile utilizing yarn.
Table 1
| EX 1 | EX 2 | EX 3 | EX 4 | |
| The draw ratio of air gap | 16 | 16 | 14 | 14 |
| Gas length (mm) | 15 | 15 | 7 | 7 |
| Draw ratio | 2.2 | 3.0 | 2.0 | 2.5 |
| Yarn dtex (dtex) | 424 | 315 | 556 | 439 |
| Yarn tenacity (cN/dtex) | 29.4 | 29.8 | 25.2 | 28.3 |
| Yarn modulus (cN/dtex) | 1031 | 1241 | 897 | 1066 |
| Yarn EAB (%) | 3.4 | 2.8 | 3.3 | 3.2 |
| Silk thread fiber number (dtex) | 18 | 13 | 23 | 18 |
| The intensity (N) of every rhizoid line | 5.3 | 3.9 | 5.8 | 5.1 |
Embodiment 5 and 6
Repeat embodiment 1, wherein difference is: in third step at about 149 DEG C further drawing.Application 2 kinds of draw ratios as shown in Table 2 below.
Table 2
| Embodiment 5 | Embodiment 6 | |
| The draw ratio of third step | 1.8 | 2.2 |
| Yarn dtex (dtex) | 290 | 213 |
| Yarn tenacity (cN/dtex) | 34.3 | 42.6 |
| Yarn modulus (cN/dtex) | 1390 | 1784 |
| Yarn EAB (%) | 3.0 | 2.9 |
| Silk thread fiber number (dtex) | 12.1 | 8.9 |
| The intensity (N) of every rhizoid line | 4.1 | 3.8 |
Embodiment 7
The material of embodiment 1 being knitted into aerial density is 260g/m
2the fabric of (stitch density be 10 space (gauge)).In order to reference, use and have mutually isostructural fabric containing the commercially available yarn knitting of 440dTex of 195 UHMWPE silk threads, the toughness of this yarn is about 31cN/dtex and by DSM
nL sells with trade name SK62.
According to the EN388 of standard and the ASTM 1790-05 of standard, these two kinds of fabrics are made to stand cutting resistance test (all duplicate).Similarly, make fabric stand Martindale (EN388) abrasion test, wherein for often kind of fabric type, measure period when observing fracture.The result of acquisition is listed in following table 3:
Table 3
| Test | Reference | Embodiment 7 |
| EN 388 – cuts index | 2.5 | 6.0 |
| EN 388 – cuts index | 3.7 | 6.1 |
| ASTM F1790-05 reference load | 2.8N | 5.6N |
| ASTM F1790-05 reference load | 2.7N | 5.6N |
| EN 388 wears away fracture circulation | 1140 circulations | 3437 circulations |
Embodiment 8
Repeat embodiment 1; But, before extrusion, in slurry, add the hard filler of about 7% total solution weight.Hard filler is mineral fubrils, namely has the filler of fibrous shape, and it is sold with trade name CF10ELS by Lapinus, NL.The fiber number of the yarn produced is 410dTex, toughness is for about 18cN/dtex and modulus is about 850cN/dTex.
Aerial density (aerial density) is become by yarn knitting to be 260g/m
2the fabric of (stitch density be 10 space).In order to reference, use the commercially available yarn knitting of 440dTex containing 130 UHMWPE silk threads to have mutually isostructural fabric, the toughness of described yarn is about 17cN/dtex and contains the hard filler of type same as above and amount.
Make these two kinds of fabrics stand with above in embodiment 7 identical cutting resistance be described in detail in detail test.Fabric is made to implement 4 Martindale abrasion tests to often kind.The result of acquisition is listed in following table 4:
Table 4
| Test | Reference | Embodiment 8 |
| EN 388 – cuts index | 15.69 | 28.15 |
| EN 388 – cuts index | - | 24.82 |
| ASTM F1790-05 reference load | 11.1N | 21.2N |
| ASTM F1790-05 reference load | 11.1N | 20.9N |
| EN 388 wears away fracture | 400 circulations | 1400 circulations |
| EN 388 wears away fracture | 459 circulations | 1600 circulations |
| EN 388 wears away fracture | 691 circulations | 1800 circulations |
| EN 388 wears away fracture | 1204 circulations | 2200 circulations |
Embodiment 9 and 10
Repeat embodiment 1; But, adopt the handling capacity of every hole 5.7g/min to be stretched about 19 times by fluid filament in air gap.In the first baking oven, them are made to stretch 6 times.In the second step, adopt various draw ratio as shown in Table 4 below and utilize the Properties Tensile yarn of yarn.
Table 5
| Embodiment 9 | Embodiment 10 | |
| Draw ratio | 3.0 | 4.0 |
| Yarn dtex (dtex) | 347 | 263 |
| Yarn tenacity (cN/dtex) | 30.9 | 34.7 |
| Yarn modulus (cN/dtex) | 1076 | 1269 |
| Yarn EAB (%) | 3.5 | 3.4 |
| Silk thread fiber number (dtex) | 14 | 11 |
| The intensity (N) of every rhizoid line | 4.3 | 3.8 |
Embodiment 11 and 14
Repeat embodiment 1, but spin head temperature is reduced to 175 DEG C, adopt the handling capacity of every hole 7.7g/min to be stretched about 5.7 times by fluid filament in the air gap of 4mm in length.In the first and second steps, adopt various draw ratio as shown in Table 6 below and utilize the Properties Tensile silk thread of yarn.In the 24 rhizoid lines leaving spinning plate, 1 rhizoid line is processed separately, thus produces embodiment 11-13; And remaining 23 rhizoid lines are processed to the yarn of 23 rhizoid lines.Only the yarn of 23 rhizoid lines of embodiment 13 correspondence is reported as embodiment 14, but the yarn of 23 rhizoid lines of embodiment 11 and 12 correspondence is not reported.
Table 6
Claims (10)
1. polyfilament yarn, its toughness is at least 30cN/dtex, and comprises many spinning ultra-high molecular weight polyethylene silk threads, it is characterized in that: the fiber number of any described spinning silk thread is at least 10dtex.
2. yarn according to claim 1, its toughness is at least 35cN/dtex, preferably at least 40cN/dtex, more preferably at least 45cN/dtex.
3. the yarn described in claim 1 or 2, its silk thread fiber number is at least 12dtex, preferably at least 14dtex, more preferably at least 16dtex.
4. the yarn according to any one of front claim, its fiber number is at least 50dtex, preferably at least 100dtex, most preferably at least 400dtex.
5. the yarn according to any one of front claim, wherein said silk thread comprises the hard filler that Mohs' hardness is at least 2.5.
6. the yarn according to any one of front claim, it also comprises the silk thread be made up of natural material and also preferably has discontinuous length, and described natural material is selected from the material group be made up of cellulose, cotton, fiber crops, wool, silk, jute, sisal hemp, coconut and flax; Wherein cotton is preferred natural material.Be included in the fabric of yarn according to any one of front claim and comprise the gloves of described fabric.
7. product, described product is selected from by the product group formed as follows: setline and fishing net, earth mat, goods net and curtain, kite string, dental floss, tennis racket line, canvas, the fabric of nonwoven fabric and other type, webbing, battery separators, capacitor, pressure vessel, flexible pipe, (sea) umbilical cable, electrical equipment, optical fiber and signal cable, automotive fittings, power transmission belt, building materials, cut resistant and resistance toly jab goods and resistance toly to cut product, protective gloves, composite motion device is ski such as, the helmet, canoe, dugout canoe, bicycle and barnacle and mast, loudspeaker cone, high-performance electronic insulant, antenna house, sail, geotextile, described product is included in the yarn according to any one of front claim.
8. the spinning UHMWPE monofilament of the polyfilament yarn according to any one of claim 1-5, to be toughness be wherein said monofilament that at least 30cN/dtex and fiber number are the gel spun monofilament of at least 10dtex.
9. monofilament according to claim 7, the intensity of wherein said monofilament is at least 4.0N, preferably at least 4.5N, more preferably at least 5.0N.
10. manufacture the method for yarn described in any one claim 1-6, described method comprises the step according to following order:
A. the super high molecular polyethylene solution in suitable solvent, preferably decahydronaphthalenes is provided in;
B. make described solution by comprising the mould of multiple spinneret orifice, wherein said spinneret orifice is discharged described solution with First Speed thus is formed the silk thread that many comprise described solution; Each spinneret orifice has outlet diameter
outlet; Described in every root that the outlet of described capillary is measured, the diameter of silk thread is D
silk;
C. the silk thread containing described solution is immersed in cooling bath, preferably cold bath; And the described silk thread immersed is rolled onto with on the work beam of second speed rotation; With
D. from described bath, take out described silk thread thus form spinning silk thread, extracting described solvent at least in part; And before, during and/or after described extraction, stretch described spinning silk thread at least one stretching step;
Wherein at drawdown (DD
operation) be resonance drawdown DD
resonance20%-90% between lower operating procedure b), wherein DD
operationbe defined as the ratio of second speed and First Speed; Wherein DD
resonancebe defined as: work as D
silkin maximum
and minimum of a value
between percentage fluctuation with at least 25% per minute time second speed and First Speed ratio; Formula 1 is wherein utilized to calculate described percentage
Wherein,
the D calculated by least 10 measured values recorded 1 minute period
silkmean value.
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|---|---|---|---|
| CN201610658439.2A CN106149140A (en) | 2012-12-20 | 2013-12-19 | Polyethylene yarn and manufacture method thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12198531.1 | 2012-12-20 | ||
| EP12198531 | 2012-12-20 | ||
| PCT/EP2013/077449 WO2014096228A1 (en) | 2012-12-20 | 2013-12-19 | Polyolefin yarns and method for manufacturing |
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|---|---|---|---|
| CN201610658439.2A Division CN106149140A (en) | 2012-12-20 | 2013-12-19 | Polyethylene yarn and manufacture method thereof |
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| CN104870700A true CN104870700A (en) | 2015-08-26 |
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| US (2) | US20150337464A1 (en) |
| EP (2) | EP3118355A1 (en) |
| JP (2) | JP6436091B2 (en) |
| KR (2) | KR20160086985A (en) |
| CN (2) | CN104870700A (en) |
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| CN101217985A (en) * | 2005-07-05 | 2008-07-09 | 帝斯曼知识产权资产管理有限公司 | Surgical repair product based on uhmwpe filaments |
| WO2009028590A1 (en) * | 2007-08-31 | 2009-03-05 | Toyo Boseki Kabushiki Kaisha | High-strength polyethylene fiber with high productivity, precursor therefor, and process for producing precursor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106955371A (en) * | 2016-01-11 | 2017-07-18 | 苏州微创脊柱创伤医疗科技有限公司 | A kind of artificial soft tissue's braid and its production and use |
| CN106955371B (en) * | 2016-01-11 | 2022-09-09 | 苏州微创脊柱创伤医疗科技有限公司 | Artificial soft tissue braided fabric and preparation method and application thereof |
| CN110892098A (en) * | 2017-07-14 | 2020-03-17 | 帝斯曼知识产权资产管理有限公司 | Uniform filled yarn |
| CN110892098B (en) * | 2017-07-14 | 2022-11-04 | 帝斯曼知识产权资产管理有限公司 | Uniform filled yarn |
| CN113273528A (en) * | 2021-06-24 | 2021-08-20 | 安徽农业大学 | Outdoor aquaculture catches and uses aquaculture net and cursory structure |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20150096412A (en) | 2015-08-24 |
| JP2017031545A (en) | 2017-02-09 |
| JP6436091B2 (en) | 2018-12-12 |
| JP2016507662A (en) | 2016-03-10 |
| US20150337464A1 (en) | 2015-11-26 |
| AU2013366684A1 (en) | 2015-07-02 |
| BR122016018714A2 (en) | 2019-08-27 |
| CN106149140A (en) | 2016-11-23 |
| EP3118355A1 (en) | 2017-01-18 |
| AU2016216564A1 (en) | 2016-09-01 |
| US20170298537A1 (en) | 2017-10-19 |
| EP2935666A1 (en) | 2015-10-28 |
| WO2014096228A1 (en) | 2014-06-26 |
| AU2016216564B2 (en) | 2018-05-10 |
| CA2894148A1 (en) | 2014-06-26 |
| KR20160086985A (en) | 2016-07-20 |
| BR112015014483A2 (en) | 2017-07-11 |
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