CN104955992B - The method of manufacture stretching multifilament yarn - Google Patents

The method of manufacture stretching multifilament yarn Download PDF

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Publication number
CN104955992B
CN104955992B CN201480005797.2A CN201480005797A CN104955992B CN 104955992 B CN104955992 B CN 104955992B CN 201480005797 A CN201480005797 A CN 201480005797A CN 104955992 B CN104955992 B CN 104955992B
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CN
China
Prior art keywords
multifilament yarn
stretching
method according
yarn
part
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CN201480005797.2A
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Chinese (zh)
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CN104955992A (en
Inventor
艾沃特·弗洛伦蒂诺斯·弗洛里蒙德斯·丹斯楚迪尔·德
安德雷斯·奥利弗·米腾扎维
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帝斯曼知识产权资产管理有限公司
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Priority to US201361756577P priority Critical
Priority to US61/756,577 priority
Priority to EP13152764 priority
Priority to EP13152764.0 priority
Application filed by 帝斯曼知识产权资产管理有限公司 filed Critical 帝斯曼知识产权资产管理有限公司
Priority to PCT/EP2014/051534 priority patent/WO2014114793A2/en
Publication of CN104955992A publication Critical patent/CN104955992A/en
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Publication of CN104955992B publication Critical patent/CN104955992B/en

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Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/12Stretch-spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/26Yarns or threads characterised by constructional features, e.g. blending, filament/fibre with characteristics dependent on the amount or direction of twist
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D10B2321/021Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene
    • D10B2321/0211Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene high-strength or high-molecular-weight polyethylene, e.g. dyneema, spectra

Abstract

The present invention relates to the method for manufacture Polyolefin multifilament yarns, methods described includes:Make part stretch multifilament yarn to reverse and stretch the part stretching multifilament yarn through torsion after twisting.

Description

The method of manufacture stretching multifilament yarn

Technical field

The present invention relates to the method for manufacture multifilament yarn (such as high-performance polyethylene (HPPE) multifilament yarn).More specifically Ground, the present invention relates to the method for manufacturing and/or cleaning multifilament yarn, wherein not needing organic spinning oil (finish).

Background technology

Generally via such as getting off to manufacture multifibres polyethylene yarn:Pass through the spinneret with a large amount of spinneret orifices (spinhole) Head spin fluid, the solution (otherwise referred to as gel) of such as molten polyethylene or polyethylene in spin solvent, to form silk. Then, cooling and drawn yarn.If using spin solvent, at least some solvents are removed for example, by evaporating or extracting.System The example for making method is melt spinning method (as disclosed in such as EP1445356), solid state process (such as institute in such as EP1627719 It is open) or gel spinning (as disclosed in such as WO 2005/066401).General description also appears in " Advanced Fibre Spinning Technology ", T.Nakajima volumes, Woodhead Publ.Ltd (1994), ISBN 185573 In 182 7, all it is incorporated herein by reference.

Manufacture polyethylene multifilament yarn when a problem be:Polyethylene is electrical insulators, therefore inclined during manufacture To in accumulation electrostatic charge;And because each monofilament of multifilament yarn is similarly powered (positive electricity or negative electricity), then each monofilament by that This Coulomb repulsion.This is represented:Multifilament yarn will tend to unclamp and non-formation entity.In addition, in the case of fracture of wire, silk end Hold by tend to move to apart from multifilament yarn main body as far as possible, so as to reduce manufactured multifilament yarn by fine hair formation Quality;Or the silk (end) for even having release is stumbled in the risk in manufacturing equipment, and therefore even need to stop life Produce to discharge fracture of wire.

Traditionally, this is solved by adding organic spinning oil into multifilament yarn during drawing process.So And, organic spinning oil is surface-active product, and due to environment reason, it should be avoided by.

A kind of approach for the influence for reducing spinning oil is had been presented in WO2004/053212, wherein suggestion uses volatilization Property spinning oil.

The content of the invention

Goal of the invention

It is an object of the invention to provide the method for improved manufacture multifilament yarn.

It is a further object to provide improved multifilament yarn or yarn configuration.

Disclosure of the invention

Improvement can be for example:One or more ambient influnence reductions, more preferable logistics, the processing of reduction or following article institute The other improvement provided by the present invention stated.

In the first aspect of the present invention, the target of the present invention, methods described are realized by manufacturing the method for multifilament yarn Comprise the following steps:Part stretching multifilament yarn is provided, part stretching multifilament yarn includes partially drawn yarn;By the part It is that 4-600 twist m stretches multifilament yarn to form the part through torsion that stretching multifilament yarn, which is reversed to the part stretching twist,; With with least 1.1 draw ratio DRptReverse part stretching multifilament yarn of the after-drawing through torsion.

For example as disclosed in WO2005/066401, in the spinneret orifice of multifibres spinning head there is shape to be adapted to provide for portion In the case of the shrinking zone for dividing the silk of stretching or adjustment in spinneret orifice, spinning process can directly provide part and stretch many gauzes Line.Part stretching multifilament yarn can also be the result stretched in the air gap after spinneret orifice.Preferably, for example after spinning After being cooled down in hardening bath, part stretching multifilament yarn is solids stages yarn.If fruit part stretching multifilament yarn is gel spinning Silk multifilament yarn, then be preferably, and before reverse part stretching multifilament yarn, has removed at least a portion solvent (with spinning Period is compared by the solvent of spinning head).

Multifilament yarn is stretched to occur in multiple steps.Reverse part stretching multifilament yarn can be online with stretching step (inline) carry out, or be not connected with stretching step and off line (offline) progress." online " represents herein:Part Drawing directly runs/is traveling in the station (station) for carrying out reverse part stretching multifilament yarn and multifilament yarn is stretched Station between." off line " is generally represented:Winding steps occur between stretching and torsion.

Brief description of the drawings

The present invention is more fully explained below with reference to illustrative embodiments and accompanying drawing, wherein

Fig. 1 shows the schematic flow diagram of multiple methods according to the present invention, and

Fig. 2 shows schematic flow diagram of the manufacture according to the method for the HPPE multifilament yarns of the present invention.

All figures have been merely shown as explaining the step required for the present invention, and other parts are omitted or only referred only to.

Ref. No. in figure

2:Mixing

4:Spinning

6:Quench and remove partial solvent

7:Stretching

8:Online stretching

10:Off line is stretched

12:Reverse

13:Reverse after-drawing

14:Online torsion after-drawing

16:Off line reverses after-drawing

18:Unstretched yarn

20:Multifilament yarn

Embodiment

The stretching of multifilament yarn can be carried out in one or more following variants (referring to Fig. 1):A) online drawing before reversing Stretch, subsequent off line reverses after-drawing;B) the online stretching before and after reverse part stretching multifilament yarn;C) it is de- before reversing Machine is stretched, and online stretching after torsion;D) with off line stretching after torsion before reversing, so the torsion of part drawing occurs In the step of stretching with the part stretching multifilament yarn before torsion and after torsion is separated (in the time and/or spatially).

Preferably, online carry out reverse part stretching multifilament yarn and torsion after-drawing.The method according to the invention can be wrapped Containing more than one torsion after-drawing step.It is excellent if carrying out multiple torsion after-drawing steps in the method according to the invention Selection of land, reverse part stretching multifilament yarn and at least one torsion online progress of after-drawing step;It is highly preferred that reverse part is drawn Stretch multifilament yarn and all torsion online progress of after-drawing step.The method according to the invention can reverse step comprising more than one Suddenly.If carrying out multiple its twisting steps in the method according to the invention, preferably, after at least one its twisting step and torsion The online progress of stretching step.

Reverse part stretching multifilament yarn can be carried out in special (stand alone type) equipment or can with stretching furnace, hardening bath, One or more of up- coiler, unwinder, spinning plate are combined into one-block apparatus.In one embodiment, for example, by Online twist system as described in US 6,155,037 carries out reverse part drawing.Described in US 6,155,037 Online twist system is hereinafter referred to as Uster twist systems.Because this kind equipment allows into part stretching multifilament yarn The end twisted with the fingers (twist) and keep off (having access to) yarn is introduced, therefore this kind equipment is particularly useful for repacking Existing equipment, such as existing stretching furnace or existing up- coiler or unwinder.Therefore, one aspect of the present invention is related to Combination, the combination of Uster twist systems and up- coiler or the Uster twist systems of Uster twist systems and stretching furnace and move back Around the combination of machine.

In particularly preferred embodiments, by being carried out as follows reverse part drawing:Wind first without reversing Part stretching multifilament yarn, then turned round using reversing bobbin cradle system and part without torsion is stretched multifilament yarn and is unwind Transfer part point stretching multifilament yarn.Preferably, arrange to reverse bobbin cradle system with reverse post-tensioning stretching process online progress unwinding and Reverse, wherein adjustment reverses the withdrawal speed and rotary speed of bobbin cradle system to adapt to online torsion post-tensioning stretching process.

The method according to the invention can also be comprised the following steps:After reverse part stretching multifilament yarn and after twisting Before stretched portion drawing, multifilament yarn is tensed in tensioning station (tensioning station).This allows maintaining part The tension force divided in stretching multifilament yarn is relatively low during reversing, and the tension force during stretching can remain sufficiently high for ensuring to want The stretching asked.The example at suitable tensioning station includes some roller bearings, brakes and friction system.

For all aspects of the invention, the stretching of multifilament yarn generally occurs at elevated temperatures.Preferably, at least One stretching step occurs at a temperature of higher than 100 DEG C;Preferably, at least one stretching step occurs higher than 120 DEG C At a temperature of.Preferably, at least one stretching step occurs at a temperature of less than multifilament yarn fusing point.It is highly preferred that spinning it All stretching steps afterwards occur at a temperature of less than multifilament yarn fusing point.It is more preferred still that all stretchings after spinning Step occurs at a temperature of than multifilament yarn fusing point low at least 5 DEG C, and more preferably lower than multifilament yarn fusing point at least At a temperature of 10 DEG C.In particular it is preferred to ground, reverse after-drawing and occur in multifilament yarn fusing point and lower than multifilament yarn fusing point 30 DEG C Between;Occur it is highly preferred that reversing after-drawing at least 5 DEG C lower than multifilament yarn fusing point (for example, comparing multifilament yarn Fusing point is low at least 10 DEG C) at a temperature of.For gel spinning UHMWPE multifilament yarns, it is preferable that stretching (particularly reverses post-tensioning Stretch) occur at a temperature of less than 138 DEG C, be preferably lower than 135 DEG C at a temperature of, be more preferably less than at a temperature of 132 DEG C. For gel spinning UHMWPE multifilament yarns, it is preferable that stretching (particularly reversing after-drawing) occurs in the temperature higher than 100 DEG C Under, be preferably higher than at a temperature of 110 DEG C, more preferably above at a temperature of 120 DEG C, more preferably above 130 DEG C of temperature Under.

In the linguistic context of the present invention, " monofilament " is understood to mean the slender bodies of indefinite length, and its length dimension is much big In its sectional dimension (such as width, thickness or radius), and there can be regular or irregular section.Monofilament can have continuous Length (being referred to as silk in the art) or discontinuous length (being referred to as chopped fiber in the art).According to the multifibres of the present invention Yarn is the slender bodies for including multifilament.

" gel spinning multifilament yarn " is understood herein to:By making the solvent comprising polymer and for the polymer Solution (otherwise referred to as gel) spinning and the multifilament yarn that manufactures.Can be by being carried out as follows the spinning of solution:In extruder The middle suspension by polymer and solvent is transformed into solution and extruded by the spinning head comprising more than one spinneret orifice described molten Liquid.Particularly preferably gel spinning Polyolefin multifilament yarns, its by the solvent comprising polyolefin and for polyolefin solution Spinning is formed, and the solvent can be after spun yarn by evaporating removing, such as cycloalkane, such as decahydro from multifilament yarn Change naphthalene, tetrahydronaphthalene or hexahydrotoluene.

Preferably, the gel spinning multifilament yarn obtained according to the present invention is high-performance gel spinning multifilament yarn, and its is tough Spend is at least 1.5N/tex, preferably at least 2.0N/tex, more preferably at least 2.5 N/tex or even at least 3.0N/tex. The toughness of multifilament yarn does not have the upper limit, but can manufacture the gel spinning multifilament yarn that toughness is usually at most about 5-6N/tex. Generally, this kind of high-performance gel spinning multifilament yarn also has for example, at least 50N/tex, preferably at least 75N/tex, more preferably Ground 100N/tex, most preferably at least 125N/tex high stretch modulus (also referred to as Young's modulus).Stretch modulus not on Limit, but the toughness of gel spinning multifilament yarn is usually at most about 180N/tex.

ASTM D2256-97 are such as based on, the tensile strength (also referred to as intensity) of multifilament yarn is determined by known method Toughness and modulus.

The fiber number of multifilament yarn obtained according to the present invention is preferably at least 2dtex, preferably at least 7 dtex, more excellent Selection of land at least 8dtex.Due to actual cause, the fiber number of multifilament yarn of the invention be at most thousands of dtex, preferably no more than 2500dtex, more preferably up to 500dtex.Preferably, the fiber number of every silk of the multifilament yarn comprising multi-filament is in 0.2- In the range of 5dtex, preferably in the range of 0.5-2dtex.The fibre of every silk of the part stretching multifilament yarn comprising multi-filament Degree is preferably in the range of 0.5-25 dtex.

Multifilament yarn be preferably chosen from by polyolefin (for example, polyethylene and polypropylene), polyester (for example, PET,And PLA), polyamide (for example, nylon and aramid fiber) composition group;It is highly preferred that multifilament yarn is polyolefin.It is excellent Selection of land, polyolefin is polypropylene or polyethylene, more preferably ultra-high molecular weight polyethylene (UHMWPE) used according to the present invention.

" HPPE multifilament yarns " is understood herein to high-performance polyethylene, and it is that Young's modulus is at least 30GPa bag Yarn containing stretching polyethylene.Particularly preferred class HPPE is gel-spun UHMwPE (UHMWPE), wherein At 135 DEG C based on UHMWPE in decahydronaphthalenes solution measurement UHMWPE intrinsic viscosity (IV) be at least 5dl/g, it is excellent Selection of land at least 10dl/g, more preferably at least 15dl/g, most preferably at least 21dl/g.Preferably, IV be at most 40dl/g, More preferably up to 30dl/g, even more preferably still at most 25dl/g.Gel spinning UHMWPE Young's modulus is generally at least 50GPa.Preferably, the toughness of HPPE multifilament yarns is at least 1GPa.Preferably, HPPE multifilament yarns include at least 90 weights Amount-% UHMWPE silks;Most preferably, HPPE multifilament yarns are constituted by UHMWPE.

" yarn configuration " is represented herein:For example it is (molten comprising part by braiding, weaving, knitting, torsion, heat treatment Melt, air winding and glued) connection at least two multifilament yarns set.

" torsion after-drawing " is represented herein:After yarn is reversed with least 4 twist ms and optionally by the yarn It is transformed into before yarn configuration, with the technique of at least 1.1 factor drawing.It should observe:Drawing constructs (example Such as, cord construction of the stretching as described in EP 0 398 434) it is from reversing after-drawing fundamentally different technique, because drawing Stretching yarn configuration realizes the fundamentally different effects rearranged by the silk of the construction of creep (creep), and not Improve the coherence (coherence) between each monofilament in a multifilament yarn with yarn configuration.In addition, except more Outside relevant tow, reverse part stretching multifilament yarn is also shown before stretching (post-twist-drawing) after twisting More preferable heat distribution and stress distribution in multifilament yarn are provided during stretching after twisting, this allows in silk level more again Homogeneous stretching.More homogeneous stretching causes the machinability of the multifilament yarn obtained to be improved and the yield of manufacture method is obtained To improvement, wire broken rate is caused to reduce because more homogeneous stretching is shown.Compared with drawing is constructed, reverse after-drawing and also lead Fiber number is caused to reduce more.

In one preferred embodiment, it is 10-500 part stretching multifilament yarn to be reversed to the part stretching twist Twist m;It is highly preferred that it is 12-200 twist ms that part drawing, which is reversed to the part stretching twist,.Optimal part stretching The twist depends on the fiber number of multifilament yarn, reverses after-drawing than, the twist of desired multifilament yarn and optional drawing after twisting The twist of multifilament yarn is applied to after stretching.

Another preferred embodiment in, with least 1.5 DRpt, more preferably at least 2 DRpt, most preferably At least 3 DRptReverse part stretching multifilament yarn of the after-drawing through torsion.Reverse after-drawing and compare DRptThe upper limit depend on reverse Draw ratio before the drawing of part before the condition (for example, type of polymer) and reverse part drawing of yarn, With the temperature for reversing after-drawing.Generally, reverse after-drawing ratio and be less than 1000;Preferably, DRptAt most 100;It is highly preferred that DRptLess than 50;It is highly preferred that DRptAt most 25;It is highly preferred that DRptAt most 10 or less than 10.

After partly the stretching twist is reverse part stretching multifilament yarn, the part stretching multifilament yarn is instant/direct Revolution/the rice having.In a preferred embodiment of the present invention, part stretching multifilament yarn is reversed to following level, Which part stretches the twist with reversing the draw ratio DR of after-drawingptBetween business (factor) between 2-250 twist ms;It is preferred that Ground, the part stretching twist/DRptBetween the twist ms of 2- 120;It is highly preferred that the part stretching twist/DRpt2-20 twist ms it Between, such as 5-20 twist ms.In one embodiment, the twist of part stretching multifilament yarn is sufficiently high, so that after reversing After stretching, it is not necessary to further reverse multifilament yarn.

Part stretching multifilament yarn can be yarn of the same race or xenogenesis yarn." yarn of the same race " is represented:Multifilament yarn is by having It is made up of the silk of same composition." xenogenesis yarn " is represented:At least one of multifilament yarn silk has and its in multifilament yarn The different composition of its silk.In one embodiment, at least one of part stretching multifilament yarn silk is selected from by (coloured or nothing Color) polyester capillaries, HD polyethylene filaments, UHMWPE, polyacrylic fibres composition group.Preferably, stretching multifilament yarn in part is included At least 75 number % UHMWPE silks;It is highly preferred that part stretching multifilament yarn includes at least 90 number % UHMWPE silks. Most preferably, the silk of part stretching multifilament yarn is constituted by UHMWPE, because this provides most strong and most uniform for multifilament yarn Performance.

Another aspect of the present invention is related to the method that spin solvent is removed from gel spinning multifibres polyethylene yarn.It is described Method comprises the following steps:Multifilament yarn comprising polyolefin filaments and spin solvent is provided, the yarn is reversed to the twist is 10-600 twist ms, and at least a portion spin solvent is removed from multifilament yarn after torsion yarn.Carry in the first step The multifilament yarn of confession can be gel spinning multifilament yarn that is non-stretched, partly stretching or stretch after twisting, it is preferable, however, that Ground, multifilament yarn is partly stretched or stretched after twisting.Preferably spin solvent is removed by evaporating or extracting.When spinning is molten When agent is cycloalkane (such as decahydronaphthalenes, tetrahydronaphthalene and/or hexahydrotoluene), evaporation is especially suitable for.When spin solvent bag When containing alkane, extraction is especially suitable for.Multifilament yarn is reversed before at least a portion solvent is removed from multifilament yarn to be allowed The transformation towards yarn configuration is carried out in the case where adding spinning oil not into multifilament yarn.In other words, this of the invention Individual aspect allows to remove operability of the spin solvent without jeopardizing yarn from multifilament yarn in more environment-friendly mode, because Not need spinning oil or needing small amount spinning oil.In the embodiment of the invention, after-drawing is reversed many Gauze line is also preferred, however, this and it is nonessential.It is preferred that the twist and optional torsion after the twist correspond to herein in connection with The twist described by the other side of the present invention.

In an embodiment of the invention, before reverse part stretching multifilament yarn, the spinning of multifilament yarn is molten Agent content is very low.In this embodiment it is preferred to, the weight based on polyethylene and spin solvent, during reversing, The spin solvent of multifilament yarn is 10ppm-1000ppm.Preferably, during reversing, the spinning of part stretching multifilament yarn is molten Agent is 20ppm-500ppm.

In another embodiment of the invention, the weight based on polyethylene and spin solvent is reversing multifilament yarn Period, the content of spin solvent of multifilament yarn is at least 0.1 weight-%;Preferably, the content of spin solvent of multifilament yarn is extremely Few 0.5 weight-%;It is highly preferred that the content of spin solvent of multifilament yarn is at least 2 weight-%;It is highly preferred that multifilament yarn Content of spin solvent be at least 5 weight-%, for example, at least 10 weight-%.Generally, during multifilament yarn is reversed, many gauzes The content of spin solvent of line is less than 90 weight-%.

The content before reversing is heavily dependent in the amount of the solvent removed after reversing multifilament yarn.In addition, The solvent of multifilament yarn through reversing after-drawing is lower, then before solvent is removed from yarn, reverses to coherence's Influence is bigger.In one embodiment, after multifilament yarn is reversed, exist during removing at least 10 weight-% torsion Spin solvent;Preferably, after multifilament yarn is reversed, the spinning existed during at least 90 weight-% torsion is removed molten Agent.Most preferably, after multifilament yarn is reversed, the spin solvent existed during at least 99 weight-% torsion is removed.Should It was observed that:If using more its twisting steps, the solvent during reversing be the first its twisting step during solvent. The fraction of the solvent removed after torsion from multifilament yarn depends on the amount existed before reversing to a certain extent.Preferably, remove Go 100% solvent, but because trace solvent can be stayed in multifilament yarn, so in one embodiment, at most removing 99.999% solvent.Preferably, the spin solvent of removing is collected and re-used by any means known.

In clean method according to this aspect of the invention, in fact it is highly preferred that ground, methods described also includes reversing post-tensioning Stretch step.Especially, it has been found that:With at least 1.1 draw ratio DRptReversing after-drawing multifilament yarn is beneficial to form HPPE multifibres Yarn.It is highly preferred that the draw ratio for reversing after-drawing is at least 1.5;Even further preferably, DRptIt is at least 2;Most preferably, DRptIt is at least 3.Reverse after-drawing and compare DRptThe upper limit depend on reverse part drawing before yarn condition (for example, poly- The type of compound) and reverse part drawing before draw ratio and reverse after-drawing temperature.Generally, after-drawing is reversed Compare DRptLess than 1000;Preferably, DRptAt most 100;It is highly preferred that DRptLess than 50;It is highly preferred that DRptAt most 25; It is highly preferred that DRptAt most 10 or less than 10.

Because the electrostatic charge effect due to being electrically isolated polymer, manufacture gel spinning multifibres HPPE traditionally needs removing Spinning oil is added during spin solvent, otherwise silk will be mutually exclusive.Unfortunately, spinning oil is surfactant, from ring From the point of view of the visual angle of border, it is not desired additive;Especially for medical applications, it should avoid spinning oil.Therefore, it is of the invention One side be related to manufacture gel spinning HPPE multifilament yarns and the method that is added without spinning oil.Flow chart in Fig. 2 refers to This method is shown.Methods described comprises the following steps:Solution of (2) 3-25 weight-% UHMWPE in spin solvent is provided (based on the UHMWPE and spin solvent in solution).Can be for example by the way that solution be provided below:In an extruder transformation UHMWPE and The suspension of spin solvent, by the solution of spinning head spinning 4 with least two spinneret orifice, the solution quenching 6 in hardening bath, And stretch 7 to form the solid-state multifilament yarn for including partly stretching UHMWPE.Then, part stretching multifilament yarn is reversed 12 It is that 2-600 twist ms stretch multifilament yarn to form the part through torsion to the twist, and with least 1.1 draw ratio DRptAfter torsion Part of the stretching 13 through torsion stretches multifilament yarn to form HPPE multifilament yarns, wherein not adding spinning into multifilament yarn Reversed in the case of finish, remove spin solvent and reverse after-drawing.Removed during this method by evaporating or extracting At least a portion spin solvent.Reverse part stretching multifilament yarn can with the stretching that is carried out before torsion online, off line or connection Machine combines progress with off line.Reverse part stretching multifilament yarn can be with reversing online after-drawing, off line or online and off line group Close and carry out.Have found, very advantageously:Stretching before torsion is carried out with torsion off line and will reversed and at least part The online progress of torsion after-drawing because this allows good traceability and compact process equipment.

The method according to the invention is particularly useful for preparation and is ready to use in medical applications, medical maintenance product, implant and doctor The polyethylene yarn in apparatus is treated, because methods described allows without using spinning oil (particularly organic spinning oil) In the case of prepare polyethylene yarn, wherein organic spinning oil contacts typically undesirable in body or with body.Medical treatment The example of application is medical components, for example blood vessel prosthesis, joint conversion thing, orthopaedic implant and spinal implant (such as first quarter moon Plate implant, surgical sutures), mesh (such as hernia net), fabric, textile, sheet material, band, web, the band of weaving or nonwoven Shape thing, artificial joint, cable are (for example, wound fixing cable, breastbone close cable, preventative or prosthese cable, long bone fracture are solid Determine cable, short bone fracture fixation cable), tubular products (for example, ligament substitute), endless loop (endless loop) product, Bag-shaped product, spherical products, support, stent graft, artificial blood vessel, Y shape hollow structure, the edge (skirts) of valve arrangement (for example, cardiac valves and periphery valve) and other medical components.

Because the use of spinning oil from the point of view of environmental being also undesirable, there is benefit in the method in accordance with the invention The polyethylene yarn in other final use products and application, the product and application such as rope, electric wire are ready to use in preparation Cable, mooring rope, setline and fishing net, telecontrol equipment, shock resistance and wear resistant products and ballistic resistant products.

Embodiment

Embodiment 1:HPPE yarns are prepared, wherein the online stretching before torsion

Fig. 1 a) flow chart for the method for preparing Polyolefin multifilament yarns is shown, wherein being carried out before torsion with reversing Online stretching.After torsion, before (later) carries out off line " torsion after-drawing ", will part stretching multifilament yarn wound on On reel (bobbin).Can be in the torsion of combination and winder unit (for example, available commercially from Alma-Sauer, Dietze& Schell, Galan and Barmag company) in reverse can with winding part stretching multifilament yarn carry out jointly.Can also be 2 Reversed and wound in individual separated step, in this case, can in such as US 6, method disclosed in 155,037 and In equipment carry out reverse and for example can precision cross winding machine (for example purchased from SSM, Dietze&Schell, Comoli, Leesona, Georg Sahm GmbH, Oerlikon and Barmag) on be wound.(that is, off line) reverses after-drawing later Part drawing that is rolled and reversing.This corresponds to the method shown in Fig. 1 a, wherein except online before reversing 12 Outside the stretching 8 of progress, off line stretching 10 can also be carried out before online stretching 8.

Embodiment 2:HPPE yarns are prepared, wherein the online stretching before and after torsion

Fig. 1 b) flow chart for the method for preparing Polyolefin multifilament yarns is shown, wherein being carried out before and after torsion With reversing online stretching.Using such as US 6, the twist cell of the type disclosed in 155,037 is reversed, wherein The yarn run during transfer by the online torsion of twist cell.In a kind of embodiment b) of stretching variants, using one Individual big its twisting step is to reach the desired twist.In the another embodiment c) of stretching variants, using multiple less Its twisting step (such as 2,3,4,5,6,7,8,9 or 10 its twisting steps) to reach the desired twist.Multiple less drawings Stretching step can be arranged in the group of the stretching step between multiple less stretching steps or between stretching step.As schemed Shown in 1b), in addition in 8 and afterwards 14 online stretching before reversing 12, can online stretching and its twisting step 8, 12nd, before 14 10 or afterwards 16 optionally with one or more off line stretching steps.

Embodiment 3:HPPE yarns are prepared, wherein the online stretching after torsion

Fig. 1 c) flow chart for the method for preparing Polyolefin multifilament yarns is shown, wherein being carried out after torsion with reversing Online stretching.In this case, part stretching multifilament yarn is prepared by the following procedure:For example 10 are stretched in the first stretching furnace (as-spun) multifilament yarn is spun into, then on the Twinstar precision cross winding machines for example purchased from Georg Sahm GmbH Winding part stretches multifilament yarn.Later, reverse and stretched portion stretches multifilament yarn after twisting.Torsion is preferably occur in In the torsion and unwinding equipment of combination, such as available commercially from such as Alma-Sauer, Dietze&Schell, Galan and Barmag torsion bobbin cradle.Or, can be by single unwinder and such as US 6, the torsion of the type disclosed in 155,037 Turn unit combination.After online torsion after-drawing 14, optionally by the further off line stretching 16 of yarn.This embodiment Advantage be:It is quick when fine-tuning unwinding using drawing process and reverse, and allowing to be related to broken yarn to start and stop.This Outside, compared with the stretching variants of embodiment 4, traceability is more easily handled, because being related to less off line process.

Embodiment 4:HPPE yarns are prepared, wherein off line is stretched before and after torsion

Fig. 1 d) flow chart of the method for preparing Polyolefin multifilament yarns is shown, wherein the off line before and after torsion Stretched.Prepare part stretching multifilament yarn as described in example 3 above as follows:Drawn for example in the first stretching furnace Stretch 10 and be spun into (as-spun) multifilament yarn, then for example purchased from Georg Sahm GmbH Twinstar precision cross windings Winding part stretches multifilament yarn on machine.Then, in later time, in torsion and recoiling facility (such as available commercially from example Such as SSM, Dietze&Schell, Comoli, Leesona, Georg Sahm GmbH, Oerlikon and Barmag) on reverse Part stretching multifilament yarn.Finally, in later time, such as torsion after-drawing is carried out in another stretching furnace.It is this The advantage of embodiment is:It allows to improve the correlation of multifilament yarn in simple cluster (constellation), and not Need to make torsion equipment match/alinement (alignment) with one or more stretching stations.However, due to the processing step It is that off line is carried out, so needing handled traceability.

Embodiment 5:Prepare part stretching HPPE yarns

It is following to prepare the reel that part stretches UHMWPE yarns:UHMWPE is prepared in an extruder in decahydronaphthalenes Solution, by the spinning head spinning solution with 200 spinneret orifices, in hardening bath quench, partly stretch the yarn being spun into And the spin solvent compared with the content of spin solvent of solution more than 99% is removed from yarn.Spinning is not provided during this method Finish.Finally, by yarn winding on a bobbin, each reel holds about 9000m.

Embodiment 6:HPPE yarns are prepared, wherein the online stretching after torsion

The reel for making the part that is prepared in embodiment 5 stretch UHMWPE yarns is subjected to such as Fig. 1 c) described in connection Machine drawing process, wherein the online torsion after-drawing ratio used is 4, and feeds via bobbin cradle unwinder is reversed to stretching furnace. Use 9 twist ms and the twist of 12 twist ms.After-drawing is reversed without using off line and spinning oil is not provided during this method.

Thus, it is seen that:When the twist is improved, the greatest drawback number of each reel and the average defect of each reel Number is reduced.

Comparative example 1:HPPE yarns are prepared, wherein not utilizing torsion

Embodiment 6 is repeated using the online torsion of 0 twist m.The yarn of generation shows low-down coherence and final After stretching, it is impossible to prepare stable reel.

Embodiment 7:HPPE yarns are prepared, wherein being stretched before and after torsion using off line

The reel for making the part that is prepared in embodiment 5 stretch UHMWPE yarns is subjected to such as Fig. 1 d) described in off line Drawing process.Point recoiled by using annular twisting mill (ring-twister) unwinding, close wind and using cross winding From step, to provide the twist of 16 twist ms.Then, after-drawing ratio is reversed using 4 off line, stretching is stretched and reversed through part UHMWPE yarns reel.Spinning oil is not provided during reversing or reversing after-drawing process.

Prepare two batches reel (each about 400g).

1st batch:50 reels, wherein 16 reels have one or more defects

2nd batch:75 reels, wherein 24 reels have one or more defects

Thus, it is seen that:Although without spinning oil is added during this method, utilizing to include and reversing yarn and torsion The method of after-drawing realizes very high quality level and high coherence.

Comparative example 2:HPPE yarns are prepared, wherein not utilizing torsion

Using the recoil without torsion, embodiment 7 is repeated.The yarn of generation shows low-down coherence and final stretching Afterwards, it is impossible to prepare stable reel.

The combination of the single feature or feature of embodiment from invention as described herein and its obvious variant can Combinations of features or exchange with other embodiment as described herein, unless those skilled in the art immediately appreciate that produced by Embodiment can not be implemented completely.

Claims (39)

1. manufacturing the method for multifilament yarn, methods described comprises the steps:
- stretching multifilament yarn in part is provided, the part stretching multifilament yarn includes partially drawn yarn,
- by part stretching multifilament yarn reverse to the part stretching twist be 4 twist ms to 600 twist ms to be formed through torsion Part stretching multifilament yarn, and
- with least 1.1 draw ratio DRptReverse the part stretching multifilament yarn through torsion described in after-drawing.
2. according to the method described in claim 1, wherein the part drawing be twisted to part stretching the twist be 10 turns/ Rice is to 500 twist ms.
3. according to the method described in claim 1, wherein the part drawing be twisted to part stretching the twist be 12 turns/ Rice is to 200 twist ms.
4. according to the method described in claim 1, wherein DRptIt is at least 1.5.
5. according to the method described in claim 1, wherein DRptIt is at least 2.
6. according to the method described in claim 1, wherein DRptIt is at least 3.
7. according to the method described in claim 1, wherein the part stretches the twist/DRptBetween 2-250 twist ms
8. method according to claim 7, wherein the part stretches the twist/DRptBetween 2-120 twist ms.
9. according to the method described in claim 1, wherein at least one of part stretching multifilament yarn silk is selected from by gathering The group that ester silk, HD polyethylene filaments, UHMWPE and polyacrylic fibres are constituted.
10. according to the method described in claim 1, wherein part stretching multifilament yarn includes at least 75 number %'s UHMWPE.
11. method according to claim 10, wherein part stretching multifilament yarn includes at least 90 number %'s UHMWPE.
12. method according to claim 10, wherein the silk of part stretching multifilament yarn is constituted by UHMWPE.
13. the method according to any one of claim 1-12, wherein reversing the part stretching multifilament yarn is and drawing Stretch the online realization of step.
14. the method according to any one of claim 1-12, wherein the step of reversing the part stretching multifilament yarn The step of with torsion after-drawing is online progress.
15. the method according to any one of claim 1-12, wherein carrying out reversing the portion by Uster twist systems Divide drawing.
16. the method according to any one of claim 1-12, wherein reversing the part stretch yarn by being carried out as follows Line:The part stretching multifilament yarn without torsion is wound first, then makes the part stretching many using torsion bobbin cradle system Silk unwinding yarn stretches multifilament yarn to reverse the part.
17. method according to claim 16, wherein arranging the torsion bobbin cradle system with reversing post-tensioning stretching process It is online to be unwind and reversed, wherein the withdrawal speed and rotary speed that adjust the torsion bobbin cradle system are online to adapt to Reverse post-tensioning stretching process.
18. the method according to any one of claim 1-12, it also comprises the steps:Reversing the part stretching Stretch after yarn and after twisting before the part drawing, the multifilament yarn is tensed in tensioning station.
19. the method according to any one of claim 1-12, wherein with most 100 draw ratio DRptReverse after-drawing The part stretches multifilament yarn to form HPPE multifilament yarns.
20. method according to claim 19, wherein DRptIt is at most 25.
21. method according to claim 19, wherein DRptIt is at most 10.
22. removing the method for spin solvent from gel spinning multifibres polyethylene yarn, it comprises the steps:
- multifilament yarn is provided, it includes polyolefin filaments and spin solvent,
- by the yarn reverse to the twist be 10-600 twist ms, and
- reverse after the yarn, at least a portion spin solvent is removed from the multifilament yarn.
23. method according to claim 22, wherein during the multifilament yarn is reversed, it is molten based on polyethylene and spinning The weight of agent, the content of spin solvent of the multifilament yarn is 10ppm-1000ppm.
24. method according to claim 23, wherein the weight based on polyethylene and spin solvent, the multifilament yarn Content of spin solvent is 20ppm-500ppm.
25. method according to claim 22, wherein during the multifilament yarn is reversed, it is molten based on polyethylene and spinning The weight of agent, the content of spin solvent of the multifilament yarn is at least 0.1 weight-%.
26. method according to claim 25, wherein the content of spin solvent of the multifilament yarn is at least 0.5 weight Amount-%.
27. method according to claim 25, wherein the content of spin solvent of the multifilament yarn is at least 2 weight-%.
28. method according to claim 25, wherein the content of spin solvent of the multifilament yarn is at least 10 weights Amount-%.
29. the method according to any one of claim 22-28, wherein after the multifilament yarn is reversed, removing extremely The spin solvent existed during few 10 weight-% torsion.
30. method according to claim 29, wherein after the multifilament yarn is reversed, removing at least 90 weight-% Torsion during the spin solvent that exists.
31. method according to claim 29, wherein after the multifilament yarn is reversed, removing at least 99 weight-% Torsion during the spin solvent that exists.
32. the method according to any one of claim 22-28, it also comprises the following steps:With at least 1.1 draw ratio DRpMultifilament yarn described in after-drawing is reversed to form HPPE multifilament yarns.
33. method according to claim 32, wherein DRptIt is at least 1.5.
34. method according to claim 32, wherein DRptIt is at least 2.
35. method according to claim 32, wherein DRptIt is at least 3.
36. manufacturing the method for gel spinning HPPE multifilament yarns, it comprises the steps:
- solution of the 3-25 weight-% UHMWPE in spin solvent is provided, based on the UHMWPE and spin solvent in solution,
- by solution described in the spinning head spinning with least two spinneret orifice, formed the solution quenching in hardening bath Comprising the part stretching solid-state multifilament yarn of UHMWPE,
- at least a portion spin solvent is removed from the solid-state multifilament yarn,
- reverse the solid-state multifilament yarn to the twist as 10-600 twist ms to form the part stretching multifilament yarn through torsion,
- with least 1.1 draw ratio DRptThe part stretching multifilament yarn through torsion described in after-drawing is reversed to form HPPE multifibres Yarn,
Wherein after being reversed in the case of spinning oil is added not into the multifilament yarn, removing spin solvent and reverse Stretching.
37. method according to claim 36, it also comprises the steps:The spinning for removing at least 99.5 weight-% is molten Agent, based on the spin solvent in solution.
38. the method according to claim 37, wherein removing at least 99.9 weight-% spin solvent.
39. the method according to claim 37, wherein removing at least 99.95 weight-% spin solvent.
CN201480005797.2A 2013-01-25 2014-01-27 The method of manufacture stretching multifilament yarn CN104955992B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101050562A (en) * 2007-04-25 2007-10-10 华东理工大学 Monofilament fiber in polyolefin class
CN101273158A (en) * 2005-07-18 2008-09-24 帝斯曼知识产权资产管理有限公司 Polyethylene multi-filament yarn
CN101688332A (en) * 2007-05-01 2010-03-31 帝斯曼知识产权资产管理有限公司 Uhmwpe fiber and process for producing thereof

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4112667A (en) * 1977-02-22 1978-09-12 Phillips Petroleum Company Apparatus and process suitable for twist-drawing a yarn
NL8104728A (en) * 1981-10-17 1983-05-16 Stamicarbon Method for the production of polyethylene filaments having high tensile strength.
EP0205960B1 (en) * 1985-06-17 1990-10-24 AlliedSignal Inc. Very low creep, ultra high moduls, low shrink, high tenacity polyolefin fiber having good strength retention at high temperatures and method to produce such fiber
NL8901266A (en) 1989-05-19 1990-12-17 Stamicarbon Process for producing a stretched rope.
JPH0655628A (en) * 1992-08-11 1994-03-01 Toyobo Co Ltd Manufacture of modified ultra-high-molecular-weight polyolefin stretched material
EP0921218B1 (en) 1997-12-03 2002-08-14 Zellweger Luwa Ag Rotary body
JP4389142B2 (en) 2001-08-08 2009-12-24 東洋紡績株式会社 Method for producing high-strength polyethylene fiber
KR101103197B1 (en) 2002-12-10 2012-01-04 디에스엠 아이피 어셋츠 비.브이. Process for making and process for converting polyolefin fibres
PL1699954T3 (en) 2004-01-01 2012-04-30 Dsm Ip Assets Bv Process for making high-performance polyethylene multifilament yarn
IL224437A (en) 2004-08-16 2014-05-28 Yuval Fuchs Ballistic resistant article comprising a plurality of polyethylene monolayers and layers of ballistic fiber
EP1847276A1 (en) * 2006-04-20 2007-10-24 DSMIP Assets B.V. Twisted suture
US7846363B2 (en) * 2006-08-23 2010-12-07 Honeywell International Inc. Process for the preparation of UHMW multi-filament poly(alpha-olefin) yarns
JP2008266843A (en) * 2007-04-23 2008-11-06 Ygk:Kk Polyolefin yarn and method for producing the same
US7966797B2 (en) * 2008-06-25 2011-06-28 Honeywell International Inc. Method of making monofilament fishing lines of high tenacity polyolefin fibers
CN103097596A (en) * 2010-09-21 2013-05-08 株式会社高纤 Super-high-molecular-weight polyolefin yarn, method for producing same, and drawing device
KR20120057904A (en) * 2010-11-29 2012-06-07 코오롱글로텍주식회사 Polypropylene fiber with auto temperature control, manufacturing method of the same, and fabric prepared from the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101273158A (en) * 2005-07-18 2008-09-24 帝斯曼知识产权资产管理有限公司 Polyethylene multi-filament yarn
CN101050562A (en) * 2007-04-25 2007-10-10 华东理工大学 Monofilament fiber in polyolefin class
CN101688332A (en) * 2007-05-01 2010-03-31 帝斯曼知识产权资产管理有限公司 Uhmwpe fiber and process for producing thereof

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