CN1703546A - Process for making a monofilament-like product - Google Patents

Process for making a monofilament-like product Download PDF

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Publication number
CN1703546A
CN1703546A CNA2003801013009A CN200380101300A CN1703546A CN 1703546 A CN1703546 A CN 1703546A CN A2003801013009 A CNA2003801013009 A CN A2003801013009A CN 200380101300 A CN200380101300 A CN 200380101300A CN 1703546 A CN1703546 A CN 1703546A
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China
Prior art keywords
product
yarn
presoma
monofilament
fiber
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Granted
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CNA2003801013009A
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CN1703546B (en
Inventor
西普里尔·戴维·韦亚
克里斯琴·亨利·彼得·德克斯
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DSM IP Assets BV
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DSM IP Assets BV
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    • 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
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • 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
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
    • 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
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
    • D02G3/402—Yarns in which fibres are united by adhesives; Impregnated yarns or threads the adhesive being one component of the yarn, i.e. thermoplastic yarn
    • 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
    • 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
    • D02G3/444—Yarns or threads for use in sports applications
    • 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
    • Y10T428/2904—Staple length fiber
    • Y10T428/2905—Plural and with bonded intersections only
    • 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

Abstract

The invention relates to a process for making a monofilament-like product from a precursor containing at least one strand of a spun yarn made from polyolefin staple fibres, comprising the steps of a) exposing the precursor to a temperature within the melting point range of the polyolefin for a time sufficient to at least partly fuse adjacent fibres and b) simultaneously stretching the precursor at a draw ratio of at least 1.0. The invention further relates to a monofilament-like product obtainable by said process showing improved abrasion resistance, and to the use of said monofilament-like product for making various semi-finished and end-use products.

Description

Be used to make the method for monofilament-like product
The present invention relates to by containing the method for the presoma manufacturing monofilament-like product of one polyamide fiber at least, described method comprises following step: a) presoma is exposed to the temperature time enough that is in the polyolefin melting range, so that adjacent fiber partial melting at least; And b) with at least 1.0 the draw ratio presoma that side by side stretches.The invention still further relates to the monofilament-like product that can obtain by described method, and relate to the purposes that described monofilament-like product is used to make various semi-finished product and final products.
From the so as can be known method of EP 0740002 B1.In this patent documentation, the method that is used for being made by the yarn of filamentary material fishing line has been described, wherein, braiding, (twisted) of twisting or the fishing line of twisting and plying made by the yarn of gel spun polyolefin filaments are exposed to the temperature time enough that is in the described polyolefinic melting range, so that adjacent silk partial melting at least, simultaneously to be in draw ratio in from 1.01 to 2.5 the scope described line that stretches.The yarn that is applicable to the method is continuous multifilament yarn, and more particularly the yarn of making by the so-called gel spun of ultra-high molecular weight polyethylene (UHMwPE) for example is called Spectra Perhaps Dyneema The commercialization yarn.
The monofilament that fishing line is normally made by synthetic polymer has the robust structure of circle of the convenient operation of the throwing that allows to be used for the bait throwing, to rotate and to rotate.Such monofilament generally has rigidity characteristics and smooth surface, and these two kinds of character combine to reduce the resistance in the throwing process and can allow longer throwing, also are convenient to discharge better from the fishing gear reel simultaneously.Weaving thread is not applicable to fishing line so, weares and teares because they trend towards online end, and possible entrap water presents and is easy to the outer surface that tangles and twine, and has the too high opaque and white of visual under water degree.Method known to EP 0740002 B1 allows to make monofilament shape fishing line from weaving thread or the twisted lines made by the polyolefin multifilament yarn, and this line does not have the described shortcoming of weaving thread.
The shortcoming of method described in EP 0740002 B1 is to utilize its resulting product to show limited resistance to fracture when being in abrasive conditions following time.
Therefore, an object of the present invention is to provide a kind of method that is used to make the monofilament-like product that does not show described shortcoming.
According to the present invention, utilization is by comprising the method for the presoma manufacturing monofilament-like product of one polyamide fiber at least, realized this purpose, described method comprises the steps: a) presoma to be exposed to the temperature time enough that is in the polyolefin melting range, so that adjacent fiber partial melting at least; And b) with at least 1.0 the draw ratio presoma that side by side stretches, wherein said polyamide fiber thigh is the spinning yarn of being made by polyolefin staple fibre (staple fibre).
Utilize the method according to this invention, monofilament-like product can be made by for example plying or braiding polyethylene yarn structure, this product shows the mar proof of raising, as represented with the fracture period when measured in the test described in below " material and method " part.
Also show surprising TENSILE STRENGTH by the resulting monofilament-like product of the method according to this invention, than that make by such spinning yarn and obviously much higher as the initial spinning yarn or the doubled yarn of presoma.Resulting monofilament-like product also has gratifying sense of touch or feel, and can easily be operated and tie a knot; In addition, it shows surprising high knot strength and knot strength efficient.Another advantage of the method according to this invention is easily to change and to control the fusing degree; Make product have the proper Performance Characteristics of design.Also have an advantage to be, resulting monofilament-like product can be applied in additional processing step effectively coats composition.
Utilize the method according to this invention, by comprising the presoma manufacturing monofilament-like product of one polyamide fiber at least.Monofilament-like product is understood that such product, promptly its outward appearance is compared with multifilament yarn or multifibres line with feel and more is similar to monofilament, but its be actually by contain plurality of fibers one is made at least, described fiber has usually less than about 50 microns diameter.Monofilament-like product can have the diameter that changes in wide region, for example from about 0.1 millimeter up to 10 millimeters.Presoma is understood that to comprise one polyamide fiber at least and goods that be used as the indefinite length of feed materials or parent material at this.Suitable presoma can have following form, for example weaving thread, doubling twisting yarn, contain many strand line or rope, can also be single-strand yarn.One polyamide fiber is understood that fibrous product, as mainly containing the yarn of (promptly containing 50 quality % or more) polyamide fiber.
The method according to this invention comprises such step, is about to presoma and is exposed to the temperature time enough that is in the polyolefinic melting range, so that adjacent fiber partial melting at least.The condition of this fusing step is selected, makes the time and the temperature that expose enough come to soften polyamide fiber, and allows it to melt in applied ad hoc structure at least in part.Polyolefinic melting range is at non-oriented polyolefinic peak value fusing point with force temperature range between the peak value fusing point of height-oriented polyamide fiber, as determined by the dsc analysis of the sweep speed of utilizing 20 ℃/min.For the UHMwPE fiber that shows 138～162 ℃ melting range usually, described temperature preferably from about 150 ℃ up to about 157 ℃ scope.The time of staying that presoma is exposed to fusion temperature can change in wide region, but usually from about 5 seconds to about 1500 seconds scope.Though higher temperature has often promoted fusion process, should carefully not apply too high temperature, because this for example may cause the loss by partial melting or other the caused product strength of molecular relaxation effect.
During fusion process, according to the fusing degree and the type of persursor material, the outward appearance of presoma becomes translucent, milky white or even the product surface outward appearance of substantially transparent from initial opaque white color.The light transmission of product increases along with the increase of the fusing degree between the fiber.The such transparency or the increase of light transmission are for being significant advantage for the application of fishing line under water.
For the monofilament-like product that shows low end wear, the outer surface layer of fiber quilt partial melting at least just is enough to meet the demands, and is seen as the increase by light transmission.But, having more high-wearing feature and product higher bending stiffness, that have more monofilament shape characteristics for manufacturing, higher fusing degree is preferred, for example, also makes the fiber joint in the more inner part of presoma or thigh.In the method according to the invention, can regulate the fusing degree by changing Exposure Temperature and/or open-assembly time.
For example, by the visual evaluation of for example bore hole or by using optics or electron microscope; Perhaps, can determine the fusing degree of products obtained therefrom by measuring mechanical performance as intensity or rigidity.Another kind may be speed and an amount of determining for example to absorb from concentrator marker pigmented fluids, as described in the EP0740002 B1.The fusing degree can also obtain from such test, in this test, will load product and rub on Metallic rod, and determine monofilament-like product is separated into the required times of exercise that it forms silk.
In the specific embodiment of this method, very low of the fusing degree on the products obtained therefrom, even immeasurability almost.Surprisingly, have been found that such product that has at high temperature stretched shows the TENSILE STRENGTH that obviously improves than its presoma; Even ABRASION RESISTANCE is just good slightly.Therefore the present invention also relates to a kind of method, is used for stretching with at least 1.1 draw ratio containing at least the braiding or the plied construction of one spinning yarn of being made by polyolefin staple fibre, is exposed to the temperature that is in the polyolefinic melting range simultaneously.Utilize the resulting product of this method to show the tensile property of raising, but still have the bending property of the initial structure of being very similar to.
The method according to this invention also comprises the presoma that stretches simultaneously of the draw ratio (being also referred to as ratio of elongation) with at least 1.0.In hot process-exposed, presoma applied at least 1 draw ratio, prevented the decline of product strength.1.1 or higher draw ratio has often especially improved TENSILE STRENGTH.So the intensity of finding product surprisingly is apparently higher than the intensity of the intensity of presoma or the thigh that wherein comprises.Surpass a certain draw ratio, this effect balance that becomes, perhaps because damage of the part of fiber or fracture, intensity even may reduce.In addition, draw ratio is high more, and the fiber number of products obtained therefrom (titre) is low more.Therefore, maximal draw ratio depends on the type of presoma and fiber thereof, and generally about at the most 50.Preferably, draw ratio from 1.1 to 40, from 1.2 to 25, more preferably from 1.3 to 10, perhaps even more preferably from 1.4 to 5.
Preferably, the product that obtains after step b) is cooled, and holds it under the tension force simultaneously.This has following advantage, and promptly the orientation on the molecular level on the fiber level or in fiber in the product that obtains in fusing and drawing process is kept better.Such tension force obtains by for example after the step of the front of this method product being twined rolling.
In the method according to the invention, in the presoma one is the spinning yarn of being made by polyolefin staple fibre at least, promptly comprise the spinning yarn of the polyolefin staple fibre of at least 50 quality %.In general, yarn can by continuous silk, cut staple or it be in conjunction with making.Natural fabric can be divided into two classes: short cut staple (cotton shape has typical shearing length or the filament length degree of 15～60mm) and long cut staple (ulotrichy has the typical shearing length of 40～200mm).Synthetic fiber at first are manufactured into continuous silk; Subsequently, they can be transformed into cut staple by cut-out or Tensile Fracture Process.Cut off and cause consistent silk distribution (all have roughly the same length) usually; Although improved system allows the certain variation of acquisition in the filament length degree distributes.Tension failure generally obtains having the cut staple of the filament length degree that more is similar to Gaussian distribution.In Tensile Fracture Process, silk is stretched between the roller of array with the friction speed operation, up to its fracture.
Cut staple can be made into yarn via the technology that logarithm thigh parallel fibers carries out drawing and twisting, and this technology is commonly referred to as spinning.Therefore, the yarn of being made by cut staple is known as spinning yarn.
The industrial yarn spinning process comprises following basic process steps: Xie Song, carded, drawing-off and spinning.Xie Song is meant separation and cleans for example cut staple of packing alternatively.Carded is for for example by making fiber further separate pine and defibre through coming being coated with between the swing roller of pin.This obtains the fiber of thin netted partial parallel, and it is formed the strand of the rope form that usually is called as rectangular (sliver).Can carry out combing then, with the orientation that improves fiber and remove short and small fiber.In drafting process, rectangular in one or more outwards drawing-off of step quilt.Several are rectangular, and perhaps identical cut staple or different cut staples can be mixed together, so that obtain uniform fibers density.Mix the yarn that cut staple also can be made the mixture that comprises different natural fibres and/or synthetic fiber in the carded stage.Before being fed to spinning machine, rectangular can slightly twisting simultaneously by further drawing-off is called rove.In spinning process, rectangular or further outwards drawing-off and twisting of rove quilt, with the combination between the fiber that overlapping is provided, and yarn is wrapped on the bobbin.A looping like this around yarn can be circular cone or columnar, and usually be called bag for short.
Described spinning process yarn that obtain twisting, sub-thread is also referred to as single thread.According to the twist direction that is applied, such yarn usually is called as S yarn or Z yarn.The single-strand yarn of twisting is quite " active " normally, and the meaning is that it often twists, tangles, tilts or be curling around self when tension force that need not be enough keeps.In order to reduce such activity, promptly can further be processed into for example maidenliness or the balance yarn of fiber satisfactorily in order to obtain, in industry, extensively adopted additional step, wherein with two strands or more the single thread of multiply combine.These integrating step usually is called as plying.For example, by two sub-thread Z yarns are twisted with the fingers twisted together with S-, perhaps, can make bifilar yarn or pairing thigh yarn by Z is in the same place with S type yarn plying.The doubled yarn that obtains like this can also be stronger and more even than single-strand yarn.
Applied in the method according to the invention spinning yarn comprises the polyolefin staple fibre of at least 50 quality %.Spinning yarn can also comprise one or more other the cut staple of maximum 50 quality %, as natural fabric or synthetic fiber, to make blended yarns.The suitable examples of such secondary staple fibres comprises that wool fibre, polyamide fiber, acrylic fiber, polyester fiber or polyamide fiber comprise aromatic polyamide fibers.
In the specific embodiment of the method according to this invention, spinning yarn comprises a certain amount of cut-out yarn of being made by thermoplastic polymer, and it has the melting range lower than described polyolefin staple fibre.Its advantage is can produce additional thermal bonding in the process of step a).Use spinning yarn can allow such possibility in the method according to the invention, because compare with making the mixing multifilament yarn, it is easier and more economical to make the mix spinning yarn.The example of suitable thermoplastic polymer comprises the copolymer of at least a alpha-olefin and other monomers, as LLDPE or ethylene-acrylic acid copolymer.The effective dose of such cut staple can be determined by experiment, and is generally about 5～25 quality %.
In another specific embodiment according to the present invention, the key component of spinning yarn is not a polyolefin staple fibre, but the cut staple of being made by high strength, high modulus filament yarn, and it has the heat resistance higher than polyolefin, and itself can not thermal bonding; As such as Kevlar Perhaps Twaron Aromatic polyamides yarn, liquid crystal polyester yarn or based on the yarn of polybenzoxazole or polybenzothiozole.Such spinning yarn also comprises the cut-out yarn of being made by thermoplastic polymer with low relatively melting range of maximum 50 quality %, for example has the polyolefin staple fibre of the fusing point that is lower than 200 ℃.The example of suitable thermoplastic polymer comprises the copolymer of at least a alpha-olefin and other monomers, as LLDPE or ethylene-acrylic acid copolymer.The advantage of this embodiment is, in the process of step a), can produce thermal bonding, and do not exist under the situation with low-melting fiber, can not by such have high-fire resistance, high strength and modulus gauze line, make monofilament-like product by it being heated stretch simultaneously.But the effective dose of the cut staple of such thermoplasticity hot melt can come by experiment to determine, and be generally about 5～25 quality %.But by described method manufacturing, based on the monofilament-like product of the spinning yarn that comprises aromatic polyamides cut staple and hot melt cut staple, combine high strength, high-wearing feature and high-fire resistance.
Spinning yarn and cut staple can also include the additive of usefulness, as stabilizing agent, colouring agent, inorganic particulate, sizing agent (sizing agent) etc.
For other the selection of cut staple, for example type, length, fiber number (dpf), whether it can together melt with polyolefin staple fibre under the temperature and time condition that is applied, and/or for the selection of additive, mainly determine by desired final performance, and those skilled in the art use common practise or by normal experiment, can finish selection.
Preferably, in the method according to the invention the spinning yarn of Ying Yonging comprise at least 60,70,80 or even the polyolefin staple fibre of 90 quality % because this can allow the mechanical performance of products obtained therefrom better.Therefore, applied spinning yarn most preferably includes only described cut staple substantially.
The cut staple that is obtained by various polyethylene yarn can selected conduct be applied to the cut staple in the method according to this invention.Specially suitable polyethylene yarn is made by the homopolymers and the copolymer of ethene or propylene.In addition, employed polyolefin can comprise a spot of one or more other monomer, especially other alpha-olefin.If selection wire property polyethylene (PE) then can obtain good result as polyolefin.Linear polyethylene is understood that such polyethylene at this, and it has per 100 carbon atoms less than one side chain, and preferably has per 300 carbon atoms less than one side chain; Side chain or side chain comprise at least 10 carbon atoms usually.This linear polyethylene can also comprise a kind of or more kinds of comonomer such as alkene of maximum 5mol%, as propylene, butylene, amylene, 4-methylpentene or octene.Except polyolefin, fiber can also comprise a spot of for such fiber habitual solvent or additive, such as antioxidant, spin finish (spinfinish), heat stabilizer, colouring agent etc.
Preferably, polyamide fiber, especially polyethylene fiber have the intrinsic viscosity (IV) greater than 5dl/g.Because the strand that it is long, the polyamide fiber with such IV has extraordinary mechanical performance, and for example high TENSILE STRENGTH, modulus and fracture absorb energy.This also is a polyolefin even more preferably have poly reason greater than the IV of 10dl/g why.According to method PTC-179 (Hercules Inc.Rev.Apr.29,1982), in 135 ℃ of following decahydronaphthalenes, dissolution time is 16 hours, and antioxidant is DBPC (solution of 2g/l), determine described IV, and the viscosity of variable concentrations is pushed out to zero-dose.Full-bodied like this polyethylene usually is called as UHMwPE.By UHMwPE solution is spinned into gelatinous fibre and before partly or completely removing solvent, during and/or this fiber of drawing-off afterwards, promptly through for example at EP 0205960A, WO01/73173 A1, Advanced fiber spinning technology, Ed.T.Nakajima, Woodhead Publ.Ltd (1994), ISBN 185,573 1827 and in the so-called gel spun technology described in this list of references of quoting can prepare UHMwPE gauze line.
Preferably, select the UHMwPE cut staple, because it combines high strength and relative low density.More specifically, the spinning yarn of Ying Yonging comprises the UHMwPE cut staple that stretch broken technology is made by multifibres UHMwPE yarn in the method according to the invention, because the yarn that the wideer fiber length distribution of such cut-out obtains having better mechanical performance.
In certain embodiments, applied spinning yarn is a single-strand spun yarn.In another embodiment, be applied in the method according to this invention as the single-strand spun yarn described in the patent application to be examined jointly of also not announcing.This single-strand spun yarn is made by the cut staple of at least 50 quality %, this cut staple from TENSILE STRENGTH with 16cN/dtex at least, at least 700cN/dtex stretch modulus and at the most the continuous polyolefin multifilament yarn of the every filametntary dawn number (denier) of 18dpf obtain; This cut staple has the average fiber length between 40～180mm; And do not show shrinkage substantially; And this spinning yarn has by 40～100tm -1(m/g) -1/2The twist that characterizes of twist coefficient.Preferably, cut staple obtains such as those fibers based on ultra-high molecular weight polyethylene (UHMwPE) by height-oriented polyamide fiber.The advantage of the method is, with compare from the method for initial EP 0740002 A1 of multifilament yarn, can make translucent monofilament-like product with higher overall productive rate and lower overall cost, wherein, described monofilament-like product for example has 10～100, the low relatively fiber number of preferred 15～50dTex, and has low relatively density.The product that obtains by the method is particularly useful for medical applications, as surgical sewing thread.
According to Koechlin equation: T=α (Nm) 1/2, twist coefficient α characterizes the twist of yarn, and T is expressed as every meter twisting number (tm -1) the twist, and Nm is metric system yarn count (1000/tex, or m/g).This twist coefficient is also referred to as (metric system) twist factor, perhaps twists multiple; For example referring to http://www.fibre2fashion.com/GLOSSARY/glossary17.htm.Preferably, twist coefficient is between 60 and 100, between 65 and 90 or even between 70 and 85.
This single-strand spun yarn shows very little activity, and enough maidenliness to be allowing further processing, and need not at first to make doubled yarn.Cut staple in the single-strand spun yarn by have at the most 18 dawn every (dpf), preferred at the most 14, more preferably at the most 10dpf and even more preferably at the most 6 or at the most the gauze line of the line density of 4dpf obtain.The line density of fiber is low more, and spinning yarn can be thin more, because need the fiber of certain minimum number in cross section, so that the yarn with sufficiently complete to be provided.In addition, under constant denier count as received, low more fiber linear density obtains high more spinning yarn TENSILE STRENGTH.Consider fibre production efficiency, preferably line density is at least 0.2,0.3 or be at least 0.5dpf.Begin to have such advantage from thinner spinning yarn, promptly can produce thinner monofilament-like product in more cost effective mode.
The single-strand spun yarn of Ying Yonging comprises the polyolefin staple fibre that does not show shrinkage substantially in the method according to the invention; This fiber does not have or only by slight veining.Shrinkage is the measuring of bending of fiber, and can be represented as poor between stretched length (the perhaps fibre length of full extension) and the crimped length (i.e. the length of fiber when not having external constraint substantially).Substantially do not show and collapse upon this and be understood that such meaning, promptly the length of the cut staple under not tensioning condition is at least 80% of stretched length.Preferably, crimped length be stretched length at least 90% in addition be more preferably at least 95%.Substantially do not show shrinkage and also be understood that not comprise nonvolatil shrinkage.For example, the UHMwPE cut staple may show some shrinkages, and this shrinkage may be introduced in cutting off manufacture process, but this shrinkage is not nonvolatil because when power that fiber is elongated (for example may appear in the spinning process) its will disappear substantially.
In the method according to the invention, one spinning yarn at least in the presoma for making by polyolefin staple fibre.Presoma can also comprise one or the multiply of being made by other cut staple and/or continuous silk, with obtain having between several strands or among the monofilament-like product of difference fusing degree, and obtain different mechanical performances and outward appearance and feel.Those skilled in the art use common practise or by normal experiment, can carry out such variation.Preferably, all in the presoma strand all are based on the spinning yarn of polyolefin staple fibre, because this allows to change fusing degree, and change the performance of product thus to a great extent.
The method according to this invention can be utilized the presoma of various structures, for example has presoma braided structure or that have plying and twisted construction and finishes.Preferably, use the presoma of thigh with plying and twisting.This has following advantage, promptly can be easier with more save the local presoma of making; And the product of gained shows more performance; Especially in wear test course, show surprising good anti-inefficacy.
The method according to this invention can also comprise the step before the step a), i.e. preliminary treatment presoma or wherein one or multiply are so that improve joint between internal fiber in the fusing step.Such pre-treatment step can comprise with a certain component or composition coating presoma; Scrub presoma, promptly wash surface component off as spin finish etc.; Perhaps application of high voltages plasma or corona treatment.
In one embodiment, come the preliminary treatment presoma by coating, for example (for example by dipping or the mineral oil that soaks into effective dose, heat transfer grade mineral oil with average molar mass of about 250～700), vegetable oil (for example coconut oil) or preferred nonvolatile polyolefin solvent, as paraffin.This pre-treatment step can be carried out under environmental condition, perhaps carries out under the high temperature that reaches the melt temperature scope that is lower than polyamide fiber.
In another embodiment, preliminary treatment comprises to presoma applying coatings composition, said composition can be the solution or the dispersion liquid of polymer, described polymer improves fiber and engages with interfibrous in fusing is being exposed to the process of higher temperature during step, perhaps otherwise improve performance.In a preferred embodiment, presoma is coated with urethane composition, as the dispersion liquid of film forming polyurethane.Such composition can also comprise improving the ABRASION RESISTANCE or the effective component of anti-shearing of monofilament-like product.Improve the small particle particle that is exemplified as high surface hardness of the component of anti-shearing, as mineral particle, ceramic particle, glass, metal etc.Coating composition can also comprise other additive, as colouring agent or stabilizing agent.
The method according to this invention can also be included in step a) and b) afterwards coating composition is coated on the product to form the step of coating.Such coating composition can comprise: typical spin finish is used for easier processing and the processing of carrying out product of operation subsequently; Be used for comprising the process control anchored compound or the composition of the composite object of described product in manufacturing subsequently; Perhaps further improve the integrality of product and the binder compositions of intensity.The latter's typical case comprise polyurethane, as ethylene-acrylic acid copolymer based on polyolefinic copolymer, binder compositions.Coating composition can be used as solution or dispersion liquid is coated.Such composition can also comprise the ABRASION RESISTANCE of further raising monofilament-like product or the component of anti-shearing.Improve the small particle particle that is exemplified as high surface hardness of the component of anti-shearing, as various mineral or ceramic particle.Coating composition can also comprise other additive, as colouring agent or stabilizing agent etc.
Compare as the method for presoma with wherein using continuous gauze line, found that the coating of the coating composition in the method according to this invention is relatively easy and effective.Significantly, at step a) and b) product that obtains afterwards is easier to accept for such coating, if particularly at the fiber of product surface only by partial melting.
The invention still further relates to comprise make by polyolefin staple fibre, the monofilament-like product of the spinning yarn of partial melting at least, this product can obtain by the method according to this invention.This product has unique texture and combines several advantageous properties; It has the translucent appearance of monofilament, and its sense of touch and feel for example are different from polyolefin monofilament shape product or polyolefin monofilament known to EP 0740002 B1.Monofilament-like product according to the present invention shows surprising high anti-breaking property in wear test course, can easily tie a knot, and the product after the knotting shows high intensity reservation.Monofilament-like product according to the present invention shows very high surprisingly TENSILE STRENGTH; Intensity than the initial spinning yarn in the presoma is obviously much higher.Usually, monofilament-like product has 10cN/dtex at least, preferred at least 15,20 or even the TENSILE STRENGTH of 25cN/dtex.For product, find high like this intensity usually based on the presoma that comprises relatively large spinning yarn based on the UHMwPE cut staple.
The monofilament-like product that obtains by the method according to this invention has can be within wide limit, for example from 10 to the 15000dTex line densities (being also referred to as fiber number) that change.Generally, this product has from 30 to 2500dTex fiber number.Product than low-titer is suitable for use as suture etc.Consider as fishing line, the perhaps application of protective garments and cloth, fiber number is preferably from 100 to 1600dTex, more preferably from 200 to 1200dTex.
The invention still further relates to monofilament-like product according to the present invention and make the purposes of various semi-finished product and final products, described semi-finished product and final products such as fishing line; Suture; Fabric; Rope; Complex yarn and they application in article of anti-shearing for example.
The invention still further relates to the semi-finished product and the final products that comprise according to monofilament-like product of the present invention.
To further specify the present invention by following example and contrast experiment now.
Material and method
Multifibres UHMwPE yarn, Dyneema 1760SK60 (DSM High PerformanceFibers, NL) have the fiber number of 1760dTex, the TENSILE STRENGTH of 28cN/dTex, the stretch modulus of 910cN/dTex and the every filametntary dawn number of about 1dpf, and be made into cut staple by for example tension failure technology described in the EP0445872 A1.The average length of cut staple is about 80mm.Cut staple is subsequently by using long cut staple type NSC equipment to be spinned into single-strand yarn.Resulting yarn have about Nm44 (about 255dTex) yarn count, apply and about 80 the corresponding twist of side reaction coefficient (Koechlin rule).This spinning yarn shows activity hardly, as indicated in following: promptly downcut the length of 100cm and with its vertical keeps and only at one end fixing, and almost do not observe the trend of any distortion.Its TENSILE STRENGTH is about 15.0cN/dTex, and stretch modulus is about 153cN/dTex, and elongation at break is about 4.3%.This material is called as SSSY later on.
Utilize the fiber of the nominal measuring length of 500mm, the chuck speed of 50%/min and Instron 2714 anchor clamps, as defined in ASTM D885M, to multifibres and spinning yarn and to the monofilament-like product definition with determine TENSILE STRENGTH (perhaps intensity) (and stretch modulus).For calculating strength, divided by fiber number, described fiber number is as determining by the fiber of weigh 10 meters (perhaps other length) with measured tensile force.Percentage elongation when percentage elongation is the fracture of measuring is represented with the percentage of the original length after the clamping sample.
Knot strength is determined by the intensity that measurement comprises the sample of Palomar knot.Palomar knot is recommended being used for fishing line to be connected to general connection on swivel base, hasp or the hook.The hook eye hole is passed at the two ends of sample, and formed simple overhand knot (overhand knot).Then hook is passed coil and will tie tension.
Knot strength efficiency is calculated as the relative value (%) of measured knotting strength and the ratio of measured TENSILE STRENGTH.
Employing is measured ABRASION RESISTANCE by the ASTM D 3108 described programs that are used for the test of definite thread friction power.Therefore, the thread friction force measuring device of describing in ASTM D 3108 (Yarn Friction Measuring Apparatus) is reequiped, make an end of sample to be tested be fixed on the eccentric mechanism or cam that is rotated by motor, the other end is by load-carrying.In test process, with sample and ceramic eye friction, and the number that circulates till when being determined to sample fails (fracture).The number that is provided is the mean value of at least 5 tests.
Comparative experiment A
As presoma (feed) material, the braided structure that application is made by multifibres gel spun UHMwPE yarn, described UHMwPE yarn have the fiber number of 224dTex, the TENSILE STRENGTH of 39cN/dTex, the stretch modulus of 1250cN/dTex and the every filametntary dawn number of about 1dpf.8 strands of described yarns that this braided structure comprises medium tightness (being expressed as 7.5 picks per centimeter) braiding (are expressed as 8 * 224/7.5; See Table 1).
This braided structure is passed bath of liquid paraffin,, and excessive oil is wiped by between bondedfibre fabric, passing as pre-treatment step.By determining that the quality on this step increases, calculating paraffin content is about 11 quality %.With the constant speed of 10m/min, braided structure is directed to first driven voller top then, enters stove, and remain under 153.3 ℃ the steady temperature.When leaving stove, braided structure is directed into second driven voller top.Regulate the speed of second roller, make 1.9 draw ratio and the rate of extension of 0.7m/min be applied in.Different draw ratios with the situation that is applied under, as in other experiments at some,, the rate of extension in the stove is kept constant by changing the sample pathlength in the stove and the speed of second roller.Stove is equipped with a plurality of rollers, makes that the sample pathlength in the stove can be from 2.8 up to 58.8 meters.
Product appearance changes to almost translucent from initial opaque white color; Its surface is still quite smooth, but compares so smoothless and glossy far and away with starting products.And it is more coarse and firmer that product is felt, is kept at an angle after bending.
Further the result of test is compiled in the table 1.Should be noted that resulting knot strength efficiency is starkly lower than reports for the similar products among EP 0740002 B1; This may be relevant with the type of employed knot.
Contrast experiment B
Carry out this experiment with Comparative experiment A, but by 6 strands of identical multifilament yarns closely similarly, applying 120 changes/centimetre (be expressed as 6/224; Twisted and plied structure is made in clockwise twisting 120Z).The paraffin content of measuring is about 12 quality %; Draw ratio is 1.8.Further the result of test is compiled in the table 1.
Example 1
12 picks/cm that have that comprise 8 strands of above-mentioned SSSY materials (are expressed as 8 * Nm44/12) braided structure and are used as presoma in table 1.Similar to Comparative experiment A, this braided structure by stove, is not still carried out any pre-treatment step and applies 1.0 draw ratio.Products obtained therefrom has and its parent material similar in appearance; It is found has the low TENSILE STRENGTH of using as thigh than originally of spinning yarn.The high intensity that product shows after knotting keeps.
Example 2-3
Repeat example 1, but before step a), add the paraffin of about 12 quality % now, and apply 1.8 and 1.7 draw ratio respectively.The more translucent outward appearance of product shows more fusing has taken place.Surface touch does not have Comparative experiment A so smooth.Two kinds of products obtained therefroms all have the higher TENSILE STRENGTH of spinning yarn that likens to the thigh use, show higher resistance to bend(ing) (firmer) and keep certain angle after bending.For example 2, the number of cycles in wear test course till fracture the time is found Comparative experiment A and exceeds more than 5 times.
Example 4-6
Make by above-mentioned SSSY material, contain 8 strands and braided structure with 9.5 parallels/cm and be used as presoma.Similar to Comparative experiment A, this braided structure by stove, is not still carried out any pre-treatment step and applies 1.0 draw ratio.Products obtained therefrom shows to have and likens the lower TENSILE STRENGTH of using into thigh of spinning yarn to; But can obtain having the knot (example 4) that high intensity keeps.If apply 1.6 or 1.7 draw ratio, TENSILE STRENGTH increases once more, as example 2-3; But ABRASION RESISTANCE is just better a little.Significantly, under the temperature and time condition that is applied, do not carrying out under the pretreated situation, the fusing degree of fiber is high not enough for obtaining high ABRASION RESISTANCE.
Example 7-9
Repeat example 4-6, but add the paraffin of about 13 quality % to presoma.The intensity of having observed with respect to original spun yarn for all samples increases; Example 7 has been confirmed the positive influences of higher fusing degree to ABRASION RESISTANCE.
Example 10-16
Make by above-mentioned SSSY material, contain 8 strands and braided structure with 7.5 parallels/cm and be used as presoma.Example 10 is confirmed not find the increase of TENSILE STRENGTH under 1.0 draw ratio; And do not carry out preliminary treatment and under selected condition, fusing seldom only takes place.As judging, add paraffin and increased the fusing degree with the raising Exposure Temperature from appearance change.From with product anti-fissile test for product when Metallic rod rubs, the fusing of enhancement also is tangible; Example 11 may tolerate 18 motions, and example 12 and 13 can tolerate about 33 motions.In wear-resisting test, 4～5 times increase of the number of cycles when having observed till rupturing.For this precursor construction, higher temperature or draw ratio do not cause the further raising of tensile property.
Example 17
Single-strand spun yarn SSSY is used as presoma.Preliminary treatment comprises by the dip coating aqueous polyurethane dispersing liquid, L9010 ex GOVI (BE).Polyurethane content is confirmed as (on products obtained therefrom) about 15 quality %.Preliminary treatment, be heated and obviously increased the TENSILE STRENGTH of product with the combination that draw ratio 1.6 stretches.Product also has higher rigidity, more transparent outward appearance, and can easily obtain having the knot that high intensity keeps.
Example 18-22
As presoma, use based on SSSY, having 120 changes/centimetre 6 strands of yarns of clockwise twisting (be expressed as 6/Nm44; 120Z).In example 19, the paraffin that adds about 13.5 quality % is as preliminary treatment, in conjunction with 1.8 draw ratio.In wear test course, this fusing product shows extraordinary anti-breaking property; Improve about 15 times with respect to contrast experiment B.Carried out pretreated sample (the example 20-22 of polyurethane; The about 16 quality % of polyurethane content) show extraordinary tensile property and knotting strength (efficient), and improved ABRASION RESISTANCE.
Example 23-24
Product is based on 18 strands of twist yarns of the paraffin with about 12.5 quality % (initial thigh is SSSY), and makes under the condition similar to the front.For these have respectively about 4100 and the resulting result of thicker product of 2500dTex fiber number consistent with other result.
Table 1
Persursor material Technology characteristics Properties of product
Type Structure Pre-treatment Temperature (℃) Draw ratio TENSILE STRENGTH (cN/dTex) Percentage elongation (%) Knotting strength (cN/dTex) Knot strength efficiency (%) ABRASION RESISTANCE (fracture period)
Comparative experiment A Braiding; The continuous yarn yarn ??8×224/7.5 Paraffin ??153.5 ??1.9 ??27.9 ??3.8 ??15.2 ??54 ?5998
Example 1 Braiding ??8×Nm44/12 No ??153.5 ??1.0 ??10.8 ??6.0 ??8.1 ??75
Example 2 Braiding ??8×Nm44/12 Paraffin ??153.5 ??1.8 ??17.2 ??2.1 ??9.2 ??54 ?32998
Example 3 Braiding ??8×Nm44/12 Paraffin ??153.5 ??1.7 ??16.5 ??2.1
Example 4 Braiding ??8×Nm44/9.5 No ??153.5 ??1.0 ??12.9 ??4.5 ??10.5 ??81
Example 5 Braiding ??8×Nm44/9.5 No ??153.5 ??1.6 ??22.4 ??2.8 ??14.9 ??67 ?7828
Example 6 Braiding ??8×Nm44/9.5 No ??153.5 ??1.7 ??22.2 ??2.5
Example 7 Braiding ??8×Nm44/9.5 Paraffin ??153.5 ??1.6 ??20.2 ??2.5 ?25171
Example 8 Braiding ??8×Nm44/9.5 Paraffin ??153.5 ??1.7 ??16.7 ??2.0
Example 9 Braiding ??8×Nm44/9.5 Paraffin ??153.5 ??1.8 ??18.5 ??2.0
Example 10 Braiding ??8×Nm44/7.5 No ??153.5 ??1.0 ??11.5 ??4.4
Example 11 Braiding ??8×Nm44/7.5 Paraffin ??153.5 ??1.6 ??20.1 ??2.5 ??11.9 ??59 ?26234
Example 12 Braiding ??8×Nm44/7.5 Paraffin ??154.0 ??1.6 ??18.1 ??2.7
Example 13 Braiding ??8×Nm44/7.5 Paraffin ??154.0 ??1.6 ??17.1 ??2.4 ?30620
Example 14 Braiding ??8×Nm44/7.5 Paraffin ??155.0 ??1.6 ??16.8 ??2.7
Persursor material Technology characteristics Properties of product
Type Structure Pre-treatment Temperature (℃) Draw ratio TENSILE STRENGTH (cN/dTex) Percentage elongation (%) Knotting strength (cN/dTex) Knot strength efficiency (%) ABRASION RESISTANCE (fracture period)
Example 15 Braiding ??8×Nm44/7.5 Paraffin ??153.5 ??1.7 ??19.8 ??2.2
Example 16 Braiding ??8×Nm44/7.5 Paraffin ??153.5 ??1.8 ??18.6 ??2.1
Comparative examples B Braiding twisting; The continuous yarn yarn ??6/224；120Z Paraffin ??153.5 ??1.8 ??29.4 ??3.9 ??17.5 ??60 ?6868
Example 17 Single-strand yarn ??Nm44 Polyurethane ??153.5 ??1.6 ??21.4 ??2.1 ??17.1 ??80
Example 18 Plying; Twisting ??6/Nm44；120Z No ??153.5 ??1.0 ??14.8 ??4.0
Example 19 Plying; Twisting ??6/Nm44；120Z Paraffin ??153.5 ??1.8 ??18.5 ??2.2 ??15.2 ??82 ?＞100000
Example 20 Plying; Twisting ??6/Nm44；120Z Polyurethane ??153.5 ??1.6 ??23.8 ??2.5
Example 21 Plying; Twisting ??6/Nm44；120Z Polyurethane ??153.5 ??1.7 ??27.3 ??2.9 ??21.5 ??79 ?24580
Example 22 Plying; Twisting ??6/Nm44；120Z Polyurethane ??153.5 ??1.8 ??24.1 ??2.5
Example 23 Plying; Twisting ??18/Nm44；120Z No ??153.5 ??1.0 ??14.5 ??4.8
Example 24 Plying; Twisting ??18/Nm44；120Z Paraffin ??153.5 ??1.6 ??19.1 ??2.8

Claims (11)

1. method of making monofilament-like product by the presoma that contains one polyamide fiber at least, described method comprises following step: a) described presoma is exposed to the temperature time enough that is in the described polyolefin melting range, so that adjacent fiber partial melting at least; And b) with at least 1.0 the draw ratio described presoma that side by side stretches, it is characterized in that described strand is the spinning yarn of being made by polyolefin staple fibre.
2. the method for claim 1, wherein said draw ratio is 1.2 to 25.
3. as each described method in the claim 1 to 2, wherein said polyolefin is a ultra-high molecular weight polyethylene.
4. as each described method in the claim 1 to 3, wherein said cut staple obtains by the tension failure of polyolefin multifilament yarn.
5. method according to any one of claims 1 to 4, wherein said presoma comprises the thigh of some plying and twisting.
6. as each described method in the claim 1 to 5, also be included in the step a) described presoma of preliminary treatment before to promote the step that internal fiber engages.
7. method as claimed in claim 6, wherein, pre-treatment step comprises to described presoma and is coated with unction.
8. method as claimed in claim 6, wherein, pre-treatment step comprises to described presoma polyurethane coating composition.
9. as each described method in the claim 1 to 8, also be included in after step a) and the step b) step to described product applying coatings composition.
10. comprise the monofilament-like product of the spinning yarn of being made by polyolefin staple fibre of partial melting at least, it is by obtaining according to each the described method in the claim 1 to 9.
11. monofilament-like product according to claim 10 is used to make as the various semi-finished product of fishing line or the object of anti-shearing the and the purposes of final products.
CN2003801013009A 2002-10-10 2003-10-10 Process for making a monofilament-like product,and monofilament-like product use Expired - Fee Related CN1703546B (en)

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