High surface area grouping

Abstract

Disclosed herein is a filamentary braid comprising a plurality of interwoven filament elements, the filament elements including one or more main filament elements and one or more loop filament elements. The loop filament elements are arranged in one or more loop-like configurations extending outward from a longitudinal axis formed by the main filament elements. The loop filament elements are made of fibers having a tensile modulus of 2.3 GPa or greater. When selective tension is applied to the loop filament elements, the loop filament elements are (i) collapsible relative to the main filament elements within the filamentary braid and / or (ii) removable from the filamentary braid.

Description

[Technical Field]

[0001] This application relates generally to materials technology, and more specifically to braids including filament elements. More specifically, this application discloses a filamentary braid including a plurality of interwoven filament elements, the filament elements including one or more main filament elements and one or more loop filament elements. The loop filament elements provide the filamentary braid with a higher surface area than a filamentary braid without the loop filament elements. The filamentary braids disclosed herein are useful in applications where slippage of the filamentary braid is undesirable, such as surgical sutures. [Background technology]

[0002] Barbed sutures are known and can reduce slippage compared to non-barbed sutures. For example, U.S. Patent No. 9,044,224 describes a barbed suture formed by inserting a monofilament segment into a multifilament elongate body. A portion of the monofilament segment extends beyond the outer surface of the multifilament elongate body to form barbs on the suture. Similarly, U.S. Patent No. 10,786,243 describes a barbed suture formed from a flocking process that bonds individual barbs to the woven yarn. Bonding can be achieved by fusion welding, application of an adhesive, ultrasonic welding, or lamination.

[0003] However, manufacturing such barbed sutures is complicated, in part because the barbs are not formed from filaments that are integral to the braid of the suture. Instead, the barbs are inserted into or glued onto the braided filaments that form the suture. Alternatively, barbs can be created by cutting an incision in the monofilament and lifting the incision away from the central axis of the filament. This complicates the manufacturing process for such barbed sutures.

[0004] Meanwhile, U.S. Patent Application Publication No. 2010 / 0298872 describes braided sutures containing protruding loops, which can be formed from filaments of a filamentary braid. These braided sutures can be manufactured by continuous braiding, with the loops formed by overfeeding each filament. Thus, these loops can be formed from filaments integrated into the suture braid. This simplifies the manufacturing of the suture compared to methods requiring the insertion or bonding of separate barbs.

[0005] However, whether the barbs / loops are formed from an integral filament or an external filament, all of these sutures can be difficult to insert into a patient. For example, if the suture is made of a non-dissolving material, the removal method must be considered before inserting the suture, as barbed sutures may only be removed in the direction opposite the tip of the barb.

[0006] There remains a need for improved filamentary braids that have sufficient grip strength for use as sutures without the above-mentioned drawbacks of being complex to manufacture and difficult to remove. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] U.S. Patent No. 9,044,224 [Patent Document 2] U.S. Patent No. 10,786,243 [Patent Document 3] US Patent Application Publication No. 2010 / 0298872 Summary of the Invention [Problem to be solved by the invention]

[0008] The present inventors have recognized that a need exists to develop a filamentary braid that has an increased surface area for improved grip, which is relatively simple to manufacture and relatively convenient to remove when no longer needed for a particular application. [Means for solving the problem]

[0009] The following disclosure describes the preparation and utility of filamentary braids that include looped filament elements that are collapsible and / or removable from the filamentary braid.

[0010] Embodiments of the present disclosure are described herein to enable one of ordinary skill in the art to make and use them, and include: (1) One aspect is: A filamentary braid comprising a plurality of interwoven filament elements, the filament elements include one or more main filament elements and one or more loop filament elements; the looped filament elements are arranged in one or more looped configurations extending outward from a longitudinal axis defined by the main filament element; The looped filament element is made of a fiber having a tensile modulus of 2.3 GPa or more; When selective tension is applied to the looped filament element, the looped filament element is (i) collapsible relative to the main filament element within the filamentary braid and / or (ii) removable from the filamentary braid. (2) Another aspect relates to a method for producing such a filamentary braid by braiding multiple bobbins, at least one of which is operated at a lower tension and / or a higher feed rate than the other bobbins, to form looped filament elements.

[0011] Additional objects, advantages, and other features of the present disclosure will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned from the practice of the present disclosure. The present disclosure encompasses other embodiments than those specifically described below, and the details herein can be modified in various respects without departing from the present disclosure. In this regard, it should be understood that the description herein is illustrative in nature and not restrictive.

[0012] Embodiments of the present disclosure are explained in the following description in view of the figures. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic diagram of an exemplary embodiment of a filamentary braid, showing looped filament elements arranged in a looped configuration extending outward from a longitudinal axis formed by a main filament element. [Figure 2] FIG. 2 is a schematic diagram of a filamentary braid in which selective tension is applied to looped filament elements, causing the looped filament elements to fold relative to the main filament elements. [Figure 3] FIG. 3 is a schematic illustration of a filamentary braid in which selective tension has been applied to a looped filament element and the looped filament element has been removed from the filamentary braid. [Figure 4] FIG. 4 is a schematic diagram of a filamentary braid in which the looped filament elements are partially, but not completely, folded. [Figure 5] FIG. 5 is a schematic diagram of a 12-carrier braiding apparatus capable of producing the filamentary braids of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0014] Embodiments of the present disclosure include various filamentary braids and methods of making filamentary braids.

[0015] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the relevant art. In case of conflict, the present specification, including definitions, will control.

[0016] Unless otherwise specified, all percentages, parts, ratios, etc. are by weight.

[0017] When an amount, concentration, or other value or parameter is given as a range or a list of upper and lower limits, this should be understood to specifically disclose all ranges formed from any pair of upper and lower limits, whether or not the range is individually disclosed. When a range of numerical values ​​is described herein, unless otherwise specified, the range is intended to include its endpoints, and all integers and fractions within the range. It is not intended to limit the scope of the present disclosure to the specific values ​​recited when defining the range.

[0018] The use of "a" or "an" herein to describe various elements and components is merely for convenience and to give a general sense of the disclosure. The description should be read to include one or at least one, and the singular also includes the plural, unless it is clear that something else is intended.

[0019] Unless expressly stated to the contrary, "or" and "and / or" refer to an inclusive condition and not an exclusive condition. For example, a condition "A or B" or "A and / or B" is satisfied by any one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), or both A and B are true (or present).

[0020] The terms "about" and "approximately" as used herein refer to being approximately the same as a referenced amount or value and should be understood to encompass ±5% of the specified amount or value.

[0021] As used herein, unless otherwise defined, the term "substantially" means all or nearly all, or the majority, as would be understood by one of ordinary skill in the art in the context in which it is used. It is intended to account for reasonable variations from 100% that would normally occur in industrial or commercial scale situations.

[0022] Throughout this specification, unless otherwise defined or described, the technical terms and methods used to measure relevant measurements are as described in ASTM D855 / D885M-10A, Standard Test Methods for Tire Cords, Tire Cord Fabrics, and Industrial Filament Yarns Made From Man-made Organic-base Fibers, published October 2014.

[0023] For convenience, many elements of the various embodiments disclosed herein are discussed separately. While lists of options are provided and numerical values ​​may be within ranges, the disclosure should not be considered limited to the individually described lists or ranges. Unless otherwise stated, every combination possible within the disclosure should be considered explicitly disclosed for all purposes.

[0024] The materials, methods, and examples herein are illustrative only and, except as specifically stated, are not intended to be limiting. Methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure.

[0025] <Filament braid> Embodiments described herein include a filamentary braid including a plurality of interwoven filament elements. The filament elements include one or more main filament elements and one or more loop filament elements. The loop filament elements are arranged in one or more loop-like configurations extending outward from a longitudinal axis formed by the main filament elements. The loop filament elements are made of fibers having a tensile modulus of 2.3 GPa or greater. When selective tension is applied to the loop filament elements, the loop filament elements are (i) collapsible relative to the main filament elements within the filamentary braid and / or (ii) removable from the filamentary braid.

[0026] As used herein, a "filament element" may be a monofilament fiber or a multifilament fiber, including, but not limited to, multiple filaments that have been combined into a multifilament, for example, by twisting or braiding the individual filaments to form the multifilament.

[0027] As used herein, a "primary filament element" is a filament element that forms the braided structure of a filamentary braid by contact with other filament elements along substantially the entire length of the filamentary braid. The interwoven primary filament elements form a longitudinal axis generally along the direction in which the braid is formed.

[0028] In contrast, "looped filament elements" are filament elements arranged in one or more looped structures that extend outward from the longitudinal axis defined by the main filament elements. This outward extension allows the looped filament elements to contact the main filament elements over substantially less than the entire length of the filament braid.

[0029] FIG. 1 is a schematic diagram of an exemplary embodiment of a filamentary braid. In FIG. 1, the filamentary braid 5 includes a plurality of filament elements. The filament elements include a main filament element 10 and a looped filament element 15. The looped filament element 15 extends outward from a longitudinal axis 20 defined by the main filament element 10. As seen in FIG. 1, the looped filament element 15 includes a portion that contacts one or more main filament elements 10 and a portion that does not contact one or more main filament elements 10. The portion of the looped filament element 15 that does not contact the main filament element 10 generally corresponds to the looped structure extending outward from the longitudinal axis 20 defined by the main filament element 10. Thus, the looped filament element 15 contacts the main filament element 10 over substantially less than the entire length of the filamentary braid 5.

[0030] FIG. 2 is a schematic diagram of a filamentary braid 5 in which selective tension is applied to looped filament elements 15, with the looped filament elements 15 folded relative to the main filament elements 10. "Selective tension" refers to tension applied to one or more of the looped filament elements 15 that is different from the tension applied to one or more of the main filament elements 10. For example, such selective tension can be (i) tension applied to one or more looped filament elements 15 without simultaneously applying tension to one or more main filament elements 10, or (ii) tension applied to one or more looped filament elements 15 that is greater than the tension simultaneously applied to one or more main filament elements 10. The folding of the looped filament elements 15 relative to the main filament elements 10 can be a complete folding, such that the looped filament elements 15 are in contact with the main filament elements 10 along substantially the entire length of the filamentary braid 5. Alternatively, the folding of the looped filament element 15 relative to the main filament element 10 may be less than complete, such that the looped filament element 15 remains in contact with the main filament element 10 over substantially less than the entire length of the filament braid 5, but in more contact than before folding, as discussed in more detail below with respect to FIG. 4.

[0031] 3 is a schematic diagram of a filamentary braid 5 with selective tension applied to looped filament elements 15 and the looped filament elements 15 removed from the filamentary braid 5. As in FIG. 2, "selective tension" refers to tension applied to one or more of the looped filament elements 15 that is different from the tension applied to one or more of the main filament elements 10, such as (i) tension applied to one or more looped filament elements 15 without simultaneously applying tension to one or more main filament elements 10, or (ii) tension applied to one or more looped filament elements 15 that is greater in magnitude than the tension simultaneously applied to one or more main filament elements 10.

[0032] 4 is a schematic diagram of a filamentary braid in which the looped filament elements are partially, but not completely, folded. In this embodiment, r1 is the radius of the looped filament elements when no tension is applied (or when the applied tension is less than the tension required to overcome static friction between the looped filament elements and the main filament elements), and r2 is the radius after overcoming static friction. Similarly, F1 is the tensile force of the looped filament elements when no tension is applied (and / or when the applied tension is less than the tension required to overcome static friction), and F2 is the tensile force after overcoming static friction.

[0033] When selective tension is applied to the looped filament element, the looped filament element can (i) collapse relative to the main filament element within the filamentary braid and / or (ii) be removed from the filamentary braid. The amount of selective tension required to collapse the looped filament element relative to the main filament element or to remove the looped filament element from the filamentary braid may vary depending on factors such as the composition of the filament element, the size (diameter and length) of the filament element, and the number of filament elements within the filamentary braid. The applied tension must be low enough to avoid damage to the filamentary braid. Such damage may occur, for example, by applying tension that exceeds the yield load of the looped filament element, thereby causing the looped filament element to stretch before (i) it collapses relative to the main filament element and / or (ii) it is removed from the filamentary braid. In the schematic diagram of FIG. 4, this means that the tension force F2 must be less than the yield load of the looped filament element. In some embodiments, the magnitude of the selective tension required to collapse the looped filament element relative to the main filament element or to remove the looped filament element from the filamentary braid can be at least 50 grams (weight), at least 100 grams, at least 200 grams, at least 300 grams, at least 400 grams, at least 500 grams, at least 600 grams, at least 700 grams, at least 800 grams, at least 900 grams, or at least 1000 grams.In some embodiments, the amount of selective tension required to collapse a looped filament element relative to a main filament element or to remove a looped filament element from a filamentary braid (without damaging the braid) can be up to 2500 grams, up to 2000 grams, up to 1500 grams, up to 1000 grams, up to 900 grams, up to 800 grams, up to 700 grams, up to 600 grams, up to 500 grams, up to 400 grams, up to 300 grams, up to 200 grams, or up to 100 grams.

[0034] To aid in selectively tensioning the looped filament element, the looped filament element may be a different color than the main filament element. In such embodiments, the degree of color difference is such that a person with normal vision can distinguish the looped filament element from the main filament element with the naked eye (i.e., unaided) or with optical aids such as a magnifying glass or microscope. The color difference can be, but need not be, a difference in hue. The color difference may also be a difference in grayscale, such as black vs. white, gray vs. white, gray vs. black, or dark gray vs. light gray. In another embodiment, the looped filament element may have a difference in radiopacity relative to the main filament element. Such a difference in radiopacity allows the looped filament element to be distinguished from the main filament element using radio wave and / or x-ray imaging techniques.

[0035] The looped filament element of the present application is made of a fiber having a tensile modulus of 2.3 GPa or greater. The tensile modulus is preferably at least 3.0 GPa, at least 4.0 GPa, at least 5.0 GPa, at least 6.0 GPa, at least 7.0 GPa, at least 8.0 GPa, at least 9.0 GPa, at least 10 GPa, at least 15 GPa, at least 20 GPa, at least 25 GPa, at least 30 GPa, at least 35 GPa, at least 40 GPa, at least 45 GPa, at least 50 GPa, at least 55 GPa, at least 60 GPa, at least 65 GPa, at least 70 GPa, or at least 75 GPa. The tensile modulus is preferably at most 200 GPa, at most 150 GPa, at most 125 GPa, at most 100 GPa, at most 95 GPa, at most 90 GPa, at most 85 GPa, or at most 80 GPa. When the tensile modulus is within the above range, the looped filament element can be collapsed relative to the main filament element in the filamentary braid and / or removed from the filamentary braid by applying a selective tension that typically does not exceed the yield strength of the fibers. Conversely, if the tensile modulus (and corresponding yield strength) of the fibers comprising the looped filament element is too low, the selective tension applied to collapse or remove the looped filament element may break or damage the looped filament element before it can be collapsed or removed.

[0036] The tensile modulus of the main filament element of the present application is not particularly limited. The tensile modulus of the main filament element may be different from the tensile modulus of the looped filament element. In some embodiments, the tensile modulus of the main filament element may be greater than the tensile modulus of the looped filament element. In other embodiments, the tensile modulus of the main filament element may be less than the tensile modulus of the looped filament element. The main filament element may be made of a fiber having a tensile modulus of less than 2.3 GPa or a tensile modulus of 2.3 GPa or greater. The tensile modulus of the fibers of the primary filament element may be at least 3.0 GPa, at least 4.0 GPa, at least 5.0 GPa, at least 6.0 GPa, at least 7.0 GPa, at least 8.0 GPa, at least 9.0 GPa, at least 10 GPa, at least 15 GPa, at least 20 GPa, at least 25 GPa, at least 30 GPa, at least 35 GPa, at least 40 GPa, at least 45 GPa, at least 50 GPa, at least 55 GPa, at least 60 GPa, at least 65 GPa, at least 70 GPa, or at least 75 GPa. The tensile modulus is preferably at most 200 GPa, at most 150 GPa, at most 125 GPa, at most 100 GPa, at most 95 GPa, at most 90 GPa, at most 85 GPa, or at most 80 GPa.

[0037] Fibers having a tensile modulus of 2.3 GPa or greater preferably contain liquid crystal polymer (LCP) filaments. LCP filaments include lyotropic and thermotropic polymer filaments. Lyotropic polymers decompose before melting, but form liquid crystals in solution under appropriate conditions (these polymers are typically solution-spun). Lyotropic polymer filaments include, for example, aramid and poly(p-phenylene benzobisoxazole) (PBO) filaments, as well as copolymer aramid filaments. Aramid filaments are commercially available from DuPont under the tradename KEVLAR® and from Teijin Limited under the tradename TWARON®. Copolymer aramid filaments are commercially available from Teijin Limited under the tradename TECHNORA®. PBO fibers are commercially available from Toyobo Co., Ltd. under the tradename ZYLON®. Thermotropic polymers exhibit liquid crystal formation in the molten state. An example of a thermotropic filament is an aromatic polyester formed by polycondensation of 4-hydroxybenzoic acid and 6-hydroxynaphthalene-2-carboxylic acid (commercially available from Kuraray Co., Ltd. under the trade name VECTRAN®).

[0038] The looped filament element preferably comprises one or more LCP filaments. The main filament element may also comprise one or more LCP filaments. A difference in surface friction between the looped filament element and the main filament element is preferred. That is, the looped filament element may have a lower surface friction than the main filament element, and conversely, the main filament element may have a lower surface friction than the looped filament element. This difference in surface friction between the looped filament element and the main filament element facilitates folding and / or removal of the looped filament element. This difference in surface friction can be achieved by using a filament element with a low-friction coating as the low-friction filament element.

[0039] In some embodiments, the looped filament element can include non-LCP filaments, so long as the fibers comprising the looped filament element have a tensile modulus of 2.3 GPa or greater. Such non-LCP filaments include, but are not limited to, polyetheretherketone filaments (100-200 MPa), ultra-high molecular weight polyethylene filaments, high modulus polyethylene (HMPE) filaments, polypropylene (1.5 GPa) filaments, polyethylene terephthalate filaments (27 MPa), polyamide filaments, high-strength polyvinyl alcohol (1.7 GPa) filaments, polyhydroquinone diimidazopyridine (PIPD) filaments, and combinations thereof, to name just a few. In some embodiments, one type of non-LCP filament can be used. In other embodiments, two or more types of non-LCP filaments can be used. In still other embodiments, certain types of non-LCP filaments are excluded from the looped filament element. For example, the looped filament element may not include HMPE filaments.

[0040] In some embodiments, the primary filament element may include non-LCP filaments. Examples of such non-LCP filaments include, but are not limited to, polyetheretherketone filaments, ultra-high molecular weight polyethylene filaments, high modulus polyethylene (HMPE) filaments, polypropylene filaments, polyethylene terephthalate filaments, polyamide filaments, high-strength polyvinyl alcohol filaments, polyhydroquinone diimidazopyridine (PIPD) filaments, and combinations thereof, to name just a few. In some embodiments, one type of non-LCP filament may be used. In other embodiments, two or more types of non-LCP filaments may be used. In still other embodiments, certain types of non-LCP filaments are excluded from the primary filament element. For example, the primary filament element may not include HMPE filaments.

[0041] Polymerized units for LCP and non-LCP filaments can include those shown in Table 1. [Table 1]

[0042] With respect to the polymerized units exemplified in Table 1 above, the number of Y substituents is equal to the maximum number of substitutable positions in the ring structure, and each Y independently represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (e.g., an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, or a t-butyl group), an alkoxy group (e.g., a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, etc.), an aryl group (e.g., a phenyl group, a naphthyl group, etc.), an aralkyl group [e.g., a benzyl group (phenylmethyl group), a phenethyl group (phenylethyl group), etc.], an aryloxy group (e.g., a phenoxy group), an aralkyloxy group (e.g., a benzyloxy group), or a mixture thereof.

[0043] LCP filaments can be obtained by melt-spinning a liquid crystalline polyester resin. The spun filaments can be further heat-treated to enhance their mechanical properties. The liquid crystalline polyester may be composed of repeating polymerized units derived from, for example, an aromatic diol, an aromatic dicarboxylic acid, or an aromatic hydroxycarboxylic acid. The liquid crystalline polyester may optionally further contain polymerized units derived from an aromatic diamine, an aromatic hydroxyamine, and / or an aromatic aminocarboxylic acid.

[0044] More specific examples of polymerized units are shown in the structures shown in Tables 2 to 4 below.

[0045] When the polymerized unit in the formula is a unit that can represent multiple structures, two or more units can be used in combination as the polymerized unit that constitutes the polymer.

[0046] In the polymerization units in Tables 2, 3, and 4, n is an integer of 1 or 2. Each unit n=1 and n=2 may exist alone or in combination. Y1 and Y2 are each independently a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (e.g., an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, or a t-butyl group), an alkoxy group (e.g., a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, etc.), an aryl group (e.g., a phenyl group, a naphthyl group, etc.), an aralkyl group (e.g., a benzyl group (phenylmethyl group), a phenethyl group (phenylethyl group), etc.), an aryloxy group (e.g., a phenoxy group), an aralkyloxy group (e.g., a benzyloxy group), or a mixture thereof. Of these groups, Y is preferably a hydrogen atom, a chlorine atom, a bromine atom, or a methyl group.

[0047] [Table 2]

[0048] [Table 3]

[0049] [Table 4]

[0050] Z in (14) of Table 3 can include a divalent group represented by the following formula: [ka]

[0051] In some embodiments, the liquid crystalline polyester may be a combination containing a naphthalene skeleton as a polymerized unit. In particular, it may contain both polymerized units (A) derived from 4-hydroxybenzoic acid and polymerized units (B) derived from 6-hydroxynaphthalene-2-carboxylic acid. For example, the units (A) may be represented by formula (A), and the units (B) may be represented by formula (B). From the viewpoint of improving melt moldability, the ratio of the units (A) to the units (B) may be in the range of 9 / 1 to 1 / 1, preferably 7 / 1 to 1 / 1, and more preferably 5 / 1 to 1 / 1. [ka]

[0052] The total of the polymerized units (A) and the polymerized units (B) may be, for example, about 65 mol % or more, about 70 mol % or more, or about 80 mol % or more, based on the total polymerized units. In some embodiments, the filaments may comprise a liquid crystalline polyester containing about 4 to about 45 mol % of the polymerized units (B) in the polymer.

[0053] Commercially available LCP filaments of the present disclosure can include VECTRAN® HT BLACK manufactured by Kuraray Co., Ltd., VECTRAN® HT manufactured by Kuraray Co., Ltd., SIVERAS® manufactured by Toray Industries, Inc., monofilament manufactured by ZEUS Corporation, and ZXION® manufactured by KB Seiren Co., Ltd.

[0054] According to the present disclosure, "aramid filaments" refer to polyamide filaments that have high heat resistance and high strength and contain a molecular skeleton composed of aromatic (benzene) rings. Aramid filaments can be classified into para-aramid filaments and meta-aramid filaments based on their chemical structure.

[0055] Examples of commercially available aramid filaments and copolymer aramid filaments include para-aramid filaments, such as KEVLAR® manufactured by DuPont, HERACRON® manufactured by Kolon, and TWARON® manufactured by Teijin Limited; and meta-aramid filaments, such as NOMEX® manufactured by DuPont and CONEX® manufactured by Teijin Limited.

[0056] In some embodiments, the lyotropic LCP filaments can include one or more copolymer aramid filaments. For example, in some embodiments, the lyotropic LCP filaments include copolyparaphenylene / 3,4'-oxydiphenylene terephthalamide filaments. This material is conventionally referred to as Technora® and is available from Teijin Limited.

[0057] Polyparaphenylene benzobisoxazole (poly(p-phenylene-2,6-benzobisoxazole (PBO)) filaments are commercially available as ZYLON® AS and ZYLON® HM manufactured by Toyobo Co., Ltd.

[0058] Commercially available non-LCP filaments include polyetheretherketone (PEEK) materials such as VICTREX™ PEEK polymer.

[0059] Other non-LCP filaments include ultra-high molecular weight polyethylene filaments, which may have an intrinsic viscosity ranging from about 5.0, or about 7.0, or about 10, to about 30, or about 28, or about 24 dL / g.

[0060] ASTM standards (e.g., Test Methods D789, D1243, D1601, and D4603, and Code of Practice D3591) are available that describe dilute solution viscosity procedures for certain polymers, such as nylon, polyvinyl chloride, polyethylene, and polyethylene terephthalate. Typically, the polymer is dissolved in a dilute solution and the drop time through a capillary tube is measured at a specific temperature in comparison to a control sample.

[0061] The weight average molecular weight of the ultra-high molecular weight polyethylene filaments may be from about 700,000, or about 800,000, or about 900,000, to about 8,000,000, or about 7,000,000, or about 6,000,000.

[0062] Since it is difficult to measure the weight average molecular weight of ultra-high molecular weight polyethylene filaments by the GPC method, the weight average molecular weight can be calculated based on the intrinsic viscosity value using the following equation described in "Polymer Handbook, Fourth Edition, Chapter 4 (John Wiley, 1999)": Equation 1

[0063] JPEG2025541858000008.jpg17155

[0064] In some embodiments, it may be preferable for the repeating units of the ultra-high molecular weight polyethylene filaments to substantially contain ethylene. However, in addition to ethylene homopolymers, copolymers of ethylene with small amounts of other monomers, such as α-olefins, acrylic acid and its derivatives, methacrylic acid and its derivatives, and vinylsilane and its derivatives, may also be used. The polyethylene filaments may have a partially crosslinked structure. The polyethylene filaments may also be blends of high-density polyethylene and ultra-high molecular weight polyethylene, low-density polyethylene and ultra-high molecular weight polyethylene, or high-density polyethylene, low-density polyethylene and ultra-high molecular weight polyethylene. The polyethylene filaments may be a combination of two or more ultra-high molecular weight polyethylenes having different weight-average molecular weights or two or more polyethylenes having different molecular weight distributions.

[0065] Commercially available ultra-high molecular weight polyethylene filaments include DYNEEMA® SK60, DYNEEMA® SK, IZANAS® SK60, and IZANAS® SK71 manufactured by Toyobo Co., Ltd., and SPECTRA FIBER® 900 and SPECTRA FIBER® 1000 manufactured by Honeywell.

[0066] These ultra-high molecular weight polyethylene filaments can be used alone or in combination.

[0067] In some embodiments, the LCP filaments in the looped filament element and / or the main filament element have a size of at least 1.0 denier per filament (dpf), at least 2.5 dpf, at least 5 dpf, at least 10 dpf, at least 15 dpf, at least 20 dpf, at least 25 dpf, at least 30 dpf, at least 35 dpf, or at least 40 dpf. In some embodiments, the LCP filaments have a size of up to 100 dpf, up to 90 dpf, up to 80 dpf, up to 70 dpf, up to 60 dpf, up to 50 dpf, up to 40 dpf, up to 35 dpf, up to 30 dpf, up to 25 dpf, up to 20 dpf, up to 15 dpf, or up to 10 dpf.

[0068] Preferably, when the LCP filaments are present in a multifilament fiber, the LCP filaments have a size of at least 1.0 dpf. Alternatively, when the LCP filaments are present in a monofilament fiber, the LCP filaments preferably have a size of at least 10 dpf.

[0069] In some embodiments, each multifilament fiber contains at least 5 LCP filaments, at least 10 LCP filaments, at least 15 LCP filaments, at least 25 LCP filaments, at least 50 LCP filaments, at least 100 LCP filaments, at least 200 LCP filaments, at least 500 LCP filaments, at least 1000 LCP filaments, or at least 2000 LCP filaments. In some embodiments, each multifilament fiber contains up to 5000 LCP filaments, up to 2000 LCP filaments, up to 1000 LCP filaments, up to 500 LCP filaments, up to 200 LCP filaments, up to 100 LCP filaments, up to 50 LCP filaments, or up to 25 LCP filaments.

[0070] In some embodiments, the filamentary braid has a cross-sectional diameter of at least 0.02 mm, at least 0.03 mm, at least 0.05 mm, at least 0.07 mm, at least 0.10 mm, at least 0.15 mm, at least 0.20 mm, at least 0.25 mm, at least 0.30 mm, at least 0.40 mm, at least 0.50 mm, at least 0.60 mm, or at least 0.70 mm. In some embodiments, the filamentary braid has a cross-sectional diameter of at most 0.80 mm, at most 0.70 mm, at most 0.60 mm, at most 0.50 mm, at most 0.40 mm, at most 0.35 mm, at most 0.30 mm, at most 0.25 mm, at most 0.20 mm, at most 0.15 mm, at most 0.10 mm, at most 0.07 mm, at most 0.05 mm, or at most 0.03 mm.

[0071] In some embodiments, the filamentary braid is a sheath that surrounds the core. Such embodiments may be referred to as a cord that includes a filamentary braid that surrounds the core. In other embodiments, the filamentary braid does not surround the core.

[0072] <Method for manufacturing filament braid> Embodiments described herein include methods of making the filamentary braids disclosed above, which typically involve braiding using multiple bobbins, at least one of which is operated at a lower tension and / or a higher feed rate than the other bobbins to form looped filament elements.

[0073] FIG. 5 illustrates one embodiment of a braiding device 130 that can be used to manufacture a filamentary braid of the present disclosure. The braiding device 130 includes a main housing 135 that rotates during operation and carries twelve carriers 140 that move independently along the top surface of the main housing 135 in a circular carrier path 145 that allows the carriers 140 to follow a continuous "figure-eight" pattern. Each carrier 140 includes a bobbin 150 that can dispense a filament bundle 155 via a guide 160 that directs the filament bundle 155 toward a central take-up shaft 165 that is controlled for axial movement by a take-up shaft moving mechanism 170. While FIG. 5 illustrates a pull-off direction for each bobbin 150, a roll-off direction for each bobbin 150 can also be used.

[0074] Aside from modifications that may be made to the braiding device 130 to enable more efficient formation of looped filament elements, the braiding device 130 functions in a similar manner as compared to conventional braiding devices. That is, a filamentary braid can be formed by diagonally crossing strands around a central take-up shaft 165, FIG. 5, such that each group of strands alternately passes over and under groups of strands aligned in the opposite direction. Alternatively, a filamentary braid can be formed without the use of a central take-up shaft 165.

[0075] In some embodiments, modifications to a braiding device that allow for more efficient formation of looped filament elements can be implemented on commercially available braiding devices. Braiding equipment is commercially available, with units having different capacities. Suitable braiding equipment includes braiding machines designed for braiding fine denier filaments and bundles, available from Steeger USA (Inman, South Carolina, USA), Herzog (Oldenburg, Germany), and other manufacturers. However, the equipment that can be modified is not limited to a particular manufacturer. The upper and lower limits for the number of carriers included in a braiding device are not particularly limited and can be determined depending on the desired braid parameters and design.

[0076] In some embodiments, the method of manufacturing a filamentary braid includes braiding using multiple bobbins, at least one of which operates at a lower tension and / or a faster feed rate than the other bobbins to form the looped filament elements. This can be accomplished, for example, by removing one or more ratchet springs and / or tension springs of the carrier 140. In such embodiments, the looped filament elements of the filamentary braid are formed from at least one bobbin operating at a lower tension and / or a faster feed rate, and the main filament elements of the filamentary braid are formed from the other bobbins.

[0077] <Embodiment> Embodiment [1] of the present invention relates to a filamentary braid including a plurality of interwoven filament elements, the filament elements include one or more main filament elements and one or more loop filament elements; the looped filament elements are arranged in one or more looped configurations extending outward from a longitudinal axis defined by the main filament element; The looped filament element is made of a fiber having a tensile modulus of 2.3 GPa or more; When selective tension is applied to the looped filament element, the looped filament element can (i) be collapsed relative to the main filament element within the filamentary braid and / or (ii) be removable from the filamentary braid.

[0078] Embodiment [2] of the present disclosure relates to the filament braid of embodiment [1], wherein the looped filament elements are a different color from the main filament elements.

[0079] Embodiment [3] of the present disclosure relates to the filamentary braid of embodiment [1] or [2], wherein the looped filament elements include one or more liquid crystal polymer filaments.

[0080] Embodiment [4] of the present disclosure relates to the filamentary braid of embodiment [3], wherein the looped filament elements are made of one or more liquid crystal polymer filaments.

[0081] An embodiment [5] of the present disclosure relates to at least one of the filamentary braids of embodiments [1] to [4], wherein the main filament element comprises one or more liquid crystal polymer filaments.

[0082] Embodiment [6] of the present disclosure relates to the filamentary braid of embodiment [5], wherein the main filament element is made of one or more liquid crystal polymer filaments.

[0083] An embodiment [7] of the present disclosure relates to at least one of the filamentary braids of embodiments [1] to [6], wherein the main filament element and the loop filament element have different surface frictions.

[0084] An embodiment [8] of the present disclosure relates to the filamentary braid of embodiment [7], wherein the main filament element, the loop filament element, or both, include a low-friction coating.

[0085] An embodiment [9] of the present disclosure relates to at least one of the filamentary braids of embodiments [1] to [8], wherein the looped filament elements are collapsible relative to the main filament elements within the filamentary braid when selective tension is applied to the looped filament elements.

[0086] An embodiment

[10] of the present disclosure relates to at least one of the filamentary braids of embodiments [1] to [9], wherein the looped filament elements are removable from the filamentary braid when selective tension is applied to the looped filament elements.

[0087] An embodiment

[11] of the present disclosure relates to at least one of the filamentary braids of embodiments [1] to

[10] , wherein the looped filament elements are monofilament fibers.

[0088] An embodiment

[12] of the present disclosure relates to at least one of the filamentary braids of embodiments [1] to

[11] , wherein the main filament element is a monofilament fiber.

[0089] An embodiment

[13] of the present disclosure relates to a method for manufacturing at least one of the filamentary braids of embodiments [1] to

[12] , comprising interweaving filament elements supplied from a plurality of bobbins, wherein at least one bobbin operates at a lower tension and / or a higher feed rate than other bobbins, the looped filament element being formed from the at least one bobbin operating at the lower tension and / or higher feed rate, and the main filament element being formed from the other bobbin.

[0090] An embodiment

[14] of the present disclosure relates to the method of embodiment

[13] , wherein the at least one bobbin operates at a lower tension than the other bobbins.

[0091] An embodiment

[15] of the present disclosure relates to at least one of the methods of embodiments

[13] to

[14] , wherein the at least one bobbin operates at a faster feed rate than the other bobbins.

[0092] The above description is presented to enable any person skilled in the art to make and use the invention, and is provided in the context of a particular application and its requirements. Various modifications to the embodiments disclosed herein will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein. In this regard, certain embodiments within the present disclosure may not represent all of the advantages of the invention when considered broadly. [Explanation of symbols]

[0093] 5: Filamentous braid of Figure 1 10: Main filament element of Fig. 1 15: The looped filament element of FIG. 20: Longitudinal axis formed by the main filament element of FIG. 130: Braiding device of FIG. 135: The enclosure of Fig. 5 140: Carrier of FIG. 145: Carrier path in FIG. 150: Bobbin in Figure 5 155: Filament bundle of Fig. 5 160: Guide for Figure 5 165: Central winding shaft of Fig. 5 170: Winding shaft moving mechanism of FIG.

Claims

1. 1. A filamentary braid comprising a plurality of interwoven filament elements, the filament elements include one or more main filament elements and one or more loop filament elements; the looped filament elements are arranged in one or more looped configurations extending outward from a longitudinal axis defined by the main filament element; the looped filament elements are made of fibers having a tensile modulus of 2.3 GPa or greater; A filamentary braid, wherein upon application of selective tension to the looped filament elements, the looped filament elements are (i) collapsible relative to the main filament elements within the filamentary braid and / or (ii) removable from the filamentary braid.

2. 10. The filamentary braid of claim 1, wherein the looped filament elements are a different color than the main filament elements.

3. The filamentary braid of claim 1 or 2, wherein the looped filament elements comprise one or more liquid crystal polymer filaments.

4. The filamentary braid of claim 3 , wherein the looped filament elements are comprised of one or more liquid crystal polymer filaments.

5. The filamentary braid of any one of claims 1 to 4, wherein the main filament element comprises one or more liquid crystal polymer filaments.

6. The filamentary braid of claim 5 , wherein the primary filament element is comprised of one or more liquid crystal polymer filaments.

7. The filamentary braid of any one of claims 1 to 6, wherein the main filament element and the loop filament element have different surface frictions.

8. 8. The filamentary braid of claim 7, wherein the main filament element, the looped filament element, or both, include a low-friction coating.

9. 9. The filamentary braid of claim 1, wherein the looped filament elements are collapsible relative to the main filament elements within the filamentary braid when selective tension is applied to the looped filament elements.

10. The filamentary braid of any one of claims 1 to 9, wherein the looped filament elements are removable from the filamentary braid when selective tension is applied to the looped filament elements.

11. The filamentary braid according to any one of claims 1 to 10, wherein the looped filament elements are monofilament fibers.

12. 12. The filamentary braid of claim 1, wherein the main filament element is a monofilament fiber.

13. 13. A method for manufacturing a filamentary braid according to any one of claims 1 to 12, comprising interweaving filament elements supplied from a plurality of bobbins, wherein at least one bobbin is operated at a lower tension and / or a higher feed rate than the other bobbins, and wherein the looped filament element is formed from the at least one bobbin operated at the lower tension and / or higher feed rate, and the main filament element is formed from the other bobbins.

14. The method of claim 13 , wherein the at least one bobbin operates at a lower tension than the other bobbins.

15. 15. The method of claim 13 or 14, wherein the at least one bobbin operates at a faster feed rate than the other bobbins.

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