High surface area braided fabric

Abstract

Disclosed herein is a filamentous braid comprising a plurality of filamentous elements knitted together, wherein the filamentous elements comprise one or more primary filamentous elements and one or more annular filamentous elements. The annular filament elements are arranged in one or more annular structures that extend outwardly from a longitudinal axis formed by the main filament elements. The annular filiform element is made of a fiber having a tensile modulus of 2.3 GPa or greater. Upon application of a selective tension to the endless filamentous element, the endless filamentous element (i) is contractible against the main filamentous element in the filamentous braid and / or (ii) is removable from the filamentous braid.

Description

Technical Field

[0001] The present application generally relates to materials technology and, more particularly, to a fabric including filamentary elements. More specifically, the present application discloses a filamentary fabric including a plurality of filamentary elements woven together, wherein the filamentary elements include one or more primary filamentary elements and one or more looped filamentary elements. The looped filamentary elements impart a higher surface area to the filamentary fabric as compared to a filamentary fabric formed without looped filamentary elements. The filamentary fabric disclosed herein can be used, for example, in applications where slippage of the filamentary fabric is not desired, such as in surgical sutures. Background Art

[0002] Barbed sutures are known and can reduce slippage as compared to non-barbed sutures. For example, US 9,044,224 describes a barbed suture formed by inserting monofilament segments into a multifilament elongate body. A portion of the monofilament segments extends beyond the outer surface of the multifilament elongate body to form barbs on the suture. Similarly, US 10,786,243 describes a barbed suture formed by a flocking process by adhering individual barb members to a braided thread. The adhesion can be performed by fusion welding, applying an adhesive, ultrasonic welding, or lamination.

[0003] However, the production of such barbed sutures is complex, in part because the barbs are not formed from filaments integrated into the fabric of the suture. Instead, the barbs are inserted or adhered to the braided filaments forming the suture. Alternatively, barbs can be produced by cutting into a monofilament and lifting the cut segment away from the central axis of the filament. This complicates the process of producing such barbed sutures.

[0004] On the other hand, US 2010 / 0298872 describes a braided suture including protruding loops, wherein the protruding loops can be formed from the filaments of the filamentary fabric. These braided sutures can be produced by continuous braiding, wherein the loops are formed by overfeeding the corresponding filaments. Thus, these loops can be formed from filaments integrated into the fabric of the suture. This simplifies the production of the suture as compared to methods that require inserting or adhering separate barbs.

[0005] However, whether the barbs / loops are formed from integrated filaments or from external filaments, all of the above sutures can be difficult to place in a patient. For example, if the suture is made of an insoluble material, a removal method must be considered before placing the suture. This is because a barbed suture can only be removed in a direction opposite to the direction in which the barbs point.

[0006] There is still a need to improve the filamentous braids having sufficient gripping strength for use as sutures without suffering from the disadvantages of the above-mentioned complex production and difficult removal. SUMMARY OF THE INVENTION

[0007] The present inventors have recognized a need to develop filamentous braids having an increased surface area for improved gripping, which are relatively simple to produce and relatively convenient to remove when no longer needed in a particular application.

[0008] The following disclosure describes the preparation and use of a filamentous braid comprising annular filamentary elements, wherein the annular filamentary elements are collapsible and / or removable from the filamentous braid.

[0009] Embodiments of the present disclosure described herein enable one of ordinary skill in the art to make and use them, including the following:

[0010] (1) In one aspect, it relates to a filamentous braid comprising a plurality of filamentary elements woven together,

[0011] wherein the filamentary elements include one or more main filamentary elements and one or more annular filamentary elements,

[0012] wherein the annular filamentary elements are arranged in one or more annular structures that extend outwardly from a longitudinal axis formed by the main filamentary elements,

[0013] wherein the annular filamentary elements are made of fibers having a tensile modulus of 2.3 GPa or greater, and

[0014] wherein, upon applying selective tension to the annular filamentary elements, the annular filamentary elements (i) are contractible against the main filamentary elements in the filamentous braid and / or (ii) are removable from the filamentous braid.

[0015] (2) In another aspect, it relates to a method of producing such a filamentous braid by using braiding of a plurality of spools, at least one of the spools being operated at a lower tension and / or a faster supply rate than the other spools to form the annular filamentary elements.

[0016] Additional objects, advantages, and features of the present disclosure will be set forth in part in the description which follows, and in part will become apparent to those having ordinary skill in the art upon examination of the following, or may be learned by practice of the present disclosure. The present disclosure encompasses other embodiments different from those specifically described herein, and details herein can be modified in many aspects without departing from the present disclosure. In this regard, the description herein is to be considered as illustrative in nature and not restrictive. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Embodiments of the present disclosure are explained in the following description in view of the accompanying drawings.

[0018] Figure 1 A schematic view of an exemplary embodiment of a filamentary fabric, showing annular filamentary elements disposed in an annular structure extending outwardly from a longitudinal axis formed by main filamentary elements.

[0019] Figure 2 A schematic view of a filamentary fabric, in which the annular filamentary elements contract against the main filamentary elements when a selective tension is applied to the annular filamentary elements.

[0020] Figure 3 A schematic view of a filamentary fabric, in which the annular filamentary elements have been removed from the filamentary fabric when a selective tension is applied to the annular filamentary elements.

[0021] Figure 4 A schematic view of a filamentary fabric, in which the annular filamentary elements have contracted partially but not completely.

[0022] Figure 5 A schematic view of a weaving apparatus with 12 carriers capable of producing the filamentary fabric of the present disclosure. DETAILED DESCRIPTION

[0023] Embodiments of the present disclosure include various filamentary fabrics and methods of producing the filamentary fabrics.

[0024] 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.

[0025] Unless otherwise indicated, all percentages, parts, ratios, etc. are by weight.

[0026] When an equivalent, concentration, or other value or parameter is given as a list of ranges or upper and lower limit values, this should be understood as specifically disclosing all ranges formed by any pair of an upper and a lower limit of any range, whether or not the ranges are separately disclosed. In the case of listing numerical ranges herein, unless otherwise stated, the range is intended to include its endpoints, as well as all integers and fractions within the range. The scope of the present disclosure is not intended to be limited to the specific values recited when defining the range.

[0027] The use of the indefinite article “a” or “an” to describe various elements and components herein is merely for convenience and to give a general meaning of the present disclosure. This description should be understood to include one or at least one, and the singular also includes the plural, unless clearly indicated otherwise.

[0028] Unless expressly stated to the contrary, “or” and “and / or” mean inclusive rather than exclusive. For example, the 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), and both A and B are true (or present).

[0029] As used herein, the terms “about” and “approximately” mean nearly the same as a reference quantity or value and should be understood to cover ±5% of the specified quantity or value.

[0030] Unless otherwise defined, the term “substantially” as used herein means all, or nearly all, or the vast 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 some reasonable deviation from 100% that would typically occur on an industrial scale or a commercial scale.

[0031] Throughout this specification, unless otherwise defined and described, the technical terms and methods for determining relevant measured values are in accordance with the description of ASTM D855 / D885M-10A(2014), Standard Test Methods for Tire Cords, Tire Cord Fabrics, and Industrial Filament Yarns Made From Man-made Organic-base Fibers, published in October 2014.

[0032] For convenience, many elements (components) of the various embodiments disclosed herein are discussed separately. Although a list of options may be provided and values may be within ranges, the present disclosure should not be regarded as limited to the separately described lists and ranges. Unless otherwise stated, every possible combination within the present disclosure should be regarded as expressly disclosed for all purposes.

[0033] The materials, methods, and examples herein are illustrative only and are not intended to be limiting unless otherwise specified. Methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present disclosure.

[0034] Filamentous fabric

[0035] The embodiments described herein include a filamentous fabric that includes a plurality of filamentous elements woven together. The filamentous elements include one or more primary filamentous elements and one or more annular filamentous elements. The annular filamentous elements are arranged in one or more annular structures that extend outwardly from a longitudinal axis formed by the primary filamentous elements. The annular filamentous elements are made of a fiber having a tensile modulus of 2.3 GPa or greater. When a selective tension is applied to the annular filamentous elements, the annular filamentous elements (i) can contract against the primary filamentous elements in the filamentous fabric and / or (ii) can be removed from the filamentous fabric.

[0036] As used herein, a "filamentous element" can be a monofilament fiber or a multifilament fiber. If it is a multifilament fiber, the filamentous element includes a plurality of filaments combined together to form a multifilament, for example, by, but not limited to, twisting or weaving individual filaments to form a multifilament.

[0037] As used herein, a "primary filamentous element" is a filamentous element that forms the woven structure of the filamentous fabric by contacting other filamentous elements along substantially the entire length of the filamentous fabric. A plurality of primary filamentous elements woven together form a longitudinal axis generally along the direction in which the fabric is formed.

[0038] In contrast, an "annular filamentous element" is a filamentous element arranged in one or more annular structures. The annular structures extend outwardly from a longitudinal axis formed by the primary filamentous elements. Due to this outward extension, the annular filamentous elements contact the primary filamentous elements over less than substantially the entire length of the filamentous fabric.

[0039] Figure 1 Schematic diagram of an exemplary embodiment of a filamentous fabric. In Figure 1In [the figure], the filamentous fabric 5 includes a plurality of filamentous elements. The filamentous elements include a main filamentous element 10 and an annular filamentous element 15. The annular filamentous element 15 extends outward from the longitudinal axis 20 formed by the main filamentous element 10. As Figure 1 shown, the annular filamentous element 15 includes a portion in contact with one or more of the main filamentous elements 10 and a portion not in contact with one or more of the main filamentous elements 10. The portion of the annular filamentous element 15 not in contact with the main filamentous element 10 generally corresponds to an annular structure extending outward from the longitudinal axis 20 formed by the main filamentous element 10. Thus, the annular filamentous element 15 is in contact with the main filamentous element 10 over less than substantially the entire length of the filamentous fabric 5.

[0040] Figure 2 is a schematic view of the filamentous fabric 5, in which when a selective tension is applied to the annular filamentous element 15, the annular filamentous element 15 contracts against the main filamentous element 10. "Selective tension" means a tension applied to one or more of the annular filamentous elements 15 that is different from the tension applied to one or more of the main filamentous elements 10. For example, such a selective tension can be (i) a tension applied to one or more of the annular filamentous elements 15 without simultaneously applying a tension to one or more of the main filamentous elements 10, or (ii) a tension applied to one or more of the annular filamentous elements 15 that is greater in degree than the tension simultaneously applied to one or more of the main filamentous elements 10. The contraction of the annular filamentous element 15 against the main filamentous element 10 can be a complete contraction, whereby the annular filamentous element 15 becomes in contact with the main filamentous element 10 over substantially the entire length of the filamentous fabric 5. Alternatively, the contraction of the annular filamentous element 15 against the main filamentous element 10 can be less than a complete contraction, whereby the annular filamentous element 15 remains in contact with the main filamentous element 10 over less than substantially the entire length of the filamentous fabric 5 but greater than their contact before contraction, as discussed in more detail below for Figure 4 is discussed in more detail.

[0041] Figure 3 is a schematic view of the filamentous fabric 5, in which when a selective tension is applied to the annular filamentous element 15, the annular filamentous element 15 has been removed from the filamentous fabric 5. As in Figure 2 "Selective tension" means a tension applied to one or more of the annular filamentous elements 15 that is different from the tension applied to one or more of the main filamentous elements 10, for example (i) a tension applied to one or more of the annular filamentous elements 15 without simultaneously applying a tension to one or more of the main filamentous elements 10, or (ii) a tension applied to one or more of the annular filamentous elements 15 that is greater in degree than the tension simultaneously applied to one or more of the main filamentous elements 10.

[0042] Figure 4Schematic diagram of a filamentary fabric, in which the annular filamentary element has contracted partially but not completely. In this embodiment, r1 is the radius when no tension is applied to the annular filamentary element (or when the applied tension is lower than the tension required to overcome the static friction between the annular filamentary element and the main filamentary element), and r2 is the radius after the static friction has been overcome. Similarly, F1 is the tension when no tension is applied to the annular filamentary element (and / or when the applied tension is lower than the tension required to overcome the static friction), and F2 is the tension after the static friction has been overcome.

[0043] When selective tension is applied to the annular filamentary element, the annular filamentary element (i) can contract against the main filamentary element in the filamentary fabric and / or (ii) can be removed from the filamentary fabric. The magnitude of the selective tension required to contract the annular filamentary element against the main filamentary element or to remove the annular filamentary element from the filamentary fabric can vary depending on factors such as the composition of the filamentary element, the dimensions (diameter and length) of the filamentary element, and the number of filamentary elements in the filamentary fabric. The applied tension must be low enough not to damage the filamentary fabric. For example, such damage may occur if the applied tension exceeds the yield load of the annular filamentary element, resulting in the annular filamentary element (i) stretching before the annular filamentary element contracts against the main filamentary element and / or (ii) stretching before the annular filamentary element is removed from the filamentary fabric. In Figure 4 the schematic diagram, this means that the pulling force F2 must be less than the yield load of the annular filamentary element. In some embodiments, the magnitude of the selective tension required to contract the annular filamentary element against the main filamentary element or to remove the annular filamentary element from the filamentary fabric can be at least 50 grams (force), 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 magnitude of the selective tension required to contract the annular filamentary element against the main filamentary element or to remove the annular filamentary element (without damaging the fabric) from the filamentary fabric can be at most 2500 grams, at most 2000 grams, at most 1500 grams, at most 1000 grams, at most 900 grams, at most 800 grams, at most 700 grams, at most 600 grams, at most 500 grams, at most 400 grams, at most 300 grams, at most 200 grams, or at most 100 grams.

[0044] To facilitate the application of selective tension to the looped filamentary element, the looped filamentary element may be a different color from the main filamentary element. In such an embodiment, the degree of color difference is such that a person with normal vision can distinguish the looped filamentary element from the main filamentary element with the naked eye (i.e., unaided) or with an optical aid such as a magnifying glass or microscope. The color difference may be a difference in hue, but does not have to be a difference in hue. The color difference may be a difference in grayscale, such as black versus white, gray versus white, gray versus black, or darker gray versus lighter gray. In another embodiment, the looped filamentary element may have a difference in radiopacity relative to the main filamentary element. Such a difference in radiopacity allows the looped filamentary element to be distinguished from the main filamentary element by using radio wave and / or x-ray imaging techniques.

[0045] The looped filamentary element in 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, by applying a selective tension that generally does not exceed the yield strength of the fiber, the looped filamentary element can contract against the main filamentary element in the filamentary fabric and / or can be removed from the filamentary fabric. Conversely, if the tensile modulus (and the corresponding yield strength) of the fiber constituting the looped filamentary element is too low, the selective tension applied to contract or remove the looped filamentary element may break or otherwise damage the looped filamentary element before the contraction or removal of the looped filamentary element.

[0046] The tensile modulus of the main filamentous element in the present application is not particularly limited. The tensile modulus of the main filamentous element may be different from that of the annular filamentous element. In some embodiments, the tensile modulus of the main filamentous element may be greater than that of the annular filamentous element. In other embodiments, the tensile modulus of the main filamentous element may be less than that of the annular filamentous element. The main filamentous element may be made of fibers having a tensile modulus of less than 2.3 GPa, or 2.3 GPa or greater. The tensile modulus of the fibers of the main filamentous 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.

[0047] Fibers having a tensile modulus of 2.3 GPa or greater preferably include liquid crystal polymer (LCP) filaments. LCP filaments include lyotropic polymer filaments 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, aromatic polyamide and poly(p-phenylene benzobisoxazole) (PBO) filaments, as well as copolymer aromatic polyamide filaments. Aromatic polyamide filaments may be obtained commercially under the trade name KEVLAR ® from DuPont, and may be obtained commercially under the trade name TWARON ® from Teijin Ltd. Copolymer aromatic polyamide filaments may be obtained commercially under the trade name TECHNORA ® from Teijin Ltd. PBO fibers may be obtained commercially under the trade name ZYLON ® from Toyobo Company Ltd. Thermotropic polymers exhibit a liquid crystal morphology in the molten form. Thermotropic filaments include, for example, aromatic polyesters formed by the polycondensation of 4-hydroxybenzoic acid and 6-hydroxynaphthalene-2-carboxylic acid, which may be obtained commercially under the trade name VECTRAN ® from KURARAY CO., LTD.

[0048] The annular filamentary element preferably comprises one or more LCP filaments. The main filamentary element may also comprise one or more LCP filaments. Preferably, there is a difference in surface friction between the annular filamentary element and the main filamentary element. That is, the annular filamentary element may have a lower surface friction than the main filamentary element, or, conversely, the main filamentary element may have a lower surface friction than the annular filamentary element. Such a difference in surface friction between the annular filamentary element and the main filamentary element facilitates the shrinkage and / or removal of the annular filamentary element. Such a difference in surface friction can be achieved by using a filamentary element with a low-friction coating as the low-friction filamentary element.

[0049] In some embodiments, the annular filamentary element may comprise non-LCP filaments, provided that the tensile modulus of the fibers constituting the annular filamentary element is 2.3 GPa or greater. Such non-LCP filaments include, but are not limited to, polyetheretherketone filaments (100 to 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 a few. In some embodiments, a single 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, a particular type of non-LCP filament is excluded from the annular filamentary element. For example, the annular filamentary element may not include HMPE filaments.

[0050] In some embodiments, the main filamentary element may comprise non-LCP filaments. 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 a few. In some embodiments, a single 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, a particular type of non-LCP filament is excluded from the main filamentary element. For example, the main filamentary element may not include HMPE filaments.

[0051] The polymerization units of the LCP and the non-LCP filaments may include those shown in Table 1.

[0052] Table 1

[0053]

[0054] Regarding the polymerization unit shown 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 tert-butyl group), an alkoxy group (e.g., a methoxy group, an ethoxy group, an isopropoxy group, a n-butoxy group, etc.), an aryl group (e.g., a phenyl group, a naphthyl group, etc.), an aralkyl group [a benzyl group (phenylmethyl), a phenethyl group (phenylethyl), etc.], an aryloxy group (e.g., a phenoxy group, etc.), an aralkyloxy group (e.g., a benzyloxy group, etc.), or a mixture thereof.

[0055] The LCP filaments can be obtained by melt spinning of a liquid crystal polyester resin. The spun filaments can be further heat-treated to enhance the mechanical properties. The liquid crystal polyester can be composed of repeating polymerization units derived from, for example, aromatic diols, aromatic dicarboxylic acids, or aromatic hydroxycarboxylic acids. The liquid crystal polyester can optionally further include polymerization units derived from aromatic diamines, aromatic hydroxyamines, and / or aromatic aminocarboxylic acids.

[0056] More specific polymerization units are shown in the following structures shown in Tables 2 to 4 below.

[0057] When the polymerization unit in the formula is a unit that can represent multiple structures, two or more units can be used in combination as the polymerization units constituting the polymer.

[0058] In the polymerization units of Tables 2, 3, and 4, n is an integer of 1 or 2, and the units where n = 1 and n = 2 can exist alone or in combination; and Y1 and Y2 can each independently be 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 - 4 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group), an alkoxy group (e.g., a methoxy group, an ethoxy group, an isopropoxy group, a n-butoxy group, etc.), an aryl group (e.g., a phenyl group, a naphthyl group, etc.), an aralkyl group (a benzyl group (phenylmethyl), a phenethyl group (phenylethyl), etc.), an aryloxy group (e.g., a phenoxy group, etc.), an aralkyloxy group (e.g., a benzyloxy group, etc.), or a mixture thereof. Among these groups, Y is preferably a hydrogen atom, a chlorine atom, a bromine atom, or a methyl group.

[0059] Table 2

[0060]

[0061] Table 3

[0062]

[0063] Table 4

[0064]

[0065] Z in (14) of Table 3 may include a divalent group represented by the following formula:

[0066]

[0067] In some embodiments, the liquid crystal polyester may be a combination including a naphthalene skeleton as a polymerization unit. In particular, it may include both a polymerization unit (A) derived from 4-hydroxybenzoic acid and a polymerization unit (B) derived from 6-hydroxy-2-naphthoic acid. For example, unit (A) may have formula (A), and unit (B) may have formula (B). From the viewpoint of improving melt moldability, the ratio of unit (a) to unit (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.

[0068]

[0069] Based on the total polymerization units, the sum of polymerization unit (A) and polymerization unit (B) may be, for example, about 65 mol% or more, or about 70 mol% or more, or about 80 mol% or more. In some embodiments, the filament may include a liquid crystal polyester that includes about 4 to about 45 mol% of polymerization unit (B) in the polymer.

[0070] The commercially available LCP filaments of the present disclosure may include VECTRAN ® HT BLACK, manufactured by KURARAY CO., LTD., VECTRAN ® HT, manufactured by Toray Industries, Inc., SIVERAS ® , monofilament manufactured by ZEUS, and ZXION manufactured by KB SEIREN, LTD. ® .

[0071] According to the present disclosure, "aromatic polyamide filament" means a polyamide filament having high heat resistance and high strength, which includes a molecular skeleton composed of aromatic (benzene) rings. Aromatic polyamide filaments can be classified into para-aromatic polyamide filaments and meta-aromatic polyamide filaments according to their chemical structures.

[0072] Examples of commercially available aromatic polyamides and copolymer aromatic polyamide filaments include para-aramid filaments such as KEVLAR manufactured by DuPont ® and HERACRON from Kolon Industries Inc. ® and TWARON manufactured by Teijin Ltd. ® ; and meta-aramid filaments such as NOMEX manufactured by DuPont ® and CONEX manufactured by Teijin Ltd. ® .

[0073] In some embodiments, the lyotropic LCP filaments can include one or more copolymer aromatic polyamide filaments. For example, in some embodiments, the lyotropic LCP filaments include copoly(p-phenylene / 3,4'-oxybiphenylene terephthalamide) filaments. This material is commonly referred to as TECHNORA ® and is available from Teijin.

[0074] Poly(p-phenylene benzobisoxazole) (poly(p-phenylene-2,6-benzobisoxazole) (PBO) filaments are commercially available as ZYLON ® AS and ZYLON ® HM through Toyobo Co., Ltd.

[0075] Commercially available non-LCP filaments include polyetheretherketone (PEEK) materials such as VICTREX™ PEEK polymers.

[0076] Other non-LCP filaments include ultra-high molecular weight polyethylene filaments. These can have an intrinsic viscosity in the range from about 5.0, or from about 7.0, or from about 10, to about 30, or to about 28, or to about 24 dL / g.

[0077] ASTM standards (such as test methods D789, D1243, D1601, and D4603, and practice D3591) that describe viscosity procedures for dilute solutions of specific polymers such as nylon, poly(vinyl chloride), polyethylene, and poly(ethylene terephthalate) are available. Generally, the polymer is dissolved in a dilute solution and the drop time through a capillary is measured at a specific temperature against a control sample.

[0078] The weight average molecular weight of the ultra-high molecular weight polyethylene filaments can be from about 700,000, or from about 800,000, or from about 900,000, to about 8,000,000, or to about 7,000,000, or to about 6,000,000.

[0079] Since it is difficult to measure the weight-average molecular weight of ultra-high molecular weight polyethylene filaments using the GPC method, the weight-average molecular weight can be determined based on the above-mentioned intrinsic viscosity value according to the following equation mentioned in "Polymer Handbook, 4th Edition, Chapter 4 (published by John Wiley in 1999)".

[0080] Weight-average molecular weight = 5.365×10 4 ×(intrinsic viscosity) 1.37

[0081] In some embodiments, the repeating unit of the ultra-high molecular weight polyethylene filament may preferably substantially contain ethylene. However, in addition to homopolymers of ethylene, copolymers of ethylene with a small amount of other monomers such as α-olefins, acrylic acid and its derivatives, methacrylic acid and its derivatives, and vinyl silane and its derivatives can be used. The polyethylene filament may have a partially crosslinked structure. The polyethylene filament may also be a blend of high-density polyethylene and ultra-high molecular weight polyethylene, a blend of low-density polyethylene and ultra-high molecular weight polyethylene, or a blend of high-density polyethylene, low-density polyethylene and ultra-high molecular weight polyethylene. The polyethylene filament may be a combination of two or more ultra-high molecular weight polyethylenes having different weight-average molecular weights, or a combination of two or more polyethylenes having different molecular weight distributions.

[0082] Commercially available ultra-high molecular weight polyethylene filaments include DYNEEMA ® SK60, DYNEEMA ® SK, IZANAS ® SK60 and IZANAS ® SK71, SPECTRA FIBER 900 manufactured by Honeywell, LTD. ® and SPECTRA FIBER 1000 ® .

[0083] These ultra-high molecular weight polyethylene filaments can be used alone or in combination.

[0084] In some embodiments, the LCP filaments in the annular filamentary element and / or the main filamentary 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 at most 100 dpf, at most 90 dpf, at most 80 dpf, at most 70 dpf, at most 60 dpf, at most 50 dpf, at most 40 dpf, at most 35 dpf, at most 30 dpf, at most 25 dpf, at most 20 dpf, at most 15 dpf, or at most 10 dpf.

[0085] 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.

[0086] In some embodiments, each multifilament fiber includes 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 includes at most 5000 LCP filaments, at most 2000 LCP filaments, at most 1000 LCP filaments, at most 500 LCP filaments, at most 200 LCP filaments, at most 100 LCP filaments, at most 50 LCP filaments, or at most 25 LCP filaments.

[0087] In some embodiments, the filamentous 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 filamentous 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.

[0088] In some embodiments, the filamentous braid is a sheath surrounding a core. Such an embodiment may be referred to as a cord comprising a filamentous braid around a core. In other embodiments, the filamentous braid does not surround a core.

[0089] Method for producing a filamentous braid

[0090] The embodiments described herein include a method for producing the filamentous braid disclosed above. The method generally involves braiding using a plurality of bobbins, at least one of which operates at a lower tension and / or a faster supply rate than the other bobbins to form the looped filamentary elements.

[0091] Figure 5 An embodiment of a braiding apparatus 130 that can be used to produce the filamentous braid of the present disclosure is shown. The braiding apparatus 130 includes a main housing 135 that rotates during operation and mounts twelve (12) spindles 140 that move independently along the upper surface of the main housing 135 in a circular spindle track 145 that enables the spindles 140 to follow a continuous "figure 8" pattern. Each spindle 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 winding shaft 165 that is controlled by a winding shaft moving mechanism 170 to move in an axial direction. Figure 5 The payout orientation of each bobbin 150 is shown; however, a roll-off orientation of each bobbin 150 can also be used.

[0092] In addition to being able to modify the braiding device 130 to enable it to more effectively form the annular filamentary element, the braiding device 130 functions in a manner similar to a conventional braiding device. That is, by diagonally crossing the strands in such a way that each set of strands alternately passes above and below a set of strands laid in opposite directions, a filamentary braid can be formed on the central winding shaft 165 in Figure 5 . Alternatively, the filamentary braid can be formed without using the central winding shaft 165.

[0093] In some embodiments, the modification that enables the braiding device to more effectively form the annular filamentary element can be made on a commercially available braiding device. The braiding device is commercially available, and units with different capabilities can be obtained. Suitable braiding devices can include braiding machines commercially available from Steeger USA (Inman, South Carolina, USA), Herzog GmbH (Oldenburg, Germany), and other manufacturers, which are designed for the braiding of fine denier filaments and bundles. However, the available devices for modification are not limited to any specific manufacturer. There are no limitations on the upper and lower limits of the number of spindles included in the braiding device, and they can be determined according to the desired braiding parameters and designs.

[0094] In some embodiments, the method for producing a filamentary braid involves braiding using a plurality of spools, where at least one spool operates at a lower tension and / or a faster supply rate than the other spools to form the annular filamentary element. This can be achieved, for example, by removing one or more ratchet springs and / or tension springs in one or more of the spindles 140. In such an embodiment, the annular filamentary element of the filamentary braid is formed by the at least one spool operating at a lower tension and / or a faster supply rate, and the main filamentary elements of the filamentary braid are formed by the other spools.

[0095] Embodiments

[0096] Embodiments [1] of the present disclosure relate to a filamentary braid that includes a plurality of filamentary elements braided together,

[0097] wherein the filamentary elements include one or more main filamentary elements and one or more annular filamentary elements,

[0098] wherein the annular filamentary elements are arranged in one or more annular structures that extend outward from a longitudinal axis formed by the main filamentary elements,

[0099] wherein the annular filamentary elements are made of fibers having a tensile modulus of 2.3 GPa or greater, and

[0100] Wherein, when a selective tension is applied to the annular filamentary element, the annular filamentary element (i) can contract against the main filamentary element in the filamentary fabric and / or (ii) can be removed from the filamentary fabric.

[0101] Embodiment [2] of the present disclosure relates to the filamentary fabric described in Embodiment [1], wherein the annular filamentary element has a different color from the main filamentary element.

[0102] Embodiment [3] of the present disclosure relates to the filamentary fabric described in Embodiment [1] or [2], wherein the annular filamentary element comprises one or more liquid crystal polymer filaments.

[0103] Embodiment [4] of the present disclosure relates to the filamentary fabric described in Embodiment [3], wherein the annular filamentary element consists of one or more liquid crystal polymer filaments.

[0104] Embodiment [5] of the present disclosure relates to the filamentary fabric according to at least one of Embodiments [1]-[4], wherein the main filamentary element comprises one or more liquid crystal polymer filaments.

[0105] Embodiment [6] of the present disclosure relates to the filamentary fabric described in Embodiment [5], wherein the main filamentary element consists of one or more liquid crystal polymer filaments.

[0106] Embodiment [7] of the present disclosure relates to the filamentary fabric according to at least one of Embodiments [1]-[6], wherein the main filamentary element and the annular filamentary element are different in surface friction.

[0107] Embodiment [8] of the present disclosure relates to the filamentary fabric described in Embodiment [7], wherein the main filamentary element, the annular filamentary element, or both the main filamentary element and the annular filamentary element comprise a low-friction coating.

[0108] Embodiment [9] of the present disclosure relates to the filamentary fabric according to at least one of Embodiments [1]-[8], wherein when a selective tension is applied to the annular filamentary element, the annular filamentary element can contract against the main filamentary element in the filamentary fabric.

[0109] Embodiment

[10] of the present disclosure relates to the filamentary fabric according to at least one of Embodiments [1]-[9], wherein when a selective tension is applied to the annular filamentary element, the annular filamentary element can be removed from the filamentary fabric.

[0110] Embodiments

[11] of the present disclosure relate to the filamentous fabric according to at least one of Embodiments [1]-

[10] , wherein the annular filamentous element is a monofilament fiber.

[0111] Embodiments

[12] of the present disclosure relate to the filamentous fabric according to at least one of Embodiments [1]-

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

[0112] Embodiments

[13] of the present disclosure relate to a method for producing the filamentous fabric according to at least one of Embodiments [1]-

[12] , comprising: weaving filamentous elements supplied from a plurality of spools together, wherein at least one spool is operated at a lower tension and / or a faster supply rate than the other spools, wherein the annular filamentous element is formed by the at least one spool operated at a lower tension and / or a faster supply rate, and wherein the main filamentous element is formed by the other spools.

[0113] Embodiments

[14] of the present disclosure relate to the method according to Embodiment

[13] , wherein the at least one spool is operated at a lower tension than the other spools.

[0114] Embodiments

[15] of the present disclosure relate to the method according to at least one of Embodiments

[13] -

[14] , wherein the at least one spool is operated at a faster supply rate than the other spools.

[0115] The foregoing description is presented to enable a person skilled in the art to make and use the invention, and the foregoing description is provided in the context of a particular application and its requirements. Various modifications to the embodiments disclosed herein will be 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. Accordingly, the 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, some embodiments within the present disclosure may not exhibit every advantage of the invention when considered broadly.

[0116] Reference numerals

[0117] 5 Figure 1 The filamentous fabric in

[0118] 10 Figure 1 The main filamentous element in

[0119] 15 Figure 1 The annular filamentous element in

[0120] 20 formed by Figure 1 The longitudinal axis formed by the main filamentous element in

[0121] 130 Figure 5 in the braiding device

[0122] 135 Figure 5 in the main housing

[0123] 140 Figure 5 in the spindle

[0124] 145 Figure 5 in the spindle rail

[0125] 150 Figure 5 in the bobbin

[0126] 155 Figure 5 in the tow

[0127] 160 Figure 5 in the guide

[0128] 165 Figure 5 in the central winding shaft

[0129] 170 Figure 5 in the winding shaft moving mechanism

Claims

1. A filamentary fabric comprising a plurality of filamentary elements woven together, wherein said filamentary elements include one or more main filamentary elements and one or more annular filamentary elements, wherein said annular filamentary elements are arranged in one or more annular structures that extend outwardly from a longitudinal axis formed by said main filamentary elements, wherein said annular filamentary elements are made of fibers having a tensile modulus of 2.3 GPa or greater, and Among them, when selective tension is applied to said annular filamentary elements, said annular filamentary elements (i) can contract against said main filamentary elements in said filamentary fabric and / or (ii) can be removed from said filamentary fabric.

2. The filamentary fabric according to claim 1, wherein said annular filamentary elements have a different color from said main filamentary elements.

3. The filamentary fabric according to claim 1 or 2, wherein said annular filamentary elements include one or more liquid crystal polymer filaments.

4. The filamentary fabric according to claim 3, wherein said annular filamentary elements consist of one or more liquid crystal polymer filaments.

5. The filamentary fabric according to any one of claims 1 to 4, wherein said main filamentary elements include one or more liquid crystal polymer filaments.

6. The filamentary fabric according to claim 5, wherein said main filamentary elements consist of one or more liquid crystal polymer filaments.

7. The filamentary fabric according to any one of claims 1 to 6, wherein said main filamentary elements and said annular filamentary elements differ in surface friction.

8. The filamentary fabric according to claim 7, wherein said main filamentary elements, said annular filamentary elements, or both said main filamentary elements and said annular filamentary elements include a low-friction coating.

9. The filamentary fabric according to any one of claims 1 to 8, wherein when selective tension is applied to said annular filamentary elements, said annular filamentary elements can contract against said main filamentary elements in said filamentary fabric.

10. The filamentary fabric according to any one of claims 1 to 9, wherein when selective tension is applied to said annular filamentary elements, said annular filamentary elements can be removed from said filamentary fabric.

11. The filamentary fabric according to any one of claims 1 to 10, wherein said annular filamentary elements are monofilament fibers.

12. The filamentary fabric according to any one of claims 1 to 11, wherein said main filamentary elements are monofilament fibers.

13. A method of producing a filamentary braid according to any one of claims 1 to 12, comprising: Weaving together filamentary elements supplied from a plurality of spools, wherein at least one spool is operated at a lower tension and / or a faster supply rate than the other spools, wherein said annular filamentary elements are formed by said at least one spool operated at a lower tension and / or a faster supply rate, and wherein said main filamentary elements are formed by said other spools.

14. The method according to claim 13, wherein said at least one spool is operated at a lower tension than said other spools.

15. The method according to claim 13 or 14, wherein said at least one spool is operated at a faster supply rate than said other spools.

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