High-strength fiber

Abstract

Provided is a high-strength fiber having excellent abrasion resistance. The high-strength fiber has, on the fiber surface, a wax and polysiloxane adhering thereto, the polysiloxane having a viscosity of at least 5000 mPa•s. When time-of-flight secondary ion mass spectrometry (TOF-SIMS) imaging is performed on said surface, with regard to a measurement region obtained from a monochrome image of 256 gradations by grayscale conversion of the intensity of ions derived from the polysiloxane, the number of pixels (excluding 0 gradation and 255 gradation) extracted as an attachment part of ions derived from the polysiloxane accounts for at least 60% of the total number of pixels constituting the measurement region.

Description

High-strength fiber Related Applications

[0001] This application claims priority from Japanese Patent Application No. 2023-105720, filed on June 28, 2023, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to a high-strength fiber having a highly viscous polysiloxane attached to the surface of the fiber in a specific manner.

[0003] To produce high-strength fibers, the molecules are generally aligned as parallel as possible to the fiber axis to impart a high degree of crystallinity. However, due to the high crystallinity, many high-strength fibers are prone to wear and fibrillation, making it necessary to improve their abrasion resistance.

[0004] For example, Patent Document 1 (JP-A-10-237767) discloses an abrasion-resistant fiber characterized in that a treating agent, in which a hydrocarbon wax having a melting point of 50 to 90° C. accounts for 80% by weight or more of the treating agent's active ingredient, is melt-adhered to the fiber surface in an amount of 4 to 10% by weight based on the weight of the fiber. This document also discloses that the treating agent contains 20% by weight or less of a polysiloxane having a viscosity of 5 to 80 centistokes at 25° C., based on the treating agent's active ingredient.

[0005] Furthermore, Patent Document 2 (JP 2009-527661 A) discloses a rope with improved fatigue resistance in repeated bending sheave (CBOS), characterized in that the rope contains high tenacity fibers and the rope and / or the fibers are coated with a composition containing an amino-functional silicone resin and neutralized low-molecular-weight polyethylene.

[0006] Japanese Patent Application Laid-open No. 10-237767 Special Publication No. 2009-527661

[0007] However, although Patent Document 1 describes the use of a polysiloxane with a viscosity of 5 to 80 centistokes as the active ingredient of the treatment agent, there is a problem in that such a treatment agent cannot sufficiently adhere to the fiber surface in the case of high molecular weight silicone. Furthermore, Patent Document 2 describes a combination of an amino-functional silicone resin and a neutralized low molecular weight polyethylene, but does not provide any details about the amino-functional silicone resin. Furthermore, there is no indication that abrasion resistance is maintained over a long period of time when repeatedly bent.

[0008] Therefore, an object of the present invention is to provide a high-strength fiber that can maintain abrasion resistance for a long period of time.

[0009] As a result of extensive research conducted by the present inventors to solve the above-mentioned problems of the conventional art, they discovered that when a wax and a specific high-viscosity polysiloxane are adhered to the surface of a fiber, if the polysiloxane adheres to the surface of the fiber in a specific adhesion manner, a synergistic effect between the polysiloxane and the wax occurs, and the abrasion resistance of the fiber is maintained for a long period of time, although the reason for this is not clear, and they have completed the present invention.

[0010] That is, the present invention can be configured in the following aspects: [Aspect 1] A wax and a polysiloxane having a viscosity of 5,000 mPa·s or more (preferably 8,000 mPa·s or more and 1,000,000 mPa·s or less, more preferably 10,000 mPa·s or more and 700,000 mPa·s or less, even more preferably 15,000 mPa·s or more and 500,000 mPa·s or less, particularly preferably 20,000 mPa·s or more and 500,000 mPa·s or less, and particularly preferably 100,000 mPa·s or more and 450,000 mPa·s or less) are attached to a fiber surface, and a flying particle is formed on the surface. A high-strength fiber in which, when time-of-flight secondary ion mass spectrometry (TOF-SIMS) imaging is performed, the number of pixels (excluding 0 and 255 gradations; i.e., 1 to 254 gradations) extracted as ion attachment sites derived from the polysiloxane accounts for 60% or more (preferably 65% ​​or more, more preferably 70% or more) of the total number of pixels constituting a measurement area obtained from a monochrome image of 256 gradations (0 gradation to 255 gradations) obtained by grayscaling the ion intensity derived from the polysiloxane. [Aspect 2] The high-strength fiber according to Aspect 1, wherein, when TOF-SIMS imaging is performed on the surface, in a measurement area obtained from a monochrome image of 256 gradations (gradation 0 to 255) obtained by grayscaling the ion intensity derived from the wax, the number of pixels extracted as ion-adhered portions derived from the wax (excluding gradation 0 and 255; i.e., gradation 1 to 254) relative to the total number of pixels constituting the measurement area is 40% or more (preferably 45% or more, more preferably 50% or more). [Aspect 3] The high-strength fiber according to Aspect 1 or 2, wherein the single fiber fineness is 0.5 to 500 dtex (preferably 1.0 to 300 dtex). [Aspect 4] The high-strength fiber according to any one of Aspects 1 to 3, wherein the high-strength fiber is a multifilament. [Embodiment 5] The high-strength fiber according to any one of embodiments 1 to 4, wherein the ratio of the deposition rate of the polysiloxane to the wax, in terms of polysiloxane / wax, is 20 / 80 to 90 / 10 (preferably 30 / 70 to 85 / 15).[Aspect 6] The high-strength fiber according to any one of Aspects 1 to 5, wherein the wax is an ester wax. [Aspect 7] The high-strength fiber according to any one of Aspects 1 to 6, wherein the melting point of the wax is 50 to 100°C (preferably 55 to 100°C, more preferably 60 to 90°C). [Aspect 8] The high-strength fiber according to any one of Aspects 1 to 7, wherein the total amount of the wax and polysiloxane is 1% by weight or more (preferably 2% by weight or more) based on the fiber weight. [Aspect 9] The high-strength fiber according to any one of Aspects 1 to 8, wherein the fiber type of the high-strength fiber is at least one selected from the group consisting of ultra-high molecular weight polyethylene fiber, aramid fiber, and liquid crystal polyester fiber. [Aspect 10] A high-strength fiber having a wax and a polysiloxane having a viscosity of 5000 mPa·s or more adhered to the fiber surface, and having an adhesion rate of the polysiloxane of 0.5% by weight or more (preferably 1.0% by weight or more, more preferably 1.5% by weight or more, even more preferably 2.0% by weight or more, and still more preferably 2.5% by weight or more) based on the fiber weight. [Aspect 11] The high-strength fiber according to any one of Aspects 1 to 10, which is used for a rope. [Aspect 12] A fiber structure comprising the high-strength fiber according to any one of Aspects 1 to 11. [Aspect 13] A rope comprising the high-strength fiber according to any one of Aspects 1 to 11.

[0011] In this specification, the term "high-strength fiber" refers to a fiber having an oil agent attached to its surface, unless otherwise specified. A high-strength fiber is composed of a fiber body mainly composed of a resin capable of forming a high-strength fiber, and a surface-attached portion formed on the fiber body and containing oil agent components such as polysiloxane and wax, which will be described later.

[0012] In this specification, the term "based on the weight of the fibers" means based on the weight of the fibers to which the wax and polysiloxane are attached.

[0013] As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms, including "at least one," unless the content clearly dictates otherwise. As used herein, the terms "and / or," "at least one," and "one or more" include any and all combinations of the associated listed items.

[0014] It should be noted that any combination of at least two elements disclosed in the claims and / or the specification and / or the drawings is included in the present invention, and in particular any combination of two or more of the claims set forth in the claims is included in the present invention.

[0015] In the present invention, the polysiloxane adheres to the fiber surface in a specific manner, thereby improving the abrasion resistance of the fiber, i.e., making it possible to suppress abrasion caused by repeated friction.

[0016] The present invention will be more clearly understood from the following description of preferred embodiments with reference to the accompanying drawings. However, the embodiments and drawings are for illustration and explanation purposes only and should not be used to define the scope of the present invention, which is defined by the appended claims.

[0017] 1 is an image showing the degree of polysiloxane adhesion to the high-strength fibers obtained in Example 1. FIG. 2 is a schematic diagram showing a method for measuring the abrasion properties of the high-strength fibers obtained in Examples and Comparative Examples.

[0018] The high-strength fiber is not particularly limited as long as it has a tensile strength of 7 cN / dtex or more. Specific examples include fibers containing various resins capable of forming high-strength fibers (hereinafter, sometimes simply referred to as high-strength resins), such as liquid crystal polyester fibers (Vectran UM (trademark) manufactured by Kuraray Co., Ltd., Vectran HT (trademark) manufactured by Kuraray Co., Ltd., Scivelas (trademark) manufactured by Toray Industries, Inc., and Zexion (trademark) manufactured by KB Seiren Co., Ltd.), ultra-high molecular weight polyethylene fibers (Toshiba Fibers, Toyobo Co., Ltd.), and the like. Examples of suitable fibers include Izanas (trademark), Dyneema (trademark) manufactured by DSM, etc.), aramid fibers (poly-p-phenylene terephthalamide fibers such as Kevlar (trademark) manufactured by DuPont-Toray Co., Ltd. and Twaron (trademark) manufactured by Teijin Limited, and copoly-p-phenylene-(3,4'-oxydiphenylene) terephthalamide fibers such as Technora (trademark) manufactured by Teijin Limited), and fibers made of poly(paraphenylene benzobisoxazole) (PBO) (Zylon (trademark) manufactured by Toyobo Co., Ltd., etc.). Of these, liquid crystal polyester fibers are preferred.

[0019] Liquid crystal polyester fibers can be produced, for example, by melt-spinning a liquid crystal polyester and, if necessary, solid-phase polymerizing the spun raw yarn. Liquid crystal polyesters are polyesters that exhibit optical anisotropy (liquid crystallinity) in the molten phase. This can be confirmed, for example, by placing a sample on a hot stage, heating it under a nitrogen atmosphere, and observing the transmitted light through the sample with a polarizing microscope. Liquid crystal polyesters are composed of structural units derived from, for example, aromatic diols, aromatic dicarboxylic acids, aromatic hydroxycarboxylic acids, etc., and the chemical structure of these structural units is not particularly limited as long as it does not impair the effects of the present invention. Furthermore, liquid crystal polyesters may also contain structural units derived from aromatic diamines, aromatic hydroxyamines, or aromatic aminocarboxylic acids, as long as it does not impair the effects of the present invention.

[0020] For example, preferred structural units include those shown in Table 1. Here, Y's may be present in a number ranging from 1 to the maximum number that can be substituted on the aromatic ring, and are each independently selected from the group consisting of 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, a t-butyl group, etc.), 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, etc.), and the like.

[0021] More preferred structural units include the structural units described in Examples (1) to (18) shown in the following Tables 2, 3, and 4. When the structural unit in the formula is a structural unit that can exhibit multiple structures, two or more of such structural units may be combined and used as structural units that constitute the polymer.

[0022]

[0023]

[0024]

[0025] In the structural units of Tables 2, 3 and 4, n is an integer of 1 or 2, and each structural unit n=1, n=2 may exist alone or in combination; Y １ and Y ２ may each independently represent 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, a t-butyl group, etc.), 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, etc.), etc. Among these, preferred Y １ and Y２ Examples of the aryl group include a hydrogen atom, a chlorine atom, a bromine atom, and a methyl group.

[0026] Examples of Z include substituents represented by the following formulas.

[0027] The liquid crystal polyester may preferably be a combination having two or more types of naphthalene skeletons as constituent units.

[0028] The liquid crystal polyester may preferably contain both a structural unit (A) derived from hydroxybenzoic acid and a structural unit (B) derived from hydroxynaphthoic acid. For example, the structural unit (A) may be represented by the following formula (A), and the structural unit (B) may be represented by the following formula (B). From the viewpoint of easily improving melt moldability, the ratio of the structural unit (A) to the structural unit (B) may preferably be in the range of 9 / 1 to 1 / 1, more preferably 7 / 1 to 1 / 1, and even more preferably 5 / 1 to 1 / 1.

[0029]

[0030] The total of the structural units (A) and the structural units (B) may be, for example, 65 mol % or more, more preferably 70 mol % or more, and even more preferably 80 mol % or more, based on the total structural units. Liquid crystal polyesters in which the structural units (B) account for 4 to 45 mol % of the polymer are particularly preferred.

[0031] The melting point of the liquid crystal polyester preferably used in the present invention is preferably 250 to 360°C, more preferably 260 to 320°C. Here, the melting point is the main absorption peak temperature observed when measured using a differential scanning calorimeter (DSC; Mettler "TA3000") in accordance with JIS K7121:2012. Specifically, 10 to 20 mg of a sample is placed in an aluminum pan in the DSC apparatus, and nitrogen is passed through as a carrier gas at 100 cc / min, and the endothermic peak is measured when the temperature is increased from room temperature (e.g., 25°C) at a rate of 20°C / min. If a clear peak does not appear in the first run of DSC measurement due to the type of polymer, the polymer may be heated at a heating rate of 50°C / min to a temperature 50°C higher than the expected flow temperature, held at that temperature for 3 minutes until completely melted, cooled to 50°C at a heating rate of -80°C / min, and then measured for an endothermic peak at a heating rate of 20°C / min.

[0032] The liquid crystal polyester may contain thermoplastic polymers such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyamide, polyphenylene sulfide, polyether ether ketone, and fluororesin, as long as the effects of the present invention are not impaired. Furthermore, various additives may be added, such as inorganic substances such as titanium oxide, kaolin, silica, and barium oxide, colorants such as carbon black, dyes, and pigments, antioxidants, ultraviolet absorbers, and light stabilizers.

[0033] The liquid crystal polyester fiber may contain 50% by weight or more of liquid crystal polyester, preferably 80% by weight or more, more preferably 90% by weight or more, even more preferably 95% by weight or more, and still more preferably 99.9% by weight or more.

[0034] The high-strength fiber may be a non-composite fiber or a composite fiber. The cross-sectional shape of the high-strength fiber is not particularly limited, and may be a normal fiber having a round cross section (including a cocoon shape), or a fiber having a modified cross section other than a round cross section. In the case of a modified cross section fiber, the cross-sectional shape may be, for example, rectangular, polygonal, triangular, hollow, flat, multi-lobed, cross-shaped, dogbone, T-shaped, V-shaped, or the like. Modified cross section fibers are often non-composite fibers.

[0035] Examples of composite fibers include sheath-core composite fibers composed of a sheath component and a core component, sea-island composite fibers composed of a sea component and an island component, side-by-side composite fibers composed of each side component, and split fibers with increased surface area of ​​the two components. Furthermore, these components may further have a sea-island structure, if necessary. Composite fibers may be made using any of the components that are capable of forming composite fibers, and preferred resins include the high-strength resins mentioned above (e.g., liquid crystal polyester, aramid, ultra-high molecular weight polyethylene, PBO, etc.). From the viewpoint of heat resistance, liquid crystal polyester, aramid, and PBO are more preferred.

[0036] Preferred conjugate fibers include sheath-core conjugate fibers in which the core component is a high-strength resin (e.g., liquid crystal polyester) and the sheath component is a flexible thermoplastic resin; and hybrid conjugate fibers in which the core component is a high-strength resin (e.g., liquid crystal polyester) and the sheath component has a sea-island structure, in which the sea component is a flexible thermoplastic resin and the island components are a high-strength resin (e.g., liquid crystal polyester).

[0037] The flexible thermoplastic resin may or may not have an aromatic ring on the main chain. Specific examples include polyolefins, polyamides, polycarbonates, polyphenylene sulfide (abbreviated as PPS), polyesters such as polyethylene terephthalate, modified polyethylene terephthalate, amorphous polyarylate, and polyethylene naphthalate (abbreviated as PEN), polyether ether ketones, and fluororesins. These flexible thermoplastic resins may be used alone or in combination of two or more, or one may be the primary thermoplastic resin (e.g., accounting for 80% by weight or more) with the remaining thermoplastic resins added. Among these, PPS and PEN are preferred as the primary thermoplastic resin. Furthermore, examples of hybrid composite fibers using a liquid crystal polyester as the core component, PEN as the sea component of the sheath component, and a liquid crystal polyester as the island component include Beckley (trademark) manufactured by Kuraray Co., Ltd.

[0038] The high strength fibers may generally have a single fiber fineness of about 0.5 to 500 dtex, preferably about 1.0 to 300 dtex. A single fiber fineness within the above range is preferred from the standpoint of handleability.

[0039] The high-strength fiber may be a monofilament or a multifilament. In the case of a multifilament, the number of filaments can be appropriately selected depending on the application, etc. For example, the number of filaments may be 2 to 5,000, preferably 3 to 4,000, more preferably 5 to 3,000, even more preferably 6 to 2,500, and still more preferably 7 to 2,000.

[0040] In the present invention, high-strength fibers refer to fibers having a strength of 7 cN / dtex or more, and may be, for example, about 8 to 100 cN / dtex, more preferably about 15 to 80 cN / dtex. The modulus of elasticity of high-strength fibers may be, for example, about 300 to 2000 cN / dtex, more preferably about 450 to 1500 cN / dtex. The strength and modulus are values ​​measured by the methods described in the examples below.

[0041] Furthermore, the high-strength fibers may contain inorganic substances such as titanium oxide, kaolin, silica, and barium oxide, colorants such as carbon black, dyes, and pigments, antioxidants, ultraviolet absorbers, light stabilizers, and various additives inside and / or on the surface of the fibers, as necessary.

[0042] (Polysiloxane) In the high-strength fiber of the present invention, a polysiloxane having a viscosity of 5,000 mPa·sec or more is adhered to the fiber surface. The high-viscosity polysiloxane having a viscosity of 5,000 mPa·sec or more contributes to improving the abrasion resistance of the high-strength fiber, and when used in combination with the wax described below, it brings about a synergistic effect in improving the abrasion resistance.

[0043] The viscosity of the polysiloxane may be preferably 8,000 mPa·s or more, more preferably 10,000 mPa·s or more, even more preferably 15,000 mPa·s or more, and particularly preferably 20,000 mPa·s or more. From the viewpoint of ease of handling, the viscosity of the polysiloxane may be preferably 1,000,000 mPa·s or less, more preferably 700,000 mPa·s or less, and even more preferably 500,000 mPa·s or less. The viscosity of the polysiloxane is a value measured by the method described in the Examples below. The viscosity of the polysiloxane attached to the fiber surface can be measured by extracting it from a fiber sample using a solvent appropriate for the type of polysiloxane. The viscosity of the polysiloxane may be, for example, 5,000 mPa·s or more and 1,000,000 mPa·s or less, preferably 8,000 mPa·s or more and 700,000 mPa·s or less, more preferably 10,000 mPa·s or more and 500,000 mPa·s or less, even more preferably 15,000 mPa·s or more and 500,000 mPa·s or less, particularly preferably 20,000 mPa·s or more and 500,000 mPa·s or less, and particularly preferably 100,000 mPa·s or more and 450,000 mPa·s or less.

[0044] The polysiloxane is not particularly limited as long as it has a viscosity at 25°C of 5,000 mPa·sec or more. Examples of the polysiloxane include polydimethylsiloxane and modified polysiloxanes obtained by modifying the same, such as phenyl-modified polysiloxane, aminoalkyl-modified polysiloxane, epoxy-modified polysiloxane, polyoxyalkylene-modified polysiloxane, and fatty acid-modified polysiloxane.

[0045] The state of adhesion of polysiloxane to the fiber surface can be ascertained by performing time-of-flight secondary ion mass spectrometry (TOF-SIMS) imaging of the fiber surface.

[0046] In TOF-SIMS, a sample introduced into a vacuum is irradiated with primary ions from a primary ion source. Secondary ions are then emitted from the sample surface in response to the irradiation of the primary ions, and reach the detector after a predetermined flight time. By measuring the distribution of this flight time, a mass spectrum of the secondary ions can be obtained. From the obtained mass spectrum, it is possible to perform imaging that reflects the in-plane distribution of any secondary ion peak. Si is used as the secondary ion. ＋ By detecting the ions, the in-plane distribution of polysiloxane can be determined.

[0047] For example, Figure 1 shows an image of the polysiloxane adhesion portion on the fiber surface when TOF-SIMS imaging was performed on the multifilament of Example 1. From the obtained image, the brightness value is divided into 256 gradations (0 gradation to 255 gradation) by grayscaling, and digitization is performed for each pixel number (number of pixels). Note that, as shown in Figure 1, in the case of a multifilament, the spaces between the fibers (between the individual fibers constituting the multifilament) are excluded from the measurement by masking.

[0048] In image analysis, pixels with a brightness value of 0 (0 gradation) can be determined as non-adhered portions, pixels with a brightness value of 255 (255 gradation) as excessively attached portions where an excessive amount of polysiloxane has adhered (portions where polysiloxane has adhered or is present locally (in the form of clumps larger than one pixel in image analysis)), and pixels with other brightness values ​​(1 to 254 gradation) can be determined as appropriately attached portions where polysiloxane has adhered in an appropriate amount (portions where polysiloxane has adhered or is present without being localized (as fine particles within one pixel)).

[0049] That is, when no polysiloxane is attached (brightness value 0), even if only wax is attached, the wax will move away from that location during use, making it difficult to expect an improvement in abrasion resistance. On the other hand, when an excessive amount of polysiloxane is attached (brightness value 255), it is difficult to expect a synergistic effect with the wax, perhaps because it inhibits the attachment of the wax. In contrast, at other brightness values, an appropriate amount of polysiloxane is attached in dots, allowing the wax to penetrate between them, making it possible to expect a synergistic effect with the wax.

[0050] The proportion of the properly adhered portion can be calculated by the following formula: Proportion of the properly adhered portion (%) = (Number of pixels in the properly adhered portion / Total number of pixels) x 100

[0051] That is, when the imaging is performed, the proportion of the properly attached portion of polysiloxane occupying the fiber surface may be 60% or more, preferably 65% ​​or more, more preferably 70% or more, as the number of pixels extracted as ion moieties derived from polysiloxane (excluding 0 gradation and 255 gradation) relative to the total number of pixels constituting the measurement area, for a measurement area obtained from a 256-gradation monochrome image obtained by grayscaling the ion intensity derived from the polysiloxane. The upper limit is not particularly limited, but may be 100% or less.

[0052] For example, when multiple measurement regions (e.g., 10 regions) are used as measurement regions, the proportion of the polysiloxane-adhered portion in the high-strength fiber may be calculated as the number of pixels (excluding 0 gradation and 255 gradation) extracted as ion moieties derived from the polysiloxane relative to the total number of pixels in all measurement regions. That is, the proportions of the properly attached portion in each measurement region may be averaged over all regions, and the average value may satisfy the above-mentioned range. For example, when multiple measurement regions are used, positions that differ from each other by 1 m or more in the fiber axial direction may be selected. When the high-strength fiber is wound around a cylindrical object such as a bobbin, from the viewpoint of excellent uniformity of abrasion resistance, 10 points (excluding both ends of the fiber) obtained by dividing the entire length of the fiber into 11 equal parts in the fiber axial direction may be selected as each measurement region, and the average value of the proportions of the properly attached portion at the 10 points may satisfy the above-mentioned range.

[0053] The higher the proportion of properly attached portions of the polysiloxane, the higher the proportion of portions on the fiber surface where the polysiloxane adheres in dots, and a synergistic effect with the wax can be expected. The presence of properly attached portions of the high-viscosity polysiloxane adhering to the fiber surface makes it possible to maintain the abrasion resistance of the high-strength fiber for a long period of time.

[0054] As long as the appropriate adhesion portion of the polysiloxane can be adhered to the fiber surface within the above-mentioned range, there are no particular limitations on the method, but it is preferable to apply a high-viscosity polysiloxane to the fiber surface after emulsifying it with an emulsifier or the like. Specific application methods include impregnation treatment, discharge treatment, coating treatment, and immersion and squeezing treatment. Such treatments may be applied, for example, to various fiber structures (e.g., filaments, tows, yarns, cut fibers, strands, ropes, cloths, etc.) made from fibers containing the above-mentioned high-strength resin (fibers before the polysiloxane is adhered). Various fiber structures may be made using the high-strength fibers after the above-mentioned treatments.

[0055] The polysiloxane adhesion rate may be, for example, 0.1 wt% or more, preferably 0.3 wt% or more, more preferably 0.5 wt% or more, even more preferably 1.0 wt% or more, even more preferably 1.5 wt% or more, 2.0 wt% or more, or 2.5 wt% or more, based on the fiber weight of the high-strength fiber. The upper limit is not particularly limited, but may be, for example, 10 wt% or less, preferably 8 wt% or less, more preferably 7 wt% or less, and even more preferably 5 wt% or less. The adhesion rate is a value measured by the method described in the Examples section below. The polysiloxane adhesion rate may be, for example, 0.1 to 10 wt%, preferably 0.3 to 8.0 wt%, more preferably 0.5 to 7.0 wt%, even more preferably 1.0 to 5.0 wt%, even more preferably 1.5 to 5.0 wt%, particularly preferably 2.0 to 5.0 wt%, and particularly preferably 2.5 to 5.0 wt%, based on the fiber weight of the high-strength fiber.

[0056] (Emulsifier) ​​Since the polysiloxane used in the present invention has a high viscosity, it is preferable to carry out a dispersion treatment when applying it to the fiber surface. The dispersion treatment is not particularly limited as long as it can control the appropriate adhesion portion of the polysiloxane on the fiber surface, and may be carried out by high-speed stirring in a solvent, but it is preferable to emulsify the polysiloxane using an emulsifier and then adhere it to the fiber.

[0057] Examples of emulsifiers that can be used include nonionic, anionic, and cationic emulsifiers. Examples of nonionic emulsifiers include polyoxyethylene ethers (e.g., polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene aryl ethers, etc.), polyethylene glycol esters, etc. Examples of anionic emulsifiers include metal soaps, alkylbenzene sulfonates such as sodium alkylbenzene sulfonate, and alkylnaphthalene sulfonates such as sodium alkylnaphthalene sulfonate. Examples of cationic emulsifiers include quaternary ammonium salts such as monoalkylammonium chloride and dialkylammonium chloride. These emulsifiers can be used alone or in combination. Of these emulsifiers, it is particularly preferable to use an anionic emulsifier and a nonionic emulsifier in combination.

[0058] The amount of emulsifier used may be about 1 to 80 parts by mass, preferably about 5 to 70 parts by mass, and more preferably about 10 to 60 parts by mass, per 100 parts by mass of polysiloxane.

[0059] (Wax) On the other hand, even if a high-viscosity polysiloxane is used alone, the abrasion resistance of high-strength fibers does not improve as much as expected. However, when such a high-viscosity polysiloxane is combined with a wax and attached to the fiber surface, the abrasion resistance of the fiber can be significantly improved, although the reason is not clear.

[0060] The following mechanism is presumed to explain the improved abrasion resistance. Specifically, wax and high-viscosity polysiloxane particles adhere to the fiber in a moderately coexistent state on at least a portion of the fiber surface, allowing the high-viscosity polysiloxane to remain on the fiber surface. It is believed that the synergistic effect of the two components significantly improves abrasion resistance. For example, fibers containing the above-mentioned high-strength resin have high molecular orientation in the fiber axis direction, making them strong, but their fiber surfaces are prone to wear. However, this mechanism, which is mediated by the specific oil agent component that covers the fiber surface of the high-strength fiber, can significantly improve abrasion resistance, regardless of the chemical structure of the fiber surface itself (i.e., the type of resin that constitutes the high-strength fiber).

[0061] Here, wax generally refers to an organic substance that is solid at room temperature and becomes liquid when heated, and may be of natural or synthetic origin. The melting point is not particularly limited, but may be, for example, 50 to 100°C, preferably 55 to 100°C, and more preferably 60 to 90°C. When the melting point of the wax is within the above range, it is easy to create a state in which the polysiloxane and the wax coexist on the fiber surface.

[0062] The state of wax adhesion on a fiber surface can be determined by performing time-of-flight secondary ion mass spectrometry (TOF-SIMS) imaging of the fiber surface, similar to the state of polysiloxane adhesion on a fiber surface. The secondary ions used in imaging wax adhesion can be appropriately selected depending on the chemical structure of the wax, and such selection is well known to those skilled in the art. When performing the imaging, the proportion of properly attached wax areas may be 20% or more, preferably 30% or more, and more preferably 40% or more. The upper limit is not particularly limited, but it may be 100% or less, or 95% or less. The imaging and image analysis of wax can be performed in accordance with the method for calculating the proportion of properly attached polysiloxane areas on a fiber surface. The higher the proportion of properly attached wax areas, the higher the proportion of areas that are attached without localization on the fiber surface (existing as fine particles within one pixel), and a synergistic effect with polysiloxane can be expected.

[0063] The wax is preferably emulsified with an emulsifier and attached to the fiber surface, similarly to the polysiloxane, and examples of the emulsifier to be used include the emulsifiers described above. The wax may be emulsified together with the polysiloxane and then applied, or the polysiloxane and the wax may be emulsified separately and then applied. When applied separately, the polysiloxane may be applied first, or the wax may be applied first.

[0064] Preferred waxes include hydrocarbon waxes, ester waxes, amide waxes, etc. These waxes may be used alone or in combination of two or more.

[0065] Examples of hydrocarbon waxes include paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, oxidized waxes of these, and hydrogenated waxes. Preferred examples include paraffin wax, polyethylene wax, oxidized waxes of these, and hydrogenated waxes. Paraffin wax is a white wax that is solid at room temperature and is primarily composed of linear hydrocarbons. The linear hydrocarbons may have a carbon number distribution of about 20 to 40, and a molecular weight of about 300 to 550, for example. Polyethylene wax is a low-molecular-weight polyethylene wax obtained by linearly polymerizing ethylene, and may have a molecular weight of, for example, 400 to 3,000.

[0066] Ester waxes are compounds having a long-chain molecular structure in which a linear or branched long-chain fatty acid and a linear or branched long-chain fatty alcohol are ester-bonded. The carbon number of the long-chain fatty acid may be, for example, 10 or more, preferably 10 to 15, and more preferably 10 to 12. The carbon number of the long-chain fatty alcohol may be, for example, 10 or more, preferably 10 to 15, and more preferably 10 to 12. The fatty acid and fatty alcohol may be saturated or unsaturated. The fatty alcohol may be a polyhydric alcohol, but is preferably a monohydric alcohol.

[0067] Amide waxes are compounds having a long-chain molecular structure in which a linear or branched long-chain fatty acid and a linear or branched long-chain aliphatic amine are amide-bonded. The carbon number of the long-chain fatty acid may be, for example, 10 or more, preferably 10 to 15, and more preferably 10 to 12. The carbon number of the long-chain aliphatic amine may be, for example, 10 or more, preferably 10 to 15, and more preferably 10 to 12. The fatty acid and the aliphatic amine may be saturated or unsaturated. The aliphatic amine may be a polyvalent amine, but is preferably a monovalent amine.

[0068] The wax deposition rate may be, for example, 0.1% by weight or more, preferably 0.3% by weight or more, based on the fiber weight of the high-strength fiber. The upper limit is not particularly limited, but may be, for example, 10% by weight or less, preferably 8% by weight or less, and more preferably 5% by weight or less. The deposition rate is a value measured by the method described in the Examples section below. The wax deposition rate may be, for example, 0.1 to 10% by weight, preferably 0.3 to 8.0% by weight, and more preferably 0.5 to 5.0% by weight, based on the fiber weight of the high-strength fiber.

[0069] The total amount of wax and polysiloxane may be, for example, 0.5% by weight or more, 1% by weight or more, and preferably 2% by weight or more, based on the weight of the high-strength fibers. The upper limit is not particularly limited, but may be, for example, 20% by weight or less, 15% by weight or less, or 10% by weight or less. The total amount of wax and polysiloxane may be, for example, 0.5 to 20% by weight, preferably 1.0 to 15% by weight, and more preferably 2.0 to 10% by weight, based on the weight of the high-strength fibers.

[0070] The ratio of the deposited polysiloxane to the wax, expressed as polysiloxane / wax (Si / W), may be, for example, 20 / 80 to 90 / 10, preferably 30 / 70 to 85 / 15, and in one preferred embodiment, 50 / 50 to 80 / 20.

[0071] The high-strength fiber of the present invention has excellent abrasion resistance, and although this differs depending on the type of high-strength resin contained in the fiber body, for example, when the fiber contains a liquid crystal polyester fiber, the number of reciprocations until breakage in the twist abrasion test described in the Examples below may be 120,000 or more, preferably 140,000 or more, more preferably 160,000 or more, and even more preferably 200,000 or more. The upper limit is not particularly limited, but may be, for example, about 2,000,000 or less.

[0072] For the high-strength fibers of the present invention, it is important that a high-viscosity polysiloxane is present, and that the high-viscosity polysiloxane and wax are present in a state that exhibits a synergistic effect on the fiber surface. There are no particular limitations on the method for applying the polysiloxane and wax to the fiber surface; the polysiloxane and wax may be applied separately, or both may be applied together. When applying the polysiloxane and wax separately, for example, the polysiloxane may be applied to the fiber surface by a roller such as an oiling roller, by a guide nozzle, or by immersion oiling, and then the wax may be applied by a roller such as an oiling roller, by a guide nozzle, or by immersion oiling. The order of application may be reversed. It is preferable to apply the polysiloxane and the wax to the fiber surface consecutively (for example, before the first application is completely dried). When polysiloxane and wax are applied together, as described above, the polysiloxane and wax may be applied to the fiber surface using a liquid mixture (preferably a liquid in which the polysiloxane and wax are emulsified). As described above, the application method can be a known method such as application with a roller, application with a guide nozzle, or immersion oiling.

[0073] The temperature at which the polysiloxane and wax are applied to the fiber surface is not particularly limited, but is preferably 0 to 50°C. The fiber having the polysiloxane and wax applied to its surface may be dried through a heating step. The temperature in the heating step may be appropriately selected depending on the type of fiber used, but may be, for example, 30 to 200°C.

[0074] (Fiber Structure) The present invention encompasses a fiber structure containing high-strength fibers. The fiber structure may be a one-dimensional structure such as continuous fibers (monofilaments, multifilaments), short fibers (cut fibers), threads, strings, belts, cords, or ropes. Alternatively, the fiber structure may be a two-dimensional structure or even a three-dimensional structure including fabrics such as woven fabrics, knitted fabrics, nonwoven fabrics, and meshes containing the high-strength fibers. The fiber structure may be composed solely of high-strength fibers, or may be composed of a combination of high-strength fibers and other fibers. For example, the fiber structure may be a composite fiber made of high-strength fibers and other fibers (e.g., a blended yarn or blended yarn made of high-strength fibers and other fibers). Furthermore, the fiber structure may be a composite fabric made of high-strength fibers and other fibers (e.g., a blended fabric made of high-strength fibers and other fibers, or a laminate of a fabric made of high-strength fibers and a fabric made of other fibers).

[0075] The high-strength fiber of the present invention is particularly useful as a constituent material for ropes. The rope need only contain the high-strength fiber of the present invention, and may also contain other fibers. The structure of the rope is not particularly limited, and may have a known structure depending on the application, such as a single-layer plied or braided structure. In the case of a plied or braided structure, the structure may be 3-strand or 4-strand, and in the case of a braided structure, the structure may be 8-strand, 12-strand, 16-strand, 32-strand, etc. The rope may also have a double structure consisting of an inner layer and an outer layer covering the inner layer. In the case of a double-structure rope, the inner layer and the outer layer may each be a plied or braided structure as described above. Furthermore, it is preferable that the double-structure rope contains high-strength fibers in the inner layer.

[0076] Depending on the structure, ropes containing high-strength fibers can be used in a variety of applications on the water, such as mooring ships, edge ropes for fishing nets, mooring floating water facilities that are set up in a floating state on the water, and ropes for mooring floating marine structures used in the exploration of marine resources to the seabed; on land, such as towing lines, cargo lines, wind power generation facilities, and substation facilities; and in fields such as sports and leisure.

[0077] Another embodiment of the present invention may include high-strength fibers having wax and polysiloxane with a viscosity of 5,000 mPa·sec or more adhered to the fiber surface, with the polysiloxane adhesion rate being 0.5 wt % or more based on the fiber weight. The viscosity and adhesion rate may be within the numerical ranges described in the section on polysiloxane.

[0078] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0079] [Fineness] The total fineness of the multifilament sample was measured based on JIS L 1013: 2010. The single fiber fineness was calculated by dividing the total fineness by the number of filaments constituting the multifilament.

[0080] [Polysiloxane Viscosity] Each polysiloxane oil sample used in the Examples and Comparative Examples was dried at 105°C for 2 hours, and the viscosity of the nonvolatile fraction was measured using an E-type viscometer (measurement temperature: 25°C). The minimum value within the measured range was used as the polysiloxane viscosity. When measuring the viscosity of polysiloxane attached to a fiber sample, the polysiloxane can be extracted from the fiber sample using a solvent appropriate for the type of polysiloxane. For example, for the fiber samples obtained in the Examples and Comparative Examples, a mixed solvent of hexane / ethanol (volume ratio 10 / 3) was used to perform Soxhlet extraction, and the polysiloxane was fractionated by preparative gel permeation chromatography, and the amount required for viscosity measurement was secured and measured.

[0081] [TOF-SIMS Imaging: Measurement of Proper Adhesion Area] The conditions used for TOF-SIMS imaging are as follows. <Measurement Conditions> Analytical device used: TOF-SIMS5 (manufactured by ION-TOF GmbH) Primary ion source: double-charged ions of bismuth clusters (Bi ３ ＋＋) Primary ion energy conditions: 25 keV Primary ion target current: 0.2 pA (frequency 10 kHz) Charge correction: Measurement was performed while performing charge correction using the electron gun attached to the device Detector: Measurement was performed in positive ion acquisition mode Measurement (secondary ion detection) range: 150 x 150 μm (random raster mode) Number of pixels: 128 x 128 pixels Number of integrations: 64 scans

[0082] <Method of analyzing the deposit distribution image> Pixels with an intensity less than 10% of the total secondary ion intensity X at the pixel with the maximum intensity in this two-dimensional image were considered to be "pixels without a sample" or "pixels where the distribution cannot be accurately evaluated" because secondary ions were not sufficiently detected due to the influence of the unevenness or electrostatic charge of the fiber, and were excluded from the subsequent analysis. After the above processing, for pixel ROIs (Region of Interest) with a value of 10% or more of X, the mass spectrum of only the ROI was reconstructed. Then, from the mass spectrum of the ROI, Si was detected as a secondary ion derived from polysiloxane. ＋ A two-dimensional image of the intensity of 1000 kJ / s was obtained. The ion intensity of each pixel in the two-dimensional image was extracted, and the maximum value Y was calculated, excluding outliers. Note that outliers refer to values ​​greater than (third quartile) + (interquartile range) × 1.5 and values ​​less than (first quartile) - (interquartile range) × 1.5. Finally, the maximum value of the color bar of the two-dimensional image was set to Y, and the minimum value to 0, and the two-dimensional image was displayed in grayscale on a linear scale. This series of operations was performed using the analysis software provided with the instrument.

[0083] <Calculation method> Conversion software used: Stirling The secondary ions measured are as follows: Polysiloxane: Si ＋ ES (ester wax): C ６ H １１ ＋ PA (paraffin wax): C ６ H １１ ＋ PE (polyethylene wax): C ６ H １１ ＋The brightness values ​​of the obtained image were divided into 256 levels by a binarization operation, and each pixel was quantified. Pixels with a brightness value of 0 were judged to be non-adhered areas, pixels with a brightness value of 255 were judged to be excessively attached areas where polysiloxane or wax was excessively attached, and pixels with other brightness values ​​were judged to be properly attached areas where polysiloxane or wax was appropriately attached. The proportion of properly attached areas was then calculated using the following formula: Proportion of properly attached areas (%) = (number of pixels in properly attached areas / total number of pixels) x 100

[0084] [Wax Melting Point] The melting point of each wax oil sample was measured according to JIS K 0064:1992. The melting point of each wax oil was the minimum value within the measured range. The melting points of the waxes used in the Examples and Comparative Examples were as follows: ES (ester wax): 80°C PA (paraffin wax): 55°C PE (polyethylene wax): 100°C. When measuring the melting point of wax attached to a fiber sample, the wax can be extracted from the fiber sample using a solvent appropriate for the type of wax. For example, for the fiber samples obtained in the Examples and Comparative Examples, the wax can be fractionated by preparative gel permeation chromatography from an extract obtained by Soxhlet extraction using a mixed solvent of hexane / ethanol (volume ratio 10 / 3), and the amount required for melting point measurement can be secured and measured.

[0085] [Polysiloxane Deposition Rate] For the samples obtained in the Examples and Comparative Examples, a mixed solvent of hexane / ethanol (volume ratio 10 / 3) was used to obtain an extract by the Soxhlet extraction method, and polysiloxane was fractionated by preparative gel permeation chromatography, and its weight was measured. The obtained weight was divided by the weight of the fiber sample subjected to extraction, and the value expressed as a percentage was calculated as the polysiloxane deposition rate.

[0086] [Wax Deposition Rate] For the samples obtained in the Examples and Comparative Examples, a mixed solvent of hexane / ethanol (volume ratio 10 / 3) was used to obtain an extract by the Soxhlet extraction method, and the wax was fractionated by preparative gel permeation chromatography, and the weight of the fraction was measured. The obtained weight was divided by the weight of the fiber sample subjected to extraction, and the value expressed as a percentage was calculated as the wax deposition rate.

[0087] [Abrasion Resistance Test] The fibers (multifilament) obtained in the Examples and Comparative Examples were twisted at 80 T / m to prepare yarn samples. Using the obtained yarns, a twisting abrasion test was conducted as shown in Figure 2. The yarns were wrapped around upper and lower pulleys and secured to prevent slippage between the pulleys and the yarn. The inner diameters of the upper and lower pulleys were both 45 mm, and the distance between the centers of the upper and lower pulleys with the yarn secured was adjusted to 500 mm. The yarns were first looped, and then twisted three times to form a twisted portion X of approximately 20 mm. The yarns were then secured to the upper and lower pulleys, and a load of 3 kg was applied to the lower pulley in the direction indicated by the arrow below. The pulley was reciprocated at an angle of 180° at a frequency of 60 times / min (MV=34.2 Hz) to wear the twisted portion of the yarn, and the number of reciprocation of the pulley until the yarn broke was counted. The upper limit of the number of reciprocation was set to 1,000,000 times.

[0088] [Tensile strength and elastic modulus] The tensile strength was measured according to JIS L1013:2010 using the fibers obtained in the examples and comparative examples, and the value obtained by dividing the tensile strength by the total fineness was used as the tensile strength. Also, the initial tensile resistance was measured according to JIS L1013:2010 and used as the elastic modulus.

[0089] Example 1 Liquid crystal polyester fiber (Vectran (trademark), manufactured by Kuraray Co., Ltd., 1670 dtex / 300 filaments, tensile strength 341 kg / mm ２ , breaking elongation 4.0%, tensile modulus 6479 kg / mm ２The polysiloxane / wax mixed oil solution shown in Table 5 was applied to the fiber in the weight ratio shown in Table 5 so that the amount of oil applied was 4.0% by weight based on the fiber weight, and the fiber was dried and then wound up.

[0090] Examples 2 to 10 Examples 2 to 4 and 6 to 9 were carried out in the same manner as Example 1, except that the viscosity of the polysiloxane, the type of wax, the weight ratio of the polysiloxane and the wax, and the amount of adhesion were adjusted according to each example, as shown in Tables 5 and 6.

[0091] Examples 5 and 10 were carried out in the same manner as Example 1, except that the viscosity of the polysiloxane, the type of wax, the weight ratio of the polysiloxane and the wax, and the amount of the wax applied were adjusted as shown in Tables 5 and 6, and the polysiloxane / wax mixed oil solution was prepared by adjusting the temperature and stirring to improve dispersibility.

[0092] Comparative Examples 1 and 2 The same procedure as in Example 1 was carried out except that, as shown in Table 5, the viscosity of the polysiloxane, the type of wax, and the weight ratio of the polysiloxane to the wax were changed.

[0093] Comparative Examples 3 and 4 The same procedures as in Example 1 were carried out except that the viscosity and amount of the polysiloxane applied were changed as shown in Table 6 and no wax was used.

[0094] The physical properties of the resulting high strength fibers are shown in Tables 5 and 6.

[0095]

[0096] As shown in Table 5, in Examples 1 to 6, in which the viscosity of the polysiloxane was high, the proportion of properly adhered areas of the polysiloxane obtained by TOF-SIMS imaging was 60% or more, and in all cases, the combination with wax improved the abrasion resistance compared to Comparative Examples 1 and 2. Furthermore, as shown in Table 6, in all cases, Examples 7 to 10 improved the abrasion resistance compared to Comparative Examples 3 and 4, in which no wax was used.

[0097] The high strength fiber of the present invention has significantly improved abrasion resistance and is therefore useful as a material for clothing, bedding and interior materials, sports materials, industrial materials, civil engineering and construction materials, transportation materials, and the like.

[0098] The high-strength fibers of the present invention are particularly useful as a constituent material for ropes. Ropes containing the high-strength fibers can be used in a variety of applications on the water, such as mooring ships, edge ropes for fishing nets, mooring floating water facilities that are set up in a floating state on the water, and ropes for mooring floating marine structures to the seabed used in marine resource exploration, etc., as well as on land, such as towing lines, cargo lines, wind power generation facilities, and power transformation facilities, and in fields such as sports and leisure.

[0099] As described above, the preferred embodiments of the present invention have been described, but various additions, modifications, or deletions can be made without departing from the spirit of the present invention, and such additions, modifications, or deletions are also included within the scope of the present invention.

Claims

1. A high-strength fiber having wax and a polysiloxane with a viscosity of 5,000 mPa·s or more attached to its surface, and when time-of-flight secondary ion mass spectrometry (TOF-SIMS) imaging is performed on said surface, in a measurement area obtained from a 256-level monochrome image obtained by grayscaling the ion intensity derived from the polysiloxane, the number of pixels (excluding 0 level and 255 level) extracted as ion-adhered areas derived from the polysiloxane is 60% or more of the total number of pixels constituting the measurement area.

2. A high-strength fiber according to claim 1, wherein when TOF-SIMS imaging is performed on the surface, in a measurement area obtained from a 256-level monochrome image obtained by grayscaling the ion intensity derived from the wax, the number of pixels (excluding 0 level and 255 level) extracted as ion attachment areas derived from the wax accounts for 40% or more of the total number of pixels constituting the measurement area.

3. The high strength fiber according to claim 1 or 2, wherein the single fiber fineness is 0.5 to 500 dtex.

4. The high strength fiber according to any one of claims 1 to 3, which is a multifilament high strength fiber.

5. A high strength fiber according to any one of claims 1 to 4, in which the ratio of the deposition rate of polysiloxane to wax, in terms of polysiloxane / wax, is 20 / 80 to 90 / 10.

6. A high strength fiber according to any one of claims 1 to 5, wherein the wax is an ester wax.

7. A high strength fiber according to any one of claims 1 to 6, wherein the wax has a melting point of 50 to 100°C.

8. A high strength fiber according to any one of claims 1 to 7, wherein the total amount of wax and polysiloxane is 1% by weight or more based on the weight of the fiber.

9. A high strength fiber according to any one of claims 1 to 8, wherein the fiber type of the high strength fiber is at least one selected from the group consisting of ultra-high molecular weight polyethylene fiber, aramid fiber, and liquid crystal polyester fiber.

10. A high-strength fiber having wax and polysiloxane with a viscosity of 5,000 mPa·sec or more adhered to the fiber surface, and the adhesion rate of said polysiloxane is 0.5% by weight or more based on the fiber weight.

11. The high strength fiber according to any one of claims 1 to 10, which is used for ropes.

12. A fiber structure comprising the high strength fiber according to any one of claims 1 to 11.

13. A rope comprising the high strength fiber according to any one of claims 1 to 11.