Classifications

• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B1/00—Constructional features of ropes or cables
  • D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
  • D07B1/162—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber enveloping sheathing
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
  • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
• • D—TEXTILES; PAPER
  • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
  • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
  • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04C—BRAIDING OR MANUFACTURE OF LACE, INCLUDING BOBBIN-NET OR CARBONISED LACE; BRAIDING MACHINES; BRAID; LACE
  • D04C1/00—Braid or lace, e.g. pillow-lace; Processes for the manufacture thereof
  • D04C1/06—Braid or lace serving particular purposes
  • D04C1/12—Cords, lines, or tows
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B1/00—Constructional features of ropes or cables
  • D07B1/02—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
  • D07B1/025—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics comprising high modulus, or high tenacity, polymer filaments or fibres, e.g. liquid-crystal polymers
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B1/00—Constructional features of ropes or cables
  • D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2201/00—Ropes or cables
  • D07B2201/10—Rope or cable structures
  • D07B2201/1096—Rope or cable structures braided
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2201/00—Ropes or cables
  • D07B2201/20—Rope or cable components
  • D07B2201/2001—Wires or filaments
  • D07B2201/201—Wires or filaments characterised by a coating
  • D07B2201/2012—Wires or filaments characterised by a coating comprising polymers
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2201/00—Ropes or cables
  • D07B2201/20—Rope or cable components
  • D07B2201/2015—Strands
  • D07B2201/2042—Strands characterised by a coating
  • D07B2201/2044—Strands characterised by a coating comprising polymers
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2205/00—Rope or cable materials
  • D07B2205/20—Organic high polymers
  • D07B2205/201—Polyolefins
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2205/00—Rope or cable materials
  • D07B2205/20—Organic high polymers
  • D07B2205/201—Polyolefins
  • D07B2205/2014—High performance polyolefins, e.g. Dyneema or Spectra
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2205/00—Rope or cable materials
  • D07B2205/30—Inorganic materials
  • D07B2205/3017—Silicon carbides
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2501/00—Application field
  • D07B2501/20—Application field related to ropes or cables
  • D07B2501/2061—Ship moorings
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core

Definitions

• This invention relates to improvements in ropes, and in particular to high tenacity synthetic ropes suitable for use in marine applications.
• Synthetic fiber ropes have been used in a variety of applications, including various marine applications.
• One type of rope that has excellent properties is rope made from high modulus polyolefin fibers and/or yarns.
• High tenacity polyolefin fibers are also known as extended chain or high molecular weight fibers. These fibers and yarns are available, for example, as SPECTRA® extended chain polyethylene fibers and yarns from Honeywell International Inc.
• Ropes formed from extended chain polyethylene fibers have been suggested for use in marine applications. See, for example, U.S. Patents 5,901,632 and 5,931,076 both to Ryan, the disclosures of which are expressly incorporated herein by reference to the extent not incompatible herewith.
• extended chain polyethylene ropes are repeatedly bent over sheaves, pulleys or posts as they are being used.
• Some synthetic ropes experience premature wear when they are subjected to repeated bending over sheaves, and particularly synthetic ropes used in marine industrial applications have experienced this problem.
• Synthetic ropes continue to replace steel wire in many marine applications. As synthetic ropes progress to replace steel wire in many cyclic bend-over sheave
• a rope having improved CBOS fatigue resistance comprising high tenacity fibers, the rope and/or the fibers being coated with a composition comprising an amino functional silicone resin and a neutralized low molecular weight polyethylene.
• a rope having improved CBOS fatigue resistance comprising a blend of high tenacity polyolefin fibers with other high tenacity fibers that are not polyolefin fibers, the rope and/or the fibers being coated with a composition comprising an amino functional silicone resin and a neutralized low molecular weight polyethylene.
• a rope having improved CBOS fatigue resistance comprising a blend of high tenacity polyolefin fibers with other high tenacity fibers, the other high tenacity fibers comprising aramid fibers and/or liquid crystal copolyester fibers, the rope and/or the fibers being coated with a composition comprising an amino functional silicone resin and a neutralized low molecular weight polyethylene.
• a method of improving the CBOS fatigue life of a rope comprising forming the rope from high tenacity fibers, and coating the rope and/or the fibers forming such rope with a composition comprising an amino functional silicone resin and a neutralized low molecular weight polyethylene.
• a method of lifting and placing heavy objects from and onto a seabed using a synthetic fiber rope comprising utilizing as such rope a rope comprising high tenacity fibers, the rope and/or the fibers being coated with a composition comprising an amino functional silicone resin and a neutralized low molecular weight polyethylene.
• a fiber is an elongate body the length dimension of which is much greater that the transverse dimensions of width and thickness. Accordingly, the term “fiber” includes monofilament, multifilament, ribbon, strip, staple and other forms of chopped, cut or discontinuous fiber and the like having regular or irregular cross-sections. The term “fiber” includes a plurality of any of the foregoing or a combination thereof.
• a yarn is a continuous strand comprised of many fibers or filaments. Fibers may also be in the form of ribbon, strip or split film or tape.
• the cross-sections of fibers useful herein may vary widely. They may be circular, flat or oblong in cross-section. They may also be of irregular or regular multi-lobal cross-section having one or more regular or irregular lobes projecting from the linear or longitudinal axis of the fibers. It is preferred that the fibers be of substantially circular, flat or oblong cross-section, most preferably substantially circular.
• ropes comprising high modulus polyolefin fibers, such as extended chain polyethylene fibers, and yarns made therefrom have been suggested for use in marine applications.
• One such use of the ropes is for heavy lifting and mooring of objects onto the seabed.
• Other applications include offshore oil and gas exploration, oceanographic, seismic and other industrial applications.
• the most preferred applications for ropes of this invention include deep sea lifting and placement.
• the fibers used in the rope construction of this invention are high tenacity fibers.
• the term "high tenacity fibers” means fibers which have tenacities equal to or greater than about 7 g/d.
• these fibers have initial tensile moduli of at least about 150 g/d and energies-to-break of at least about 8 J/g as measured by ASTM D2256.
• the terms "initial tensile modulus”, “tensile modulus” and “modulus” mean the modulus of elasticity as measured by ASTM 2256 for a yarn.
• the high tenacity fibers have tenacities equal to or greater than about 10 g/d, more preferably equal to or greater than about 16 g/d, even more preferably equal to or greater than about 22 g/d, and most preferably equal to or greater than about 28 g/d.
• the high tenacity fibers may be used alone in the rope construction, or more preferably are used as blends of two or more high tenacity fibers of different chemical composition in the rope construction.
• High tenacity fibers useful herein include highly oriented high molecular weight polyolefin fibers, particularly high modulus polyethylene fibers and polypropylene fibers, aramid fibers, polybenzazole fibers such as polybenzoxazole (PBO) and polybenzothiazole (PBT), polyvinyl alcohol fibers, polyacrylonitrile fibers, polyamide fibers, polyester fibers, liquid crystal copolyester fibers, glass fibers, carbon fibers or basalt or other mineral fibers, as well as rigid rod polymer fibers, and mixtures and blends thereof.
• Preferred high strength fibers useful in this invention include polyolefin fibers, aramid fibers and liquid copolyester fibers, and mixtures and blends thereof.
• yarns that form the ropes can be made from a blend of two or more of such high tenacity fibers, preferably the yarns that make up the rope are formed from a single high tenacity fiber type, and two or more yarns of different fiber types are used to form the rope.
• Preferred blends are blends of high tenacity polyethylene fibers and aramid fibers, and blends of high tenacity fibers and liquid crystal copolyester fibers, as well as blends of aramid fibers and liquid crystal copolyester fibers.
• the fibers utilized in the rope construction preferably comprise extended chain (also known as high molecular weight, high tenacity or high modulus) polyolefin fibers, particularly high modulus polyethylene fibers and polypropylene fibers.
• extended chain also known as high molecular weight, high tenacity or high modulus
• polyolefin fibers particularly high modulus polyethylene fibers and polypropylene fibers.
• suitable fibers are those of weight average molecular weight of at least about 150,000, preferably at least about one million and more preferably between about two million and about five million.
• Such high molecular weight polyethylene fibers may be spun in solution (see U.S. Pat. No.
• polyethylene means a predominantly linear polyethylene material that may contain minor amounts of chain branching or comonomers not exceeding about 5 modifying units per 100 main chain carbon atoms, and that may also contain admixed therewith not more than about 50 wt % of one or more polymeric additives such as alkene-1-polymers, in particular low density polyethylene, polypropylene or polybutylene, copolymers containing mono-olefins as primary monomers, oxidized polyolefins, graft polyolefin copolymers and polyoxymethylenes, or low molecular weight additives such as antioxidants, lubricants, ultraviolet screening agents, colorants and the like which are commonly incorporated.
• polymeric additives such as alkene-1-polymers, in particular low density polyethylene, polypropylene or polybutylene, copolymers containing mono-olefins as primary monomers, oxidized polyolefins, graft polyolefin copolymers and
• High tenacity polyethylene fibers are available, for example, under the trademark SPECTRA® fibers and yarns from Honeywell International Inc. of Morristown, New Jersey, U. S. A
• the tenacity of the polyethylene fibers are at least about 7 g/d, preferably at least about 15 g/d, more preferably at least about 20 g/d, still more preferably at least about 25 g/d and most preferably at least about 30 g/d.
• the initial tensile modulus of the fibers is preferably at least about 300 g/d, more preferably at least about 500 g/d, still more preferably at least about 1,000 g/d and most preferably at least about 1,200 g/d.
• the polyethylene employed is a polyethylene having fewer than about one methyl group per thousand carbon atoms, more preferably fewer than about 0.5 methyl groups per thousand carbon atoms, and less than about 1 wt. % of other constituents.
• polypropylene fibers of weight average molecular weight at least about 200,000, preferably at least about one million and more preferably at least about two million may be used.
• extended chain polypropylene may be formed into reasonably well oriented filaments by the techniques prescribed in the various references referred to above, and especially by the technique of U.S. Pat. No. 4,413,110. Since polypropylene is a much less crystalline material than polyethylene and contains pendant methyl groups, tenacity values achievable with polypropylene are generally substantially lower than the corresponding values for polyethylene. Accordingly, a suitable tenacity is preferably at least about 8 g/d, more preferably at least about 11 g/d.
• the initial tensile modulus for polypropylene is preferably at least about 160 g/d, more preferably at least about 200 g/d.
• the melting point of the polypropylene is generally raised several degrees by the orientation process, such that the polypropylene filament preferably has a main melting point of at least 168 0 C, more preferably at least 17O 0 C.
• the particularly preferred ranges for the above described parameters can advantageously provide improved performance in the final article.
• Employing fibers having a weight average molecular weight of at least about 200,000 coupled with the preferred ranges for the above-described parameters (modulus and tenacity) can provide advantageously improved performance in the final article.
• aramid fibers suitable fibers formed from aromatic polyamides are described in U.S. Pat. No. 3,671,542, which is incorporated herein by reference to the extent not inconsistent herewith.
• Preferred aramid fibers will have a tenacity of at least about 20 g/d, an initial tensile modulus of at least about 400 g/d and an energy-to-break at least about 8 J/g, and particularly preferred aramid fibers will have a tenacity of at least about 20 g/d and an energy-to-break of at least about 20 J/g.
• aramid fibers will have a tenacity of at least about 23 g/d, a modulus of at least about 500 g/d and an energy-to-break of at least about 30 J/g.
• poly(p-phenylene terephthalamide) filaments which have moderately high moduli and tenacity values are particularly useful in forming ballistic resistant composites. Examples are Twaron® T2000 from Teijin which has a denier of 1000. Other examples are Kevlar® 29 which has 500 g/d and 22 g/d as values of initial tensile modulus and tenacity, respectively, as well as Kevlar® 129 and KM2 which are available in 400, 640 and 840 deniers from du Pont.
• Aramid fibers from other manufacturers can also be used in this invention.
• Copolymers of poly(p-phenylene terephthalamide) may also be used, such as co-poly(p-phenylene terephthalamide 3,4' oxydiphenylene terephthalamide).
• Also useful in the practice of this invention are poly(m-phenylene isophthalamide) fibers sold by du Pont under the trade name Nomex®.
• High molecular weight polyvinyl alcohol (PV-OH) fibers having high tensile modulus are described in U.S. Pat. No. 4,440,711 to Kwon et al, which is hereby incorporated by reference to the extent it is not inconsistent herewith.
• High molecular weight PV-OH fibers should have a weight average molecular weight of at least about 200,000.
• Particularly useful PV-OH fibers should have a modulus of at least about 300 g/d, a tenacity preferably at least about 10 g/d, more preferably at least about 14 g/d and most preferably at least about 17 g/d, and an energy to break of at least about 8 J/g.
• PV-OH fiber having such properties can be produced, for example, by the process disclosed in U.S. Pat. No. 4,599,267.
• the PAN fiber should have a weight average molecular weight of at least about 400,000.
• Particularly useful PAN fiber should have a tenacity of preferably at least about 10 g/d and an energy to break of at least about 8 J/g.
• PAN fiber having a molecular weight of at least about 400,000, a tenacity of at least about 15 to 20 g/d and an energy to break of at least about 8 J/g is most useful; and such fibers are disclosed, for example, in U.S. Pat. No. 4,535,027.
• Suitable liquid crystal copolyester fibers for the practice of this invention are disclosed, for example, in U.S. Pat. Nos. 3,975,487; 4,118,372 and 4,161,470. Liquid crystal copolyester fibers are available under the designation Vectran® fibers from Kuraray America Inc.
• Suitable polybenzazole fibers for the practice of this invention are disclosed, for example, in U.S. Pat. Nos. 5,286,833, 5,296,185, 5,356,584, 5,534,205 and 6,040,050.
• Polybenzazole fibers are available under the designation Zylon® fibers from Toyobo Co.
• Rigid rod fibers are disclosed, for example, in U.S. Pat. Nos. 5,674,969, 5,939,553, 5,945,537 and 6,040,478. Such fibers are available under the designation M5® fibers from Magellan Systems International.
• one type of high tenacity fibers is a polyolefin fiber, more preferably a polyethylene fiber.
• the percent of high tenacity polyethylene fibers in the ropes may vary widely, depending upon the other type of high tenacity fibers employed and the desired properties of the fibers.
• the high tenacity polyethylene fibers may comprise from about 20 to about 80 weight percent, more preferably from about 30 to about 70 weight percent, and most preferably from about 40 to about 60 weight percent, based on the total weight of the high tenacity fibers in the rope.
• ropes may be formed from about 80 to about 20 weight percent high tenacity polyethylene fibers and correspondingly from about 20 to about 80 weight percent of aramid fibers; more preferably from about 70 to about 30 weight percent of the high tenacity polyethylene fibers and correspondingly from about 30 to about 70 weight percent of aramid fibers; most preferably from about 40 to about 60 weight percent high tenacity polyethylene fibers and correspondingly from about 60 to about 40 weight percent of aramid fibers.
• the rope comprises from about 70 to 55 weight percent aramid fibers and correspondingly from about 30 to about 45 weight percent high tenacity polyethylene fibers, based on the total weight of the high tenacity fibers in the rope.
• all or substantially all of the fibers in the rope are formed from aramid fibers.
• ropes may be formed from about 80 to about 20 weight percent high tenacity polyethylene fibers and correspondingly from about 20 to about 80 weight percent of liquid crystal copolyester fibers; more preferably from about 70 to about 30 weight percent of the high tenacity polyethylene fibers and correspondingly from about 30 to about 70 weight percent of liquid crystal copolyester fibers; most preferably from about 40 to about 60 weight percent high tenacity polyethylene fibers and correspondingly from about 60 to about 40 weight percent of liquid crystal copolyester fibers.
• the rope comprises from about 70 to 55 weight percent liquid crystal copolyester fibers and correspondingly from about 30 to about 45 weight percent high tenacity polyethylene fibers, based on the total weight of the high tenacity fibers in the rope.
• all or substantially all of the fibers in the rope are formed from liquid crystal copolyester fibers.
• fibers formed from fluoropolymers include fibers formed, for example, from polytetrafluoroethylene (preferably expanded polytetrafluoroethylene), polychorotrifluoroethylene (both homopolymers and copolymers (including terpolymers)), polyvinyl fluoride, polyvinylidene fluoride, ethylene- tetrafluoroethylene copolymers, ethylene-chlorotrifluorethylene copolymers, fluorinated ethylene-propylene copolymers, perfluoroalkoxy polymer, and the like, as well as blends of two or more of the foregoing.
• polytetrafluoroethylene preferably expanded polytetrafluoroethylene
• polychorotrifluoroethylene both homopolymers and copolymers (including terpolymers)
• polyvinyl fluoride polyvinylidene fluoride
• ethylene- tetrafluoroethylene copolymers ethylene-chlorotrifluorethylene
• Especially preferred fluoropolymer fibers are those formed from polytetrafluoroethylene, and in particular expanded polytetrafluoroethylene fibers. Such fibers are available, for example, from Lenzing Plasties GmbH & Co. KG and WL Gore & Associates.
• the portion of the fluoropolymer fibers that are blended with the high tenacity fibers may vary widely depending on the type of fluoropolymer and the end use application.
• the amount of fluoropolymer fibers in the blend may range from about 1 to about 40 percent by weight, more preferably from about 5 to about 25 percent by weight, and most preferably from about 10 to about 20 percent by weight, based on the total weight of the blended fibers.
• the amount of the high tenacity fibers may range from about 60 to about 99 percent by weight, more preferably from about 75 to about 95 percent by weight, and most preferably from about 80 to about 90 percent by weight, based on the total weight of the blended fibers.
• the different types of fibers useful in the ropes of this invention may be blended in any suitable manner. For example, strands of one type of fibers may be twisted with strands of another type of fibers to form a combined strand that is then braided into a rope. Alternatively, the fibers can be combined as a bicomponent fiber, having a sheath and a core. Other constructions may also be employed. The different types of fibers may be present at any desired location in the rope.
• the ropes of this invention preferably comprise blends of two or more high tenacity fibers, or consist essentially of blends of two or more high tenacity fibers, optionally together with the fluoropolymer fibers.
• These ropes may be of any suitable construction, such as braided ropes, twisted ropes, wire-lay ropes, parallel core ropes, and the like. Most preferably, the rope is a braided rope.
• the ropes may be of any suitable diameter and may be formed in any suitable manner from the desired fibers and/or yarns. For example, in forming a braided rope a conventional braiding machine may be employed which has a plurality of yarn bobbins.
• Yarns from one type of high tenacity fibers may be formed into a subrope which is then formed into a rope (such as by braiding) with a subrope formed of yarns from the other type of high tenacity fibers.
• a subrope may be formed from blends of the high tenacity fibers and such subrope may be formed into a rope using other such subropes or different types of subropes, by braiding or any other desired technique.
• the high tenacity yarns that form the rope may be of any suitable denier, and the yarns of the fluoropolymer fiber may be of the same or different denier than the yarns of the high tenacity fibers.
• the high tenacity yarns may have a denier of from about 50 to about 5000, more preferably from about 75 to about 2000 denier, still more preferably from about 200 to about 2000, and most preferably from about 650 to about 1500 denier.
• the fluoropolymer yarns may have a denier of from about 50 to about 2500, and more preferably from about 400 to about 1600.
• a certain coating composition is applied to the rope construction. Either the individual fibers or yarns, or blends of the fibers or yarns, are coated with the coating composition and then a rope is formed from the coated fibers or yarns, or the rope is first formed and then is coated with the coating composition.
• the coating composition comprises an amino functional silicone resin and a neutralized low molecular weight polyethylene. The two components may be admixed in any desired ratio, such as from about 1 to about 99 percent by weight of the neutralized low molecular weight polyethylene and a corresponding amount of the amino functional silicone resin. All percents are by weight of the total weight of the composition, unless otherwise indicated.
• the neutralized low molecular weight polyethylene is present in an amount of from about 30 to about 90 percent by weight, with the amino functional silicone resin correspondingly being present in an amount of from about 10 to about 70 percent by weight. More preferably, the neutralized low molecular weight polyethylene is the major component of the coating, such as from about 55 to about 85 percent by weight of coating composition, with the amino functional silicone resin being present in an amount of from about 15 to about 45 percent by weight.
• the composition may contain a variety of other additives, depending on the desired end properties.
• the coating composition used herein is sometimes referred to as an overfinish composition.
• the amino functional silicone is preferably in the form of an emulsion.
• the emulsion comprises from about 20 to about 40 percent by weight of the silicone resin, and has a pH in the range of about 4.5 to about 6.5.
• the emulsion preferably includes a non-ionic emulsifier.
• the neutralized low molecular weight polyethylene is in the form of an emulsion.
• the polyethylene is fully neutralized.
• the low molecular weight polyethylenes are also known as polyethylene waxes and are sometimes called wax dispersions.
• these polyethylene waxes, also called resins generally have a molecular weight of less than about 6000 Dalton, more preferably less than about 5000 Dalton, even more preferably below about 3500 Dalton, and most preferably between about 300 and about 3000 Dalton.
• the coating components may be mixed in any suitable manner.
• the amino functional silicone emulsion may be added to the neutralized low molecular weight polyethylene in a stainless steel or other inert vessel
• the vessel is preferably equipped with an agitator for appropriate mixing under low shear conditions (laminar flow).
• laminar flow By adding the amino functional silicone emulsion to the neutralized low molecular weight polyethylene permits the pH of the system to remain on the basic side.
• the low molecular weight polyethylene may be added to the amino functional silicone emulsion.
• the mixing may be conducted at any suitable temperature, preferably between about 15 and about 45 0 C, more preferably between about 20 to about 30 0 C.
• the coating composition has a relatively high solids content, such as on the order of at least about 25% by weight and more preferably at least about 30% by weight. Most preferably, the solids content of the coating composition is from about 33 to about 35% by weight. It has been found that the use of high solids content coating emulsions permits higher pick up of the coating composition on the fiber/yarn or rope.
• any suitable coating device may be employed.
• coating apparatus include lube rolls, kiss rolls, dip baths and finish applicators.
• a constant temperature is desired to provide uniform application and superior performance as the viscosity of the system is impacted by temperature differences.
• the rope may be dipped into a bath containing the coating composition, with excess composition squeezed out followed by air drying, or the rope may be coated and then passed through a heating device to accelerate drying followed by air drying.
• the final pick up is at least about 0.5 percent by weight, more preferably at least about 5 percent by weight, and most preferably from about 10 to about 30% by weight .
• a braided rope was formed from high tenacity polyethylene yarns and from liquid crystal copolyester yarns.
• the polyethylene yarn employed was SPECTRA® 1000 yarn from Honeywell International Inc., having a denier of 1300, a tenacity of 35 g/d and a modulus of 1150 g/d.
• the liquid crystal copolyester yarn was
• Vectran® HT Type 97 yarn from Kuraray America Inc. having a denier of 1500, a tenacity of about 25 g/d and a modulus of about 600 g/d.
• the yarns were coated with an overfinish composition.
• the overfinish composition was prepared from an amino functional silicone resin and a neutralized low molecular weight polyethylene.
• the amino functional silicone resin was an emulsion having a silicone content of 35 weight percent, a pH of 4.5-6.5 and included a non-ionic emulsifier, available from Dow
• the neutralized low molecular weight polyethylene was a neutralized non-ionic polyethylene wax emulsion (F Kunststoffone® 1566 from Apollo Chemical), having a solids content between 29% and 31%, and pH in the range of between 9.0 and 1 1.
• the coating composition was prepared by blending the neutralized low molecular weight polyethylene into the amino functional silicone resin emulsion, with the resulting composition comprising 70% by weight of the neutralized low molecular weight polyethylene.
• the yarn was coated by dipping the fiber in the overfinish composition at room temperature. The amount of pick up of the coating on the yarn was approximately 15 percent.
• the coated yarn was braided into a 12-strand rope with an approximate diameter of 5 mm diameter.
• the yarn was braided into a rope by first twisting three coated yarns together into a cord at 0.5 turns per inch. Cords were twisted in the "S" direction and the "Z" direction. Twelve cords were then loaded onto a 12-strand braider in an alternating fashion (S, Z, S, Z, etc.). Three cords were then braided together resulting in a 12-strand braided rope.
• the rope was comprised of about 63% by weight of the polyethylene fibers and about 37% by weight of the liquid crystal copolyester fibers.
• the rope was tested for its cyclic bend over sheave (CBOS) resistance.
• CBOS cyclic bend over sheave
• the ropes are bent approximately 180 degrees over a free rolling sheave or pulley.
• the ropes are placed under load and cycled over the sheave until the rope reaches failure.
• the test was run with a D:d ratio of 10 over a 1.3 inch (3.3 cm) pulley at 75 cycles per minute, with a 100 kg load on the sheave (50 kg of tension on each side of the rope).
• the number of cycles was determined based on an average of 5 positions before there was failure of the rope. The results are shown in Table 1, below.
• Example 1 As a control for Example 1, a braided rope was formed in the same manner but no overfinish composition was used. This rope was also tested for its CBOS resistance, and the results are shown in Table 1, below.
• Example 1 is repeated, except that the rope is formed from 40% by weight of high tenacity polyethylene fibers and 60% by weight of liquid crystal copolyester fibers, and has a diameter of about 40 mm. Similar results are noted.
• Example 1 is repeated, except that the rope is formed from 40% by weight of high tenacity polyethylene fibers and 60% by weight of aramid fibers, and has a diameter of about 40 mm. Similar results are noted.
• Example 5 is repeated, except that the rope is formed from 40% by weight of high tenacity polyethylene fibers and 60% by weight of aramid fibers, and has a diameter of about 40 mm. Similar results are noted.
• Example 5 is repeated, except that the rope is formed from 40% by weight of high tenacity polyethylene fibers and 60% by weight of aramid fibers, and has a diameter of about 40 mm. Similar results are noted.
• Example 5 is repeated, except that the rope is formed from 40% by weight of high tenacity polyethylene fibers and 60% by weight of aramid fibers, and has a diameter of about 40 mm. Similar results are noted.
• Example 5 is repeated, except that the rope is formed from 40% by weight of high tenacity polyethylene fibers and 60% by weight of aramid fibers, and has
• Example 1 is repeated except that the ropes are formed from uncoated yarns and after fabrication the ropes are coated with the overfinish composition by dipping the rope in the overfinish composition at room temperature. Similar results are noted.
• the present invention provides ropes which have significantly improved CBOS fatigue resistance. As a result, these ropes can be employed in many demanding applications, including such marine applications as lifting and lowering heavy objects from the seabed.

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• Engineering & Computer Science (AREA)
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• Crystallography & Structural Chemistry (AREA)
• Manufacturing & Machinery (AREA)
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• Braiding, Manufacturing Of Bobbin-Net Or Lace, And Manufacturing Of Nets By Knotting (AREA)

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