Classifications

• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B29/00—Apparatus for mountaineering
  • A63B29/02—Mountain guy-ropes or accessories, e.g. avalanche ropes; Means for indicating the location of accidentally buried, e.g. snow-buried, persons
  • A63B29/028—Ropes specially adapted for mountaineering
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
• • 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
  • Y10T428/249921—Web or sheet containing structurally defined element or component
• • 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
  • Y10T428/2964—Artificial fiber or filament
  • Y10T428/2967—Synthetic resin or polymer
• • 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
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/30—Woven fabric [i.e., woven strand or strip material]

Definitions

• the present invention relates to son, fibers or filaments, in particular based on polyamide, used especially for making ropes. It relates more particularly climbing ropes comprising these son, fibers or filaments, which have good mechanical properties, especially in high relative humidity conditions.
• the properties that must present spun articles are different according to their use. These include, for example, toughness, elongation at break, fatigue strength, transparency, gloss, whiteness, dyeability, shrinkage, retention capacity, water, fire resistance, stability and longevity to heat.
• a property that may be required, especially for applications in so-called technical wire fields, is the breaking strength, as well as the damping capacity during an impact.
• ropes, ropes, ropes which are used in many areas such as the maritime domain, the climbing field, etc. They can for example be used to moor boats and ships, for example pleasure boats.
• thermoplastic polymer obtained from a composition comprising:
• the invention provides a method of preparing these son, fibers, or filaments.
• the invention provides an article comprising the son, fibers and / or filaments of the invention, in particular climbing ropes.
• the invention provides the use of the article in high humidity conditions.
• the invention proposes the use of a novolak resin in the field of climbing ropes.
• the invention therefore relates, in a first object, son, fibers or filaments based on thermoplastic polymer obtained from a composition comprising: - a polymeric matrix
• thermoplastic polymer suitable in the context of the invention: polyolefins, polyesters, polyalkylene oxides, polyoxyalkylenes, polyhaloalkylenes, poly (alkylene phthalate or terephthalate) poly (phenyl or phenylene), poly (phenylene oxide or sulfide), polyvinyl acetates, polyvinyl alcohols, polyvinyl halides, polyvinyl polyvinylidene halides, polyvinyl nitriles, polyamides, polyimides, polycarbonates, polymers of acrylic or methacrylic acid, polyacrylates or methacrylates, natural polymers such as cellulose and its derivatives, synthetic polymers such as synthetic elastomers , or thermoplastic copolymers comprising at least one monomer identical to any one of the monomers included in the abovementioned polymers, as
• thermoplastic polymers of the invention include semicrystalline or amorphous polyamides, such as aliphatic polyamides, semi-aromatic polyamides and, more generally, linear polyamides obtained by polycondensation between an aliphatic or aromatic saturated diacid, and a saturated aromatic or aliphatic primary diamine, the polyamides obtained by condensation of a lactam, an amino acid or linear polyamides obtained by condensation of a mixture of these different monomers.
• semicrystalline or amorphous polyamides such as aliphatic polyamides, semi-aromatic polyamides and, more generally, linear polyamides obtained by polycondensation between an aliphatic or aromatic saturated diacid, and a saturated aromatic or aliphatic primary diamine, the polyamides obtained by condensation of a lactam, an amino acid or linear polyamides obtained by condensation of a mixture of these different monomers.
• these copolyamides may be, for example, hexamethylene polyadipamide, polyphthalamides obtained from terephthalic acid and / or isophthalic acid such as the polyamide marketed under the trade name AMODEL, copolyamides obtained from adipic acid, hexamethylene diamine and caprolactam.
• the thermoplastic polymer may be a polyester, such as polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), copolymers and mixtures thereof.
• the thermoplastic polymer is selected from the group of (co) polyamides comprising: polyamide 6, polyamide 6.6, polyamide 4, polyamide 11, polyamide 12, polyamides 4-6, 6-10, 6-12, 6-36, 12-12, their copolymers and mixtures.
• the son, fibers and filaments of the invention may be based on a mixture of thermoplastic polymers or thermoplastic copolymers.
• the son, fibers or filaments of the invention are obtained from a composition comprising a novolak resin.
• Novolac resins are polyhydroxy compounds, for example condensation products of phenolic compounds with aldehydes. These condensation reactions are generally catalyzed by an acid.
• the phenol compounds may be chosen alone or in a mixture from phenol, cresol, xylenol, naphthol, alkyphenols, such as butylphenol, terbutylphenol or isooctylphenol; or any other substituted phenol.
• aldehyde is formaldehyde.
• acetaldehyde paraformaldehyde, butyraldehyde, crotonaldehyde, and glycoxal.
• the resin is a condensation product of phenol and formaldehyde.
• the novolak resin has the following formula
• t is between 1 and 20, preferably between 8 and 13.
• the resins used advantageously have a molecular weight between 500 and 3000 g / mol, preferably between 800 and 2000 g / mol.
• Durez® products As novolac commercial resin, there may be mentioned Durez® products, Vulkadur® or Rhenosin®.
• composition from which the yarns, fibers or filaments of the invention are obtained comprises between 0.1 and 20% by weight, preferably between 1 and 10% by weight, of novolak resin.
• the son, fibers, and filaments of the invention may comprise additives such as reinforcing fillers, flame retardants, stabilizers for
• the overall title of the son of the invention can be chosen throughout the range of usual son titles, for example between 200 dtex and 3000 dtex.
• the yarns, fibers, filaments of the invention are yarns which have an overall count of between 700 and
• the title strand of the son of the invention can be chosen throughout the range of the usual son of titles.
• Strand titer is usually greater than or equal to 0.3 dtex. It is usually less than the equivalent in dtex with a diameter of 800 microns in the case of large diameter monofilaments.
• the yarns, fibers, filaments of the invention are yarns which have a strand titer of between 3 and 10 dtex.
• the invention also relates to a process for preparing the son, fibers and filaments of the invention, by spinning the composition comprising the thermoplastic polymer matrix and the novolak resin.
• the composition may be prepared according to any method known to those skilled in the art.
• the composition can be achieved by introducing the novolak resin into the molten polymer in a mixing device, for example upstream of a spinning device. It may be for example an introduction into the molten stream of the matrix, or else by means of a master batch ("master-batch" in English).
• the son, fibers or filaments are made according to the usual spinning techniques from a composition comprising the thermoplastic polymer matrix and the novolak resin.
• the spinning can be carried out immediately after the polymerization of the matrix, the latter being in molten form. It can be made from a granule comprising the composition.
• the son, fibers, filaments according to the invention may be subjected to all the treatments that may be performed in subsequent steps in the spinning step. They can in particular be relaxed or stretched, textured, curled, heated, twisted, dyed, sized, cut ... These complementary operations can be performed continuously and be integrated after the spinning device or be performed discontinuously. The list of operations subsequent to spinning has no limiting effect.
• composition By spinning the composition, it is possible to obtain, for example, continuous multifilament yarns, short or long fibers, monofilaments, yarns of fibers, plies, ribbons, cables, etc.
• the invention also relates, in a third object, an article comprising the son, fibers and / or filaments of the invention.
• the article may be a rope, rope or rope comprising at least threads, fibers, filaments described above, including multifilament yarns.
• Such articles can be obtained in particular from a single type of yarn, fibers, filaments or on the contrary from a mixture of yarns, fibers, filaments of different types.
• the rope, rope or rope comprises at least in part threads, fibers, filaments according to the invention.
• fibers, filaments - for example yarns, fibers, filaments containing no novolak resin -, yarns, fibers or filaments of different natures can be used in the rope, rope, rope of the invention.
• the rope, rope or rope advantageously comprises at least 50% by weight of yarns, fibers, filaments of the invention.
• the rope, rope or rope is preferably a climbing rope.
• Climbing ropes undergo significant mechanical stress.
• Climbing ropes generally consist of a core or core of ropes surrounded by a braided tubular sheath.
• the soul and the sheath are generally made of threads. There may be connections between the wires of the soul and the wires of the sheath.
• the son, fibers, filaments of the invention are advantageously present in the core of the rope, as opposed to the sheath.
• advantageously at least 50% by weight of the son, fibers, filaments of the core consist of son, fibers, filaments of the invention.
• the yarns, fibers, filaments of the invention are present both in the core and in the sheath of the rope.
• the rope of the invention not only has a significant resistance to the possible falls of the climber during its use, but also it allows to dampen these falls to preserve the climber of significant damage caused by the fall, especially in conditions of use of the rope at high humidity levels.
• the invention also relates to the use of the rope of the invention under relative humidity conditions greater than or equal to 80%, preferably greater than or equal to 90%.
• the invention also relates to the use of the rope of the invention in mooring or anchoring devices for boats, ships, floating docks, light pontoons, anchor buoys, navigation or tracking.
• the invention relates to the use of a novolak resin as described above in the field of climbing ropes.
• the article of the invention may also be a paper machine felt. Typically these felts comprise fibers and monofilament fabrics.
• the felt may be produced from the blend of fibers of the invention and conventional fibers.
• the felt may also be produced from fabrics comprising monofilaments of the invention and conventional monofilaments. These felts are usually used in wet conditions.
• the article of the invention may also be an airbag fabric generally obtained from multifilaments, or a textile article.
• the article of the invention may finally be a reinforcing article of tires.
• These items may for example be ropes. They can be obtained from multifilaments or monofilaments of the invention. They can also be obtained from mono or multifilament mixtures according to the invention and conventional. Other details or advantages of the invention will appear more clearly in view of the examples given below.
• the EN892 standard is a specific standard that evaluates the usage property of climbing ropes.
• the ropes are preconditioned (72h to 65% RH) then subjected to a succession of falls under defined conditions of rope mass, height, length of the rope, and waiting time between 2 falls.
• Several quantities are measured among which:
• the underlying physical property in this test is a property of damping or dissipation of energy.
• a "good” rope must absorb as quickly as possible the kinetic energy of the fall.
• the evaluation in dynamic mechanical tests of the elastic modulus G 'and the viscous module G "and their G7G' ratio, called tan ⁇ is often used to quantify this ability to dissipate energy. being this time possible on any type of material, whether the finished product (the rope), the constituent unitary material of the rope (the multi-filament or the monofilament) or any other piece obtained from of the same polymer formulation (an injected part for example).
• the polyamide 6 is pre-dried in a vacuum oven in order to reduce its water content to a value of approximately 500 ppm.
• the mixture of polyamide 6 pellets and novolak resin pellets is made on a Leistritz 34 co-rotating twin-screw extruder.
• the extrusion temperature is about 270 to 280 ° C.
• Examples 5 to 8 Spinning and Drawing of the Compositions
• the dtex-containing, multi-filament multifilament yarns comprising 12 strands (unit title after stretching approximately 7dtex) are made from the granules of Examples 1 to 4 on a laboratory spinning / drawing position FOURNE .
• This spinning is carried out using a single-screw extruder, a title pump and a die, the spinning temperature is 265-270 ° C and the winding speed 300m / min.
• This spinning step takes place under perfectly stable conditions.
• the speed of call can be maintained without difficulties and no breakage of strands is perceptible.
• This shows that the phenol-formaldehyde resin is perfectly compatible with the PA6 matrix in a spinning process.
• a step of stretching in recovery is carried out, by passing on heating rollers, then a relaxation and a winding.
• the winding is done at about 400m / min.
• the call speed of the last rollers is adjusted to obtain a wire having an elongation at break of about 20%. This corresponds to a draw ratio of 4.35.
• Plate moldings 100 x 100 x 1 mm are produced from the granules of Examples 1 and 4 on a DEMAG H200-80 press, which respectively corresponds to Examples 9 and 10.
• the temperature of the sheath is of the order of 285 mm. at 290 ° C.
• DMA evaluations are carried out on specimens cut from the previous plates.
• the DMA evaluations are carried out under 3 different hygrometric equilibrium conditions of the test pieces, at respective values of 50%, 75% and 95% RH. These hygrometric equilibria are obtained at the end of accelerated preconditionings, carried out at 70 ° C.
• the conditioning times required to reach equilibrium were estimated by following the water recovery. They are at least 96h at 50% RH, 48h at 75% RH and 24h at 95% RH.
• Table 3 and Figure 1 specify the values of the dissipation coefficient tan ⁇ measured with this method of DMA at the temperature of 25 ° C, corresponding to the typical temperature of stress during the impact of the climbing rope:
• Table 3 and Figure 1 shows that the damping capacity (tan ⁇ factor) is improved at 25 ° C between 50 and 95% RH for the add-on system according to the invention.
• the polyamide 6.6 is pre-dried in a vacuum oven in order to reduce its water content to a value of about 0.1 to 0.2% by weight.
• the mixture of the polyamide 6.6 pellets and the novolac resin pellets is made on a Leistritz 34 co-rotating twin-screw extruder. A classic, relatively shearless profile is used on this extruder.
• the extrusion temperature is about 280 to 295 ° C depending on the area.
• the extrusion takes place without any notable difficulty.
• the extrusion conditions are perfectly stable and in total, 4 batches of 10kg each of granules are produced:
• Plate moldings 100 ⁇ 100 ⁇ 1 mm are produced from the granules of Examples 1 1 to 14 on a DEMAG H200-80 press, which respectively corresponds to Examples 15 to 18.
• the temperature of the sheath is of the order of 280 to 290 ° C depending on the area.
• the DMA evaluations are carried out under 2 different conditions of hygrometric equilibrium of the test pieces, at respective values of 0 and 50% RH.
• the value 0% RH corresponds to a sample taken directly from the press followed by conditioning in an inert atmosphere before evaluation.
• the hygrometric equilibrium for the value 50% RH is obtained at the end of an accelerated preconditioning, carried out at 70 ° C.
• the conditioning time required to reach equilibrium was estimated by following the water recovery. It is about 75 hrs at 50% RH.
• Table 5 and Figure 2 specify the values of the dissipation coefficient tan ⁇ measured with this method of DMA at a temperature of 25 ° C, corresponding to the typical temperature of loading during the impact of the climbing rope:
• Table 5 and Figure 2 shows that the damping capacity (the tan ⁇ factor) is improved at 25 ° C between 0 and 50% RH for the additive system according to the invention.
• Global title multifilament dtex 84 and having 12 strands are made from the following formulations on a FOURNE laboratory spinning / stretching position.
• PA66 granules and Rhenosin® PR95 pellets are added directly to the spinning position.
• This spinning is carried out using a single-screw extruder, a title pump and a die, the spinning temperature is 280-290 ° C and the winding speed 300m / min. This spinning step takes place under perfectly stable conditions. The speed of call can be maintained without difficulties and no breakage of strands is perceptible. This shows that the phenol-formaldehyde resin is perfectly compatible with the PA6.6 matrix in a spinning process.
• a step of stretching in recovery is carried out, by passing on heating rollers, then a relaxation and a winding.
• the winding is done at about 400m / min.
• the call speed of the last rollers is adjusted to obtain a wire having an elongation at break of about 20%.

Landscapes

• General Chemical & Material Sciences (AREA)
• Textile Engineering (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Physical Education & Sports Medicine (AREA)
• General Health & Medical Sciences (AREA)
• Pulmonology (AREA)
• Artificial Filaments (AREA)
• Ropes Or Cables (AREA)
• Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2007
  • 2007-10-16 FR FR0707229A patent/FR2922223B1/fr not_active Expired - Fee Related
• 2008
  • 2008-10-10 WO PCT/EP2008/063600 patent/WO2009050114A2/fr active Application Filing
  • 2008-10-10 US US12/738,118 patent/US20110034098A1/en not_active Abandoned
  • 2008-10-10 CN CN2008801120713A patent/CN101896233A/zh active Pending
  • 2008-10-10 EP EP08839787A patent/EP2200721A2/de not_active Withdrawn
  • 2008-10-15 TW TW97139611A patent/TW200928026A/zh unknown
  • 2008-10-16 AR ARP080104499 patent/AR068883A1/es unknown

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