EP2481847A1 - Fibre haute résistance stabilisée contre les UV - Google Patents

Fibre haute résistance stabilisée contre les UV Download PDF

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Publication number
EP2481847A1
EP2481847A1 EP11152724A EP11152724A EP2481847A1 EP 2481847 A1 EP2481847 A1 EP 2481847A1 EP 11152724 A EP11152724 A EP 11152724A EP 11152724 A EP11152724 A EP 11152724A EP 2481847 A1 EP2481847 A1 EP 2481847A1
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EP
European Patent Office
Prior art keywords
high strength
cross
strength fiber
fiber according
silicone polymer
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11152724A
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German (de)
English (en)
Inventor
Pieter Gijsman
Martin Pieter Vlasblom
Gerardus Aben
Hans Schneiders
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DSM IP Assets BV
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DSM IP Assets BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by DSM IP Assets BV filed Critical DSM IP Assets BV
Priority to EP11152724A priority Critical patent/EP2481847A1/fr
Priority to PCT/EP2012/051560 priority patent/WO2012104302A1/fr
Priority to BR112013019527A priority patent/BR112013019527A2/pt
Priority to US13/981,434 priority patent/US20140023863A1/en
Priority to CN201280006919.0A priority patent/CN103339315B/zh
Priority to KR1020137022860A priority patent/KR101925790B1/ko
Priority to AU2012213480A priority patent/AU2012213480B2/en
Priority to EP12703488.2A priority patent/EP2670904B1/fr
Priority to SG2013055934A priority patent/SG192086A1/en
Publication of EP2481847A1 publication Critical patent/EP2481847A1/fr
Withdrawn legal-status Critical Current

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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35Heterocyclic compounds
    • D06M13/355Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358Triazines
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12Aldehydes; Ketones
    • D06M13/13Unsaturated aldehydes, e.g. acrolein; Unsaturated ketones; Ketenes ; Diketenes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/2246Esters of unsaturated carboxylic acids
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35Heterocyclic compounds
    • D06M13/352Heterocyclic compounds having five-membered heterocyclic rings
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35Heterocyclic compounds
    • D06M13/355Heterocyclic compounds having six-membered heterocyclic rings
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6433Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing carboxylic groups
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6436Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/65Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing epoxy groups
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/653Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain modified by isocyanate compounds
    • DTEXTILES; PAPER
    • D07ROPES; CABLES OTHER THAN ELECTRIC
    • D07BROPES OR CABLES IN GENERAL
    • D07B1/00Constructional features of ropes or cables
    • D07B1/02Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
    • D07B1/025Ropes 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/18Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/25Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
    • DTEXTILES; PAPER
    • D07ROPES; CABLES OTHER THAN ELECTRIC
    • D07BROPES OR CABLES IN GENERAL
    • D07B2201/00Ropes or cables
    • D07B2201/20Rope or cable components
    • D07B2201/2001Wires or filaments
    • D07B2201/201Wires or filaments characterised by a coating
    • D07B2201/2012Wires or filaments characterised by a coating comprising polymers
    • DTEXTILES; PAPER
    • D07ROPES; CABLES OTHER THAN ELECTRIC
    • D07BROPES OR CABLES IN GENERAL
    • D07B2205/00Rope or cable materials
    • D07B2205/20Organic high polymers
    • D07B2205/201Polyolefins
    • D07B2205/2014High performance polyolefins, e.g. Dyneema or Spectra
    • DTEXTILES; PAPER
    • D07ROPES; CABLES OTHER THAN ELECTRIC
    • D07BROPES OR CABLES IN GENERAL
    • D07B2401/00Aspects related to the problem to be solved or advantage
    • D07B2401/20Aspects related to the problem to be solved or advantage related to ropes or cables
    • D07B2401/202Environmental resistance
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/2964Artificial fiber or filament
    • Y10T428/2967Synthetic resin or polymer

Definitions

  • the present invention relates to high strength fibers having improved UV stability and the use thereof in, for instance, ropes and fishing nets.
  • HPPE fibers in particular high performance polyethylene (HPPE) fibers are generally considered to be relatively stable when exposed to UV, under certain circumstances the HPPE fibers show a loss in tenacity as a result of weathering, which leads to a reduced life time. These circumstances can in particular occur when such high strength fibers are used in ropes or in fishing lines or fishing nets.
  • HPPE high performance polyethylene
  • the present invention now provides a high strength fiber coated with a coating composition, wherein the coating composition contains a UV absorber.
  • the advantage of applying the UV absorber in the coating of the fiber is that the stabiliser protects the fiber against the influence of UV light without having an effect on the mechanical properties of the fiber. Moreover, use of such an absorber does not affect the manufacturing process of the fiber in any way.
  • the UV stabiliser is preferably present in an amount of 2 to 80 wt.% compared to the total weight of the coating composition, based on solids, i.e. the dry coating composition. Preferably the amount is 5 to 60 wt.% of stabiliser.
  • Preferred UV absorbers are compounds that absorb UV radiation such that the UV radiation interacts less with the polymer.
  • Preferred stabilisers absorb UV in the range of 290 to 400 nm.
  • the stabilisers according to the invention can be organic or inorganic absorbers.
  • inorganic stabilisers are carbon black, titanium dioxide (TiO 2 ), ZnO and CeO 2 .
  • organic stabilisers are those falling in the classes of hydroxybenzophenones, hydroxyphenylbenzotriazoles, oxalanilides, phenyl esters, benzooxazinones, cyanoacrylates, formamidine, benzylidene malonates and hydroxyphenyl triazines.
  • UV stabilisers suitable for the invention are for instance described in WO2006/082145 , WO2009/060043 and WO2007/08814 .
  • hydroxybenzophenones are 2-Hydroxy-4-n-octoxybenzophenone; 2-Hydroxy-4-methoxybenzophenone; 2-Hydroxy-4-n-dodecyloxy-benzophenone; 2,4-Dihydroxybenzophenone;2-Propenoic acid, 2-(4-benzoyl-3-hydroxyphenoxy)ethyl ester; Methanone, [2-hydroxy-4-(phenylmethoxy)phenyl]phenyl-; 2,2'-Dihydroxy-4-methoxybenzophenone; 2,2',4,4'-Tetrahydroxy benzophenone; 2,2'-Dihydroxy-4,4'-dimethoxybenzophenone; Poly-4-(2-acryloyloxyethoxy)-2-hydroxybenzophenone; Bis-(2-methoxy-4-hydroxy-5-benzoylphenyl)-methane; Methanone, [3-(2,4-dihydroxybenzoyl)
  • hydroxyphenylbenzotriazoles are 2-(2'-Hydroxy-3',5'-di-t-butyl-phenyl)-benzotriazole; 2-(2'-Hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole; Phenol, 2-(5-chloro-2H-benzotriazol-2-yl)-4,6-bis-(1,1-dimethylethyl)-; 2-(2'-Hydroxy-3,5'-di-t-amylphenyl) benzotriazole; Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl- ; Phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1-dimethylethyl)-; Phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-
  • oxalanilides are 2-Ethoxy-5-t-butyl-2'-ethyl-oxalanilide; 2-Ethyl, 2'-ethoxy-oxalanilide; N-(2-ethoxy-phenyl)-N'-(4-iso-dodecylphenyl)-ethanediamin.
  • phenyl esters are 4-t-Butyl-phenyl-salicylate; 2,4-Di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate; Benzoic acid, 2-hydroxy-, phenyl ester.
  • Benzooxazinones are 2.2'-(1,4-Phenylene)bis[4H-3,1-benzoxazin-4-one.
  • cyanoacrylates are Ethyl 2-cyano-3,3-diphenylacrylate; 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate; 1,3-bis-[2'-cyano-3',3-diphenylacryloyl)oxy]-2,2-bis- ⁇ [2-cyano-3',3'-diphenylacryloyl)oxy]methyl ⁇ propane.
  • hydroxyphenyl triazines are 2-[4,6-Diphenyl-1,3,5-triazin-2-yl]-5-(hexyl)oxy-phenol; Propanoic acid, 2-[4-[4,6-bis([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]-, isooctyl ester; Phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)- ; 2-[4-[(2-Hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6- bis(2,4-dimethylphenyl)-1,3,5-triazine;: 2-[4-[(2-Hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl
  • the coating composition containing the UV absorber further comprises a carrier.
  • the carrier can be any known coating for high strength fibers such as a wax, a polyacrylate coating, a polyurethane coating or silicone coating.
  • the invention provides a high strength fiber as described above wherein the coating comprises a cross-linked silicone polymer as a carrier for the light stabiliser.
  • the coating on the high strength fibers is obtained by applying a coating composition comprising a cross-linkable silicone polymer.
  • the coating composition may be cured, e.g. by heating to cause cross-linking of the cross-linkable silicone polymer.
  • the cross-linking may also be induced by any other suitable methods known to the skilled person.
  • the temperature for curing the coating composition is from 20 to 200 °C, preferably from 50 to 170 °C, more preferably 120 to 150 °C.
  • the curing temperature should not be too low, for the curing to be effective. Should the curing temperature become too high, there is a risk that the high strength fiber deteriorates and loses its strength.
  • the weight of the fibers before and after coating followed by curing is measured to calculate the weight of the cross-linked coating.
  • the weight of the cross-linked coating is 1 to 20 wt.%, based on the total weight of the fiber, preferably 1 to 10 wt.%.
  • the weight of the cross-linked coating is 1 to 30 wt.% based on the total weight of rope and coating, preferably 2 to 15 wt.%.
  • the degree of the cross-linking may be controlled.
  • the degree of the cross-linking may be controlled by e.g. the temperature or the time period of the heating.
  • the degree of the cross-linking if performed in other ways, may be controlled in methods known to the skilled person.
  • the measurement of the degree of the cross-linking may be performed as follows:
  • the fibers provided with the (at least partially) cross-linked coating is dipped in a solvent.
  • the solvent is chosen with which the extractables (mainly monomers)groups in the polymer would dissolve which are not cross-linked and the cross-linked network would not dissolve.
  • a preferred solvent is hexane.
  • the preferred degree of cross-linking is at least 30%, i.e. at least 30 wt%, based on the total weight of the coating, of the coating remains on the fibers or rope after extraction with the solvent. More preferably the degree of cross-linking is at least 50%. The maximum degree of cross-linking is about 100%.
  • the cross-linkable silicone polymer comprises a silicone polymer having a reactive end-group. It was found that a cross-linking in the endgroups of the silicone polymer results in a good bending resistance. A silicone polymer which is cross-linked at the end groups rather than at the branches in the repeating unit results in a less rigid coating. Without being limited thereto, the inventors attribute the improved properties of the rope to the less rigid structure of the coating.
  • the cross-linkable end-group is an alkylene end group, more preferably a C 2 -C 6 alkylene end group.
  • the end group is a vinyl group or a hexenyl group.
  • a vinyl group is preferred.
  • the coating composition further contains a cross-linker.
  • the cross-linker preferably has the formula: Si(CH 3 ) 3 -O-(SiCH 3 H-O) m - Si(CH 3 ) 3 (2) wherein m is a number n is a number from 2 to 200, preferably from 10 to 100, more preferably from 20 to 50.
  • the coating composition further comprises a metal catalyst for cross-linking the cross-linkable silicone polymer, the metal catalyst preferably being a platinum, palladium or rhodium, more preferably platinum metal complex catalyst.
  • a metal catalyst for cross-linking the cross-linkable silicone polymer preferably being a platinum, palladium or rhodium, more preferably platinum metal complex catalyst.
  • the coating composition is a multi-component silicone system comprising a first emulsion comprising the cross-linkable silicone polymer and the cross-linker and a second emulsion comprising the cross-linkable silicone polymer and the metal catalyst.
  • the weight ratio between the first emulsion and the second emulsion is from about 100:1 to about 100:30, preferably 100:5 to 100:20, more preferably 100:7 to 100:15.
  • the coating compositions as described above are known in the art. They are often referred to as addition-curing silicone coatings or coating emulsions.
  • the cross-linking or curing takes place when the vinyl end groups react with the SiH group of the cross-linker.
  • Examples of such coatings are Dehesive® 430 (cross-linker) and Dehesive® 440 (catalyst) from Wacker Silicones; Silcolease® Emulsion 912 and Silcolease® catalyst 913 from Bluestar Silicones; and Syl-off ® 7950 Emulsion Coating and Syl-off ® 7922 Catalyst Emulsion from Dow Corning.
  • the UV stabiliser of the invention can be included in the carrier composition prior to cross-linking.
  • fibers are understood to mean elongated bodies of indefinite length and with length dimension much greater than width and thickness.
  • the term fiber thus includes a monofilament, a multifilament yarn, a ribbon, a strip or tape and the like, and can have regular or irregular cross-section.
  • the term fibers also includes a plurality of any one or combination of the above.
  • the coating according to the invention can be applied to a single fiber or filament, but also to a bundle of more than one fiber, also referred to as a yarn.
  • Fibers having the form of monofilaments or tape-like fibers can be of varying titer, but typically have a titer in the range of 10 to several thousand dtex, preferably in the range of 100 to 2500 dtex, more preferably 200-2000 dtex.
  • Multi-filament yarns contain a plurality of filaments having a titer typically in the 0.2 - 25 dtex range, preferably about 0.5-20 dtex.
  • the titer of a multifilament yarn may also vary widely, for example from 50 to several thousand dtex, but is preferably in the range of about 200-4000 dtex, more preferably 300-3000 dtex.
  • high strength fibers for use in the invention are meant having a tenacity of at least 1.5, more preferably at least 2.0, 2.5 or even at least 3.0 N/tex.
  • Tensile strength, also simply strength, or tenacity of filaments are determined by known methods, as based on ASTM D2256-97.
  • high-strength polymeric filaments also have a high tensile modulus, e.g. at least 50 N/tex, preferably at least 75, 100 or even at least 125 N/tex.
  • HPPE fibers high performance polyethylene (HPPE) fibers, fibers manufactured from polyaramides, e.g. poly(p-phenylene terephthalamide) (known as Kevlar®); poly(tetrafluoroethylene) (PTFE); aromatic copolyamid (co-poly-(paraphenylene/3,4'-oxydiphenylene terephthalamide)) (known as Technora®); poly ⁇ 2,6-diimidazo-[4,5b-4',5'e]pyridinylene-1,4(2,5-dihydroxy)phenylene ⁇ (known as M5); poly(p-phenylene-2, 6-benzobisoxazole) (PBO) (known as Zylon®); thermotropic liquid crystal polymers (LCP) as known from e.g.
  • HPPE high performance polyethylene
  • polyaramides e.g. poly(p-phenylene terephthalamide) (known as Kevlar®); poly(tetrafluoroethylene) (PT
  • HPPE fibers are herein understood to be fibers made from ultra-high molar mass polyethylene (also called ultra-high molecular weight polyethylene; UHMWPE), and having a tenacity of at least 1.5, preferably at least 2.0, more preferably at least 2.5 or even at least 3.0 N/tex. There is no reason for an upper limit of tenacity of HPPE fibers in the rope, but available fibers typically are of tenacity at most about 5 to 6 N/tex.
  • the HPPE fibers also have a high tensile modulus, e.g. of at least 75 N/tex, preferably at least 100 or at least 125 N/tex. HPPE fibers are also referred to as high-modulus polyethylene fibers.
  • the HPPE fibers in the invention are one or more multi-filament yarns.
  • HPPE fibers, filaments and multi-filament yarn can be prepared by spinning of a solution of UHMWPE in a suitable solvent into gel fibers and drawing the fibers before, during and/or after partial or complete removal of the solvent; that is via a so-called gel-spinning process.
  • Gel spinning of a solution of UHMWPE is well known to the skilled person; and is described in numerous publications, including EP 0205960 A , EP 0213208 A1 , US 4413110 , GB 2042414 A , EP 0200547 B1 , EP 0472114 B1 , WO 01/73173 A1 , and in Advanced Fiber Spinning Technology, Ed. T. Nakajima, Woodhead Publ. Ltd (1994), ISBN 1-855-73182-7, and in references cited therein, all incorporated herein by reference.
  • HPPE fibers, filaments and multi-filament yarn can also be prepared by melt-spinning of UHMWPE, although the mechanical properties such as tenacity are more limited compared to HPPE fibers made by the gel-spinning process.
  • the upper limit of the molecular weight of the UHMWPE which can be melt-spun is lower than the limit with the gel-spinning process.
  • the melt-spinning process is widely known in the art, and involves heating a PE composition to form a PE melt, extruding the PE melt, cooling the extruded melt to obtain a solidified PE, and drawing the solidified PE at least once.
  • the process is mentioned e.g. in EP1445356A1 and EP1743659A1 , which are incorporated herein by reference.
  • UHMWPE is understood to be polyethylene having an intrinsic viscosity (IV, as measured on solution in decalin at 135°C) of at least 5 dl/g, preferably of between about 8 and 40 dl/g.
  • IV intrinsic viscosity
  • M n and M w molar mass
  • M w 5.37 * 10 4 [IV] 1.37 (see EP 0504954 A1 ) an IV of 8 dl/g would be equivalent to M w of about 930 kg/mol.
  • the UHMWPE is a linear polyethylene with less than one branch per 100 carbon atoms, and preferably less than one branch per 300 carbon atoms; a branch or side chain or chain branch usually containing at least 10 carbon atoms.
  • the linear polyethylene may further contain up to 5 mol% of one or more comonomers, such as alkenes like propylene, butene, pentene, 4-methylpentene or octene.
  • the UHMWPE contains a small amount, preferably at least 0.2, or at least 0.3 per 1000 carbon atoms, of relatively small groups as pending side groups, preferably a C1-C4 alkyl group.
  • a fiber shows an advantageous combination of high strength and creep resistance. Too large a side group, or too high an amount of side groups, however, negatively affects the process of making fibers.
  • the UHMWPE preferably contains methyl or ethyl side groups, more preferably methyl side groups.
  • the amount of side groups is preferably at most 20, more preferably at most 10, 5 or at most 3 per 1000 carbon atoms.
  • the HPPE according to the invention may further contain small amounts, generally less than 5 mass%, preferably less than 3 mass% of customary additives, such as anti-oxidants, thermal stabilisers, colorants, flow promoters, etc.
  • customary additives such as anti-oxidants, thermal stabilisers, colorants, flow promoters, etc.
  • the UHMWPE can be a single polymer grade, but also a mixture of two or more different polyethylene grades, e.g. differing in IV or molar mass distribution, and/or type and number of comonomers or side groups.
  • the high strength fibers with the coating containing an UV absorber of the invention can be used in any application where high strength fibers are normally applied.
  • the high strength fibers can be used in ropes, fishing lines and nets.
  • the coating can also be applied to an article containing high strength fibers, such as a rope or fishing net.
  • the invention also relates to an article, preferably a rope or fishing net, coated with a coating composition, wherein the coating composition contains a UV absorber. Preferred embodiments of UV absorber and of the coating composition are as described above.
  • the samples were UV-tested according to ISO 4982-2 against their untreated reference yarns over a maximum of 120 days. The time until tenacity decreased with 50% was determined.
  • a coating composition was prepared from a first emulsion comprising a reactive silicone polymer preformulated with a cross-linker and a second emulsion comprising a silicone polymer and a metal catalyst.
  • the first emulsion was an emulsion available from Dow Corning containing 30.0-60.0 wt% of dimethylvinyl-terminated dimethyl siloxane and 1.0-5.0 wt% of dimethyl, methylhydrogen siloxane (Syl-off ® 7950 Emulsion Coating).
  • the second emulsion was an emulsion available from Dow Corning containing 30.0-60.0 wt% of dimethylvinyl-terminated dimethyl siloxane and a platinum catalyst (Syl-off ® 7922 Catalyst Emulsion).
  • the first emulsion and the second emulsion were mixed at a weight ratio of 8.3:1.
  • a third solution is prepared of water and the UV stabiliser, or if the UV stabiliser is in itself a water based solution, this is used as is.
  • the mixture of fist emulsion and second emulsion is diluted with this third solution to a predetermined solid content (see Table 1).
  • the amount of UV stabiliser can be determined by adjusting the amount of third solution added.
  • HPPE fibers delivered by DSM in the Netherlands as Dyneema ® SK 75, 1760dtex, were dipped in the coating composition at room temperature. The fibers were heated in an oven at a temperature of 120°C so that cross linking takes place.
EP11152724A 2011-01-31 2011-01-31 Fibre haute résistance stabilisée contre les UV Withdrawn EP2481847A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP11152724A EP2481847A1 (fr) 2011-01-31 2011-01-31 Fibre haute résistance stabilisée contre les UV
PCT/EP2012/051560 WO2012104302A1 (fr) 2011-01-31 2012-01-31 Fibre de polyoléfine de masse moléculaire extrêmement élevée stabilisée
BR112013019527A BR112013019527A2 (pt) 2011-01-31 2012-01-31 fibra de poliolefina de ultra-alto peso molecular estabilizada
US13/981,434 US20140023863A1 (en) 2011-01-31 2012-01-31 Stabilized ultra high molecular weight polyolefin fiber
CN201280006919.0A CN103339315B (zh) 2011-01-31 2012-01-31 经稳定的超高分子量聚烯烃纤维
KR1020137022860A KR101925790B1 (ko) 2011-01-31 2012-01-31 안정화된 초고분자량의 폴리올레핀 섬유
AU2012213480A AU2012213480B2 (en) 2011-01-31 2012-01-31 Stabilized ultra high molecular weight polyolefin fiber
EP12703488.2A EP2670904B1 (fr) 2011-01-31 2012-01-31 Fibre polyoléfine a ultra haut poids moleculaire stabilisée
SG2013055934A SG192086A1 (en) 2011-01-31 2012-01-31 Stabilized ultra high molecular weight polyolefin fiber

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EP11152724A EP2481847A1 (fr) 2011-01-31 2011-01-31 Fibre haute résistance stabilisée contre les UV

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014187948A1 (fr) * 2013-05-23 2014-11-27 Dsm Ip Assets B.V. Fibre de pe-uhpm
WO2016039630A1 (fr) * 2014-09-12 2016-03-17 Offshore & Trawl Supply As Carenage pour corde
WO2016133670A1 (fr) * 2015-02-20 2016-08-25 Dow Global Technologies Llc Fibres de carbone obtenues à partir de fibres de précurseur de polyoléfine traitées au silicium
WO2017060461A1 (fr) * 2015-10-09 2017-04-13 Dsm Ip Assets B.V. Corps allongé composite

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LT2828333T (lt) * 2012-03-20 2016-10-10 Dsm Ip Assets B.V. Poliolefino pluoštas
NO20150074A1 (en) * 2015-01-15 2016-02-22 Calorflex As A mooring member
JP6256669B1 (ja) 2016-03-18 2018-01-10 株式会社村田製作所 金属製多孔膜、それを用いた分級方法、および分級装置
US20180037726A1 (en) * 2016-08-04 2018-02-08 Veerag Mehta Ultra highmolecular weight polyethylene compositions
CN108914595A (zh) * 2018-04-11 2018-11-30 巢湖市瀚海渔具有限公司 一种高强度复合渔网丝的制备方法
TWI754918B (zh) * 2020-04-20 2022-02-11 財團法人紡織產業綜合研究所 光變色聚丙烯纖維及其製備方法
CN112941935A (zh) * 2021-02-05 2021-06-11 常州科旭纺织有限公司 一种带颜色的含hppe纤维的纱线及其染色方法

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2042414A (en) 1979-02-08 1980-09-24 Stamicarbon Dry-spinning polymer filaments
US4384016A (en) 1981-08-06 1983-05-17 Celanese Corporation Mutiaxially oriented high performance laminates comprised of uniaxially oriented sheets of thermotropic liquid crystal polymers
US4413110A (en) 1981-04-30 1983-11-01 Allied Corporation High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore
EP0205960A2 (fr) 1985-06-17 1986-12-30 AlliedSignal Inc. Fibre de polyoléfine à haute ténacité, à faible retrait, à module très élevé et à très bas fluage et ayant une bonne rétention de résistance à haute température ainsi que sa méthode de fabrication
EP0213208A1 (fr) 1985-02-15 1987-03-11 Toray Industries, Inc. Fil multifilament en polyethylene
EP0200547B1 (fr) 1985-05-01 1991-07-03 Mitsui Petrochemical Industries, Ltd. Article moulé à haut degré d'orientation en polyéthylène de poids moléculaire très élevé et son procédé de fabrication
JPH03249289A (ja) * 1990-02-21 1991-11-07 Toyobo Co Ltd 複合ブレードロープ
EP0504954A1 (fr) 1991-02-18 1992-09-23 Dsm N.V. Feuille microporeuse en polyéthylène et procédé pour sa fabrication
US5246988A (en) 1990-02-26 1993-09-21 Alliedsignal Inc. Stabilized polymeric article and method of producing
JPH05287680A (ja) * 1992-03-31 1993-11-02 Kuraray Co Ltd 耐候性と耐摩耗性の改良された高強力高弾性率繊維の製造方法
EP0697481A2 (fr) * 1994-07-23 1996-02-21 Ciba-Geigy Ag Compositions aqueuses pour le traitement textile contenant un agent UV-absorbant
EP0472114B1 (fr) 1985-01-11 1999-04-14 AlliedSignal Inc. Articles formés de polyéthylène à poids moléculaire moyen ayant un haut module
WO2001073173A1 (fr) 2000-03-27 2001-10-04 Honeywell International Inc. Filament a tenacite et module eleves
EP1445356A1 (fr) 2001-08-08 2004-08-11 Toyo Boseki Kabushiki Kaisha Fibre en polyethylene haute resistance
WO2006082145A1 (fr) 2005-02-02 2006-08-10 Ciba Specialty Chemicals Holding Inc. Absorbeurs d’uv au benzotriazole decales vers les longues longueurs d’onde et leur utilisation
EP1743659A1 (fr) 2005-07-13 2007-01-17 Tyco Healthcare Group Lp Sutures monofilamentaires fabriqué a partir d'une composition contenant de polyéthylène à poids moléculaire ultra-élevé
WO2007008814A2 (fr) 2005-07-12 2007-01-18 Tibco Software Inc. Automates finis inferentiels
WO2009060043A2 (fr) 2007-11-06 2009-05-14 Dsm Ip Assets Bv Procédé de fabrication de polyéthylène de masse moléculaire élevée
US20100071119A1 (en) * 2006-03-29 2010-03-25 Chapman Therman Products, Inc. Yarns and fabrics that shed liquids, gels, sparks and molten metals and methods of manufacture and use

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4316033A (en) * 1980-05-30 1982-02-16 General Electric Company Alkoxysilylbenzotriazoles
JP3249289B2 (ja) * 1994-04-08 2002-01-21 帝人株式会社 ディスク着脱装置
US6652975B2 (en) * 2001-03-02 2003-11-25 Lucent Technologies Inc. Adherent silicones
EP1308084A1 (fr) * 2002-10-02 2003-05-07 Ciba SC Holding AG Combinaison UV-absorbante avec un effet synergistique
WO2004087222A1 (fr) * 2003-03-31 2004-10-14 Fujimori Kogyo Co., Ltd. Temoin de sterilisation du plasma et materiau d'emballage pour sterilisation
PT1954870T (pt) * 2005-12-02 2016-11-10 Dsm Ip Assets Bv Corda contendo fibras de polietileno de alto desempenho
JP5287680B2 (ja) * 2009-11-19 2013-09-11 船井電機株式会社 回転入力装置および携帯機器

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2042414A (en) 1979-02-08 1980-09-24 Stamicarbon Dry-spinning polymer filaments
US4413110A (en) 1981-04-30 1983-11-01 Allied Corporation High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore
US4384016A (en) 1981-08-06 1983-05-17 Celanese Corporation Mutiaxially oriented high performance laminates comprised of uniaxially oriented sheets of thermotropic liquid crystal polymers
EP0472114B1 (fr) 1985-01-11 1999-04-14 AlliedSignal Inc. Articles formés de polyéthylène à poids moléculaire moyen ayant un haut module
EP0213208A1 (fr) 1985-02-15 1987-03-11 Toray Industries, Inc. Fil multifilament en polyethylene
EP0200547B1 (fr) 1985-05-01 1991-07-03 Mitsui Petrochemical Industries, Ltd. Article moulé à haut degré d'orientation en polyéthylène de poids moléculaire très élevé et son procédé de fabrication
EP0205960A2 (fr) 1985-06-17 1986-12-30 AlliedSignal Inc. Fibre de polyoléfine à haute ténacité, à faible retrait, à module très élevé et à très bas fluage et ayant une bonne rétention de résistance à haute température ainsi que sa méthode de fabrication
JPH03249289A (ja) * 1990-02-21 1991-11-07 Toyobo Co Ltd 複合ブレードロープ
US5246988A (en) 1990-02-26 1993-09-21 Alliedsignal Inc. Stabilized polymeric article and method of producing
EP0504954A1 (fr) 1991-02-18 1992-09-23 Dsm N.V. Feuille microporeuse en polyéthylène et procédé pour sa fabrication
JPH05287680A (ja) * 1992-03-31 1993-11-02 Kuraray Co Ltd 耐候性と耐摩耗性の改良された高強力高弾性率繊維の製造方法
EP0697481A2 (fr) * 1994-07-23 1996-02-21 Ciba-Geigy Ag Compositions aqueuses pour le traitement textile contenant un agent UV-absorbant
WO2001073173A1 (fr) 2000-03-27 2001-10-04 Honeywell International Inc. Filament a tenacite et module eleves
EP1445356A1 (fr) 2001-08-08 2004-08-11 Toyo Boseki Kabushiki Kaisha Fibre en polyethylene haute resistance
WO2006082145A1 (fr) 2005-02-02 2006-08-10 Ciba Specialty Chemicals Holding Inc. Absorbeurs d’uv au benzotriazole decales vers les longues longueurs d’onde et leur utilisation
WO2007008814A2 (fr) 2005-07-12 2007-01-18 Tibco Software Inc. Automates finis inferentiels
EP1743659A1 (fr) 2005-07-13 2007-01-17 Tyco Healthcare Group Lp Sutures monofilamentaires fabriqué a partir d'une composition contenant de polyéthylène à poids moléculaire ultra-élevé
US20100071119A1 (en) * 2006-03-29 2010-03-25 Chapman Therman Products, Inc. Yarns and fabrics that shed liquids, gels, sparks and molten metals and methods of manufacture and use
WO2009060043A2 (fr) 2007-11-06 2009-05-14 Dsm Ip Assets Bv Procédé de fabrication de polyéthylène de masse moléculaire élevée

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Advanced Fiber Spinning Technology", 1994, WOODHEAD PUBL. LTD
DATABASE WPI Week 199151, Derwent World Patents Index; AN 1991-372454, XP002652174 *
DATABASE WPI Week 199348, Derwent World Patents Index; AN 1993-383646, XP002652173 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014187948A1 (fr) * 2013-05-23 2014-11-27 Dsm Ip Assets B.V. Fibre de pe-uhpm
EA032464B1 (ru) * 2013-05-23 2019-05-31 ДСМ АйПи АССЕТС Б.В. Свмпэ-волокно
WO2016039630A1 (fr) * 2014-09-12 2016-03-17 Offshore & Trawl Supply As Carenage pour corde
WO2016133670A1 (fr) * 2015-02-20 2016-08-25 Dow Global Technologies Llc Fibres de carbone obtenues à partir de fibres de précurseur de polyoléfine traitées au silicium
WO2017060461A1 (fr) * 2015-10-09 2017-04-13 Dsm Ip Assets B.V. Corps allongé composite
CN114381858A (zh) * 2015-10-09 2022-04-22 帝斯曼知识产权资产管理有限公司 复合的长物体

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WO2012104302A1 (fr) 2012-08-09
EP2670904B1 (fr) 2017-03-22
AU2012213480B2 (en) 2016-12-15
CN103339315B (zh) 2015-09-02
KR101925790B1 (ko) 2019-02-26
BR112013019527A2 (pt) 2017-03-28
KR20140010389A (ko) 2014-01-24
EP2670904A1 (fr) 2013-12-11
US20140023863A1 (en) 2014-01-23
CN103339315A (zh) 2013-10-02

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