EP2481847A1 - UV-Stabilized high strength fiber - Google Patents

UV-Stabilized high strength fiber 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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Prior art keywords
high strength
cross
strength fiber
fiber according
silicone polymer
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German (de)
French (fr)
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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
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    • DTEXTILES; PAPER
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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

Abstract

The present invention provides a high strength fiber coated with a coating composition, wherein the coating composition contains a UV absorber. The UV absorber can be selected from the group consisting of hydroxybenzophenones, hydroxyphenylbenzotriazoles, oxalanilides, phenyl esters, benzooxazinones, cyanoacrylates, formamidine, benzylidene malonates and hydroxyphenyl triazines and combinations thereof. Such fibers are particularly useful in ropes and fishing nets.

Description

  • The present invention relates to high strength fibers having improved UV stability and the use thereof in, for instance, ropes and fishing nets.
  • Although high strength 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.
  • In US5246988 it is described to make a heat and oxidation stable article where a nitrogen-containing antioxidant is included in a carrier which is a lubricant. Such heat and oxidation stable coatings are not always suitable to improve resistance to UV radiation. Moreover, there is a need to improve coating compositions used.
  • 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.
  • Examples of inorganic stabilisers are carbon black, titanium dioxide (TiO2), ZnO and CeO2.
  • Examples of organic stabilisers are those falling in the classes of hydroxybenzophenones, hydroxyphenylbenzotriazoles, oxalanilides, phenyl esters, benzooxazinones, cyanoacrylates, formamidine, benzylidene malonates and hydroxyphenyl triazines.
  • Examples of UV stabilisers suitable for the invention are for instance described in WO2006/082145 , WO2009/060043 and WO2007/08814 .
  • Further examples of 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)phenyl][2-hydroxy-4-(2-propenyloxy)phenyl]-; 2,2-Dihydroxy-4,4'-dimethoxy-benzophenone-5,5'-bis-(sodiumsulphonate); 2-Hydroxy-4-methoxy-benzophenone-5-sulfonic acid; Methanone, [2-hydroxy-4-(2-hydroxyethoxy)phenyl]phenyl-; Mixture of 2,2',4,4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone ; 1,4-bis(4-benzoyl-3-hydroxyphenoxy)-butane; 2-Butenoic acid, 2-(4-benzoyl-3-hydroxyphenoxy)-1-[(4-benzoyl-3-hydroxyphenoxy)methyl]ethyl ester.
  • Further examples of 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-tetramethylbutyl)-; Benzene propanoic acid, 3-(2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-1,6-hexanediylester; Bis[2-hydroxy-5-t-octyl-3-(benzotriazol-2-yl)phenyl]methane; 2-[2-Hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]2H-benzotriazole; 2-[2-Hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole; Bis[2-hydroxy-5-methyl-3-(benzotriazol-2-yl)phenyl]methane; 2(2'-Hydroxy-5-metacrylyloxyethylphenyl)2H-benzotriazole; Phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1-dimethylethyl)-6-(2-methylpropyl)-; Isomer mixture from the alkylation of 2-(2H-benzotriazole-2-yl)-p-cresol with dodecane; α-[3-[3-(2H-Benzotriazole-2-yl)-5-(1,1-dimethylethel_-4-hydroxyphenyl]-1-oxopropyl]-ω-hydrxypoly(oxox-1,2-etahediyl); α-[3-[3-(2H-Benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-[3-[3-(2H-Benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]]poly(oxy-1,2-etanediyl); Benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- C7-9-branched and linear alkyl esters;2-(2H-Benzotriazol-2-yl)-6-(1-methyl-1 - phenylethyl)4-(1,1,3,3-tetramethylbutyl)phenol; 2-(2'-Hydroxy-5'-(2-hydroxyethyl))-benzotriazole; 2-(2-hydroxy-4-octyloxyphenyl)- 2H-benzotriazole; Sodium Benzotriazolyl Butylphenol Sulfonate; Octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)fenyl]propionaat ;2-Ethylhexyl-3-[3-tertbutyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2yl) phenyl]propionaat; Phenol, 2-(2H-benzotriazol-2-yl)-6-[[3-(1,1-dimethylethyl)-2-hydroxy-5-methylphenyl]methyl]-4-(1,1,3,3-tetramethylbutyl)-.
  • Further examples of oxalanilides are 2-Ethoxy-5-t-butyl-2'-ethyl-oxalanilide; 2-Ethyl, 2'-ethoxy-oxalanilide; N-(2-ethoxy-phenyl)-N'-(4-iso-dodecylphenyl)-ethanediamin.
  • Further examples of 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.
  • Further examples of Benzooxazinones are 2.2'-(1,4-Phenylene)bis[4H-3,1-benzoxazin-4-one.
  • Examples of 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.
  • Further examples include N-(p-Ethoxy-carbonylphenyl)-N'-methyl-N'-phenylformamidine; N-(p-Ethoxy-carbonylphenyl)-N'-ethyl-N'-phenylformamidine, and 2-Propenoic acid, 3-(4-methoxyphenyl)-, 2-ethylhexyl ester; Propanedioic acid, [(4-methoxyphenyl)-methylene]-dimethyl ester; Tetra-ethyl-2,2'-(1,4-phenylene-dimethylidene)-bismalonate.
  • Examples of 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]-4,6-bis(2,4- dimethylphenyl)-1,3,5-triazine; 2-[4-[(2-Hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4- dimethylphenyl)-1,3,5-triazine; 2,4-Bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine; 5,5'-Bis(2-ethylhexyloxy)-2,2'-[6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl]diphenol; Propanoic acid, 2,2',2"-[1,3,5-triazine-2,4,6-triyltris[(3-hydroxy-4,1-phenylene)oxy]]tris-, 1,1',1"-trioctyl ester;
    Most preferred compounds are those with the structures as shown below:
    Figure imgb0001
    Figure imgb0002
    Figure imgb0003
  • According to a preferred aspect of the invention 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.
  • In particular, 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.
  • Such a coating is for instance described in unpublished patent application PCT/EP2010/060813 which is incorporated herein by reference.
  • In the present invention, the coating on the high strength fibers is obtained by applying a coating composition comprising a cross-linkable silicone polymer. After the application of the coating composition to the fibers, 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. For a fiber, 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.%. For a rope, preferably, 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. By weighing the rope or the fibers after the dipping in such a solvent, the weight of the non-cross-linked portion can be determined and the ratio of the cross-linked silicone to the extractables can be calculated.
  • 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%.
  • Preferably, 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.
  • Preferably, the cross-linkable end-group is an alkylene end group, more preferably a C2-C6 alkylene end group. In particular the end group is a vinyl group or a hexenyl group. In general, a vinyl group is preferred.
  • Preferably, the cross-linkable silicone polymer has the formula:

             CH2=CH-(Si(CH3)2-O)n-CH=CH2     (1)

    wherein n is a number from 2 to 200, preferably from 10 to 100, more preferably from 20 to 50.
  • Preferably, the coating composition further contains a cross-linker. The cross-linker preferably has the formula:

             Si(CH3)3-O-(SiCH3H-O)m- Si(CH3)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.
  • Preferably, 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. Such catalysts are know to the skilled person.
  • Preferably, 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.
  • Preferably, 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.
  • Within the context of the present invention, 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.
  • Thus, 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.
  • With 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. Generally such 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.
  • Examples of such fibers are 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. US 4,384,016 ; but also polyolefins other than polyethylene e.g. homopolymers and copolymers of polypropylene. Also combinations of fibers manufactured from the above referred polymers can be used in the rope of the invention. Preferred high-strength fibers however are fibers of HPPE, polyaramides or LCP.
  • Most preferred fibers are high performance polyethylene (HPPE) fibers. 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.
  • In a preferred embodiment, 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. Intrinsic viscosity is a measure for molar mass (also called molecular weight) that can more easily be determined than actual molar mass parameters like Mn and Mw. There are several empirical relations between IV and Mw, but such relation is dependent on molar mass distribution. Based on the equation Mw = 5.37 * 104 [IV]1.37 (see EP 0504954 A1 ) an IV of 8 dl/g would be equivalent to Mw of about 930 kg/mol. Preferably, 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.
  • In one embodiment, 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. Such 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. For this reason, 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. 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. In particular the high strength fibers can be used in ropes, fishing lines and nets.
  • Although the invention is here described as a high strength fiber with a coating, according to another embodiment, the coating can also be applied to an article containing high strength fibers, such as a rope or fishing net. Thus, 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.
  • Methods of making a rope or fishing net are known to the skilled person.
  • The invention is further illustrated by the Examples below.
  • Analytical methods Weathering
  • 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.
  • Mechanical properties
  • Tensile properties were determined on a Zwick 1435, according to ASTM D 2256.
  • Examples
  • 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. Table 1 Example Silicone coating wt.% Stabiliser type Stabiliser in final dried coating wt.% Time until tenacity is reduced with 50% hours Comparative A 0 None - 1618 Comparative B 4 None - 1618 Comparative C 8 None - 1618 1 4 Tinuvin 477-DW®* 10 2747 2 4 Tinuvin 477-DW® 20 2049 3 4 Tinuvin 477-DW® 30 2747 4 8 Tinuvin 477-DW® 10 2500 5 8 Tinuvin 477-DW® 20 2750 6 8 Tinuvin 477-DW® 30 3250 *Obtainable from Ciba Inc.
  • It can be seen from the examples above that the addition of stabiliser significantly improves the time until tenacity is reduced when the fiber is exposed to UV radiation.

Claims (16)

  1. A high strength fiber coated with a coating composition, wherein the coating composition contains a UV absorber.
  2. The high strength fiber according to claim 1, wherein the UV absorber is capable of absorbing UV radiation in the range of 290 to 400 nm.
  3. The high strength fiber according to claim 1 or 2, wherein the UV absorber is selected from the group consisting of hydroxybenzophenones, hydroxyphenylbenzotriazoles, oxalanilides, phenyl esters, benzooxazinones, cyanoacrylates, formamidine, benzylidene malonates and hydroxyphenyl triazines or combinations thereof.
  4. The high strength fiber according to claim 3, wherein the UV stabiliser isselected from hydroxybenzotriazoles and hydroxyphenyl triazines.
  5. The high strength fiber according to claim 4, wherein the UV stabliliser is a compound having the formula:
    Figure imgb0004
  6. The high strength fiber according to any of the preceding claims, which is a high performance polyethylene (HPPE) fiber, made of ultrahigh molecular weight polyethylene (UHMWPE) having an intrinsic viscosity of at least 5 dl/g determined in decalin at 135 °C.
  7. The high strength fiber according to any of the preceding claims, wherein the coating comprises a cross-linked silicone polymer as a carrier for the UV absorber.
  8. The high strength fiber according to claim 7, wherein the degree of cross-linking of the cross-linked silicone polymer is at least 20%.
  9. The high strength fiber according to claim 7 or 8, wherein the coating comprising the cross-linked silicone polymer is obtained by applying to the fiber, a coating composition comprising a cross-linkable silicone polymer; and
    cross-linking the cross-linkable silicone polymer.
  10. The high strength fiber according to claim 9, wherein the cross-linkable silicone polymer comprises a silicone polymer having a cross-linkable end-group, preferably an C2-C6 alkylene end group.
  11. The high strength fiber according to claim 9 or 10, wherein the cross-linkable silicone polymer has the formula:

             CH2=CH-(Si(CH3)2O)n-CH=CH2     (1)

    wherein n is a number from 2 to 200.
  12. The high strength fiber according to any one of claims 9 to 11, wherein the coating composition further comprises a cross-linker having the formula:

             Si(CH3)3O-(SiCH3HO)m -Si(CH3)3     (2)

    wherein m is a number of 2 to 200.
  13. The high strength fiber according to any one of claims 9 to 11, wherein the coating composition further comprises a platinum catalyst.
  14. Use of a high strength fiber according to any of claims 1 to 13 for making a rope.
  15. Use of a high strength fiber according to any of claims 1 to 13 for making a fishing net.
  16. An article, preferably a rope or fishing net, containing high strength fibers,
    wherein the article is coated with a coating composition containing a UV absorber.
EP11152724A 2011-01-31 2011-01-31 UV-Stabilized high strength fiber Withdrawn EP2481847A1 (en)

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