WO2014088926A1 - Revêtements primaires aptes à durcir sous l'effet d'un rayonnement pour fibre optique - Google Patents

Revêtements primaires aptes à durcir sous l'effet d'un rayonnement pour fibre optique Download PDF

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WO2014088926A1
WO2014088926A1 PCT/US2013/072549 US2013072549W WO2014088926A1 WO 2014088926 A1 WO2014088926 A1 WO 2014088926A1 US 2013072549 W US2013072549 W US 2013072549W WO 2014088926 A1 WO2014088926 A1 WO 2014088926A1
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radiation curable
optical fiber
primary coating
coating
polar
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PCT/US2013/072549
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English (en)
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Wendell Wayne Cattron
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Dsm Ip Assets Bv
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/104—Coating to obtain optical fibres
    • C03C25/1065—Multiple coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/326—Polyureas; Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to radiation curable primary coatings for optical fibers, optical fibers coated with said coatings and methods for the preparation of coated optical fibers.
  • An optical fiber is a flexible, transparent fiber made of glass (silica) or plastic, slightly thicker than a human hair. It functions as a waveguide, or "light pipe", to transmit light between the two ends of the fiber.
  • Optical fibers are widely used in fiber-optic communications, which permits transmission over longer distances and at higher bandwidths (data rates) than other forms of communication.
  • Optical Fibers are used instead of metal wires because signals travel along them with less loss and are also immune to electromagnetic interference.
  • Optical fibers typically include a transparent core surrounded by a transparent cladding material with a lower index of refraction. Light is kept in the core by total internal reflection. This causes the fiber to act as a waveguide. Fibers that are capable of having more than one light signal travel along them simultaneously (otherwise known as being able to support many propagation paths or transverse modes) are called multi-mode fibers ("MMF"), while those optical fibers that are capable of having only one light signal travel along them (otherwise known as supporting only a single mode) are called single-mode fibers (“SMF"). Multi-mode fibers generally have a wider core diameter of from about 50 microns to about 63 microns core diameter. In comparison single-mode fibers have a core diameter of from about 8 microns to about 10.
  • MMF are typically used for short-distance communication links and for applications where high power must be transmitted.
  • One current location where MMF are typically used is at data centers, where huge amounts of data have to be processed.
  • SMF are used for most communication links longer than 1 050 meters (3,440 ft.).
  • Both single mode and multi-mode optical fibers are typically coated with two or more radiation curable coatings known as a "dual-layer" coating approach. These coatings are typically applied to the optical fiber in liquid form, and then exposed to radiation to effect curing.
  • the type of radiation that may be used to cure the coatings should be that which is capable of initiating the polymerization of one or more radiation curable components of such coatings. Radiation suitable for curing such coatings is well known, and includes ultraviolet light (hereinafter "UV") and electron beam (“EB”).
  • UV ultraviolet light
  • EB electron beam
  • the preferred type of radiation for curing coatings used in the preparation of coated optical fiber is UV.
  • the inner primary coating is the coating which directly contacts the optical fiber and it is also referred to as just the Primary Coating, and the coating that covers the Primary Coating is called the Outer Primary Coating, Outer Secondary Coating or just the Secondary Coating.
  • the inner primary coating is designed to act as a shock absorber to minimize attenuation caused by microbending.
  • the outer secondary coating protects the primary coating against mechanical damage and acts as a barrier to lateral forces. It is known in the art of radiation curable coatings for optical fibers that Primary Coatings are advantageously softer than Secondary Coatings. One advantage of the softness of the Primary Coating is that this coating enhances the flexibility of the fragile Optical Fiber.
  • Fiber optic coatings are applied using one of two methods: wet-on-dry and wet-on-wet. In wet-on-dry, the fiber passes through a primary coating applicator, which is then UV cured - then through the secondary coating applicator, which is subsequently cured. In wet-on-wet, the fiber passes through both the primary coating application and the secondary coating applicator, and then passes through UV curing.
  • Fiber optic coatings are applied in concentric layers to prevent damage to the fiber during the drawing application and to maximize fiber strength and microbending resistance. Unevenly coated fiber will experience non-uniform forces when the coating expands or contracts, and is susceptible to greater signal attenuation. Under proper drawing and coating processes, the coatings are concentric around the fiber, continuous over the length of the application and have constant thickness.
  • Fiber optic coatings protect the glass fibers from scratches that could lead to strength degradation. The combination of moisture and scratches accelerates the aging and deterioration of fiber strength. When fiber is subjected to low stresses over a long period, fiber fatigue can occur as evidence by microbending. Over time or in extreme conditions, these factors combine to cause microscopic flaws in the glass fiber to propagate, which can ultimately result in microbending induces attenuation which is evidence of fiber failure, [00010] Microbends are sharp but microscopic curvatures in an optical fiber involving local axial displacements of a few micrometers and spatial wavelengths of a few millimeters. Microbends can be induced by thermal stresses and/or mechanical lateral forces. When present, microbends attenuate the signal transmission capabil ity of the coated optical fiber. Attenuation is the undesirable reduction of signal carried by the optical fiber.
  • optical fiber primary coating is suitable for both single mode and multi-mode optical fiber.
  • the first aspect of the instant claimed invention is a radiation curable Primary Coating composition
  • a radiation curable Primary Coating composition comprising
  • (iii) is more non-polar than polar, meaning it is lipophilic, such that the HLB value is less than about 10; (iv) is present in the composition at about 20 wt.% to about 60 wt.%; and
  • (vii) is more polar than non-polar, meaning it is hydrophilic, such that the HLB value is greater than about 10;
  • (viii) is present in the composition at from about 0.5 wt.% to about 20 wt.%.
  • the first aspect of the instant claimed invention is a radiation curable Primary Coating composition
  • a radiation curable Primary Coating composition comprising
  • (iii) is more non-polar than polar, meaning it is lipophilic, such that the HLB value is less than about 10;
  • (vii) is more polar than non-polar, meaning it is hydrophilic, such that the HLB value is greater than about 10;
  • (viii) is present in the composition at from about 0.5 wt.% to about 20 wt.%.
  • Multifunctional as used in this patent application means difunctional or greater. It does not include monofunctional.
  • it is critical that the selection of the diluent monomers includes a first diluent monomer, wherein the first diluent monomer is monofunctional and lipophilic and includes a second diluent monomer, wherein the second di luent monomer is multifunctional and is hydrophilic.
  • a “lipophile” is a molecule that is attracted to, and tends to be dissolved in oils.
  • a “hydrophile” is a molecule or other molecular entity that is attracted to, and tends to be dissolved by, water.
  • a hydrophilic molecule or portion of a molecule is one that has a tendency to interact with or be dissolved by water and other polar substances.
  • a hydrophobic moiety in contrast is not attracted to and does not dissolve in water.
  • surfactants are usually organic compounds that are amphophilic, meaning they contain both hydrophobic groups and hydrophilic groups. Put another way, a surfactant combines both hydrophilic and hydrophobic parts into one molecule and is known to induce an order into a system which is exhibited by a phase separation of a hydrophilic region and a hydrophobic region.
  • Surfactants are used to make emulsions or water in oil emulsions or oil in water emulsions and form micelles.
  • Ethoxylated nonyl phenol acrylate is a known diluent monomer and is commercially available, as SR-504, from Sartomer or as AgiSyn® 2895 available from
  • Ethoxylated nonyl phenol acrylate has long been used in radiation curable coatings for optical fiber as a diluent monomer.
  • Ethoxylated nonyl phenol acrylate is made from a surfactant, ethoxylated nonyl phenol .
  • the acrylate portion of ethoxylated nonyl phenol acrylate must be connected to the polar part of ethoxylated nonyl phenol, through the -OH group which is at the polar end of the ethoxylated nonyl phenol.
  • Ethoxylated nonyl phenol acrylate a very polar, monofunctional acrylate diluent monomer that acts like a surfactant in the radiation curable primary coating compositions of the instant claimed invention.
  • the first diluent monomer used in a radiation curable primary coating is a very polar monofimctional acrylate, such as ethoxylated nonyl phenol acrylate, it is believed, without intending to be bound thereby, that this type of chemistry causes the crosslinks to form first in the more polar regions of the coating where the acrylate groups are. This is where the cure speed of the radiation curable coating is faster as compared to the non-polar regions of the coating where the cure speed is slower because the
  • Legacy coatings are considered pre-Supercoatings, see US Patent Number 8,426,020, "D 1381 Supercoatings for Optical Fiber”.
  • Legacy coatings are formulated such that they are not capable of curing fast enough over a line speed of from about 600 meters per minute to about 2400 meters per minute and still have sufficient formation of in-situ modulus, in-situ Tg and %RAU.
  • HLB Hydrophilic-Lipophilic Balance
  • Mh is the molecular mass of the hydrophilic portion of the molecule
  • M is the molecular mass of the whole molecule, giving a result on a scale of 0 to 20.
  • An HLB value of 0 corresponds to a completely lipophilic/hydrophobic molecule
  • a value of 20 corresponds to a completely hydrophilic/lipophobic molecule.
  • the HLB value can be used to predict the properties of a moiety:
  • a value ⁇ 10 lipid soluble (water insoluble);
  • a value > 10 water soluble (lipid insoluble); A value from 4 to 8 indicates an anti-foaming agent;
  • a value from 7 to 1 1 indicates a W/O (water in oil) emulsifier
  • a value from 12 to 16 indicates O/W (oil in water) emulsifier
  • a value from 1 1 to 14 indicates a wetting agent
  • a value from 12 to 15 indicates a detergent
  • a value of 16 to 20 indicates a solubilizer or hydrotrope.
  • the first diluent monomer is more non-polar than polar, such that the HLB value is less than about 10; and the second diluent monomer is hydrophilic, such that the HLB value is greater than about 10,
  • SR349 is an ETHOXYLATED (3) BISPHENOL A DIACRYLATE.
  • SR344 is a POLYETHYLENE GLYCOL (400) DIACRYLATE
  • SR504 is ETHOXYLATED (4) NONYL PHENOL ACRYLATE
  • SR 504 can be used as the first diluent monomer in the instant claimed invention because it is lipophilic (HLB ⁇ 10) and monofunctional, but it cannot be used as the second diluent monomer in the instant claimed invention because it is not hydrophilic and is monofunctional.
  • Miramer® M 144 is EO (4) PEA and is available from Miwon Specialty Chemical Co. Ltd.
  • TMP6EOTA Ethoxylated (Six moles of ethylene oxide) trimethylolpropane triacrylate
  • TMP9EOTA Ethoxylated ( 10 moles of ethylene oxide) trimethylolpropane triacrylate
  • TMP 1 5EOTA Ethoxylated (1 5 moles of ethylene oxide) trimethylolpropane triacrylate
  • TMP20EOTA Ethoxylated (20 moles of ethylene oxide) trimethylolpropane triacrylate
  • (meth)acrylate oligomers and how to synthesize them, diluent monomers, photoinitiators, adhesion promoters and other additives such as antioxidants, stabilizers and slip additives may be found in the following list of issued US patents and published US patent applications, all of which are incorporated by reference, in their entirety: 5496870, 5664041 , 5837750, 6040357, 6052503, 6054217, 6080483, 61 10593, 6136880, 6214899, 6240230, 6298189, 6306924, 63 19549, 6323255, 6339666, 6350790, 6359025, 6362249, 6391459, 6391936, 6438306, 6472450, 6534557, 6579618, 6599956, 6661959, 66801 18, 6797740, 6961 508, 7067564, 7076142, 7171 103, 721443 1 , 7276543,
  • the oligomers useful in the various aspects of the present invention will be described in the following sections.
  • the oligomers are urethane (meth)acrylate oligomers, comprising a (meth)acrylate group, urethane groups and a backbone (the term (meth)acrylate including acrylates as well as methacrylate functionalities).
  • the typical method of synthesizing the oligomer is the following.
  • a hybrid "outside in” method of oligomer synthesis is used.
  • the proposed benefit of using this hybrid "outside in” method is based on the different reactivity of the secondary hydroxyl of the Acclaim® polypropylene glycol (Acclaim® polyol is a polyether polyol based on propylene oxide available from Bayer), which is about an order of magnitude less reactive than the primary hydroxyls used for the ends of the oligomer.
  • a desired feature of this method of oligomer synthesis is as follows. First, when no catalyst is added, the polyols are mixed to ensure that the primary hydroxyls of the HEA and the 2-ethyl-hexyl alcohol are in a low, consistent concentration in the polypropylene glycol.
  • the isocyanate, such as IPDI is added to this and the objective is that the end groups add to one end of the IPDL.
  • the differential reactivity of the NCO one each IPDI helps to make sure that this happens.
  • the catalyst is added making the PPG4000 react to the mono-end capped isocyanate.
  • the advantage of using the bismuth catalyst is good adhesion promoter stability is obtained in the formulated product and it is less toxic and more environmentally friendly than tin.
  • (iii) is more non-polar than polar, meaning that it is lipophilic, such that the HLB value is less than about 10;
  • (vii) is more polar than non-polar, meaning that it is hydrophilic, such that the HLB value is greater than about 10;
  • (viii) is present in the composition at from about 0.5 wt.% to about 20 wt.%.
  • the first diluent monomer can be selected from the group consisting of ethoxylated nonyl phenol acrylates, which are sold commercially by Sartomer as SR 504 and SR 504 D and by AGI-DSM Chemicals as AgiSyn® 2895.
  • An additional first diluent monomer is MiramerTM M 144 which is EO (4) PEA, available from Miwon Specialty Chemical Co. Ltd
  • the second diluent monomer can be selected from the group consisting of polyethylene glycol (200 MW) diacrylate (sold commercially by Sartomer as SR259, polyethylene glycol (400 MW) diacrylate (sold commercially by Sartomer as SR344 and by AGI-DSM Chemicals as AgiSyn® 2834), polyethylene glycol (600 MW) diacrylate (sold commercially by Sartomer as SR610 and by AGI-DSM Chemicals as AgiSyn® 2835), ethoxylatedi 5 trimethylolpropane triacrylate (sold commercially by Sartomer as
  • Additional Second Diluent monomers include highly ethoxylated (20 mole EO) trimethylolpropane triacrylate (sold commercially by Sartomer as SR415 and AGI-DSM Chemicals as AgiSyn® 2867 ), ethoxylated (30) bisphenol A diacrylate (sold
  • the first diluent monomer is ethoxylated nonyl phenol acrylate, available from Sartomer as SR 504 or SR 504D and available as AgiSyn® 2895 available from AGI-DSM Corporation.
  • the first diluent monomer is SR 504D.
  • SR 504D is a commercially available diluent monomer that has long been used in Primary Coatings. To date, applicants are unaware of any use of this monomer, in radiation curable primary coatings for optical fiber, in connection with a second diluent monomer wherein the second diluent monomer is multifunctional and is hydrophilic, such that the HLB value is greater than about 10. Hydrophilic diluent monomers include SR 344. SR 344 has previously been used as a diluent monomer in radiation curable secondary coatings for optical fibers, but not used in any primary coating that applicants are aware of.
  • SR 504 and SR 504D include unreacted alcohol moieties wherein these unreacted alcohol moieties contain from about 0 wt.% to less than 5 wt.% of unhindered free hydroxyl groups.
  • Photoinitiators are well known in the art of optical fiber coatings. See the previously incorporated by reference US Patents and US Published Patent Applications for information about all acceptable photoinitiators.
  • the photoinitiator can be selected from the group consisting of solid or liquid bis acyl phosphine oxide and solid or liquid bis acyl phosphine (see D 1479 Stable Liquid BAP Photoinitiator and its use in Radiation Curable Compositions, published as US 20120129969, D 1479 Stable Liquid BAP Photoinitiator and its use in Radiation Curable Compositions, published as US 20130237626 and D1492 Liquid BAPO Photoinitiator and its use in Radiation Curable Compositions, published as US
  • the photoinitiator is a mixture of bis acyl phosphine oxide and
  • 1 -hydroxy-cyclohexyl-phenyl-ketone is to eliminate the chance of waviness on the surface of the primary which is expected to be done by increasing the surface cure of the primary coating, before the secondary is applied on wet-on-dry fiber coating system.
  • the coating composition from all the ingredients, in an embodiment, the following takes place.
  • the oligomer is blended with the monomers, photoinitiator, heat stabilizer, and all other ingredients, except for the acrylated silane, at 70°C, for an hour.
  • the coating mixture is cooled to less than 55°C and more than or equal to 50°C, with this temperature being chosen to maintain the stability of the acrylated silane.
  • the acrylated silane is added and stirred for an hour. At the end of the hour the coating composition is then filtered to less than one micron.
  • the film modulus of the primary coating is from greater than or equal to about 0.1 MPa to less than or equal to about 1 .5 MPa. In an embodiment the modulus of a cured film of the radiation curable Primary Coating composition is from greater than or equal to 0.5 MPa to less than or equal to about 1.0 MPa. In an embodiment the modulus of a cured film of the radiation curable Primary Coating composition is from greater than or equal to 0.65 MPa to less than or equal to about 1 .0 MPa. In an
  • the film modulus of the primary coating a cured film of the radiation curable Primary Coating composition has a modulus of greater than or equal to 0.85 MPa to less than or equal to about 1 .0 MPa.
  • the film modulus of the secondary coating is from greater than about 0,80 GPa to less than or equal to about 2.8 GPa. In an embodiment, the film modulus of the secondary coating is about 1.5 GPa.
  • the in-situ modulus of the primary coating is from greater than or equal to about 0.1 MPa to less than or equal to about 1.5 MPa. In an embodiment the in-situ modulus of the primary coating is from greater than or equal to about 0.15 MPa to less than or equal to about 1 .0 MPa. In an embodiment the in-situ modulus of the cured primary coating is from greater than or equal to about 0.3 MPa to less than or equal to about 0.9 MPa. In an embodiment the in-situ modulus of a cured radiation curable Primary Coating composition is from greater than or equal to 0.65 MPa to less than or equal to about 1 .0 MPa. In an embodiment the in-situ modulus of the cured primary coating is from greater than or equal to 0.85 MPa to less than or equal to about 1 .0 MPa.
  • the in-situ modulus of the secondary coating is from greater than about 0.80 GPa to less than or equal to about 2.8 GPa. In an embodiment, the in-situ modulus of the secondary coating is from greater than about 1 .80 GPa to less than or equal to about 2.8 GPa. In an embodiment, the in-situ modulus of the secondary coating is from greater than about 2.00 GPa to less than or equal to about 2.8 GPa. In an embodiment, the in-situ modulus of the secondary coating is from greater than about 2.40 GPa to less than or equal to about 2.8 GPa.
  • the in-situ modulus of the secondary coating is from greater than about 1.20 GPa to less than or equal to about 2.2 GPa. In an embodiment, the in-situ modulus of the secondary coating is from greater than about 1.30 GPa to less than or equal to about 1.60 GPa. In an embodiment, the in-situ modulus of the secondary coating is about 1 .5 GPa. In an embodiment, the in-situ modulus of the secondary coating is about 1 .8 GPa.
  • a low modulus primary in an embodiment 0.80 MPa, in an embodiment 0.65 MPa
  • SR 9087 is an alkoxylated phenol acrylate monomer from Sartomer
  • Irganox 1035 thiodiethylene bis (3,5-di- er/-butyl-4-hydroxyhydrocinnamate),
  • IPD1 isophorone diisocyanate available from Bayer
  • TDI a mixture of 80 % 2,4-toluene diisocyanate and 20 % 2,6-toluene
  • TDS 100 % 2,4-toluene diisocyanate, a solid
  • Photomer* 4066 ethoxylated nonolphenol acrylate, available from Cognis
  • Miramer® M 144 EO (4) PEA is available from Miwon Specialty Chemical Co. Ltd. acrylated silane 3-acryloxypropyltrimethoxysilane available from Gelest, Inc. as
  • the viscosity is measured using a Physica MC l O Viscometer.
  • the test samples are examined and if an excessive amount of bubbles is present, steps are taken to remove most of the bubbles. Not all bubbles need to be removed at this stage, because the act of sample loading introduces some bubbles.
  • the instrument is set up for the conventional Z3 system, which is used.
  • the samples are loaded into a disposable aluminum cup by using the syringe to measure out 1 7 cc.
  • the sample in the cup is examined and if it contains an excessive amount of bubbles, they are removed by a direct means such as centrifugation, or enough time is allowed to elapse to let the bubbles escape from the bulk of the liquid. Bubbles at the top surface of the liquid are acceptable.
  • the bob is gently lowered into the liquid in the measuring cup, and the cup and bob are installed in the instrument.
  • the sample temperature is allowed to equilibrate with the temperature of the circulating liquid by waiting five minutes.
  • the rotational speed is set to a desired value which will produce the desired shear rate.
  • the desired value of the shear rate is easily determined by one of ordinary ski ll in the art from an expected viscosity range of the sample.
  • the shear rate is typically 50 s "1 or 100 s "1 .
  • the instrument panel reads out a viscosity value, and if the viscosity value varied only slightly (less than 2 % relative variation) for 1 5 seconds, the measurement is complete. If not, it is possible that the temperature had not yet reached an equilibrium value, or that the material is changing due to shearing. If the latter case, further testing at different shear rates will be needed to define the sample's viscous properties.
  • the results reported are the average viscosity values of three test samples. The results are reported either in centipoises (cps) or milliPascal - seconds (mPa s), which are equivalent.
  • compositions demonstrate the desired temperature thinning properties of a radiation curable coating for optical fiber in that as the temperature increases, mimicking the application temperature of the coating on cooling glass optical fiber, the viscosity of the composition decreases, making it sufficiently thin to appropriately pass through the coating dies and onto the fiber.
  • Dabco LV 33 catalyst triethyline diamine 280-57-9 0. 10
  • TPP catalyst triphenyl phosphine 603-35-0 0.08
  • Fable 4 Ingredients in the Secondary Composition of Example 5
  • Draw tower simulator is custom designed and constructed based on detailed examination of actual glass fiber draw tower components. All the measurements (lamp positions, distance between coating stages, gaps between coating stages and UV lamps, etc.) are duplicated from glass fiber drawing towers. This helps mimic the processing conditions used in fiber drawing industry.
  • One known DTS is equipped with five Fusion F600 lamps - two for the upper
  • the second lamp in each stage can be rotated at various angles between 1 5- 135°, allowing for a more detailed study of the curing profile.
  • the "core" used for the known DTS is 130.0 ⁇ 1 .0 ⁇ stainless steel wire. Fiber drawing applicators of different designs, from different suppliers, are available for evaluation. This configuration allows the application of optical fiber coatings at similar conditions that actually exist at industry production sites.
  • the draw tower simulator has already been used to expand the analysis of radiation curable coatings on optical fiber.
  • a method of measuring the Primary Coating' s in-situ modulus that can be used to indicate the coating's strength, degree of cure, and the fiber's performance under different environments in 2003 was reported by P. A. M. Steeman, J.J. M. Slot, H. G. H. van Melick, A. A. F. v.d. Ven, H. Cao, and R. Johnson, in the Proceedings of the 52nd IWCS, p. 246 (2003).
  • Steeman et al. reported on how the rheological high shear profile of optical fiber coatings can be used to predict the coatings' processability at faster drawing speeds P. A. M.
  • the draw tower simulator can be used to investigate further the properties of primary and Secondary Coatings on an optical fiber.
  • Example 2 The Primary Coating of Example 2 and the Secondary Coating of Example 5 are used to coat wire in a draw tower simulator.
  • the wire is run at five different line speeds, 750 meters/minute, 1200
  • Drawing is carried out using wet on dry mode.
  • Wet on dry mode means the liquid Primary Coating is applied wet, and then the liquid Primary Coating is cured to a solid layer on the wire. After the Primary Coating is cured, the Secondary Coating is applied and then cured as well.
  • the cured Primary Coating on the wire is tested for initial %RAU, initial in-situ modulus and initial Tube T g .
  • the coated wire is then aged for one month at 85°C and 85 % relative humidity.
  • the cured Primary Coating on the wire is then aged for one month at 85 °C and 85 % relative humidity and tested for %RAU, in-situ modulus and aged Tube T g .
  • Temperatures for the two coatings are 55 °C.
  • the dies are set to 40 °C.
  • Carbon dioxide level is 5-8 liters/min at each die.
  • Nitrogen level is 20 liters/min at each lamp.
  • Pressure for the primary coating is 1 bar at 25 m/min and goes up to 3 bar at 1000 m/min.
  • %RA U Percent Reacted Acrylate Unsaturation for the Primary Coating
  • Degree of cure on the inside Primary Coating on an optical fiber or metal wire is determined by FTIR using a diamond ATR accessory.
  • FTIR instrument parameters include: 100 co-added scans, 4 cm " 1 resolution, DTGS detector, a spectrum range of 4000-650 cm “ 1 , and an approximately 25 % reduction in the default mirror velocity to improve signal-to-noise.
  • Two spectra are required; one of the uncured liquid coating that corresponds to the coating on the fiber or wire and one of the inner Primary Coating on the fiber or wire.
  • a thin film of contact cement is smeared on the center area of a 1 -inch square piece of 3-mil Mylar film. After the contact cement becomes tacky, a piece of the optical fiber or wire is placed in it.
  • the coatings on the fiber or wire are sliced through to the glass using a sharp scalpel.
  • the coatings are then cut lengthwise down the top side of the fiber or wire for approximately 1 centimeter, making sure that the cut is clean and that the outer coating does not fold into the Primary Coating.
  • the coatings are spread open onto the contact cement such that the Primary Coating next to the glass or wire is exposed as a flat film.
  • the glass fiber or wire is broken away in the area where the Primary Coating is exposed.
  • the liquid should be the same batch that is used to coat the fiber or wire if possible, but the minimum requirement is that it must be the same formulation.
  • the final format of the spectrum should be in absorbance.
  • the exposed Primary Coating on the Mylar film is mounted on the center of the diamond with the fiber or wire axis parallel to the direction of the infrared beam. Pressure should be put on the back of the sample to insure good contact with the crystal.
  • the resulting spectrum should not contain any absorbances from the contact cement. If contact cement peaks are observed, a fresh sample should be prepared. It is important to run the spectrum immediately after sample preparation rather than preparing any multiple samples and running spectra when all the sample preparations are complete.
  • the final format of the spectrum should be in absorbance.
  • a short length ( ⁇ 2 mm) of coating layer is stripped off using a stripping tool at the location ⁇ 2 cm from a fiber end.
  • the fiber is cut to form the other end with 8 mm exactly measured from the stripped coating edge to the fiber end.
  • the portion of the 8 mm coated fiber is then inserted into a metal sample fixture, as schematically shown in Figure 6 of the paper [ 1 ] referenced above.
  • the coated fiber is embedded in a micro tube in the fixture; the micro tube consisted of two half cylindrical grooves; its diameter is made to be about the same as the outer diameter ( ⁇ 245 ⁇ ) of a standard fiber.
  • the fiber is tightly gripped after the screw is tightened; the gripping force on the Secondary Coating surface is uniform and no significant deformation occurred in the coating layer.
  • the fixture with the fiber is then mounted on a DMA (Dynamic Mechanical Analysis) instrument: Rheometrics Solids Analyzer (RSA-II).
  • the metal fixture is clamped by the bottom grip.
  • the top grip is tightened, pressing on the top portion of the coated fiber to the extent that it crushed the coating layer.
  • the fixture and the fiber must be vertically straight.
  • the non-embedded portion of the fiber should be controlled to a constant length for each sample; 6mm in our tests. Adjust the strain-offset to set the axial pretension to near zero (-1 g ⁇ 1 g).
  • Shear sandwich geometry setting is selected to measure the shear modulus G of the Primary Coating.
  • the sample width, W, of the shear sandwich test is entered to be 0.24 mm calculated according to ation:
  • R j and R p are bare fiber and Primary Coating outer radius respectively.
  • the sample length of 8 mm (embedded length) and thickness of 0.03 mm (Primary Coating thickness) are entered in the shear sandwich geometry.
  • the tests are conducted at room temperature ( ⁇ 23 °C).
  • the test frequency used is 1.0 radian/second.
  • the shear strain ⁇ is set to be 0.05.
  • a dynamic time sweep is run to obtain 4 data points for measured shear storage modulus G.
  • the reported G is the average of all data points.
  • This measured shear modulus G is then corrected according to the correction method described in the paper [ 1 ] referenced above.
  • the correction is to include the glass stretching into consideration in the embedded and the non-embedded parts.
  • tensile modulus of the bare fiber (E ) needs to be entered.
  • Ef 70 GPa.
  • Ef 120 GPa.
  • the corrected G value is further adjusted by using the actual Rf and R values.
  • fiber geometry including i?/and R p values is measured by PK2400 Fiber Geometry System.
  • Rf is 65 ⁇ for the 130 ⁇ diameter stainless steel S314 wires used; R p is measured under microscope.
  • E tensile storage modulus
  • T g glass transition temperatures of Primary and Secondary Coatings on a dual-coated glass fiber or a metal wire fiber are measured by this method. These glass transition temperatures are referred to as "Tube T g ".
  • RSA-II the gap between the two grips of RSAI1 can be expanded as much as 1 mm. The gap is first adjusted to the minimum level by adjusting strain offset.
  • a simple sample holder made by a metal plate folded and tightened at the open end by a screw is used to tightly hold the coating tube sample from the lower end. Slide the fixture into the center of the lower grip and tighten the grip. Using tweezers to straighten the coating tube to upright position through the upper grip. Close and tighten the upper grip.
  • test frequency is set at
  • the geometry type is selected as cylindrical.
  • the geometry setting was the same as the one used for secondary in-situ modulus test.
  • the sample length is the length of the coating tube between the upper edge of the metal fixture and the lower grip, 1 1 mm in our test.
  • the diameter (D) is entered to be 0.16 mm according to the following equation:
  • R S and R P are secondary and Primary Coating outer radius respectively.
  • a dynamic temperature step test is run from the starting temperature (100 °C in our test) till the temperature below the Primary Coating T g or -80 °C. After the run, the peaks from tan ⁇ curve are reported as Primary Coating T g (corresponding to the lower temperature) and Secondary Coating T g (corresponding to the higher temperature). Note that the measured glass transition temperatures, especially for primary glass transition temperature, should be considered as relative values of glass transition temperatures for the coating layers on fiber due to the tan ⁇ shift from the complex structure of the coating tube.
  • Example 2 94.23 98.48 measured Not measured
  • the primary coating has an in-situ T g of -52 °C and the secondary coating has an in-situ T g of 71 °C.

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Abstract

La présente invention porte sur une composition de revêtement primaire apte à durcir sous l'effet d'un rayonnement. Le revêtement primaire apte à durcir sous l'effet d'un rayonnement comprend au moins deux monomères de diluant ; le premier monomère de diluant contenant un segment polaire et un segment non polaire ; étant monofonctionnel ; étant lipophile, de telle sorte que la valeur de rapport hydrophile-lipophile (HLB) est inférieure à environ 10 ; et étant présent dans la composition à environ 20 % en poids à environ 60 % en poids ; et le second monomère de diluant contenant un segment polaire et un segment non polaire ; étant multifonctionnel ; étant hydrophile, de telle sorte que la valeur HLB est supérieure à environ 10 ; et étant présent dans la composition à d'environ 0,5 % en poids à environ 20 % en poids.
PCT/US2013/072549 2012-12-03 2013-12-02 Revêtements primaires aptes à durcir sous l'effet d'un rayonnement pour fibre optique WO2014088926A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016100148A1 (fr) * 2014-12-18 2016-06-23 Corning Incorporated Composition de gainage de fibres optiques comprenant un agent de renfort non réactif
WO2022063135A1 (fr) * 2020-09-23 2022-03-31 上海飞凯材料科技股份有限公司 Composition de revêtement durcissable par ultraviolets et son utilisation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5837750A (en) * 1995-03-13 1998-11-17 Dsm N.V. Radiation curable optical fiber coating composition
US20080226912A1 (en) * 2006-12-14 2008-09-18 Norlin Tyson Dean D1365 bj radiation curable primary coating for optical fiber
US20120128313A1 (en) * 2009-10-09 2012-05-24 Xiaosong Wu Radiation curable coating for optical fiber

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5837750A (en) * 1995-03-13 1998-11-17 Dsm N.V. Radiation curable optical fiber coating composition
US20080226912A1 (en) * 2006-12-14 2008-09-18 Norlin Tyson Dean D1365 bj radiation curable primary coating for optical fiber
US20120128313A1 (en) * 2009-10-09 2012-05-24 Xiaosong Wu Radiation curable coating for optical fiber

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016100148A1 (fr) * 2014-12-18 2016-06-23 Corning Incorporated Composition de gainage de fibres optiques comprenant un agent de renfort non réactif
WO2022063135A1 (fr) * 2020-09-23 2022-03-31 上海飞凯材料科技股份有限公司 Composition de revêtement durcissable par ultraviolets et son utilisation

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