EP0861453A1 - Composes matriciels pour former des rubans de fibres optiques - Google Patents

Composes matriciels pour former des rubans de fibres optiques

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Publication number
EP0861453A1
EP0861453A1 EP96937910A EP96937910A EP0861453A1 EP 0861453 A1 EP0861453 A1 EP 0861453A1 EP 96937910 A EP96937910 A EP 96937910A EP 96937910 A EP96937910 A EP 96937910A EP 0861453 A1 EP0861453 A1 EP 0861453A1
Authority
EP
European Patent Office
Prior art keywords
matrix
polymer
radiation curable
vinyl ether
ultraviolet radiation
Prior art date
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Withdrawn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
EP96937910A
Other languages
German (de)
English (en)
Inventor
Alvin C. Levy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lightguide Materials Inc
Original Assignee
Lightguide Materials Inc
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Filing date
Publication date
Application filed by Lightguide Materials Inc filed Critical Lightguide Materials Inc
Publication of EP0861453A1 publication Critical patent/EP0861453A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/02033—Core or cladding made from organic material, e.g. polymeric material

Definitions

  • the invention relates to optical fibers.
  • the present invention relates to novel ribbon systems composed of optical fibers and a removable matrix wherein the polymer systems of the optical fibers and the removable matrix use different initiator systems.
  • a number of coated optical fibers or color-coded, coated optical fibers are first arranged in a flat array.
  • the fiber coating is generally an ultraviolet (UV) curable acrylate and the optional color-coding material is either a solvent based vinyl ink or a UV curable acrylate based ink.
  • the fiber array is then overcoated with a thin layer of what is referred to as a "matrix coating," which is then cured.
  • the purpose of the cured material is to provide integrity to the ribbon structure.
  • the most common matrix materials are UV curable acrylates and such matrix materials are present in, e.g. , the AT&T Accuribbon ® .
  • the AT&T Accuribbon ® product literature shows a matrix material having a thickness of as little as 0.03 mm at the top of the fiber up to as great as 0.125 mm in the valleys between adjacent fibers.
  • the present invention provides a system which overcomes the prior art disadvantages because the present invention, for example, does not require gel treatment or a special peel layer to permit easy removal of the fibers from the ribbon.
  • the present invention provides a removable matrix for retaining one or more optical fibers having an outermost layer comprising a first polymer with a first initiator system, the matrix comprising a second polymer having a second initiator system substantially different from the first initiator system.
  • the present invention provides an optical fiber and matrix ribbon, the ribbon comprising one or more optical fibers, wherein the fibers have an outermost layer comprising a free-radical initiated, ultraviolet radiation curable acrylate polymer, and a removable matrix for retaining the one or more optical fibers, wherein the matrix comprises a cationically initiated, ultraviolet radiation curable polymer.
  • the present invention provides an ink for use on an acrylate polymer coated optical fiber, wherein the ink comprises an inhibitor of cationically initiated polymerization.
  • the present invention provides a matrix comprised of a cationically initiated, ultraviolet radiation curable vinyl ether polymer. Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. Detailed Description of the Preferred Embodiments
  • the term “removable” means that the matrix and the optical fiber may be separated or peeled apart without damaging the outermost layer of the optical fiber.
  • the "outermost layer” of the optical fiber may either be the actual outer polymer coating of the fiber or, when present, the coating layer formed by any ink applied to the optical fiber, whichever is outermost.
  • the term “initiator system” is used to describe the various polymerization initiation reactions, including, but not limited to, cationic initiator systems, anionic initiator systems and free-radical initiator systems.
  • the term “radiation” is applied to a cure system for polymers which requires the input of energy, e.g.
  • a "radiation curable” polymer is one which can be cured by the application of radiation and an “ultraviolet radiation curable polymer” is one which is cured by the application of ultraviolet radiation.
  • the term “ribbon” is used herein to refer to an article resulting from one or more optical fibers, with or without an ink coating, coated with a matrix compound. While the “ribbon” is generally described as a flat cable of multiple optical fibers, such limitation is not necessary and shall not be construed as a limitation on the present invention.
  • substantially different initiator systems means that the initiator systems of the major portions of the specified polymers are different. For instance, a polymer having a major portion of a free-radical initiated acrylate and a minor portion of a cationically initiated polyol would have a substantially different initiator system from a polymer having a major portion of a cationically initiated polyol, cycloaliphatic epoxide or vinyl ether and a minor portion of a free-radical initiated acrylate polymer.
  • the present invention provides a removable matrix for retaining one or more optical fibers having an outermost layer comprising a first polymer with a first initiator system, the matrix comprising a second polymer having a second initiator system substantially different from the first initiator system.
  • the first and second polymers are radiation curable polymers.
  • the first polymer comprises a free radical initiated, ultraviolet radiation curable polymer and the second polymer comprises a cationically initiated, ultraviolet radiation curable polymer.
  • the present invention also discloses the matrix wherein the free radical initiated, ultraviolet radiation curable first polymer is an acrylate polymer.
  • the matrix second polymer further comprises a partial adhesion promoting amount of a free-radical initiated, radiation curable acrylate polymer and wherein the cationically initiated, ultraviolet radiation curable polymer comprises a major portion of the matrix and the free-radical initiated, ultraviolet radiation curable acrylate polymer comprises a minor portion of the matrix, whereby the presence of the free-radical initiated, ultraviolet radiation curable acrylate polymer promotes partial adhesion between the outermost layer of the one or more fibers and the matrix.
  • the cationically initiated, ultraviolet radiation curable second polymer comprises a mixture of cycloaliphatic epoxide and a polyol.
  • the cationically initiated, ultraviolet radiation curable second polymer comprises a vinyl ether polymer.
  • the vinyl ether polymer is a vinyl ether encapped ester oligomer, a vinyl ether encapped urethane oligomer, a vinyl ether encapped ester monomer, a vinyl ether encapped alcohol, or a mixture thereof.
  • the vinyl ether encapped ester oligomer is Allied Signal 150B
  • the vinyl ether encapped urethane oligomer is Vectomer 2032
  • the vinyl ether encapped monomer is bis-(4- vinyloxybutyl) isophthalate
  • the vinyl ether encapped monomer is 4- vinyloxy butyl benzoate.
  • the first polymer comprises a cationically initiated, ultraviolet radiation curable polymer and the second polymer comprises a free radical initiated, ultraviolet radiation curable polymer.
  • the free radical initiated, ultraviolet radiation curable polymer is an acrylate polymer.
  • the matrix further comprises a partial adhesion promoting amount of a cationically initiated, ultraviolet radiation curable polymer and wherein the free-radical initiated ultraviolet radiation curable polymer comprises a major portion of the matrix and the cationically initiated, ultraviolet radiation curable polymer comprises a minor portion of the matrix, whereby the presence of the cationically initiated, ultraviolet radiation curable polymer promotes partial adhesion between the outermost layer of the one or more fibers and the matrix.
  • the present invention provides an optical fiber and matrix ribbon, the ribbon comprising one or more optical fibers, wherein the fibers have an outermost layer comprising a free -radical initiated, ultraviolet radiation curable acrylate polymer, and a removable matrix for retaining the one or more optical fibers, wherein the matrix comprises a cationically initiated, ultraviolet radiation curable polymer.
  • the matrix further comprises a free-radical initiated, radiation curable acrylate polymer and wherein the cationically initiated, ultraviolet radiation curable polymer comprises a major portion of the matrix and the free-radical initiated, ultraviolet radiation curable acrylate polymer comprises a minor portion of the matrix, whereby the presence of the free-radical initiated, ultraviolet radiation curable acrylate polymer promotes partial adhesion between the outermost layer of the one or more fibers and the matrix.
  • the cationically initiated, ultraviolet radiation curable polymer comprises a vinyl ether polymer.
  • the vinyl ether polymer is a vinyl ether encapped ester oligomer, a vinyl ether encapped urethane oligomer, a vinyl ether encapped ester monomer, a vinyl ether encapped alcohol, or a mixture thereof.
  • the vinyl ether encapped ester oligomer is Allied Signal 150B
  • the vinyl ether encapped urethane oligomer is Vectomer 2032
  • the vinyl ether encapped monomer is bis-(4- vinyloxybutyl) isophthalate
  • the vinyl ether encapped monomer is 4- vinyloxybutyl benzoate.
  • the present invention provides a ribbon wherein the outermost layer of the one or more fibers comprises an ink coating, wherein the ink comprises a free-radical initiated, radiation curable acrylate polymer.
  • the ink further comprises an inhibitor of cationically initiated polymerization.
  • the inhibitor is water, a basic compound, or a mixture thereof. More specifically, the inhibitor is a pigment capable of interacting with the cation, or a hindered amine light stabilizer, such as bis-(2,2,6,6-tetramethyl-4-piperidyl) sebacate, or the inhibitor is l-vinyl-2- pyrrolidone.
  • the ribbon comprises one or more optical fibers, wherein the fibers have an outermost layer comprising a cationically initiated, ultraviolet radiation curable polymer, and a removable matrix for retaining the one or more optical fibers, wherein the matrix comprises a free-radical initiated, ultraviolet radiation curable acrylate polymer.
  • the matrix further comprises a cationically initiated, ultraviolet radiation curable polymer and wherein the free-radical initiated, ultraviolet radiation curable acrylate polymer comprises the major portion of the matrix and the cationically initiated, ultraviolet radiation curable polymer comprises the minor portion of the matrix, whereby the presence of the cationically initiated, ultraviolet radiation curable polymer promotes partial adhesion between the outermost layer of the one or more fibers and the matrix.
  • the cationically initiated, ultraviolet radiation curable polymer comprises a vinyl ether polymer.
  • the outermost layer of the one or more fibers comprises an ink coating, wherein the ink comprises a cationically initiated, ultraviolet radiation curable polymer.
  • the ink further comprises an inhibitor of free-radical initiated polymerization.
  • the inhibitor comprises a benzoquinone derivative, such as hydroquinone, naphthaquinone, or a mixture thereof.
  • the present invention provides an ink for use on an acrylate polymer coated optical fiber, wherein the ink comprises an inhibitor of cationically initiated polymerization.
  • the inhibitor is water, a basic compound, or a mixture thereof.
  • the inhibitor is a pigment capable of interacting with the cation.
  • the basic compound comprises a hindered amine light stabilizer, such as bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate.
  • the inhibitor is l-vinyl-2-pyrrolidone.
  • the inhibitor is an initiator of free radical initiated polymerization, such as 2-methyl-l-[4-(methylthio)phenyl]-2-morpholinopropanone-l .
  • the present invention also provides a matrix comprised of a cationically initiated, ultraviolet radiation curable vinyl ether polymer.
  • the vinyl ether polymer is a vinyl ether encapped ester oligomer, a vinyl ether encapped urethane oligomer, a vinyl ether encapped ester monomer, a vinyl ether encapped alcohol, or a mixture thereof.
  • the vinyl ether encapped ester oligomer is Allied Signal 150B
  • the vinyl ether encapped urethane oligomer is Vectomer 2032
  • the vinyl ether encapped monomer is bis-(4-vinyloxybutyl) isophthalate
  • the vinyl ether encapped monomer is 4-vinyloxybutyl benzoate.
  • the present invention involves the selection and formulation of the matrix material or both the matrix material and the ink such that an optical fiber cable manufacturer may choose the level of adhesion between the coated or the color-coded, coated optical fibers and the matrix coating used in the fiber ribbon.
  • an optical fiber cable manufacturer may choose the level of adhesion between the coated or the color-coded, coated optical fibers and the matrix coating used in the fiber ribbon.
  • neither a gel treatment nor a special application of a peel layer is required to facilitate easy removal of the fibers from the ribbon.
  • the present invention proposes the use of a cationically initiated, UV curable material as the major portion of the matrix coating formulation.
  • the use of polymers having distinct initiator systems prevents extensive cross-linking or other binding between the outermost layer of the optical fiber and the matrix.
  • the matrix coating may also contain free-radical initiated, UV curable acrylates to properly balance the adhesion, /. e. , to increase the adhesion to the ink or fiber coating to a desired level.
  • the use of some acrylate materials reduces the raw material cost of the completed matrix compound because acrylate materials are presently less expensive then cationically initiated materials.
  • the use of high molecular weight acrylates and the functionality of the acrylate may be manipulated to increase or decrease adhesion. For instance, a higher molecular weight acrylate would provide for less adhesion because the functional equivalent weight (i.e. , weight divided by degree of functionality) would be higher.
  • the degree of functionality of the acrylate polymer used can also be chosen to increase or reduce the adhesion, where an increase in the degree of functionality would increase the adhesion.
  • formulation latitude is further increased if the ink (which forms the outermost layer of the optical fiber) used to optionally color-code the fiber contains a component which slightly inhibits the cure of the matrix compound at the interface between the matrix compound and the ink.
  • the degree of inhibition of cure influences the level of adhesion at the interface and hence the relative ease of removing the fiber from the matrix coating.
  • the ink used to color-code the fiber can have many different chemistries with the exception that, for systems using a cationically initiated, UV curable polymer in the matrix, the major components cannot be cationically initiated UV curable materials.
  • Examples of commonly used inks are solvent based vinyl inks and free-radical initiated, UV curable acrylate inks.
  • cationically initiated materials are inhibited by molecules which can hydrogen bond or react with the cation and therefore remove it from its role in the reaction.
  • inhibitors include, but are not limited to, water, bases (even very weak bases present in the fiber coating, such as hindered amine light stabilizers), other components often present in UV curable acrylates such as N vinyl pyrrolidone (1- vinyl-2-pyrrolidone), and even selected pigments capable of interacting with the cation.
  • bases even very weak bases present in the fiber coating, such as hindered amine light stabilizers
  • other components often present in UV curable acrylates such as N vinyl pyrrolidone (1- vinyl-2-pyrrolidone)
  • selected pigments capable of interacting with the cation can vary widely by component and with concentration.
  • the ink can be comprised substantially of cationically initiated UV materials where a UV ink is used.
  • the matrix compound in this case is comprised substantially of free radical initiated, UV curable acrylate components.
  • inhibition of cure can be controlled by including a low level of a free-radical scavenger in the ink or the fiber coating where the color coding inks are not used.
  • a benzoquinone derived free-radical scavenger such as hydroquinone or naphthaquinone can be added to the ink.
  • Preferred matrix material formulations useful for the present invention are given in Tables 1 and 2. Table 1 details formulations where the reactive components are based on vinyl euier chemistry. Table 2 contains formulations based on cycloaliphatic epoxides and polyols chemistry and mixed systems of the two chemistries.
  • Allied Signal 150B (Allied Signal, Inc. , Morristown, NJ) is a vinyl ether encapped polyester oligomer having a viscosity of 340,000 cps at 60 °C and a weight average molecular weight of from 2000 to 3500.
  • Vectomer 2032 (Allied Signal, Inc. , Morristown, NJ) is a vinyl ether encapped urethane oligomer which has a viscosity of 30,000 cps at 70 °C and a weight average molecular weight of 4800 to 6600.
  • Bis-(4- vinyloxybutyl) isophthalate is a difunctional (with respect to cationic cure) vinyl ether monomer with a viscosity of 85 cps at 25 °C and is sold under the trade name Vectomer 4010 (Allied Signal, Inc., Morristown, NJ).
  • 4- vinyloxybutyl benzoate is a monofunctional vinyl ether monomer (with respect to cationic cure) having a viscosity of 7 cps at 25 °C and is available under the trade name Vectomer 3010 (Allied Signal, Inc., Morristown, NJ).
  • Rapi- Cure CHVE International Specialty Products, Inc. , Wayne NJ.
  • vinyl ethers include, but are not limited to, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, butyl vinyl ether, ethyleneglycol vinyl ether, diethyleneglycol divinyl ether, butanediol monovinyl ether, butanediol divinyl ether, ethyleneglycol butyl vinyl ether, triethyleneglycol methyl vinyl ether, cyclohexanedimethanol monovinyl ether, 2-ethylhexyl vinyl ether, Poly-THF-divinyl ether 290, pluriol-E-200-divinyl ether, cyclohexyl vinyl ether, tert-butyl vinyl ether, tert-amyl vinyl ether, ethyleneglycol divinyl ether, diethyleneglycol monovinyl ether, hexanediol monovinyl
  • Ebecryl 8804 is the trade name for an aliphatic urethane acrylate oligomer with a viscosity of 10,000 - 24,000 cps at 65 °C, a molecular weight of 1 ,400 and a functionality of 2.4 (UCB Radcure Inc. , Smyrna, GA).
  • Tripropylene glycol diacrylate (TRPGDA) is a difunctional monomer with a viscosity of 12 cps at 25 °C (UCB Radcure Inc. , Smyrna, GA).
  • Trimethylopropane triacrylate is a trifunctional monomer with a viscosity of 85 cps at 25 °C (UCB Radcure Inc. , Smyrna, GA).
  • 1 ,6- hexanediol diacrylate is a difunctional monomer with a viscosity of 6 cps at 25 °C (UCB Radcure Inc. , Smyrna, GA).
  • ⁇ - carboxyethyl acrylate (0-CEA) is a monofunctional monomer with a viscosity of 75 cps at 25 °C (UCB Radcure Inc. , Smyrna, GA).
  • Isobornyl acrylate is a monofunctional monomer with a viscosity of 9.5 cps at 25°C (UCB Radcure Inc., Smyrna, GA).
  • Octyl/decyl acrylate is a monofunctional monomer with a viscosity of 2 cps at 25 °C (UCB Radcure Inc. , Smyrna, GA).
  • Oxyethylated phenol acrylate (Ebecryl ® 110) is a monofunctional monomer with a viscosity of 75 cps at 25 °C (UCB Radcure Inc. , Smyrna, GA).
  • Tetraethylene glycol diacrylate is a difunctional monomer with a viscosity of 20 cps at 25 °C (UCB Radcure Inc. , Smyrna, GA).
  • Bisphenol-A derivative diacrylate is a difunctional monomer with a viscosity of 20 cps at 25 °C (UCB Radcure Inc. , Smyrna, GA).
  • Ebecryl ® 150 is a difunctional monomer with a viscosity of 1,500 cps at 25 °C (UCB Radcure Inc. , Smyrna, GA).
  • OTA-480 is a trifunctional monomer with a viscosity of 85 cps at 25 °C (UCB Radcure Inc. , Smyrna, GA).
  • Pentaerythritol triacrylate (PETA-K) is a trifunctional monomer with a viscosity of 500 cps at 25°C (UCB Radcure Inc. , Smyrna, GA).
  • PETA-LQ is a lower functionality version of PETA-K with a viscosity of 1,500 cps at 25 °C (UCB Radcure Inc. , Smyrna, GA).
  • Trimethylolpropane ethoxy triacrylate (TMPEOTA) is a trifunctional monomer with a viscosity of 20 cps at 25 °C (UCB Radcure Inc., Smyrna, GA).
  • DPHPA di-pentaerythritol
  • UPHPA di-pentaerythritol
  • Ebecryl ® acrylates suitable for the present purposes include, but are not limited to, Ebecryl ® 80, 81, 82, 220, 230, 244, 264, 265, 270, 284, 285, 436, 438, 450, 505, 524, 525, 584, 585, 586, 588, 600, 605, 616, 629, 639, 657, 745, 754, 767, 770, 810, 830, 860, 870, 1290, 1608, 1657, 1701 , 1755, 1810, 3200, 3201 , 3409, 3500, 3502, 3600, 3603, 3604, 3605, 3608, 3700, 3700-20H, 3700-20T, 3700-25R, 3701, 3701-20T, 3702, 3703, 4827, 4830, 4833, 4834, 4849, 4866, 4881 , 4883, 6602, 6700, 8301, 8402, 8800, 8800- 20R, or 8803 (
  • Ar 3 SPF 6 in the presence of UV light can serve as the initiator in the cationic polymerization of vinyl ether oligomers and monomers and is sold under the trade name UVI 6990 (Union Carbide, Danbury, CT).
  • UVI 6990 Union Carbide, Danbury, CT.
  • 2,2-dimethoxy-2-phenylacetophenone is a Norish Type 1 Cleavage photo initiator with a melting point of 63-66 °C and is available sold under the trade name Irgacure 651 (Ciba-Geigy Corp. , Hawthorne, NY).
  • Irgacure 651 serves as the free radical source on exposure to UV light for the polymerization of acrylate monomers and oligomers.
  • Octadecyl 3-(3' ,5'- di-tert-butyl-4'-hydroxyphenyl) propionate is a thermal oxidative stabilizer which is available under the trade name Irganox 1076 (Ciba-Geigy Corp. , Hawthorne, NY).
  • the propenyl ether of propylene carbonate (RAPI- CURE PEPC) has a molecular weight of 158 and a viscosity of 13 cps at 25 °C (International Specialty Products, Wayne, NJ or Charlotte, NC). PEPC helps to solubilize the UV 6990.
  • SF 1188 is the trade name for the copolymer of a polymethyl siloxane and a polyoxy alkene ether having a viscosity of 600-1200 cps at 25° C, a density of 1.04 g/cc avg., and a surface tension of 25.5 dynes/cm 2 (GE Silicones, Waterford, NY).
  • SF 1188 is an anti-blocking agent which prevents tacking together of adjacent layers of ink or matrix when the product is wound upon itself.
  • UVR-6110 is the trade name for 3,4-
  • Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate which has an epoxy equivalent weight of 131 - 143 and a viscosity at 25 °C of 350 - 450 cps (Union Carbide, Danbury, CT.). See Carroy, Antoine, Aspects of Photoinitiaion: Cationic UV-Curing Efficiency of Cycloaliphatic Epoxide-Based Systems Through Photoinitiator and UV-Wavelength Selection (1993).
  • UVR-6128 is the trade name for bis-(3,4- epoxycyclohexyl) adipate which has an epoxide equivalent weight of 350- 450 and a viscosity at 25 °C 190 - 210 cps (Union Carbide, Danbury, CT.).
  • Tone 0301 is the trade name for an e-caprolactone triol which has an hydroxyl equivalent weight of 98 - 103 and a viscosity of 2250 cps at 55°C (Union Carbide, Danbury, CT.). Tone 0301 is trifunctional with respect to reactivity.
  • Tone 0201 is the trade name for a caprolactone diol having an average molecular weight of 530 and a viscosity of 65 cps at 55 °C (Union Carbide, Danbury, CT.). Tone 0201 is difunctional with respect to reactivity.
  • the 95°C/95% relative humidity (RH) conditioning was done in a
  • Blue M Power-O-Matic 60 (Blue M Electric, Blue Island, IL) temperature/humidity oven. Samples were conditioned for at least 24 hours at ambient after removal from the oven before testing. Viscosity was determined using either a Brookfield model LVF or a model RVT (Brookfield Engineering Laboratory, Inc. , Stoughton, MA) viscometer. Tensile data show a range of values from about 100 to 1000 MPa. The data show the usual variation in properties with crosslink density and the backbone flexibility. The effect of crosslink density is illustrated in Table 1 where use of the monofunctional monomer Vectomer 3010 in place of the difunctional monomer Vectomer 4010 (Formulations 1A and IN) leads to decrease in modulus associated with the decrease in crosslink density.
  • Stability data as measured by modulus change after conditioning at 95°C/95 % RH for 20 and 30 days are given in Table 1 and after 6 days in Table 2.
  • the modulus should not change by more than about 20% after 30 days at 85°C/85% RH.
  • the precision of the modulus measurement is approximately +1-5 % . Therefore, the precision of the modulus change measurement will be greater than 5 % .
  • the data presented in the tables indicate good retention of modulus for vinyl ether formulation 1A. At 20 days the vinyl ether formulations with approximately 20% acrylate monomer are reasonably stable as is the vinyl ether formulation IB based on the vinyl ether urethane oligomer. However, at 30 days all these latter materials have markedly increased in modulus.
  • Vectomer 2032 type oligomer may, therefore, be limited by stability requirements in the particular application of the system. Nonetheless, the basic and underlying concept of the present invention has been shown. This is also a practical limitation in the amount of acrylate monomer that can be added while maintaining adequate temperature and humidity stability for many applications. Chemical kinetics would suggest that all of the above formulations would have been acceptable after 30 days at 85°C/85% RH. Moreover, the color stability of the vinyl ether compounds based on the ester type oligomer (Formulations 1A, IF, 1G and 1H) was good, showing only a slight off color tint after the 30 day test. Matrix compound IB was significantly off color and would not be acceptable without further stabilization in applications where color stability is an important criteria.
  • a matrix compound (formula 2A) based on cycloaliphatic epoxides and polyols showed poor performance in the 95°C/95% RH test indicating that this type compound is limited to applications where high temperature, high humidity stability is not critical.
  • Specific formulations for the inks tested are given in Table 3.
  • 2-methyl-l-[4-(methylthio)phenyl]-2- morpholinopropanone- 1 is a free radical-type photoinitiator which is sold under the trade name Irgacure 907 (Ciba-Geigy Corp. , Hawthorne, NY).
  • TiO 2 is a white pigment available from multiple sources, e.g.
  • Test plaques for determination of T-peel Adhesion were prepared as follows. An approximate 75 micron thickness of Desolite ® Product Code 950-044 optical fiber coating (DSM Desotech Inc. , Elgin, IL), an industry-known UV curable acrylate coating, having a viscosity of 5000 cps at 25°C and a tensile modulus upon curing of 690 MPa at 23°C, 50% relative humidity, is cured at a cure dose of 500 mj/cm 2 using a Fusion Systems D bulb under a nitrogen blanket. The cured film is held for at least one day before proceeding to the next step.
  • DSM Desotech Inc. Elgin, IL
  • UV curable acrylate coating having a viscosity of 5000 cps at 25°C and a tensile modulus upon curing of 690 MPa at 23°C, 50% relative humidity
  • an approximate 10 micron thickness layer of a UV curable acrylate polymer based ink is then applied and cured under a nitrogen blanket with a Fusion Systems H bulb at a cure dose of 250 mj/cm 2 (this step is skipped for non-color coded testing).
  • the color coded composite is then held for at least one day before proceeding.
  • an approximately 75 micron thick layer of matrix compound is applied at a temperature of 60 °C and then cured with a Fusion Systems H bulb at a cure dose of 500 mj/cm 2 under a nitrogen blanket.
  • a release layer is applied to the top of the composite to provide a non- bonded layer at the top of the test composite.
  • the finished composite is again held for at least 48 hours.
  • UV1 and UV2 both contain an urethane acrylate oligomer. Therefore, the inks in those cases contain an oligomer which is more chemically similar to the IB matrix compound than the 1A matrix compound. Hence, the adhesion of IB to the ink is greater than 1A to the ink.
  • various acrylate components are added to the 1A type matrix (matrix materials 1C through 1M), the adhesion can be increased to obtain a desired level. The greater the acrylate content of the matrix, the greater the chemical similarity between the matrix and the ink and, therefore, the greater the adhesion. Once the matrix acrylate content has reached about 50%, the adhesion is too high to obtain a meaningful test.
  • the peel occurs between the back-up tape and the matrix compound indicating that the peel adhesion level between the ink and the matrix compound is at a higher level than can be determined by this test configuration.
  • the peel interface is between the ink and the matrix compound or between the matrix compound and fiber coating material where no ink is present.
  • the data shows that if the ink is based on a ester acrylate oligomer, that the matrix compound IB above would have lower peel adhesion to the ink than would matrix compound 1A. Moreover, in a mixed acrylate/vinyl ether or other cationic cure system, both cationic and free radical type UV activated initiators are required.
  • ink contains an inhibitor of the cationic cure matrix materials
  • four different blends of ink were prepared by adding 1.0 percent by weight of four components to formulation 1A in Table 1. These materials were Irgacure 651, Irgacure 907 (previously described as an initiator for acrylate systems), l-vinyl-2- pyrrolidone (NVP), and a hindered amine light stabilizer bis-(2, 2,6,6- tetramethyl-4-piperidyl) sebacate which is sold under the trade name Tinuvin 770 (Ciba-Geigy Corp., Hawthorne, NY). The materials were cured as previously described for matrix compounds.
  • the blends containing Tinuvin 770 and Irgacure 907 did not cure but remained viscous liquids even after exposure to UV light.
  • the blend containing NVP upon exposure to UV light, yielded a undercured, tacky film which was too fragile for tensile analysis.
  • the blend containing Irgacure 651 was well-cured.
  • the viability of cure inhibition in a free-radical based polymer matrix was tested by the addition of 0.5% and 0.25 % by weight of naphthaquinone to the acrylate coating Desotech ® 950-44. A similar amount was added in the reverse case for matrix IN.
  • UV2 As can be seen, there is a decrease in adhesion when going from the Irgacure 651 to the Irgacure 907 containing ink. Examination of the molecular structure of Irgacure 907 shows it to be a hindered amine. UV3 and UV4 inks have a combination of Irgacure 651 and Irgacure 907 initiators. In combination with matrix 1A, both of these inks also show lower adhesion relative to UV2 and Matrix 1A. When the hindered amine light stabilizer Tinuvin 770 is added to the ink (UV5) and Matrix IN is used, a similar drop in peel adhesion is seen relative to the UV2/1N combination.
  • Table 4 also describes peel adhesion data for cationic cure systems based on cycloaliphatic epoxide/polyol combinations. As can be seen from tests conducted with Matrix materials 2A through 2E, values are somewhat higher than those obtained using formulations based on vinyl ether chemistry. In fact, it appears necessary to use Irgacure 907 in the ink to properly reduce the peel adhesion. Furthermore, use of the trifunctional polyol 0301 results in lower adhesion than does polyol 0201. Increasing the level of 0201 also increases the adhesion. When combinations of the two chemistries are used as in formula 2F, the adhesion reading falls between the values reported for the non-mixed formulations.
  • the optical fiber coating is a cationic material
  • Table 4 also demonstrates that this is the case.
  • Matrix 1A was cured first, i.e. , as the optical fiber coating
  • subsequent cure of the acrylate ink UV2 or acrylate matrix IL on the vinyl ether coating surface resulted in poor adhesion.
  • the ink used where the fiber coating is substantially a cationic cure compound should also be comprised substantially of a cationic cure components and the matrix compounds should be comprised substantially of free radical initiated acrylate type components.

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  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)

Abstract

La présente invention concerne une matrice amovible, qui sert à retenir une ou plusieurs fibres optiques ayant une couche extérieure faite d'un premier polymère ayant un premier système d'amorçage, par exemple un polymère d'acrylate pouvant être durci aux ultraviolets et amorcé par des radicaux libres, la matrice étant alors formée à partir d'un deuxième polymère ayant un deuxième système d'amorçage sensiblement différent du premier, par exemple un polymère d'éther de vinyle pouvant être durci aux ultraviolets et amorcé par cations. L'invention concerne aussi une fibre optique et un ruban de matrice, ce ruban étant fait de fibres optiques qui ont une couche extérieure faite d'un polymère d'acrylate pouvant être durci aux ultraviolets, amorcé par des radicaux libres, et une matrice amovible, servant à retenir les fibres optiques; cette matrice comprend un polymère pouvant être durci aux ultraviolets et amorcé par des cations. L'invention concerne encore une fibre optique et un ruban de matrice qui est formé à partir de fibres optiques ayant une couche extérieure faite d'un polymère pouvant être durci aux ultraviolets et amorcé par des cations, et une matrice amovible pour retenir les fibres optiques, cette matrice étant faite à partir d'un polymère d'acrylate pouvant être durci aux ultraviolets et amorcé par des radicaux libres. L'invention concerne également une encre destinée à être employée sur une fibre optique recouverte d'un polymère d'acrylate, cette encre comportant un inhibiteur de polymérisation amorcée par des cations. L'invention concerne enfin une matrice constituée par un polymère d'éther de vinyle pouvant être durci aux ultraviolets et amorcé par des cations.
EP96937910A 1995-11-13 1996-11-07 Composes matriciels pour former des rubans de fibres optiques Withdrawn EP0861453A1 (fr)

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US55812595A 1995-11-13 1995-11-13
US558125 1995-11-13
PCT/US1996/017800 WO1997018493A1 (fr) 1995-11-13 1996-11-07 Composes matriciels pour former des rubans de fibres optiques

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US6197422B1 (en) 1997-05-06 2001-03-06 Dsm, N.V. Ribbon assemblies and radiation-curable ink compositions for use in forming the ribbon assemblies
US6130980A (en) * 1997-05-06 2000-10-10 Dsm N.V. Ribbon assemblies and ink coating compositions for use in forming the ribbon assemblies
EP1408017A3 (fr) * 1997-05-06 2006-01-11 DSM IP Assets B.V. Compositions d'encre durcissant
KR100509076B1 (ko) * 1997-05-06 2005-08-18 코닌클리즈케 디에스엠 엔.브이. 방사선-경화성 잉크 조성물
AU8131998A (en) * 1997-06-11 1998-12-30 Dsm N.V. Optical glass fiber ribbon assemblies, matrix forming compositions and ink coating compositions for use in forming ribbon assemblies
US6085010A (en) * 1997-06-11 2000-07-04 Dsm N.V. Optical glass fiber ribbon assemblies and radiation-curable compositions for use in forming ribbon assemblies
US6301415B1 (en) 1997-08-14 2001-10-09 Dsm N.V Optical glass fiber ribbon assemblies, matrix forming compositions radiation-curable compositions
US6391936B1 (en) 1997-12-22 2002-05-21 Dsm N.V. Radiation-curable oligomers radiation-curable compositions, coated optical glass fibers, and ribbon assemblies
US6018605A (en) * 1997-12-31 2000-01-25 Siecor Operations Photoinitiator--tuned optical fiber and optical fiber ribbon and method of making the same
US6040357A (en) * 1998-05-28 2000-03-21 Dsm N.V. Method of making a radiation-curable ink composition, radiation-curable ink composition and ribbon assembly
JP2003506754A (ja) * 1999-08-09 2003-02-18 ボーデン ケミカル インコーポレイテッド 熱剥離性光ファイバリボン
US6898356B2 (en) * 2001-03-15 2005-05-24 Sumitomo Electric Industries, Ltd. Split type optical fiber tape core
WO2002081396A1 (fr) 2001-04-05 2002-10-17 Borden Chemical, Inc. Ruban de fibres optiques a matrice pigmentee et procedes de fabrication et d'utilisation associes
FR2847347B1 (fr) 2002-11-18 2005-01-28 Nexans Procede de fabrication d'un ruban a fibres optiques et ruban a fibres optiques
FR2851053B1 (fr) * 2003-02-07 2005-06-03 Nexans Ruban a fibres optiques et procede de fabrication d'un ruban a fibres optiques
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WO1997018493A1 (fr) 1997-05-22
CA2237393A1 (fr) 1997-05-22

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