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WO1991003503A1 - Compositions de revetement primaire pour fibres de verre optique - Google Patents

Compositions de revetement primaire pour fibres de verre optique Download PDF

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Publication number
WO1991003503A1
WO1991003503A1 PCT/US1990/004976 US9004976W WO9103503A1 WO 1991003503 A1 WO1991003503 A1 WO 1991003503A1 US 9004976 W US9004976 W US 9004976W WO 9103503 A1 WO9103503 A1 WO 9103503A1
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WO
WIPO (PCT)
Prior art keywords
acrylate
meth
prepolymer
hydroxy
functionality
Prior art date
Application number
PCT/US1990/004976
Other languages
English (en)
Inventor
Erwin S. Poklacki
Timothy E. Bishop
Original Assignee
Desoto, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Desoto, Inc. filed Critical Desoto, Inc.
Publication of WO1991003503A1 publication Critical patent/WO1991003503A1/fr

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Classifications

    • 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
    • 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
    • C03C25/106—Single 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
    • C03C25/104—Coating to obtain optical fibres
    • C03C25/1065—Multiple coatings
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Definitions

  • This invention relates to polyurethane (meth)acrylate oligomers and coating compositions containing the same which are suitable as primary coatings for optical glass fibers.
  • the coatings exhibit a reduced modulus and improved adhesion to glass.
  • Background of the Invention Optical glass fibers are frequently coated with two superposed photocured coatings. The coating which contacts the glass is a relatively soft, primary coating. The outer, exposed coating is a much harder secondary coating that provides resistance to handling forces, such as those encountered when the fiber is cabled.
  • optical glass fibers with photocured coating compositions usually using ultraviolet light
  • Photocuring compositions are selected because of their rapid cure speed. Faster cure speed is generally desirable to increase the production of optical glass fibers.
  • Important properties of the cured coating include adhesion to the glass, resistance to water absorption and resistance to microbending especially at low service temperatures.
  • compositions typically include an acrylate-terminated polycarbonate diol-based polyurethanes.
  • Coatings produced from these conventional compositions have an acrylate functionality of 2 or more and are too hard to be utilized as primary coatings. These coatings can also exhibit poor adhesion and poor resistance to microbending.
  • the usual mono(meth)acrylate ethers having a low glass transition temperature are added to these compositions in an amount sufficient to provide adequate flexibility, the water resistance and adhesion of the coating can be undesirably reduced.
  • compositions suitable for use as a primary optical glass fiber coating and comprises a polyurethane (meth)acrylate oligomer having a (meth)acrylate functionality of about 1.9 or less and a mono(meth) crylate. Coatings produced therefrom are soft and flexible while retaining good water resistance and adhesion.
  • This invention provides new polyurethane (meth)acrylate oligomers and photocurable liquid coating compositions containing the same.
  • the coating composition is suitable for use as a primary coating for optical glass fibers.
  • the oligomer comprises the reaction product of a prepolymer or admixture of prepolymers, a diisocyanate, and a hydroxy (meth) crylate, and has a (meth)acrylate functionality of about 1.9 or less.
  • Preferred prepolymers are polycarbonate diols that are present in an amount sufficient to provide excess hydroxy functionality as compared to the free nitrogen-carbon-oxygen group (NCO) functionality of the diisocyanate as reduced by the hydroxy functionality of the hydroxy (meth)acrylate to achieve the desired (meth)acrylate functionality.
  • the coating composition comprises: (1) the polyurethane (meth)acrylate oligomer; and (2) a mono(meth)acrylate having a glass transition temperature (T fl ) below about -20°C.
  • the coating composition can also include a small amount of a monoethylenically unsaturated material having a T g greater than about 40°C. and a strong capacity for hydrogen bonding.
  • Coatings produced from the present coating composition have a high adhesion to glass, low water absorption and fast cure speeds. These coatings are flexible, exhibiting a very low tensile modulus, e.g., preferably less than about 1.5 megapascals (MPa) .
  • many conventional- coating compositions include an acrylate-terminated polyurethane having an acrylate functionality of 2 or more utilize a mono(meth)acrylate which is usually a polyether to provide, and adjust, the flexibility of the coatings made therefrom.
  • these mono(meth)acrylate polyethers which typically have a T g of less than about - 0°C, reduce the water resistance and the adhesion of the coating.
  • the present composition utilizes a polyurethane (meth)acrylate oligomer having a (meth)acrylate functionality of about 1.9 or less which imparts flexibility to the coatings.
  • the mono(meth)acrylate includes a
  • Coatings produced from the present composition can contain unreacted hydroxy groups if excess hydroxy functionality is utilized in the production of the oligomer. Unreacted hydroxy groups are conventionally expected to reduce the water resistance of a coating due to the group's hydrophilic nature. However, the present coatings exhibit less loss of water resistance than is expected for the amount of excess hydroxy functionality present.
  • the photocurable liquid coating compositions disclosed herein are suitable for use as a primary coating for optical glass fibers.
  • the coating composition comprises: (1) the polyurethane (meth)acrylate oligomer having a
  • (meth)acrylate functionality of about 1.9 or less and • (2) the mono(meth)acrylate having a glass transition temperature (T g ) below about -20°C.
  • the term "functionality”, and various grammatical forms thereof, indicates the average number of groups present per molecule of the referred to material that are capable of participating in a chemical reaction.
  • the number associated with the term functionality describes the average number of reactive groups present per molecule.
  • a (meth)acrylate functionality of about 1.9 or less means that for a given sample of the oligomer, the sum of the (meth)acrylate groups present divided by the number of oligomer molecules present is about 1.9 or less.
  • (meth)acrylate”, and various grammatical forms thereof, identifies esters that are the reaction product of an acrylic or a methacrylic acid with the hydroxy group, or groups, of an alcohol or other hydroxy containing organic compound.
  • glass transition temperature and various grammatical forms thereof, is defined as the temperature at which the homopolymer of the referred to material changes from a vitreous state to a plastic state.
  • the polyurethane (meth)acrylate oligomer is the reaction product of a prepolymer or mixture of prepolymers, an organic diisocyanate and a hydroxy (meth)acrylate.
  • the prepolymer is a carbon chain that can comprise oxygen and/or nitrogen atoms, the terminal (meth)acrylate functionality is added to the prepolymer by use of the diisocyanate. Selection of the prepolymer can affect the physical properties of the coatings produced from the oligomer-containing composition.
  • the prepolymer has at least one prepolymer functional group that is reactive with the isocyanate group, e.g., a hydroxy, mercapto, amine or similar group.
  • a preferred prepolymer functional group is the hydroxy group. If the prepolymer is monofunctional it is used in admixture with other polyfunctional prepolymers in a proportion to obtain the desired (meth)acrylate functionality of the oligomer.
  • the prepolymer, or admixture thereof preferably has a functionality of about 1.5 to about 3, most preferably about 1.8 to about 2.5, groups that are reactive with the isocyanate group.
  • the number average molecular weight of the prepolymer is about 500 to about 2,000, preferably about 800 to about 1,800, daltons.
  • Prepolymers are selected from the group consisting of polycarbonates, polyesters, polyethers and mixtures thereof.
  • the polycarbonate diols are conventionally produced by the alcoholysis of diethylcarbonate with a diol.
  • the diol is an alkylene diol having about 2 to about 12 carbon atoms, e.g., 1,4-butane diol, 1,6-hexane diol, 1,12-dodecane diol and the like.
  • the diol has about 4 to about 8 carbon atoms. Mixtures of these diols can also be utilized.
  • the polycarbonate diol can contain ether linkages in the backbone in addition to carbonate groups.
  • polycarbonate copolymers of alkylene oxide monomers and the previously described alkylene diols are suitable.
  • Suitable alkylene oxide monomers include ethylene oxide, tetrahydrofuran oxide and the like. These copolymers produce cured coatings that exhibit a lower modulus and also inhibit crystallinity of the liquid coating composition, as compared to polycarbonate diol homopolymers. Admixtures of polycarbonate diols and polycarbonate copolymers can be utilized.
  • Suitable polycarbonate diols include Duracarb 122, commercially available from PPG Industries and Permanol KM10-1733, commercially available from Permuthane, Inc., MA.
  • Duracarb 122 is produced by the alcoholysis of diethylcarbonate with hexane diol.
  • Illustrative polyesters include polybutylene adipate, polycaprolactones and the like.
  • Illustrative polyethers include poly(propylene oxide), poly(tetramethylene glycol) and the like.
  • diisocyanates alone or in admixture with one another can be utilized.
  • Representative diisocyanates include isophorone diisocyanate (IPDI) , toluene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, cyclohexylene diisocyanate, methylene dicyclohexane diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, -phenylene diisocyanate, 4-chloro-l,3-phenylene diisocyanate, 4,4*-biphenylene diisocyanate, 1,5-naphthylene diisocyanate,
  • 1,4-tetramethylene diisocyanate 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, and the like.
  • a preferred diisocyanate is IPDI.
  • the hydroxy (meth)acrylate can be a mono(meth)acrylate or a poly(meth)acrylate. Monohydric monoacrylates are presently preferred.
  • the (meth)acrylate terminal group in the oligomer is introduced with a urethane linkage by the reaction of the isocyanate group with a hydroxy group of the hydroxy (meth)acrylate.
  • Suitable monohydric acrylates are the C 2 -C 4 alkyl acrylates. Illustrative of these acrylates are 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and the like. Also suitable are reaction products of 2-hydroxylethyl acrylate with one or more molecules of caprolactone. Mixtures of these acrylates are also suitable. The methacrylate counterparts of the above acrylates can also be utilized.
  • the reaction to produce the oligomer is preferably conducted in a diluent which reduces the viscosity of the oligomer.
  • a diluent which reduces the viscosity of the oligomer.
  • the diluent is preferably not reactive in the oligomer synthesis but is reactive during the cure of the coating composition.
  • the oligomer of the present invention has a (meth)acrylate functionality of about 1.9 or less before the diluent is added due to the chemical reaction of producing the oligomer.
  • These diluents contribute to the low modulus of the cured film and hence typically have a T g below about -20°C.
  • octyl/decyl acrylate an admixture of octyl acrylate and decyl acrylate
  • polytetramethy1ene glycol diacrylate the mono(meth) crylates illustrated hereinafter, the like, and mixtures thereof.
  • a minor amount of a catalyst for the urethane-for ing reaction is typically utilized, e.g., about 0.03 to about 0.1, preferably about 0.05 weight percent of dibutyl tin dilaurate.
  • a minor amount, i.e., less than about 0.1 weight percent, of a inhibitor can be present to control the oligomer producing reaction.
  • Illustrative inhibitors include butylated hydroxy toluene, phenothiazine, and the like.
  • a sparge of inert gas e.g., dry air, nitrogen, carbon dioxide or the like, is utilized to ensure that there is no moisture present which can adversely affect the production of the oligomer.
  • the reactants for the production of the oligomer i.e., the prepolymer, the diisocyanate, and the hydroxy (meth)acrylate, can be combined and reacted simultaneously in a suitable vessel.
  • a preferred method of producing the polyurethane (meth)acrylate oligomer is to introduce the diluent, the diisocyanate and the inhibitor into the vessel and elevate the temperature thereof to about 30°C. to about 50°C. while agitating and sparging with an inert gas. The agitation and the sparge are maintained throughout the reaction. Next, the catalyst can be introduced into the vessel. The hydroxy
  • (meth)acrylate is then slowly introduced into the vessel, typically over a time period of about 15 minutes to about one hour.
  • the reaction is maintained at an elevated temperature for a time period sufficient to consume substantially all of the hydroxy functionality of the hydroxy (meth)acrylate and produce a (meth)aerylate-terminated urethane isocyanate.
  • substantially all of the hydroxy functionality is consumed in a time period of about 0.5 to about 2 hours.
  • the temperature of the reactants can then be increased to facilitate admixing by further reducing the viscosity.
  • the prepolymer is introduced into the vessel and reacted with the (meth)acrylate-terminated urethane isocyanate.
  • the temperature of the. reactants is further elevated to about 50°C. to about 70°C. and maintained at that temperature for a time period sufficient to reduce the NCO content to less than about 0.2 percent, preferably less than about 0.1 percent of the oligomer.
  • this reduced NCO content is achieved in a time period of about 1.5 to about 10 hours, albeit this reaction can be left to run overnight without adversely affecting the oligomer.
  • additional diluent can be added to produce an oligomer-diluent admixture having the desired viscosity at the temperature at which subsequent admixing of the oligomer-diluent admixture with the other constituents of the present coating composition is performed.
  • This method of producing the oligomer is preferred because reaction of all of the hydroxy functionality of the hydroxy (meth)acrylate is desired and this may not occur if the prepolymer is reacted with the diisocyanate first or with the diisocyanate and the hydroxy (meth)acrylate.
  • the prepolymer utilized is an admixture of monofunctional and polyfunctional prepolymers, the mole percent of each can be selected to enable use of a stoichiometrically correct proportion of prepolymer admixture to NCO functionality of the diisocyanate after the NCO functionality is reduced by the hydroxy functionality of the hydroxy (meth)acrylate.
  • a stoichiometric excess supplied by the polyfunctional prepolymer can be present in the prepolymer admixture.
  • stoichiometric excess of the polyfunctional prepolymer is added to the vessel to provide an excess of prepolymer functionality as compared to the NCO functionality present after the initial NCO functionality of the diisocyanate is calculated to be, or actually, reduced by the hydroxy functionality of the hydroxy (meth)acrylate.
  • the amount of this excess prepolymer functionality is that which is effective to provide a lowered modulus and a coating that satisfactorily protects the fiber.
  • NCO functionality present for the purpose of calculating the excess prepolymer functionality required when a polyfunctional prepolymer is utilized.
  • One way is to subtract the hydroxy functionality of the hydroxy (meth)acrylate from the NCO functionality of the diisocyanate.
  • the hydroxy (meth)acrylate and the diisocyanate are reacted, as described above, to consume essentially all of the hydroxy functionality of the hydroxy (meth)acrylate and the NCO functionality of the resultant (meth)acrylate-terminated urethane isocyanate reaction product is then conventionally measured. The proper amount of prepolymer can then be calculated.
  • the oligomer Preferably, up to about 40, more preferably about 10 to about 35, percent excess prepolymer functionality is present in the oligomer when a polyfunctional prepolymer is utilized.
  • the prepolymer is a polyhydroxy prepolymer such as a polycarbonate diol then excess hydroxy functionality in the above amounts would be present.
  • the (meth)acrylate functionality of the oligomer is about 1.9 or less, preferably at least about 1.5 and most preferably about 1.5 to about 1.8.
  • the number average molecular weight of the polycarbonate polyurethane (meth)acrylate oligomer is about 600 to about 15,000, preferably about 1,000 to about 5,000 daltons.
  • polymer chains, provided by the prepolymer, having unreacted terminal groups extending from the oligomer reduce the modulus of the cured coating because they remain free to move as the cured coating is flexed. Changing the length and number of these free polymer chains changes the modulus obtained.
  • An additional constituent of the coating composition is the mono(meth)acrylate having a T g below about -20°C. As previously discussed, the mono(meth)acrylate can function as a diluent during the production of the oligomer. The T g of the mono(meth)acrylate can be as low as about -90°C.
  • Suitable mono(meth)acrylates include ethoxy- ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, nonyl-substituted phenoxyethyl (meth)acrylate, and the like.
  • Suitable mono(meth)acrylates include the (meth)acrylate of the C 7 -C 10 , preferably C ⁇ -C 9 , alkyl substituted phenol that is alkoxylated with a C 2 -C 4 alkylene oxide so that it contains about 1 to about 10 moles of the oxide per mole of the phenol.
  • the (meth)acrylate of the alkoxylated phenol contains about 3.5 to about 4 moles of oxide per mole of the phenol.
  • Suitable alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. Presently, ethylene oxide is preferred.
  • Commercially available illustrative acrylates of the alkoxylated phenol include alkoxylated nonyl phenol acrylates such as Aronix M-lll, Aronix M-113 and Aronix M-117 from Toa Gosei, Japan.
  • the coating composition can further include a monoethylenically unsaturated material having a high T g and a strong capacity for hydrogen bonding.
  • These monoethylenically unsaturated materials typically have a T g greater than about 40°C. and are illustrated by N-vinyl monomers, e.g., N-vinyl pyrrolidone, N-vinyl caprolactam, mixtures thereof and the like.
  • N-vinyl monomers e.g., N-vinyl pyrrolidone, N-vinyl caprolactam, mixtures thereof and the like.
  • the monoethylenically unsaturated material is also utilized.
  • the T g of this monoethylenically unsaturated material can be as high as about 120°C.
  • the wavelength of the light utilized to cure the coating compositions of the present invention can vary somewhat depending upon the photoinitiator selected.
  • the light utilized is usually in the ultraviolet range which extends from about 200 to about 400 nanometers (nm) however, light of a longer wavelength, e.g., light having a wavelength of up to about 600 nm, preferably up to about 520 nm, can be utilized.
  • the photoinitiators utilized are conventional components of light curable ethylenically unsaturated coatings.
  • Preferred photoinitiators are aryl ketones, e.g., benzophenone, acetophenone, diethoxy acetophenone, benzoin, benzil, anthraquinone, and the like.
  • Commercial photoinitiators are illustrated by Irgacure 184 which is hydroxycyclohexyl phenyl ketone and is available from Ciba-Geigy Corp., Ardsley, NY, and Lucirin TPO which is available from BASF, Chattanooga, TN.
  • Volatile organic solvents are preferably not utilized in the present coating composition.
  • the polyurethane (meth)acrylate oligomer is present in the coating composition in an amount in the range of about 30 to about 80, preferably about 45 to about 70 weight percent based on the total weight of the coating composition.
  • the mono(meth)acrylate is present in the coating composition in an amount in the range of about 10 to about 70, preferably about 20 to about 55 weight percent based on the total weight of the coating composition.
  • an aliquot of the mono(meth)acrylate can be utilized as a diluent to reduce the viscosity of the oligomer during synthesis thereof, to produce an oligomer-diluent admixture.
  • the remainder of the mono(meth)acrylate is admixed therewith subsequently.
  • the photoinitiator is present in the coating composition in a range of about 0.5 to about 10, preferably about 2 to about 6, weight percent based on the total weight of the coating composition.
  • the monoethylenic " material having a high T g when utilized, is preferably present in the coating composition in a range of about 1 to about 15, more preferably about 2 to about 6 weight percent based on the total weight of the coating composition.
  • the viscosity of the coating composition is about 3,000 to about 12,000 centipoise (cp) , preferably about 4,000 to about 10,000 cp.
  • the coating composition can further include - conventional adhesion promoters, light stabilizers and antioxidants.
  • Silanes are conventional adhesion promoters which can be present typically in an amount less than about 1 weight percent.
  • Illustrative silanes include gamma methacryloxypropyl trimethoxy silane, commercially available from Dynasylan Inc., Switzerland under the trade designation MEMO and gamma mercaptopropyl trimethoxy silane which is commercially available from Union Carbide under the designation A-189.
  • Conventional light stabilizers such as hindered amines which provide ultraviolet stability for the cured composition can be present in amounts less than about 1 weight percent.
  • Illustrative commercial stabilizers include the following Ciba-Geigy Corp., Ardsley, NY products: bis(2,2,6,6,-tetramethyl- 4-piperidinyl) sebacate commercially available under the trade designation Tinuvin 770; and Tinuvin 292.
  • An illustrative antioxidant is thiodiethylene
  • the present coating compositions can be applied as a primary coating to glass fibers utilizing conventional processes.
  • the coating thickness typically is about 10 to about 40 microns.
  • a suitable vessel having agitation, a dry air sparge, and a heat source was provided.
  • the agitation, sparge and heat source were utilized during the entire synthesis.
  • the isophorone diisocyanate, butylated hydroxy toluene and about 90 weight percent of the octyl/decyl acrylate of oligomer A, about 90 weight percent of the phenoxyethyl acrylate of oligomer B or about 85 weight percent of phenoxyethyl acrylate of oligomer C were introduced into the vessel and the temperature of these reagents elevated to, and maintained at, 40°C.
  • the dibutyl tin dilaurate was introduced into the vessel.
  • the hydroxyethyl acrylate was then introduced into the vessel over a time period of about half an hour.
  • the reagents present in the vessel were then reacted for a time period of one hour.
  • the NCO functionality was conventionally calculated.
  • the amount of polycarbonate diol required was determined to provide 120 percent hydroxy functionality for oligomers A and B and 133 percent hydroxy functionality for oligomer C, as compared to the NCO functionality present.
  • the temperature of the reagents present was elevated to 60°C.
  • the polycarbonate diol was then quickly introduced into the vessel and the temperature elevated to 70°C. This temperature was maintained until the NCO content was less than 0.1 percent.
  • Oligomer-diluent admixture A had a theoretical functionality of about 1.7 and a viscosity of about 40,600 millipascal seconds (mPa»s) at a temperature of 25°C.
  • the oligomer produced from admixture A had a calculated number average molecular weight of about 3800 daltons.
  • Oligomer-diluent admixture B had a theoretical functionality of about 1.7 and a viscosity of about 88,100 mPa s at a temperature of 25°C.
  • the oligomer produced from admixture B had a measured number average molecular weight of about 3800 daltons.
  • Oligomer-diluent admixture C had a theoretical functionality of about 1.5 and a viscosity of about 81,100 mPa « " S at a temperature of 25°C.
  • the oligomer produced from admixture C had a calculated number average molecular weight of about 4100 daltons.
  • compositions of the present invention were utilized to prepare coating compositions of the present invention.
  • the constituents of these compositions, and proportions utilized, are presented in TABLE II, below.
  • the compositions were prepared by admixing all of the constituents in a suitable vessel at an elevated temperature of 55°C. for a time period of 20 minutes. Substantially homogeneous coating compositions were produced.
  • the oligomer-diluent admixture A of EXAMPLE 1 was utilized.
  • the oligomer-diluent admixture B of EXAMPLE 1 was utilized.
  • a photoinitiator commercially available from BASF, Chattanooga, TN.
  • a silane adhesion promoter commercially available fro Dynasylan Inc., Switzerland.
  • a light stabilizer commercially available from Ciba-Geigy, Ardsley, NY. 7
  • a antioxidant commercially available from Ciba-Geigy Corp., Ardsley, NY.
  • the viscosity was measured using a Brookfield Model RVTDV viscometer operated in accordance with the instructions provided therewith. The temperature of each sample tested was 25°C. The cure speed [Joules/square centimeter
  • a film for determination of the modulus of the coating was prepared by drawing down a 3 mil coating on glass plates using a Bird bar, commercially available from Pacific Scientific, Silver Springs, MD. The coating was cured using the "D" lamp . The coating was cured at a dose of about 1.0 J/sq cm which provided complete cure. The film was then conditioned at
  • MPa is acceptable to the optical glass fiber industry albeit a lower modulus is desirable in many applications.
  • the present composition satisfies this desire by producing coatings having a modulus of 1.4 MPa or less.
  • films were prepared by drawing down 3 mil coatings on glass plates using the Bird bar. The coatings were cured using the "D" lamp. The films were then conditioned at a temperature of 23 + 2°C. and a relative humidity of 50 ⁇ 5% for a time period of 7 days. A portion of the film was utilized to test dry adhesion. Subsequent to dry adhesion testing, the remainder of the film to be tested for wet adhesion was further conditioned at a temperature of 23 + 2°C. and a relative humidity of 95% for a time period of 24 hours. A layer of a polyethylene wax/water slurry was applied to the surface of the further conditioned film to retain moisture.
  • the test was performed utilizing an apparatus including a universal testing instrument, e.g., the Instron Model 4201, and a device, including a horizontal support and a pulley, positioned in the testing instrument.
  • a universal testing instrument e.g., the Instron Model 4201
  • a device including a horizontal support and a pulley, positioned in the testing instrument.
  • sample specimens that appeared to be uniform and free of defects were cut in the direction of the draw down. Each specimen was 6 inches long and 1 inch wide and free of tears or nicks.
  • the first one inch of each specimen was peeled back from the glass plate.
  • the plate was secured to the horizontal support with the affixed end of the specimen adjacent to the pulley.
  • a wire was attached to the peeled-back end of the specimen, run parallel to the specimen and then run through the pulley in a direction perpendicular to the specimen.
  • the free end of the wire was clamped in the upper jaw of the testing instrument which was then activated. The test was continued until the average force value became relatively constant.
  • the optical glass fiber industry requires a dry adhesion of at least 50 grams and a wet adhesion of at least 20 grams.
  • the present coatings greatly exceed the dry and wet adhesion requirements of the industry.
  • a 10 mil draw-down of the composition was made on a glass plate utilizing a Bird bar.
  • the composition was cured utilizing the "D" lamp to provide a dose of 1.0 J/sq cm.
  • Three test samples each having dimensions of 1/2" x 1 1/2" were cut from the cured coating.
  • Each sample was weighed utilizing an analytical balance to obtain weight measurement J and then immersed in separate containers of deionized water. After a time period of 24 hours, the samples were removed from the water, blotted to remove excess water on the surface and reweighed to obtain weight measurement K.
  • the samples were then placed in aluminum pans and maintained therein at ambient conditions, i.e., ambient temperature (about 20° - 30°C.) and ambient humidity, for a time period of 120 hours.
  • the samples were then reweighed to obtain weight measurement L.
  • the following formulations were utilized to calculate the water absorption and the extractables.

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  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

Des oligomères de polyuréthane (méth)acrylate ayant une fonctionnalité (méth)acrylate d'environ 1,9 ou moins ainsi que des compositions de revêtement liquides photopolymérisables comprenant l'oligomère sont décrits. Ces compositions comprennent l'oligomère et un mono(méth)acrylate.
PCT/US1990/004976 1989-09-01 1990-08-31 Compositions de revetement primaire pour fibres de verre optique WO1991003503A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US40194889A 1989-09-01 1989-09-01
US401,948 1989-09-01

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WO1991003503A1 true WO1991003503A1 (fr) 1991-03-21

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AU (1) AU6406490A (fr)
CA (1) CA2024379A1 (fr)
WO (1) WO1991003503A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5345528A (en) * 1993-07-28 1994-09-06 At&T Bell Laboratories Method for enhancing the pullout strength of polymer-coated optical fiber
US5381504A (en) * 1993-11-15 1995-01-10 Minnesota Mining And Manufacturing Company Optical fiber element having a permanent protective coating with a Shore D hardness value of 65 or more
US5402516A (en) * 1993-09-30 1995-03-28 At&T Bell Laboratories Optical fiber apparatus
US5506051A (en) * 1994-01-27 1996-04-09 Nicolectronix Ltd. Laboratories Transparent sheet composites for use as bullet-proof windows
JP2009108206A (ja) * 2007-10-30 2009-05-21 Three Bond Co Ltd 硬化性シート組成物
US9526686B2 (en) 2009-07-21 2016-12-27 Nail Alliance, Llc Compositions for removable gel applications for nails and methods of their use
CN112074493A (zh) * 2018-05-03 2020-12-11 康宁股份有限公司 具有低拔出力的光纤涂层
US11104758B2 (en) 2018-06-29 2021-08-31 3M Innovative Properties Company Orthodontic articles prepared using a polycarbonate diol, and methods of making same
US11225535B2 (en) 2018-06-29 2022-01-18 3M Innovative Properties Company Photopolymerizable compositions including a polyurethane methacrylate polymer prepared using a polycarbonate diol, articles, and methods
CN114736549A (zh) * 2022-03-23 2022-07-12 武汉长盈鑫科技有限公司 一种适用于uv-led固化的frp涂覆树脂组合物及其制备方法
US11584817B2 (en) 2018-06-29 2023-02-21 3M Innovative Properties Company Orthodontic articles comprising cured free-radically polymerizable composition with improved strength in aqueous environment
US11945900B2 (en) 2018-06-29 2024-04-02 3M Innovative Properties Company Orthodontic articles prepared using a polycarbonate diol, polymerizable compositions, and methods of making the articles

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2107354A1 (fr) * 1991-04-03 1992-10-04 Randall T. Lake Compositions de revetement sechables aux ultra-violets, et procedes connexes
FR2713625B1 (fr) * 1993-12-09 1996-02-23 Vetrotex France Sa Procédé de production de fils de verre ensimés et produits résultants.
FR2713626B1 (fr) * 1993-12-09 1996-02-23 Vetrotex France Sa Procédé de fabrication de fils de verre ensimés et fils de verre en résultant.

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US3891523A (en) * 1970-01-19 1975-06-24 Dainippon Ink & Chemicals Photopolymerizable, isocyanate-containing prepolymers
JPS5974115A (ja) * 1982-10-20 1984-04-26 Matsushita Electric Works Ltd ラジカル重合性プレポリマ−の製法
US4480079A (en) * 1982-04-12 1984-10-30 Imperial Chemical Industries Plc Copolymerization of unsaturated urethane monomers
US4691045A (en) * 1984-12-06 1987-09-01 Nippon Shokubai Kagaku Co., Ltd. Hydroxyl group-containing (meth)acrylate oligomer, prepolymer therefrom, and method for use thereof
US4690501A (en) * 1985-07-08 1987-09-01 Desoto, Inc. Ultraviolet curable optical glass fiber coatings from acrylate terminated, end-branched polyurethane polyurea oligomers
JPS62227916A (ja) * 1986-03-28 1987-10-06 Nitto Electric Ind Co Ltd 硬化性組成物の製造方法
US4932750A (en) * 1982-12-09 1990-06-12 Desoto, Inc. Single-coated optical fiber
US4952241A (en) * 1986-07-25 1990-08-28 Bayer Aktiengesellschaft (Meth)acylic acid derivatives containing urethane groups

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Publication number Priority date Publication date Assignee Title
US3891523A (en) * 1970-01-19 1975-06-24 Dainippon Ink & Chemicals Photopolymerizable, isocyanate-containing prepolymers
US4480079A (en) * 1982-04-12 1984-10-30 Imperial Chemical Industries Plc Copolymerization of unsaturated urethane monomers
JPS5974115A (ja) * 1982-10-20 1984-04-26 Matsushita Electric Works Ltd ラジカル重合性プレポリマ−の製法
US4932750A (en) * 1982-12-09 1990-06-12 Desoto, Inc. Single-coated optical fiber
US4691045A (en) * 1984-12-06 1987-09-01 Nippon Shokubai Kagaku Co., Ltd. Hydroxyl group-containing (meth)acrylate oligomer, prepolymer therefrom, and method for use thereof
US4690501A (en) * 1985-07-08 1987-09-01 Desoto, Inc. Ultraviolet curable optical glass fiber coatings from acrylate terminated, end-branched polyurethane polyurea oligomers
JPS62227916A (ja) * 1986-03-28 1987-10-06 Nitto Electric Ind Co Ltd 硬化性組成物の製造方法
US4952241A (en) * 1986-07-25 1990-08-28 Bayer Aktiengesellschaft (Meth)acylic acid derivatives containing urethane groups

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5345528A (en) * 1993-07-28 1994-09-06 At&T Bell Laboratories Method for enhancing the pullout strength of polymer-coated optical fiber
EP0636590A1 (fr) * 1993-07-28 1995-02-01 AT&T Corp. Procédé d'amélioration de la résistance à l'arrachement de fibres optiques revêtues de polymère
US5402516A (en) * 1993-09-30 1995-03-28 At&T Bell Laboratories Optical fiber apparatus
EP0646820A3 (fr) * 1993-09-30 1998-01-28 AT&T Corp. Câble optique
US5381504A (en) * 1993-11-15 1995-01-10 Minnesota Mining And Manufacturing Company Optical fiber element having a permanent protective coating with a Shore D hardness value of 65 or more
USRE36146E (en) * 1993-11-15 1999-03-16 Minnesota Mining And Manufacturing Company Optical fiber element having a permanent protective coating with a shore D hardness value of 65 or more
US5506051A (en) * 1994-01-27 1996-04-09 Nicolectronix Ltd. Laboratories Transparent sheet composites for use as bullet-proof windows
JP2009108206A (ja) * 2007-10-30 2009-05-21 Three Bond Co Ltd 硬化性シート組成物
US9526686B2 (en) 2009-07-21 2016-12-27 Nail Alliance, Llc Compositions for removable gel applications for nails and methods of their use
CN112074493A (zh) * 2018-05-03 2020-12-11 康宁股份有限公司 具有低拔出力的光纤涂层
US11104758B2 (en) 2018-06-29 2021-08-31 3M Innovative Properties Company Orthodontic articles prepared using a polycarbonate diol, and methods of making same
US11225535B2 (en) 2018-06-29 2022-01-18 3M Innovative Properties Company Photopolymerizable compositions including a polyurethane methacrylate polymer prepared using a polycarbonate diol, articles, and methods
US11584817B2 (en) 2018-06-29 2023-02-21 3M Innovative Properties Company Orthodontic articles comprising cured free-radically polymerizable composition with improved strength in aqueous environment
US11708428B2 (en) 2018-06-29 2023-07-25 3M Innovative Properties Company Photopolymerizable compositions including a polyurethane methacrylate polymer prepared using a polycarbonate diol, articles, and methods
US11945900B2 (en) 2018-06-29 2024-04-02 3M Innovative Properties Company Orthodontic articles prepared using a polycarbonate diol, polymerizable compositions, and methods of making the articles
US12297316B2 (en) 2018-06-29 2025-05-13 Solventum Intellectual Properties Company Orthodontic articles prepared using a polycarbonate diol, polymerizable compositions, and methods of making the articles
CN114736549A (zh) * 2022-03-23 2022-07-12 武汉长盈鑫科技有限公司 一种适用于uv-led固化的frp涂覆树脂组合物及其制备方法
CN114736549B (zh) * 2022-03-23 2022-09-30 武汉长盈鑫科技有限公司 一种适用于uv-led固化的frp涂覆树脂组合物及其制备方法

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CA2024379A1 (fr) 1991-03-02
AU6406490A (en) 1991-04-08

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