WO1996017000A1 - Radiation-curable coating composition and coating - Google Patents
Radiation-curable coating composition and coating Download PDFInfo
- Publication number
- WO1996017000A1 WO1996017000A1 PCT/NL1995/000406 NL9500406W WO9617000A1 WO 1996017000 A1 WO1996017000 A1 WO 1996017000A1 NL 9500406 W NL9500406 W NL 9500406W WO 9617000 A1 WO9617000 A1 WO 9617000A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating composition
- weight
- oligomer
- urethane
- composition according
- Prior art date
Links
Classifications
-
- 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
-
- 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
- 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
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic 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
- C08G18/70—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
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
-
- 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
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds 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
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
- C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2938—Coating on discrete and individual rods, strands or filaments
Definitions
- This invention relates to a radiation-curable oligomer coating composition.
- the invention further relates to an optical glass fiber coated with the coating composition.
- An optical fiber is generally coated with one or more layers of coating to protect and reinforce the optical fiber.
- the coating is typically applied using a coating composition.
- the coating composition Depending on whether the coating composition is used as an inner primary coating, which is the coating immediately contacting the optical fiber, an outer primary coating, a single coating, or a matrix material, the coating composition must satisfy many requirements.
- the requirements of coating compositions include being liquid at room temperature, having a good processability and having a high curing rate.
- the requirements of coatings made by curing the coating composition include exhibiting very little physical change over a wide temperature range, a good resistance to water sensitivity under humid conditions, a low water and oil absorption, a high thermal and light resistance, and low extractables.
- Low extractables typically means only a small portion of material in the coating can be extracted into water, organic solvents, or cable filling gels. /17000 PCr/Nl_>5/00406
- a further requisite of an inner primary coating composition is a refractive index high enough to refract errant signals escaping from the glass fiber away from the glass fiber.
- a refractive index is higher than or equal to about 1.48.
- the coatings must also have adequate adhesion to optical fibers while still being strippable, such as for field splicing.
- the coatings should also be resistant to color changes, such as yellowing.
- Many coating compositions have been formulated in order to meet these strict requirements for optical fiber coatings.
- European patent application 0200366 discloses a UV-curable resin composition consisting of a polyurethane derived from a polyether polyol and a hydrogenated diene (polyolefin) polymer having hydroxy groups. The polyether and polyolefin are reacted with diisocyanate. According to the examples, 2,4-toluene diisocyanate or isophorone diisocyanate is used in the preparation of the polyurethane. If 2,4-toluene diisocyanate is used to prepare the polyurethane, this can result in instability of the coating shown as yellowing.
- isophorone diisocyanate is used as a diisocyanate, as in example 5 of EP '366, it was found that yellowing can be avoided.
- the difficulty is that the refractive index of a primary coating prepared from such a composition is too low to refract errant signals escaping from a glass fiber away from the glass fiber.
- European patent application 0566801 describes a radiation curable coating composition for an optical fiber consisting of (A) 10% to 90% by weight of a reactively terminated urethane oligomer which is the reaction product of a polyether polyol, an aliphatic polyisocyanate and an endcapping monomer, (B) 5-80% of one or more diluents, (C) 0.1 to 3.0% of an organo-functional silane adhesion promoter, and optionally (D) 0.1-10.0% of a photoinitiator.
- polyalkylene glycol nonylphenylether acrylate is added to the coating compositions in examples I to X. It was found that the addition of polyalkylene glycol nonylphenylether acrylate has a deleterious effect on the resistance to water sensitivity and oil of the coating compositions.
- European patent application 0539030 describes a coating material for an optical fiber consisting of an ethylenically terminated urethane oligomer derived from a polyester polyol containing dimer acid residues .
- TMXDI tetramethylenexylene diisocyanate
- No advantages of using TMXDI over the other isocyanates mentioned are provided.
- this disclosure is directed to a urethane based on a specific polyester polyol.
- This coating composition can be used to form inner primary coatings having a refractive index sufficiently high to refract errant signals escaping from a glass fiber away from the glass fiber.
- An embodiment relates to a coating composition
- a coating composition comprising: (A) about 30 to about 80% by weight of urethane oligomer having reactive termini; (B) about 15 to about 65% by weight of one or more reactive diluents, each diluent being terminated with at least one end group capable of reacting with the reactive terminus of (A); optionally (C) 0 to about 10% by weight of at least one photoinitiator; optionally (D) 0 to about 5.0% by weight antioxidant; and optionally (E) 0 to about 30% by weight adhesion promotor.
- the urethane oligomer comprises at least three types of moieties, a polyether and/or polyolefin block, an aromatic group having one or more alkyl substituents, and reactive termini.
- the three types of moieties are connected via urethane and/or urea linkages.
- the aromatic groups are connected to urethane and/or urea linkages via the one or more alkyl substituents.
- the urethane oligomer is obtained by the reaction of (i) at least one oligomer based on a polyether, a polyolefin, a copolymer thereof, or mixtures thereof, each oligomer having at least two groups selected from the group of hydroxyl groups and amine groups, (ii) an aromatic polyisocyanate, wherein the isocyanate groups are not directly linked to the aromatic group, and (iii) a hydroxy functional ethylenically unsaturated monomer.
- the urethane oligomer having reactive termini has the general formula (1): wherein:
- R 1 is a reactive terminus
- R 2 is an aromatic group having one or more alkyl substituents, wherein the urethane (0-CO-NH-) group and L are attached to the one or more alkyl substituents,
- R 3 is an oligomer based on a polyether, a polyolefin, a copolymer of a polyether and a polyolefin, or mixtures thereof, L is a urethane linkage, a urea linkage, or mixtures thereof, and Y is 2 or greater .
- a further embodiment relates to a glass fiber having at least one coating formed by curing at least one of the coating compositions defined herein.
- the coating compositions provide a cured coating having a high refractive index and good resistance to color change, and an improved resistance to solvents.
- A about 30 to about 80% by weight of a urethane oligomer having reactive termini;
- B about 15 to about 65% by weight of one or more reactive diluents, each diluent being terminated with at least one end group capable of reacting with the reactive terminus of (A); optionally (C) 0 to about 10% by weight of photoinitiator; optionally (D) 0 to about 5.0% by weight of an antioxidant; and optionally (E) 0 to about 30% by weight of an adhesion promotor.
- the urethane oligomer comprises at least three types of moieties, a polyether and/or polyolefin block, an aromatic group having one or more alkyl substituents, and reactive termini.
- the at least three types of moieties are connected via urethane and/or urea linkages.
- the aromatic groups are connected to urethane and/or urea linkages via the one or more alkyl substituents.
- the three types of moieties are connected via urethane linkages and the aromatic groups are connected to urethane linkages via the one or more alkyl substituents.
- the urethane oligomer is obtained by the reaction of (i) at least one oligomer based on a polyether, a polyolefin, a copolymer thereof, or mixtures thereof, each oligomer having at least two groups selected from the group of hydroxyl groups and amine groups, (ii) an aromatic polyisocyanate, wherein the isocyanate groups are not directly linked to the aromatic groups, and (iii) a hydroxy functional ethylenically unsaturated monomer.
- the oligomer (i) based on a polyether, a polyolefin, or a copolymer thereof, for example, can have at least one hydroxyl group and at least one amine group, or at least two amine groups, or at least two hydroxyl groups. More than one type of oligomer (i) can be present. Furthermore, during the reaction, the oligomer (i) can be linked via urethane and/or urea linkages to another oligomer (i) to thereby form a larger backbone.
- the oligomer (i) has at least two hydroxyl groups and substantially no amine groups which can react with the aromatic isocyanate.
- the urethane oligomer with reactive termini has the general formula (1): R 3 -[L-R 2 -NH-CO-0-R 1 ] ⁇ wherein:
- R 1 is a reactive terminus
- R 2 is an aromatic group having one or more alkyl substituents, wherein the urethane (0-C0-NH-) group and L are attached to the one or more alkyl substituents
- R 3 is an oligomer based on a polyether, a polyolefin, a copolymer of a polyether and a polyolefin, or mixtures thereof
- L is a urethane linkage, a urea linkage, or mixtures thereof
- Y is 2 or greater, preferably 2 to 5, more preferably 2 to 3, and most preferably 2.
- the oligomer R 3 is polyfunctional such that each of the groups -L-R 2 -NH-CO-0- R 1 is directly linked to the oligomer R 3 .
- the coating composition can contain mixtures of urethane oligomers of different functionality, for example, mixtures of urethane oligomers having different Y values.
- L is preferably a urethane linkage.
- the coating composition can optionally contain a small quantity of monofunctional oligomer R 3 , where Y is equal to 1. In such a case, the average functionality of the oligomer R 3 is preferably greater than about 1.8.
- a radiation curable coating composition adapted for use as a primary coating on glass optical fibers, which when coated and cured on glass optical fibers in combination provides:
- said coating composition comprising: a urethane oligomer comprising three moieties,
- a further embodiment relates to a radiation curable coating composition which is adapted for use as a primary coating on glass optical fibers, which when coated and cured on glass optical fibers in combination provides: (1) a refractive index of a magnitude adequate to refract errant light signals away from the glass optical fiber;
- a further embodiment relates to a glass fiber having at least one coating formed by curing at least one of the coating compositions defined herein.
- the coating compositions can be cured to form coatings having a refractive index sufficiently high to refract errant signals escaping from a glass fiber away from the glass fiber, for example, of at least approximately 1.48, even if only non-aromatic SXZ reactive diluents are used as component (B). Furthermore, the cured coatings have good color stability.
- the coatings formed from the coating compositions have an excellent resistance to organic solvents.
- the hexane absorption is less than about 40 wt.%, and the hexane extraction is less than about 7 wt.%, using the test methods described herein.
- the coatings formed from the coating compositions have an excellent resistance to inorganic solvents.
- the water absorption is less than about 1 wt.%, and the water extraction is less than about 1 wt.%, using the test methods described herein.
- the coatings have the required characteristics for inner- primary optical fiber coatings with regard to toughness, low modulus at low temperature. Furthermore, the coatings have good adhesion to the optical fiber and yet are strippable, such as for field splicing.
- the reactive terminus (R 1 ) of the urethane oligomer can be, for example, provided by acrylate, methacrylate, vinylether, maleate or fumerate functionality. This functional group can be, for example, attached to the urethane groups via a low molecular weight polyol. As a reactive terminus, acrylate or vinylether functionality is preferred.
- low molecular weight polyols examples include butane-diol, hexane- diol, and the like.
- Other low molecular weight polyols that can be used include ethylene glycol, 1,2-propylene glycol, and their oligomers up to about 12 units.
- Monomers having an (meth)acrylate functional group include, for example, hydroxy functional acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and the like.
- Monomers having a vinyl ether functional group include, for example, 4-hydroxybutyl vinyl ether, and triethylene glycol monovinyl ether.
- Monomers having a maleate functional group include, for example, the methylester of hydroxy ethyl maleate. For example, ⁇ - hydroxyethyl acrylate can be reacted with the polyisocyanate to provide the terminal reactive group.
- the aromatic polyisocyanate used to make the urethane oligomer has two or more isocyanate functional groups attached to its core (R 2 ).
- the core (R 2 ) comprises at least one aromatic group and at least one alkyl group, wherein the isocyanate groups are not directly linked to an aromatic group.
- the core (R 2 ) comprises one or two aromatic groups and one to six alkyl groups, such as, xylene derivatives.
- the alkyl groups have one to eight carbon atoms.
- the aromatic isocyanate has the general formula (2):
- R 4 and R s are saturated hydrocarbon groups and can be in any of the ortho, meta or para positions with respect to each other, or mixtures thereof.
- the saturated hydrocarbon groups are in the meta position with respect to each other.
- R 4 and R 5 which can be the same or different, comprise 1-6 carbon atoms. More preferably, R 4 and R 5 are both propylene.
- the aromatic group in formula 2 can be substituted with alkyl or aryl groups.
- the oligomer having at least two groups selected from the group of hydroxyl groups and amine groups (hereinafter "the oligomer polyol/polyamine") , used to make the oligomer part R 3 of the urethane oligomer, can have more than one hydroxyl group and/or amine group that can react with polyisocyanate.
- the oligomer polyol/polyamine has less than 3 (on average) hydroxyl groups and/or amine groups that can react with the polyisocyanate.
- the oligomer part (R 3 ) comprises one or more polyether oligomers, one or more polyolefin oligomers, a copolymer thereof, or mixtures thereof. If more than one polyether or polyolefin, or a mixture of a polyether and a polyolefin, are used to form the oligomer part R 3 , they can be linked, for example, via urethane and/or urea linkages. In such a case, the oligomer part R 3 can be formed before combining with R 1 , R 2 , and polyisocyanate, or can be formed in situ when the urethane oligomer is formed.
- the oligomer polyol/polyamine preferably has a molecular weight of more than about 200, more preferably higher than 250, more preferably higher than 400, and most preferably higher than 500.
- Molecular weight is the calculated molecular weight of the molecule concerned. In case of a polymer structure, it is the calculated molecular weight of the expected structure, based on the starting materials and reaction conditions. The molecular weight can also be determined using conventional techniques.
- the equivalent weight of the urethane oligomer (based on acrylate) is preferably less than about 5,000, and more preferably less than about 2,500.
- the backbone of the urethane oligomer can comprise one or more polymer blocks coupled with each other via urethane and/or urea linkages.
- the use of a polyether as the backbone has the advantage that it results in coatings having a low glass transition temperature and good mechanical properties such as tensile strength and modulus, and good resistance to oil. If the backbone is a polyolefin, the resulting coatings have further improved resistance against water absorption.
- the polyether can be, for example, a substantially non-crystalline polyether or aliphatic polyether.
- the polyether comprising repeating units of one or more of the following monomer groups: -0-CH 2 -CH 2 -0-; -0-CH 2 -CH-0-; -0-CH 2 -CH 2 -CH 2 -0-; CH 3 -0-CH 2 -CH 2 -CH 2 -CH 2 -0- ; -0-CH 2 -CH-CH 2 -CH 2 -0- ,
- the polyether is made from, for example, ethylene oxide, propylene oxide, tetrahydrofuran, methyl- substituted tetrahydrofuran, 1,2-epoxybutane, and the like.
- a polyether that can be used is a polyether containing both branched and non-branched oxyalkylene repeating units, which is the polymerization product of 20 percent by weight of 3-methyltetrahydrofuran and 80 percent by weight of tetrahydrofuran, both of which have undergone a ring opening polymerization.
- This polyether copolymer is marketed as PTG-L 1000 (Hodogaya Chemical Company of Japan).
- polyether that can be used is PTG-L 2000 (Hodogaya Chemical Company of Japan) .
- oligomer polyol/polyamine include, for example, the following polyether polyols: Arcol PPG-1025, Pluracol P-2010 (BASF), Poly THF-1000 and Poly THF-2000 (BASF), BO and PO polyols from Dow Chemical, and Terathane 2000 from DuPont.
- examples of the oligomer polyol/polyamine include, for example, polyoxyalkyleneamines, such as, polyethyleneglycol diamine and polypropyleneglycol diamine, which are commercially available under the trade name Jeffamine (Texaco).
- the polyolefin used as the backbone of the oligomer polyol can be, for example, a linear or branched hydrocarbon containing a plurality of hydroxyl end groups.
- Hydrocarbon is used herein to represent a non-aromatic or aliphatic compound containing a majority of methylene groups (-CH 2 -) and which can contain internal unsaturation and/or pendent unsaturation. Fully saturated, for example, hydrogenated, hydrocarbons are preferred because the long term stability of the cured optical fiber coating increases as the degree of unsaturation decreases.
- Hydrocarbon polyols include, for example, hydroxyl- terminated, fully or partially hydrogenated 1,2- polybutadiene; 1,4- 1,2-polybutadiene copolymers, 1,2- polybutadiene-ethylene or -propylene copolymers, polyisobutylene polyol, mixtures thereof, and the like.
- the hydrocarbon polyol is a substantially fully hydrogenated 1,2-polybutadiene or 1,2-polybutadiene- ethene copolymer.
- the oligomer polyol/polyamine preferably comprises at least one polyolefin oligomer.
- Block copolymers of polyethers and polyolefins can also be used.
- mixtures of oligomer polyol/polyamines can be used as well.
- mixtures of polyether polyol/polyamines and polyolefin polyol/polyamines are used.
- Known processes of producing urethane oligomers in general can be used to produce the urethane oligomer. However, the process of making the urethane oligomer preferably proceeds as follows.
- a hydroxy functional ethylenically unsaturated monomer which can be the reactive terminus R 1 , and polyisocyanate
- a stoichiometric balance between hydroxy functionality and the polyisocyanate is used and the reactants are maintained at a reaction temperature of below about 40'C.
- the hydroxy functionality will then be substantially consumed.
- the mole ratio of the isocyanate groups to the hydroxy groups of the ethylenically unsaturated monomer is preferably in the range of about 2:1 to about 1.2:1, and more preferably about 1.5:1.
- the hydroxy functional ethylenically unsaturated monomer attaches to the isocyanate via an urethane linkage.
- the reaction product of the isocyanate and the ethylenically unsaturated monomer is further reacted with the oligomer polyol/polyamine, preferably in a molar ratio between about 1.8:1 to about 2.0:1 if the oligomer polyol/polyamine has only two groups selected from hydroxyl groups and amine groups. If the oligomer polyol/polyamine has a higher or lower (average) hydroxyl/amine functionality, the molar ratio is preferably proportionally higher or lower.
- End-capped is used herein to represent that a functional group caps the ends of the oligomer polyol/polyamine.
- the mole ratio of isocyanate should be increased by one mole of isocyanate reactive groups for each mole of urethane and/or urea linkages required to link the polymer blocks. For example, if 1 mole of polyether diol, 1 mole of a polyolefin diol and 2 moles of hydroxy functional ethylenically unsaturated monomer are to be reacted, about 3 moles of diisocyanate would be required.
- a significant amount of aliphatic polyisocyanate can be used as long as the amount of aromatic polyisocyanate is sufficient to result in a coating having a refractive index sufficiently high to refract errant signals escaping from a glass fiber away from the glass fiber.
- the coating composition preferably comprises at least about 1 weight %, preferably at least about 6 weight % aromatic groups originating from the polyisocyanate.
- aromatic diisocyanate such as TMXDI
- aliphatic diisocyanate can be used.
- the aromatic diisocyanate can be specifically used to connect the polyether blocks, or to connect the hydroxy ethylacrylate to the oligomer, or the two diisocyanates can be used at random.
- the urethane and urea reactions can take place in the presence of a catalyst.
- catalysts that can be used include dibutyltin dilaurate, diazabicyclooctane crystals, and the like.
- the coating composition comprises one or more reactive diluents (B).
- the coating composition comprises a mixture of (B-l) a reactive diluent which is terminated with one end group capable of reacting with the reactive terminus of, and (B-2) a multifunctional diluent which is terminated with at least two end groups capable of reacting with the reactive terminus of.
- reactive diluent (B-l) is present, preferably it is present in an amount of more than about 5 wt.% and less than about 60 wt.%, more preferably less than 45 wt.%.
- Reactive diluent (B-l) can be a mixture of diluents as explained below.
- reactive diluent (B-2) is present, preferably it is present in an amount of more than about 5 wt.% and less than about 35 wt.%, more preferably less than 25 wt.%.
- Reactive diluent (B-2) can be a mixture of multifunctional diluents.
- the reactive diluents can be used in the coating compositions to lower the viscosity and/or to provide required properties, such as hardness.
- Reactive diluents preferably have a molecular weight of less than about 550 or a viscosity at room temperature of less than about 300 mPas.s (measured as 100% diluent).
- the reactive diluent B-l preferably comprises a monomer having an acrylate or vinyl ether functionality and an C 4 -C 20 alkyl or polyether moiety.
- monomer diluents are hexylacrylate, 2-ethylhexylacrylate, isobornylacrylate, isodecylacrylate, laurylacrylate, stearylacrylate, ethoxyethoxyethylacrylate, laurylvinylether, 2-ethylhexylvinyl ether, and the like.
- This type of reactive diluent preferably is present in an amount between about 1 and about 35 wt.%.
- the reactive diluent B-l can also be a compound comprising an aromatic group.
- Conventional coating compositions use an aromatic moiety to adjust the refractive index of the coating composition to a value above 1.48, which is important if the coating is used as an inner primary optical fiber coating.
- aromatic moieties are not necessary, because the refractive index is already high enough to refract errant signals escaping from a glass fiber away from the glass fiber. Nevertheless, the use of this type of compound might be useful to enhance the compatibility of the several coating constituents.
- a diluent having an aromatic group examples include: ethyleneglycolphenyletheraerylate, polyethyleneglycolphenyletheracrylate, polypropyleneglycolphenyletheracrylate, and alkyl- substituted phenyl derivatives of the above examplary monomers, such as polyethyleneglycolnonyl- phenyletheracrylate.
- This type of reactive diluent preferably is present in an amount between about 1 and about 35 wt.%, and more preferably in an amount of less than 10 wt.%.
- Reactive diluent B-2 preferably is a diluent having two groups capable of polymerization using actinic radiation.
- a diluent having three or more of such reactive groups can be present as well.
- Examples of such diluents are C 2 -C 18 hydrocarbondiol-diacrylates, C 4 -C l ⁇ hydrocarbon- divinylethers, C 3 -C 18 hydrocarbon triacrylates, and the polyether analogues thereof: such as 1,6- hexanedioldiacrylate, trimethylolpropanetriacrylate, hexanedioldivinylether, triethyleneglycoldiacrylate, pentaerythritoltriacrylate, ethoxylated bisphenol-A diacrylate, and tripropyleneglycol diacrylate.
- the coating compositions can further comprise: (C) 0.1-10 % by weight of ne or more photoinitiators.
- the photoinitiator can be useful when ultraviolet radiation is used to cure the coating composition.
- a photoinitiator is typically not useful in other embodiments, for example, when electron beam cure of a free radical system is used . In cationally cured systems, however, a photoinitiator can be useful even when an electron beam cure is used.
- the photoinitiator when used in a small but effective amount to promote radiation cure, must provide reasonable cure speed without causing premature gelation of the composition.
- the cure speed desired will depend on the application of the coating and a skilled artisan will easily be able to adjust the amount and type of photoinitiator to obtain the desired cure speed.
- the type of photoinitiator which is used will be dependent on whether a free radical-type system or a cationic cure type-system is used, and a person of ordinary skill in the art will easily understand what type of photinitiator to use.
- Free radical-type photoinitiators include, for example: hydroxycyclohexylphenyl ketone; hydroxymethylphenylpropanone; dimethoxyphenylacetophenone; 2-methyl-l-[4-(methyl thio)-phenyl]-2-morpholino- propanone-1; l-(4-isopropylphenyl)-2-hydroxy-2- methylpropan-1-one; 1-(4-dodecyl-phenyl)-2-hydroxy-2- methylpropan-1-one; 4-(2-hydroxyethoxy)phenyl-2(2-hydroxy- 2-propyl)-ketone; diethoxyphenyl acetophenone; 2,4,6 trimethylbenzoyl diphenylphosphineoxide, a mixture of (2,6-dimethoxy benzoyl)-2,4,4 trimethylpentylphosphineoxide and 2-hydroxy-2-methyl-l- phenyl-propan-1-one, and mixtures of these.
- Cationic cure-type photoinitiators include, for example: aromatic onium salts such as iodonium, sulfonium, arsonium, azonium, bromonium, or selenonium, which are preferably chemically modified to render them more hydrophobic, for example, by incorporating saturated hydrocarbon moieties such as alkyl or alkoxy substituents of from about 4 to about 18 carbon atoms.
- aromatic onium salts such as iodonium, sulfonium, arsonium, azonium, bromonium, or selenonium, which are preferably chemically modified to render them more hydrophobic, for example, by incorporating saturated hydrocarbon moieties such as alkyl or alkoxy substituents of from about 4 to about 18 carbon atoms.
- Particularly preferred cationic cure initiators include, for example, (4-octyloxyphenyl) phenyl iodonium hexafluoro antimonate; (4- octyloxyphenyl) diphenyl sulfonium hexafluoro antimonate; (4-decyloxyphenyl) phenyl iodonium hexafluoro antimonate; (4-octyloxyphenyl) phenyl iodonium hexafluoro phosphate; and (4-octadecyloxyphenyl) phenyl iodonium hexafluoro antimonate.
- antioxidants include stabilizers and adhesion promotors.
- As an antioxidant one or more of the following compounds can be used, for example: thiobisphenols, alkylidene- bisphenols, alkyl phenols, hydroxybenzyl compounds, phoshpites, phosphonites, and amines.
- General trade names include Irganox, Naugard, Ultranox and Santoflex. Some common ones that are used are Irganox 1035 and Irganox 245.
- organofunctional alkoxysilanes can be used, for example, ⁇ -mercaptopropyltrimethoxysilane, vinyltrimethoxyether , silane, methacryloxy propyltrimethoxy silane, and the like.
- compositions include, lubricants, and wetting agents.
- a liquid coating composition can be applied to a substrate and subsequently cured.
- the cure can be conducted using ultraviolet or visible radiation.
- the coating can also be cured by electron beam irradiation without using a catalyst.
- More than one coating can be applied. For example, a first coating can be applied and cured followed by a second coating, and so on until the desired number of coatings have been applied.
- the layers can be applied on top of each other as liquids, a wet-on-wet process, with one final curing step at the end.
- the coating compositions described herein can be used to provide underlying coatings, including the inner primary coating, which can be relatively soft in comparison to the outermost coating.
- the coating compositions described herein can also be used to provide an outermost layer (outer primary layer) that is tough or hard that can protect the optical fiber and underlying coatings.
- the coatings can be made sufficiently tough, for example, by reducing the molecular weight of the urethane oligomer, and/or increasing the amount of cross-link density by using polyfunctional diluents, such as, hexanediol diacrylate, tripropyleneglycol diacrylate, and trimethylolpropane triacrylate.
- polyfunctional diluents such as, hexanediol diacrylate, tripropyleneglycol diacrylate, and trimethylolpropane triacrylate.
- the coatings provide sufficient adhesion to optical fibers and which is easily removed or stripped as a unit without leaving significant coating residue on the so stripped glass fiber.
- TXDI 2,3,5,6 tetramethylene-( ⁇ - ⁇ ')xylenediisocyanate
- DBTDL dibutyltin dilaurate
- BHT butylated hydroxytoluene
- the oligomer prepared in example I was mixed with the components as shown in Table 1.
- CGI-1700 is a photoinitiator produced by Ciba Geigy.
- Irganox 245 is a stabilizer produced by Ciba-Geigy.
- Table 2 shows the properties of the liquid and cured coating compositions.
- the water soak extraction and absorption were measured using the following procedure.
- a drawdown of each material to be tested was made at a film thickness of about 150 microns (6 mils) on a glass plate and cured.
- the cured film was cut to form three sample specimens, approximately 3 cm x 3 cm (1- 5 inches x 1J$ inches), on the glass plate.
- the glass plate containing the three sample specimens was heated at 60°C for one hour and then placed in a desiccator for 15 minutes.
- 125 ml (4 oz.) of deionized or distilled water was poured into three 125 ml (4 oz.) glass jars, maintained at a temperature of 23 + . 2°C.
- Each of the sample specimens were removed from the glass plate and weighed on an analytical balance using corrugated Teflon paper to prevent sticking. Each sample specimen was then placed into one of the jars of water.
- sample specimens were soaked in the water for 30 minutes and then removed from the glass jars. The water remaining on the surface of the sample specimens was removed by blotting them with lint free wiping tissue.
- sample specimens were removed from the glass jars and reweighed as above.
- the sample specimens were placed onto a glass plate and heated at 60°C for one hour, and then placed in a desiccator for 15 minutes. The sample specimens were reweighed as before.
- the percent weight change at each time interval for each sample specimen was determined. The values for the three sample specimens at each time interval were averaged. The water absorption reported is the largest, positive average percent weight change.
- the water extraction for each sample specimen was determined by dividing the difference of the initial and 21-day dried weights by the initial dried weight and multiplying by 100. The reported value is the average of the three sample specimen values.
- the total water sensitivity is the sum of the absolute values of the water absorption and the water extraction.
- test samples were prepared by casting a film of the material, having a thickness in the range of 0.02 mm to 0.4 mm, on a glass plate.
- the sample film was cured using a UV processor.
- a specimen approximately 35 mm (1.4 inches) long and approximately 12 mm wide was cut from a defect-free region of the cured film.
- a cotton-tipped applicator was used to coat the cut specimen with talc powder.
- the film thickness of the specimen was measured at five or more locations along the length. The average film thickness was calculated to ⁇ 0.001 mm. The thickness cannot vary by more than 0.01 mm over this length. Another specimen was taken if this condition was not met. The width of the specimen was measured at two or more locations and the average value calculated to ⁇ 0.1 mm.
- the geometry of the sample was entered into the instrument.
- the length field was set at a value of 23.2 mm and the measured values of width and thickness of the sample specimen were entered into the appropriate fields.
- the temperature sweep used included cooling the test samples to about -60°C or about -80°C and increasing the temperature at about l°/minute until the temperature reached about 60°C to about 70°C.
- the test frequency used was 1.0 radian/second.
- the test material was applied to the glass plates and cured using a UV processor. The thickness of the cured film was about 75 microns. The cured films were held at 50 % relative humidity, at about 23°C, for seven days prior to testing. Prior to removing the plates from the environmental chamber, a layer of slurry (fine powdered polyethylene and water) was applied to the surface of the drawdown to retain the moisture.
- slurry fine powdered polyethylene and water
- Test specimens approximately 1 inch in width and 5 inches long, were cut parallel to the direction in which the drawdown of the cured film was prepared. A thin layer of talc was applied to the first and third strips on each drawdown to reduce blocking during the adhesion test. The instrument was calibrated prior to testing. The crosshead speed was set to 10.00 inch/min. For each material, the force required to remove four test specimens from the glass plate was measured and recorded on a strip chart recorder. The value reported is the average of the four measured values. The test specimens remaining on the glass plate were then held at 95% relative humidity, at about 23°C, in an environmental chamber for 1 more day. Prior to removing the plates from the environmental chamber, a layer of slurry (fine powdered polyethylene and water) was applied to the surface of the drawdown to retain the moisture. For each material, the force to remove four test specimens from the glass plate was measured as above.
- the tensile strength of cured samples was tested using a universal testing instrument, Instron Model 4201 equipped with a personal computer and software "Series IX Materials Testing System.”
- the load cells used were 2 and 20 pound capacity.
- the ASTM D638M was followed, with the following modifications.
- a drawdown of each material to be tested was made on a glass plate and cured using a UV processor.
- the cured film was conditioned at 23 ⁇ 2°C and 50 + . 5% relative humidity for a minimum of sixteen hours prior to testing.
- test specimens having a width of .5+. 0.002 inches and a length of 5 inches, were cut from the cured film. To minimize the effects of minor sample defects, sample specimens were cut parallel to the direction in which the drawdown of the cured film was prepared. If the cured film was tacky to the touch, a small amount of talc was applied to the film surface using a cotton tipped applicator. The test specimens were then removed from the substrate. Caution was exercised so that the test specimens were not stretched past their elastic limit during the removal from the substrate. If any noticeable change in sample length had taken place during removal from the substrate, the test specimen was discarded.
- top surface of the film was talc coated to eliminate tackiness, then a small amount of talc was applied to the bottom surface of test specimen after removal from the substrate.
- the average film thickness of the test specimens was determined. At least five measurements of film thickness were made in the area to be tested (from top to bottom) and the average value used for calculations. If any of the measured values of film thickness deviates from the average by more than 10% relative, the test specimen was discarded. All specimens came from the same plate.
- the appropriate load cell was determined by using the following equation:
- the crosshead speed was set to 1.00 inch/min, and the crosshead action was set to "return at break”.
- the crosshead was adjusted to 2.00 inches jaw separation.
- the air pressure for the pneumatic grips was turned on and adjusted as follows: set approximately 20 psi(1.5 Kg/cm 2 ) for primary optical fiber coatings and other very soft coatings; set approximately 40 psi(3Kg/cm 2 ) for optical fiber single coats; and set approximately 60 psi (4.5 Kg/cm 2 ) for secondary optical fiber coatings and other hard coatings.
- the temperature near the Instron Instrument was measured and the humidity was measured at the location of the humidity gage. This was done just before beginning measurement of the first test specimen.
- Specimens were only analyzed if the temperature was within the range 23 ⁇ 1.0°C and the relative humidity was within 50 ⁇ 5%. The temperature was verified as being within this range for each test specimen. The humidity value was verified only at the beginning and the end of testing a set of specimens from one plate.
- test specimen was tested by suspending it into the space between the upper pneumatic grips such that the test specimen was centered laterally and hanging vertically. Only the upper grip was locked. The lower end of the test specimen was pulled gently so that it has no slack or buckling, and it was centered laterally in the space between the open lower grips. While holding the specimen in this position, the lower grip was locked. The sample number was entered and sample dimensions into the data system, following the instructions provided by the software package.
- the temperature and humidity were measured after the last test specimen from the current drawdown was tested.
- the values for tensile strength, % elongation, and (secant or segment) modulus were checked to determine whether any one of them deviated from the average enough to be an "outlier.” If the modulus value was an outlier, it was discarded. If there were less than six data values for the tensile strength, then the entire data set was discarded and repeated using a new plate.
- the hexane absorption was measured in the same manner as the water absorption above, except that hexane was substituted for water and the samples were soaked in the hexane only for 1 day.
- the hexane extractables was measured in the same as the water extractables except that hexane was substituted for water and the time intervals for measuring the weight of the sample were 15 minutes, 30 minutes, 1 hour, 2 hours, 6 hours, and 24 hours. The weight change in percent of the samples were measured over each time interval. The hexane extractables reported was the highest weight change in percent.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8518624A JPH10510237A (en) | 1994-11-29 | 1995-11-29 | Radiation curable coating composition and coating |
AU38831/95A AU691356B2 (en) | 1994-11-29 | 1995-11-29 | Radiation-curable coating composition and coating |
DE69507335T DE69507335T2 (en) | 1994-11-29 | 1995-11-29 | OPTICAL FIBERGLASS COATED WITH A RADIATION-CURABLE COATING COMPOSITION |
EP95938063A EP0794971B1 (en) | 1994-11-29 | 1995-11-29 | Optical glass fiber coated with a radiation-curable coating composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US34818794A | 1994-11-29 | 1994-11-29 | |
US08/348,187 | 1994-11-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996017000A1 true WO1996017000A1 (en) | 1996-06-06 |
Family
ID=23366961
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL1995/000406 WO1996017000A1 (en) | 1994-11-29 | 1995-11-29 | Radiation-curable coating composition and coating |
Country Status (7)
Country | Link |
---|---|
US (1) | US5907023A (en) |
EP (1) | EP0794971B1 (en) |
JP (1) | JPH10510237A (en) |
AU (1) | AU691356B2 (en) |
CA (1) | CA2206120A1 (en) |
DE (1) | DE69507335T2 (en) |
WO (1) | WO1996017000A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999008975A1 (en) * | 1997-08-15 | 1999-02-25 | Dsm N.V. | Radiation-curable resin composition |
WO2000064831A1 (en) * | 1999-04-23 | 2000-11-02 | Dsm N.V. | Liquid curable resin composition and cured products |
US6579618B1 (en) | 1997-08-15 | 2003-06-17 | Dsm N.V. | Coated optical fiber and radiation curable resin composition |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6066436A (en) * | 1996-09-09 | 2000-05-23 | Polyfibron Technologies, Inc. | Aqueous developable photosensitive polyurethane-methacrylate |
AU4969697A (en) * | 1996-11-08 | 1998-06-03 | Dsm N.V. | Radiation-curable optical glass fiber coating compositions, coated optical glass fibers, and optical glass fiber assemblies |
US6144795A (en) * | 1996-12-13 | 2000-11-07 | Corning Incorporated | Hybrid organic-inorganic planar optical waveguide device |
WO1998041484A1 (en) * | 1997-03-18 | 1998-09-24 | Dsm N.V. | Method for curing optical fiber coatings and inks by low power electron beam radiation |
US20060193278A1 (en) * | 1997-10-15 | 2006-08-31 | Wolfgang Theimer | Mobile telephone for Internet applications |
JPH11231524A (en) * | 1998-02-17 | 1999-08-27 | Jsr Corp | Production of plasma display panel |
US6110593A (en) * | 1998-05-21 | 2000-08-29 | Dsm N.V. | Radiation-curable optical fiber primary coating system |
US6204304B1 (en) * | 1998-09-28 | 2001-03-20 | Lucent Technologies Inc. | Vinyl ether-based optical fiber coatings |
US6215931B1 (en) * | 1999-01-26 | 2001-04-10 | Alcatel | Flexible thermoplastic polyolefin elastomers for buffering transmission elements in a telecommunications cable |
US6326416B1 (en) * | 1999-04-29 | 2001-12-04 | Corning Incorporated | Coating composition for optical fibers |
US6316516B1 (en) * | 1999-04-29 | 2001-11-13 | Corning Incorporated | Coating composition for optical fibers |
WO2000069941A1 (en) * | 1999-05-14 | 2000-11-23 | Dsm N.V. | Process for preparing uniformly consistent radiation-curable compositions |
US6759121B2 (en) | 2000-07-13 | 2004-07-06 | 3M Innovative Properties Company | Clear adhesive sheet |
US6472065B1 (en) | 2000-07-13 | 2002-10-29 | 3M Innovative Properties Company | Clear adhesive sheet |
US6579914B1 (en) | 2000-07-14 | 2003-06-17 | Alcatel | Coating compositions for optical waveguides and optical waveguides coated therewith |
EP1358276A2 (en) * | 2001-01-12 | 2003-11-05 | DSM IP Assets B.V. | Radiation-curable composition and products coated therewith |
US7068902B2 (en) * | 2001-08-17 | 2006-06-27 | Alcatel | Radiation-curable coating composition for optical fibers comprising all-in-one oligomeric system |
JP2005504698A (en) * | 2001-09-07 | 2005-02-17 | ボーデン ケミカル インコーポレイテッド | Coated optical fiber using adhesion promoter, method for producing and using the same |
US6864019B2 (en) * | 2002-06-27 | 2005-03-08 | Imation Corp. | Recording material formulations for holographic media |
JP2006249264A (en) * | 2005-03-11 | 2006-09-21 | Jsr Corp | Liquid curable resin composition |
CN101426853A (en) * | 2006-04-20 | 2009-05-06 | 米德韦斯瓦科公司 | Compositions for carton sealing |
EP2267050A1 (en) * | 2009-05-19 | 2010-12-29 | Cytec Surface Specialties, S.A. | Radiation Curable Compositions |
KR101362615B1 (en) | 2009-12-17 | 2014-02-12 | 디에스엠 아이피 어셋츠 비.브이. | Led curing of radiation curable optical fiber coating compositions |
US20180127593A1 (en) * | 2016-11-08 | 2018-05-10 | Corning Incorporated | Fiber coatings with low modulus and high critical stress |
JP2019007992A (en) * | 2017-06-20 | 2019-01-17 | 住友電気工業株式会社 | Optical fiber and optical fiber ribbon |
CN115521452B (en) * | 2022-05-23 | 2024-02-02 | 武汉中科先进材料科技有限公司 | Photo-curing oligomer, preparation method thereof and photo-curing coating containing photo-curing oligomer |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2115373A1 (en) * | 1970-03-30 | 1971-10-21 | Dainippon Ink & Chemicals | Photosensitive composition |
US3850770A (en) * | 1969-10-24 | 1974-11-26 | Kansai Paint Co Ltd | Radiation curable compositions from acrylurethane resins |
US3954584A (en) * | 1973-06-20 | 1976-05-04 | Kansai Paint Company | Photopolymerizable vinylurethane liquid composition |
EP0200366A1 (en) * | 1985-03-29 | 1986-11-05 | Nippon Telegraph And Telephone Corporation | UV-Ray curable resin composition and coated optical fiber |
US4844604A (en) * | 1987-11-13 | 1989-07-04 | Desoto, Inc. | Optical fiber bundling material and bundled optical fibers |
EP0423713A2 (en) * | 1989-10-18 | 1991-04-24 | Takeda Chemical Industries, Ltd. | Photocurable adhesive and production of laminated articles using the same |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60251152A (en) * | 1984-05-26 | 1985-12-11 | Nitto Electric Ind Co Ltd | Coating material for optical glass fiber |
JP2627626B2 (en) * | 1987-10-20 | 1997-07-09 | 日本合成ゴム株式会社 | Composition for optical fiber coating |
US4943600A (en) * | 1989-03-10 | 1990-07-24 | Desoto, Inc. | Photocurable polyamine-ene compositions having improved cure speed |
US5139872A (en) * | 1990-08-29 | 1992-08-18 | Allied-Signal Inc. | Vinyl ether based optical fiber coatings |
GB9121655D0 (en) * | 1991-10-11 | 1991-11-27 | Ici Plc | Optical fibre coating |
CA2082614A1 (en) * | 1992-04-24 | 1993-10-25 | Paul J. Shustack | Organic solvent and water resistant, thermally, oxidatively and hydrolytically stable radiation-curable coatings for optical fibers, optical fibers coated therewith and processes for making same |
JPH06211960A (en) * | 1993-01-14 | 1994-08-02 | Daiso Co Ltd | Polymerizable composition and high refractive index plastic lens obtained therefrom |
-
1995
- 1995-11-29 CA CA002206120A patent/CA2206120A1/en not_active Abandoned
- 1995-11-29 EP EP95938063A patent/EP0794971B1/en not_active Expired - Lifetime
- 1995-11-29 DE DE69507335T patent/DE69507335T2/en not_active Expired - Fee Related
- 1995-11-29 WO PCT/NL1995/000406 patent/WO1996017000A1/en active IP Right Grant
- 1995-11-29 JP JP8518624A patent/JPH10510237A/en active Pending
- 1995-11-29 AU AU38831/95A patent/AU691356B2/en not_active Ceased
-
1997
- 1997-06-16 US US08/876,295 patent/US5907023A/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3850770A (en) * | 1969-10-24 | 1974-11-26 | Kansai Paint Co Ltd | Radiation curable compositions from acrylurethane resins |
DE2115373A1 (en) * | 1970-03-30 | 1971-10-21 | Dainippon Ink & Chemicals | Photosensitive composition |
US3954584A (en) * | 1973-06-20 | 1976-05-04 | Kansai Paint Company | Photopolymerizable vinylurethane liquid composition |
EP0200366A1 (en) * | 1985-03-29 | 1986-11-05 | Nippon Telegraph And Telephone Corporation | UV-Ray curable resin composition and coated optical fiber |
US4844604A (en) * | 1987-11-13 | 1989-07-04 | Desoto, Inc. | Optical fiber bundling material and bundled optical fibers |
EP0423713A2 (en) * | 1989-10-18 | 1991-04-24 | Takeda Chemical Industries, Ltd. | Photocurable adhesive and production of laminated articles using the same |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999008975A1 (en) * | 1997-08-15 | 1999-02-25 | Dsm N.V. | Radiation-curable resin composition |
US6579618B1 (en) | 1997-08-15 | 2003-06-17 | Dsm N.V. | Coated optical fiber and radiation curable resin composition |
WO2000064831A1 (en) * | 1999-04-23 | 2000-11-02 | Dsm N.V. | Liquid curable resin composition and cured products |
US8367204B2 (en) | 1999-04-23 | 2013-02-05 | Dsm Ip Assets B.V. | Liquid curable resin composition and cured products |
Also Published As
Publication number | Publication date |
---|---|
JPH10510237A (en) | 1998-10-06 |
AU691356B2 (en) | 1998-05-14 |
AU3883195A (en) | 1996-06-19 |
US5907023A (en) | 1999-05-25 |
DE69507335T2 (en) | 1999-09-09 |
CA2206120A1 (en) | 1996-06-06 |
EP0794971B1 (en) | 1999-01-13 |
DE69507335D1 (en) | 1999-02-25 |
EP0794971A1 (en) | 1997-09-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU691356B2 (en) | Radiation-curable coating composition and coating | |
AU691678B2 (en) | Silane oligomer and radiation curable coating composition containing the oligomer | |
EP0815063B1 (en) | Glass optical fiber coated with radiation curable coating composition | |
US6107361A (en) | Solvent-free, radiation-curable, optical glass fiber coating composition and solvent-free method for making a solvent-free, radiation-curable, optical glass fiber coating composition | |
US6852770B2 (en) | Radiation-curable composition and products coated therewith | |
EP1172391B9 (en) | Coated optical waveguides | |
EP1497239A2 (en) | Coated optical fibers | |
US6472450B2 (en) | Radiation-curable optical fiber coating composition | |
EP1349898B1 (en) | Radiation curable compositions comprising alkoxylated aliphatic reactive diluents | |
CA2215236C (en) | Radiation curable optical fiber coating composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU CA JP |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1995938063 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2206120 Country of ref document: CA Ref country code: CA Ref document number: 2206120 Kind code of ref document: A Format of ref document f/p: F |
|
WWP | Wipo information: published in national office |
Ref document number: 1995938063 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1995938063 Country of ref document: EP |