WO2001083393A2 - Composition de resine liquide durcissable pour fibres optiques - Google Patents

Composition de resine liquide durcissable pour fibres optiques Download PDF

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Publication number
WO2001083393A2
WO2001083393A2 PCT/NL2001/000321 NL0100321W WO0183393A2 WO 2001083393 A2 WO2001083393 A2 WO 2001083393A2 NL 0100321 W NL0100321 W NL 0100321W WO 0183393 A2 WO0183393 A2 WO 0183393A2
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
resin composition
curable resin
liquid curable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NL2001/000321
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English (en)
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WO2001083393A3 (fr
Inventor
Masahito Mase
Hitomi Nomiyama
Junji Yoshizawa
Zen Komiya
Takashi Ukachi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSR Corp
Koninklijke DSM NV
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JSR Corp
DSM NV
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Publication date
Application filed by JSR Corp, DSM NV filed Critical JSR Corp
Priority to AU2001250679A priority Critical patent/AU2001250679A1/en
Publication of WO2001083393A2 publication Critical patent/WO2001083393A2/fr
Publication of WO2001083393A3 publication Critical patent/WO2001083393A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates

Definitions

  • the present invention relates to a liquid curable resin composition exhibiting excellent light resistance, suitable as a coating material for optical fibers, optical fiber ribbons, and the like, and to a cured product thereof.
  • a resin coating is applied for protection and reinforcement over glass fiber produced by spinning molten glass.
  • a structure consisting of a primary flexible coating layer formed on the surface of optical fiber and a secondary rigid coating layer applied thereon is known.
  • Optical fiber ribbons in which a number of optical fibers provided with a resin coating are bundled side by side in a plane using a bundling material are also well known.
  • a resin composition for forming the primary coating layer is called a primary material
  • a resin composition for forming the secondary coating layer is called a secondary material
  • a resin composition used for the bundling material for optical fiber ribbons is called a ribbon matrix material.
  • a method of applying these resins a method of applying a liquid curable resin composition and then curing the composition using heat or light, in particular, ultraviolet rays has been widely used.
  • coating materials used therefor must exhibit only a slight change in characteristics over a long period of time.
  • Coated optical fibers and optical fiber ribbons are often stored before and after shipment in a warehouse under fluorescent light. This causes the color of the coating materials to become yellowish during storage. The cause of such a change in color is considered to be related to the presence of the hindered phenol-type antioxidant which is added to ensure heat stability of the cured product. However, antioxidants which do not impair the color stability have not yet been known.
  • An object of the present invention is to provide a liquid curable resin composition for optical fibers of which the cured product exhibits excellent heat stability when used as a coating material for optical fibers or optical fiber ribbons and small changes in color when stored under fluorescent light.
  • a further object of the invention is to provide coated optical fibers and ribbon structures having at least one coating that exhibits excellent heat stability and small change in color when stored under fluorescent light, as these products are particularly useful in the industry.
  • a liquid curable resin composition of which the cured product exhibits heat stability and color stability under fluorescent light can be obtained by combining a urethane (meth)acrylate oligomer, an unsaturated polymerizable compound, a photoinitiator, and a suitable antioxidant. This finding has led to the completion of the present invention.
  • the present invention provides coated optical fibers and ribbon structures having at least one coating layer, which coating before before curing is comprising (A) a urethane (meth)acrylate oligomer comprising a polyether backbone (B) an unsaturated polymerizable compound, (C) a photoinitiator and an antioxidant (D) in which the cured composition as a 200 ⁇ m thick film exhibits a yellowing index after five days exposure of less than 5, and a Youngs modulus retention rate of more than 70% after aging for 30 days at 100°C.
  • A a urethane (meth)acrylate oligomer comprising a polyether backbone
  • B an unsaturated polymerizable compound
  • C a photoinitiator and an antioxidant
  • D in which the cured composition as a 200 ⁇ m thick film exhibits a yellowing index after five days exposure of less than 5, and a Youngs modulus retention rate of more than 70% after aging for 30 days at 100°C.
  • the present invention provides a liquid curable resin composition
  • a liquid curable resin composition comprising (A) a urethane (meth)acrylate oligomer, (B) an unsaturated polymerizable compound, (C) a photoinitiator, and (D) a compound shown by the following formula (1),
  • R a represents a hydrogen atom or an alkyl group having 1-4 carbon atoms and R b and R° individually represent alkyl groups having 1-12 carbon atoms, or 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methyIphenyl acrylate, and a cured product obtained by photocuring the composition.
  • R a represents a hydrogen atom or an alkyl group having 1-4 carbon atoms and R b and R° individually represent alkyl groups having 1-12 carbon atoms, or 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methyIphenyl acrylate, and a cured product obtained by photocuring the composition.
  • the urethane (meth) acrylate (A) used in the present invention is produced by reacting a polyol, diisocyanate, and (meth)acrylate containing a hydroxyl group.
  • the urethane (meth)acrylate (A) is produced by reacting isocyanate groups of a diisocyanate with hydroxyl groups of a polyol and a (meth)acrylate containing a hydroxyl group.
  • the polyol is generally denoted as constituting the backbone of the urethane oligomer.
  • the polyol is e.g. a polyether diol
  • the urethane oligomer is said to comprise a polyether backbone.
  • a method of reacting these compounds a method of reacting a polyol, diisocyanate, and (meth)acrylate containing a hydroxyl group all together; a method of reacting a polyol with a diisocyanate, and then reacting the resulting product with a (meth)acrylate containing a hydroxyl group; a method of reacting a diisocyanate with a (meth)acrylate containing a hydroxyl group, and then reacting the resulting product with a polyol; a method of reacting a diisocyanate with a (meth)acrylate containing a hydroxyl group, reacting the resulting product with a polyol, and further reacting the resulting product with a (meth)acrylate containing a hydroxyl group; and the like can be given.
  • polyether diols obtained by ring-opening polymerization of one ion-polymerizable cyclic compound such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, and polydecamethylene glycol
  • polyether diols obtained by ring-opening copolymerization of two or more ion-polymerizable cyclic compounds and the like.
  • cyclic ethers such as ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, oxetane, 3,3-dimethyloxetane, 3,3-bischloromethyloxetane, tetrahydrofuran, 2- methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyloxetane, vinyltetrahydrofuran, vinylcyclohexene oxide, phenyl glycidyl ether, butyl g
  • Polyether diols obtained by ring-opening copolymerization of these ion-polymerizable cyclic compounds and cyclic imines such as ethyleneimine, cyclic lactonic acids such as ⁇ - propyolactone and glycolic acid lactide, or dimethylcyclopolysiloxanes can also be used.
  • ion-polymerizable cyclic compounds examples include combinations of tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3- methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1 -oxide and ethylene oxide, a ternary copolymer of tetrahydrofuran, butene-1-oxide, and ethylene oxide, and the like can be given.
  • the ring-opening copolymers of the ion-polymerizable cyclic compounds may be either a random copolymer or a block copolymer.
  • Examples of commercially available products of these polyether diols include PTMG650, PTMG1000, PTMG2000 (manufactured by Mitsubishi Chemical Corp.), EXCENOL 1020, 2020, 3020, PREMINOL PML-4002, PML- 5005 (manufactured by Asahi Glass Co., Ltd.), UNISAFE DC1100, DC1800, DCB1000 (manufactured by Nippon Oil and Fats Co., Ltd.), PPTG1000, PPTG2000, PPTG4000, PTG400, PTG650, PTG1000, PTG2000, PTG-L1000, PTG-L2000 (manufactured by Hodogaya Chemical Co., Ltd.), Z-3001-4, Z-3001-5, PBG2000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ACCLAIM 2200, 2220, 3201 , 3205, 4200, 4220, 8200, 12200 (manufactured by
  • the above polyether diols are preferable as the polyol compound.
  • a polyester diol, polycarbonate diol, polycaprolactone diol, and the like can also be used. These diols may be used in combination with the polyether diols.
  • the polyether diol is used preferably in at least 20 wt.% of the diol total weight, more preferably at least 40 wt.%. In another embodiment of the present invention, the polyether diol is used in an amount of more than 80wt.% of the diol total weight.
  • the structural units of these compounds may be polymerized by a random polymerization, block polymerization, or graft polymerization without specific limitations.
  • polyester polyols obtained by reacting a polyhydric alcohol such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1 ,6-hexanediol, neopentyl glycol, 1 ,4-cyclohexanedimethanol, 3-methyl- 1,5-pentanediol, 1,9-nonanediol, and 2-methyl-1,8-octanediol with a polybasic acid such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid, and the like can be given.
  • a polyhydric alcohol such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1 ,6-hexane
  • Kurapol P-1010, P-2010, F-1010, F- 2010, PMIPA-2000, PKA-A, PKA-A2, PNA-2000 (manufactured by Kuraray Co., Ltd.), and the like can be given.
  • polycarbonate diols polycarbonate of polytetrahydrofuran, polycarbonate of 1 ,6-hexanediol, and the like can be given.
  • polycarbonate diols Nippolan 980, 981 , 982, 983 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Duracarb 120, 122, 124, 140, 142 (manufactured by PPG), PLACCEL CD 205, 208, 210, 220, 205PL, 208PL, 210PL, 220PL, 205HL, 208HL, 210HL, 220HL (manufactured by Daicel Chemical Industries, Ltd.), and the like can be given.
  • polycaprolactone diols obtained by reacting ⁇ -caprolactone and dihydric diols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1 ,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1 ,4-cyclohexanedimethanol, and 1,4-butanediol can be given.
  • dihydric diols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1 ,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1 ,4-cyclohexanedimethanol, and 1,4-butanediol can be given.
  • L212AL, 220, L220AL (manufactured by Daicel Chemical Industries, Ltd.), and the like can be given.
  • Diols other than those mentioned above can also be used.
  • other polyols ethylene glycol, propylene glycol, 1 ,4-butanediol, 1,5- pentanediol, 1 ,6-hexanediol, neopentyl glycol, 1 ,4-cyclohexanedimethanol, ⁇ - methyl- ⁇ -valerolactone, hydroxy-terminal polybutadiene, hydroxy-terminal hydrogenated polybutadiene, castor oil-modified polyol, diol terminated compound of polydimethylsiloxane, polydimethylsiloxanecarbitol-modified polyol, and the like can be given.
  • diamines may be used in combination with the diols having a polyoxyalkylene structure.
  • diamines ethylenediamine, tetramethylenediamine, hexamethylenediamine, p- phenylenediamine, 4,4'-diaminodiphenylmethane, diamines containing a hetero atom, polyether diamines, and the like can be given.
  • the number average molecular weight of these polyols is preferably from 50 to 15,000, and particularly preferably from 100 to 8,000.
  • the following compounds may be used as polyols having a cyclic structure.
  • Examples include alkylene oxide addition diol of bisphenol A, alkylene oxide addition diol of bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, alkylene oxide addition diol of hydrogenated bisphenol A, alkylene oxide addition diol of hydrogenated bisphenol F, alkylene oxide addition diol of hydroquinone, alkylene oxide addition diol of naphthohydroquinone, alkylene oxide addition diol of anthrahydroquinone, 1 ,4- cyclohexane diol, and its alkylene oxide addition diol, tricyclodecane diol, tricyclodecanedimethanol, pentacyclopentadecane diol, pentacyclopentadecanedimethanol, and the like.
  • alkylene oxide addition diol of bisphenol A and tricyclodecanedimethanol are preferable.
  • Uniol DA400, DA700, DA1000, DB400 manufactured by Nippon Oil and Fats Co., Ltd.
  • Polyols having a cyclic structure are used preferably in secondary coatings, matrix materials and inks.
  • Examples of a diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1 ,3-xylylene diisocyanate, 1 ,4-xylylene diisocyanate, 1 ,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'- diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'- biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis(2-isocyanate ethyl)fumarate, 6-iso
  • 2,4- tolylene diisocyanate isophorone diisocyanate, xylylene diisocyanate, and methylenebis(4-cyclohexylisocyanate) are preferable.
  • Aliphatic isocyanates are particularly preferred because of a reduced tendency for yellowing.
  • a (meth)acrylate containing a hydroxyl group 2- hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, 1 ,4-butanediol mono(meth)acrylate, 2-hydroxyalkyl (meth)acryloyl phosphate, 4- hydroxycyclohexyl (meth)acrylate, 1 ,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and (meth)acrylates shown by the following formula (2) or (3) can be given:
  • R 1 represents a hydrogen atom or a methyl group and n is an integer from 1 to 15.
  • Compounds obtained by the addition reaction of (meth)acrylic acid and a compound containing a glycidyl group such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth)acrylate can also be used.
  • a compound containing a glycidyl group such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth)acrylate
  • these (meth)acrylates containing a hydroxyl group 2-hydroxyethyl (meth)acrylate and 2- hydroxypropyl (meth)acrylate are particularly preferable.
  • the proportion of the polyol, diisocyanate, and (meth)acrylate containing a hydroxyl group is determined so that isocyanate groups in the diisocyanate and a hydroxyl group in the (meth)acrylate containing a hydroxyl group are 1.1 to 3 equivalents and 0.2 to 1.5 equivalents respectively for one equivalent of hydroxyl groups in the polyol. It is preferable that the equivalent of hydroxyl groups in the polyol and (meth)acrylate containing a hydroxyl group be almost equal to the equivalent of isocyanate groups in the diisocyanate.
  • Part of the (meth)acrylate containing a hydroxyl group may be replaced by compounds having a functional group which can be added to an isocyanate group.
  • compounds having a functional group which can be added to an isocyanate group For example, ⁇ -mercaptotrimethoxysilane, ⁇ - aminotrimethoxysilane, and the like can be used. Use of these compounds improves adhesion to substrates such as glass.
  • a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1 ,4-diazabicyclo[2.2.2]octane, or 2,6,7-trimethyl-1 ,4-diazabicyclo[2.2.2]octane in an amount from 0.01 to 1 part by weight for 100 parts by weight of the reactant.
  • the reaction is carried out at 10-90°C, and preferably at 30-80°C.
  • the proportion of the urethane (meth)acrylate oligomer (A) is 10-90 wt% (hereinafter indicated by simply "%") of the composition. It is particularly preferable that the proportion of the urethane (meth)acrylate oligomer (A) be 20-70% to ensure excellent applicability when applying the composition to optical fibers, and flexibility and long-term reliability of the cured coating.
  • a urethane (meth)acrylate obtained by reacting 1 mol of the diisocyanate with 2 mols of the (meth)acrylate containing a hydroxyl group may be added to the liquid curable resin composition of the present invention.
  • a urethane (meth)acrylate a reaction product of hydroxyethyl (meth)acrylate, 2,5-bis(isocyanatemethyl)-bicyclo[2.2.1]heptane, and 2,6- bis(isocyanatemethyl)-bicyclo[2.2.1]heptane, a reaction product of hydroxyethyl (meth)acrylate and 2,4-tolylene diisocyanate, a reaction product of hydroxyethyl (meth)acrylate and isophorone diisocyanate, a reaction product of hydroxypropyl (meth)acrylate and 2,4-tolylene diisocyanate, a reaction product of hydroxypropyl (meth)acrylate and isophorone diisocyan
  • vinyl group- containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam
  • alicyclic structure-containing (meth)acrylates such as isobornyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine, and the like can be given.
  • Further examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy butyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2-6, and preferably 2-4 carbon atoms
  • R 3 represents a hydrogen atom or an alkyl group having 1-12, and preferably 1-9 carbon atoms
  • m is an integer from 0 to 12, and preferably from 1 to 8.
  • Aronix M-101 , M-102, M-111 , M-113, M- 114, M-117 manufactured by Toagosei Co., Ltd.
  • Viscoat LA STA, IBXA, 2-MTA, #192, #193
  • NK Ester AMP-10G AMP-20G, AMP-60G
  • Light Acrylate L-A, S-A, IB-XA, PO-A, PO-200A, NP-4EA, NP-8EA manufactured by Kyoeisha Chemical Co., Ltd.
  • FA-511, FA-512A, FA- 513A manufactured by Hitachi Chemical Co., Ltd.
  • Polyfunctional compounds can be given as examples of the unsaturated polymerizable compound (B).
  • unsaturated polymerizable polyfunctional compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1 ,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropanetrioxyethyl (meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(2- hydroxyethyl)isocyanurate di(meth)acrylate, tricyclodecaned
  • Yupimer UV SA1002, SA2007 manufactured by Mitsubishi Chemical Corp.
  • Viscoat#195, #215, #230, #260, #700 manufactured by Osaka Organic Chemical Industry, Ltd.
  • KAYARAD HDDA manufactured by Nippon Kayaku Co., Ltd.
  • ARONIX M-210, M-215, M- 315 manufactured by Toagosei Co., Ltd.
  • tricyclodecanedimethanol diacrylate Yupimer UV SA1002
  • Viscoat #230 and #700 are preferable.
  • the proportion of the unsaturated polymerizable compound (B) is preferably 15-80%, and particularly preferably 20-70% of the composition. If the proportion is less than 15%, applicability of the composition may be impaired due to increased viscosity. Moreover, toughness of the cured product decreases and cure shrinkage rate increases. If the proportion exceeds 80%, the curing rate of the composition decreases.
  • the photoinitiator (C) is preferably 15-80%, and particularly preferably 20-70% of the composition. If the proportion is less than 15%, applicability of the composition may be impaired due to increased viscosity. Moreover, toughness of the cured product decreases and cure shrinkage rate increases. If the proportion exceeds 80%, the curing rate of the composition decreases.
  • the photoinitiator (C) examples of the photoinitiator
  • Irgacure 184, 261, 369, 500, 651, 819, 907, 1700, 1850, 2959, CGI-403, Darocur 1173 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Lucirin TPO (manufactured by BASF), and the like can be given.
  • Darocur 1173 manufactured by Ciba Specialty Chemicals Co., Ltd.
  • Lucirin TPO manufactured by BASF
  • Lucirin TPO is particularly preferable.
  • the proportion of the photoinitiator (C) is preferably 0.01-10%, and particularly preferably 0.01-4% of the composition.
  • the component (D) used in the liquid curable resin composition of the present invention is a compound suitable to impair most useful stability characteristics. Stability characteristics are exemplified by a combination of heat stability and stability under fluorescent lights; the cured coating exhibits preferably a yellowing index after five days exposure of fluorescent light of less than 5, and a Youngs modulus retention rate of more than 70% after aging for 30 days at 100°C. Coated optical fibers having a cured coating with said properties are most useful, as the coated fibers have excellent storage stability.
  • the test methods are fully described in the experimental fully described in the experimental section.
  • the Yellowing index is less than 4.
  • the Youngs modulus retention rate is about 80% or more, particularly preferrred about 90% or more.
  • R a which is an alkyl group having 1-4 carbon atoms, is preferably a methyl group.
  • R b and R° are preferably alkyl groups having 5-12, and preferably 6-12 carbon atoms. 4,6-
  • Bis(octylthiomethyl)-o-cresol a compound shown by the formula (1) provided that R a is a methyl group and both R b and R c are alkyl groups having eight carbon atoms, is commercially available as Irganox 1520, 1520L, and 1520LR (manufactured by Ciba Specialty Chemicals Co., Ltd.).
  • 2-Tert-butyl-6-(3'-tert-butyl- 5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate is commercially available as Sumilizer GM (manufactured by Sumitomo Chemical Co., Ltd.).
  • the proportion of the component (D) is 0.01-3%, preferably 0.03-1%, and particularly preferably 0.05-0.5% of the composition for ensuring heat stability and color stability under fluorescent light.
  • other curable oligomers or polymers, reactive dilutents, or other additives may be added to the liquid curable resin composition of the present invention, insofar as the characteristics of the liquid curable resin composition are not impaired.
  • polyester (meth)acrylate epoxy (meth) acrylate, polyamide (meth)acrylate, a siloxane polymer having a (meth)acryloyloxy group, a reactive polymer obtained by reacting acrylic acid and a copolymer of glycidyl methacrylate and other vinyl monomers, and the like can be given.
  • Amines may be added to the liquid curable resin composition to prevent generation of hydrogen gas, which causes transmission loss in optical fibers.
  • amines diethylamine, isopropylamine, dibutylamine, ethanolamine, diethanolamine, and the like can be given.
  • additives such as coloring agents, UV absorbers, light stabilizers, silane coupling agents, heat polymerization inhibitors, leveling agents, surfactants, preservatives, plasticizers, lubricants, solvents, fillers, wettability improvers, and coating surface improvers may be added in addition to the above components.
  • UV absorbers benzophenone-type UV absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2- hydroxy-4-n-dodecyloxybenzophenone
  • benzotriaole-type UV absorbers such as 2-(2'-hydroxy-5'-methylphenyl)benzotriaoIe and 2-(2'-hydroxy-5'-t- octylphenyl)benzotriaole
  • commercially available products such as Tinuvin P, 234, 320, 326, 327, 328, 329, 213 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Seesorb 101, 102, 103, 712, 704 (manufactured by Shipro Kasei Kaisha, Ltd.), Sumisorb 110, 130, 140 (manufactured by Sumitomo Chemical Industries Co., Ltd.), and the like can be given.
  • silane coupling agents ⁇ -aminopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, and ⁇ -(meth)acryloxypropyltrimethoxysilane
  • commercially available products such as SH6062, SH6030 (manufactured by Toray-Dow Corning Silicone Co. Ltd.), KBM 403, 503, 803, 903, 5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like can be given.
  • the viscosity of the liquid curable resin composition of the present invention is 200-20,000 mPa-s/25°C, and preferably 2000-15,000 mPa s/25°C.
  • the Young's modulus after curing is preferably 100-2500 MPa.
  • the Young's modulus after curing is preferably 0.5-3 MPa.
  • the cure speed preferably is about 0.5 J/cm 2 or less, more preferably about 0.3 J/cm 2 or less. The cure speed is defined as the energy applied to achieve 90% of the ultimate modulus.
  • the water absorption of the coatings preferably is less than 5 wt.%.
  • the optical fiber preferably glass fiber
  • the fiber is drawn from a perform and has a diameter of about 125 ⁇ m.
  • the fiber is coated with a primary and a secondary coating before the glass is touched. Both coatingss, generally are 25- 30 ⁇ m thick, but this can be choosen differently, e.g. 5 ⁇ m-500 ⁇ m.
  • the coated optical fiber generally needs to be colored to enable identification in the field.
  • an ink layer can be applied on the coated optical fiber, or the secondary coating can contain color identification means (pigments, dyes).
  • the coated and colored optical fibers can be used in cabling for example for loose tube cables, or ribbon cables.
  • multiple coated optical fibers (generally 2, 4, 8, 12 up to 24) are bonded together, generally in a plane. Bonding can take place through edge-bonding or encasing. Sometimes two or more matrix coatings are applied. Another type of matrix material is used to bind a plurality of ribbons either in a plane, or stacked. These materials are also called bundling materials. For any of these coating layers, the cured coating of the present invention is advantageous.
  • the liquid curable resin composition of the present invention is cured using heat and/or radiation.
  • Radiation used herein includes infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, -rays, ⁇ -rays, ⁇ -rays, and the like. UV and UV-vis radiation is particularly preferred.
  • a reaction vessel equipped with a stirrer was charged with 117.12 g of isophorone diisocyanate, 0.24 g of 2,6-di-t-butyl-p-cresol, 0.08 g of phenothiazine, and 0.40 g of dibutyltin dilaurate. 37.08 g 2-hydroxyethyl acrylate was added dropwise to the mixture at 30°C or lower. After the addition, the mixture was allowed to react at 30°C for 40 minutes. The mixture was then heated to 45°C and allowed to react for a further one hour.
  • a reaction vessel equipped with a stirrer was charged with 898.07 g of polypropylene glycol with a number average molecular weight of 4000 ("ACCLAIM 4200" manufactured by Lyondell), 74.76 g of isophorone diisocyanate, 0.24 g of 2,6-di-t-butyl-p-cresol, and 0.08 g of phenothiazine.
  • the mixture was cooled to 15°C while stirring. After the addition of 0.80 g of dibutyltin dilaurate, the mixture was slowly heated to 35°C for one hour while stirring. Then, the mixture was allowed to react at 50°C.
  • a reaction vessel equipped with a stirrer was charged with 65 parts by weight of the urethane acrylate oligomer UA-1 obtained in Synthesis Example 1, 26 parts by weight of nonylphenol EO-modified acrylate ("Aronix M- 113" manufactured by Toagosei Co., Ltd.), 8 parts by weight of N-vinylcaprolactam (manufactured by ISP Japan, Ltd.), 1 part by weight of 1 ,6- hexanediol diacrylate ("Viscoat #230" manufactured by Osaka Organic Chemical Industry, Ltd.), and 1.2 parts by weight of 2,4,6- trimethylbenzoyldiphenylphosphine oxide ("Lucirin TPO" manufactured by BASF).
  • nonylphenol EO-modified acrylate (“Aronix M- 113" manufactured by Toagosei Co., Ltd.)
  • N-vinylcaprolactam manufactured by ISP Japan, Ltd.
  • Viscoat #230 manufactured by Os
  • a liquid curable resin composition was prepared in the same manner as in Example 1 except for using 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'- hydroxybenzyl)-4-methylphenyl acrylate ("Sumilizer GM” manufactured by Sumitomo Chemical Co., Ltd.) instead of 4,6-bis(octylthiomethyl)-o-cresol.
  • a reaction vessel equipped with a stirrer was charged with 63 parts by weight of the urethane acrylate oligomer UA-2 obtained in Synthesis Example 2, 12 parts by weight of nonylphenol EO-modified acrylate ("Aronix M- 113" manufactured by Toagosei Co., Ltd.), 8 parts by weight of N- vinylcaprolactam (manufactured by ISP Japan, Ltd.), 15 parts by weight of isobornyl acrylate ("IBXA” manufactured by Osaka Organic Chemical Industry Co., Ltd.), 2 parts by weight of 1,6-hexanediol diacrylate ("Viscoat #230" manufactured by Osaka Organic Chemical Industry, Ltd.), 1.2 parts by weight of 2,4,6- trimethylbenzoyldiphenylphosphine oxide ("Lucirin TPO" manufactured by BASF), and 0.15 part by weight of 2-hydroxy-4-methoxybenzophenone ("Seesorb 101" manufactured by Shipro Kasei Kaisha, Ltd.).
  • the mixture was stirred at 50°C to prepare a homogeneous solution. Then, 0.1 part by weight of diethyla ine and 1.0 part by weight of ⁇ -mercaptopropyltrimethoxysilane were added to the mixture. 0.3 part by weight of 4,6-bis(octylthiomethyl)-o-cresol ("Irganox 1520L" manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to the mixture to obtain a liquid curable resin composition.
  • a liquid curable resin composition was prepared in the same manner as in Example 1 except that 4,6-bis(octylthiomethyl)-o-cresol was not added.
  • a liquid curable resin composition was prepared in the same manner as in Example 1 except for using pentaerythritoltetrakis[3-(3,5-di-tert- butyl-4-hydroxyphenyl)propionate] ("Irganox 1010" manufactured by Ciba Specialty Chemicals Co., Ltd.) instead of 4,6-bis(octylthiomethyl)-o-cresol. Comparative Example 3
  • a liquid curable resin composition was prepared in the same manner as in Example 1 except for using thiodiethylenebis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate] ("Irganox 1035" manufactured by Ciba Specialty Chemicals Co., Ltd.) instead of 4,6-bis(octylthiomethyl)-o-cresol.
  • a liquid curable resin composition was prepared in the same manner as in Example 1 except for using benzenepropanoic acid, 3,5-bis(1 ,1- dimethylethyl)-4-hydroxy-.C 7 -C 9 branched alkyl ester ("Irganox 1135" manufactured by Ciba Specialty Chemicals Co., Ltd.) instead of 4,6- bis(octylthiomethyl)-o-cresol.
  • a liquid curable resin composition was prepared in the same manner as in Example 1 except for using hexamethylenebis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate] ("Irganox 259" manufactured by Ciba Specialty Chemicals Co., Ltd.) instead of 4,6-bis(octylthiomethyl)-o-cresol.
  • a liquid curable resin composition was prepared in the same manner as in Example 1 except for using 4,4'-thio-bis-(3'-methyl-6-tert- butylphenol) ("Sumilizer WX-R" manufactured by Sumitomo Chemical Industries Co., Ltd.) instead of 4,6-bis(octylthiomethyl)-o-cresol.
  • a liquid curable resin composition was prepared in the same manner as in Example 3 except that 4,6-bis(octylthiomethyl)-o-cresol was not added.
  • a liquid curable resin composition was prepared in the same manner as in Example 3 except for using thiodiethylenebis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate] ("Irganox 1035" manufactured by Ciba Specialty Chemicals Co., Ltd.) instead of 4,6-bis(octylthiomethyl)-o-cresol.
  • a liquid curable resin composition was prepared in the same manner as in Example 3 except for using benzenepropanoic acid, 3,5-bis(1 ,1- dimethylethyl)-4-hydroxy-.C 7 -C 9 branched alkyl ester ("Irganox 1135" manufactured by Ciba Specialty Chemicals Co., Ltd.) instead of 4,6- bis(octylthiomethyl)-o-cresol.
  • the liquid compositions were applied to a glass plate using an applicator with a thickness of 254 ⁇ m.
  • the applied compositions were irradiated with ultraviolet rays in a nitrogen atmosphere using a 3.5 kW metal halide lamp ("SMX-3500/F-OS", manufactured by ORC Co., Ltd.) at a dose of 0.1 J/cm 2 to obtain cured films with a thickness of about 130 ⁇ m.
  • the cured films on the glass plate were irradiated with fluorescent light at a temperature of 23°C and relative humidity of 50%.
  • fluorescent lamp "FL20SSN/18" manufactured by Toshiba Corporation was used. Illuminance at the surface of the cured films was 1200 Ix.
  • the degree of yellowing of the cured films before irradiation of fluorescent light and after irradiation for a predetermined period of time were evaluated by a yellowness index (Yl) using a colorimeter ("SZ- ⁇ 80 spectrocolorimeter" manufactured by Nippon Denshoku Industries Co., Ltd.). The smaller the Yl value, the less the degree of yellowing.
  • the heat stability of the cured products of the compositions obtained in Examples and Comparative Examples was evaluated.
  • the liquid compositions were applied to a glass plate using an applicator with a thickness of 381 ⁇ m.
  • the applied compositions were irradiated with ultraviolet rays in air using a 3.5 kW metal halide lamp ("SMX-3500/F-OS", manufactured by ORC Co., Ltd.) at a dose of 0.5 J/cm 2 to obtain cured films.
  • the cured films removed from the glass plate were irradiated with ultraviolet rays from the other side at a dose of 0.5J/cm 2 .
  • the thickness of the resulting films was about 200 ⁇ m.
  • the cured films were allowed to stand for 12 hours or more at a temperature of 23°C and relative humidity of 50%. The initial Young's modulus of the cured films was then measured. The cured films were allowed to stand in an oven at 100°C for 30 days. The Young's modulus of these cured films was then measured. Heat stability was evaluated by calculating the variation between the initial Young's modulus and the Young's modulus after heating.
  • the cured films were cut into sheets with a width of 6 mm.
  • the modulus of elasticity of the sheets was measured using a tensile tester.
  • the tensile rate was 1 mm/minute and the distance between chucks was 25 mm.
  • the Young's modulus was calculated by dividing the load at 2.5% elongation by the cross section of the test specimen and 0.025. The results are shown in Table 1.
  • Sumilizer GM 2-Tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.)
  • Irganox 1010 2-Tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.)
  • Irganox 1010 2-Tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.)
  • Irganox 1035 (manufactured by Ciba Specialty Chemicals Co., Ltd.) Irganox 1035:
  • Sumilizer WX-R 4,4'-Thio-bis-(3-methyl-6-tert-butyl-phenol) (manufactured by Sumitomo
  • the cured products of the liquid curable resin compositions comprising the component (D) exhibited excellent stability in fluorescent light and superior heat stability.
  • the cured products made from the liquid curable resin composition of the present invention exhibit excellent light resistance and superior heat stability.
  • the resin composition is suitable for use as a coating material for optical fibers.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
  • Polymerisation Methods In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)

Abstract

L'invention concerne une composition de résine liquide durcissable pour fibres optiques (A) comprenant un oligomère uréthane (méth)acrylate, en particulier un oligomère comprenant un squelette polyéther, (B) un composé polymérisable insaturé, (C) un photoinitiateur, et (D) un antioxydant dont l'action induit dans le revêtement durci, un indice de jaunissement inférieur à 5 après cinq jours d'exposition et un taux de rétention de module d'élasticité de plus de 70 % après 30 jours de vieillissement à 100 DEG C. Le composé D peut notamment être un composé représenté par la formule générale (1) dans laquelle R<a> désigne un atome d'hydrogène ou un groupe alkyle ayant entre 1 et 4 atomes de carbone et R<b> et R<c> désignent individuellement des groupes alkyle ayant entre 1 et 12 atomes de carbone, ou 2-tert-butyl-6-(3'-tert-butyl-5'-méthyl-2'-hydroxybenzyl)-4-méthylphénylacrylate.
PCT/NL2001/000321 2000-05-01 2001-04-25 Composition de resine liquide durcissable pour fibres optiques Ceased WO2001083393A2 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003011938A1 (fr) * 2001-07-27 2003-02-13 Corning Incorporated Revetement de fibre optique a faible module possedant une resistance a la traction elevee
WO2003074579A1 (fr) * 2002-03-04 2003-09-12 Dsm N.V. Composition de resine liquide durcissante
WO2005014679A1 (fr) * 2003-07-16 2005-02-17 Duga Uk Ltd Composes d'acrylate d'urethane a durcissement induit par la lumiere
US7715675B2 (en) 2003-07-18 2010-05-11 Corning Incorporated Optical fiber coating system and coated optical fiber
EP1997784A4 (fr) * 2006-03-23 2013-10-23 Furukawa Electric Co Ltd Module de fibre optique
CN111961382A (zh) * 2020-07-23 2020-11-20 珠海市斗门联邦彩色塑料印制有限公司 一种夜光涂料及其制备方法和含其的收缩标签

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JP5625186B2 (ja) * 2009-10-09 2014-11-19 ディーエスエム アイピー アセッツ ビー．ブイ． Ｄ１４５２ｇｂ光ファイバ用放射線硬化性被覆材
WO2011086930A1 (fr) * 2010-01-15 2011-07-21 日本曹達株式会社 Composition de dérivé de polybutadiène
JP5610200B2 (ja) * 2010-06-10 2014-10-22 三菱レイヨン株式会社 注型用活性エネルギー線硬化性樹脂組成物および光学部品
JP6130154B2 (ja) * 2013-01-31 2017-05-17 デンカ株式会社 硬化性樹脂組成物
JP6335853B2 (ja) * 2015-08-27 2018-05-30 アイカ工業株式会社 手芸用紫外線硬化樹脂組成物
JP6286085B1 (ja) * 2017-03-30 2018-02-28 第一工業製薬株式会社 ポリウレタン樹脂組成物および封止物
JP7217977B2 (ja) * 2020-02-04 2023-02-06 アジア原紙株式会社 活性エネルギー線硬化型組成物
JP7335903B2 (ja) * 2021-01-13 2023-08-30 古河電気工業株式会社 光ファイバテープ心線及び光ファイバケーブル

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0721124B2 (ja) * 1986-03-17 1995-03-08 住友化学工業株式会社 光フアイバ被覆用樹脂組成物
KR100243803B1 (ko) * 1991-04-03 2000-02-01 찰스 디. 스톰즈 자외선 경화성 투명 도료 조성물 및 가공방법
US6048911A (en) * 1997-12-12 2000-04-11 Borden Chemical, Inc. Coated optical fibers

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003011938A1 (fr) * 2001-07-27 2003-02-13 Corning Incorporated Revetement de fibre optique a faible module possedant une resistance a la traction elevee
WO2003074579A1 (fr) * 2002-03-04 2003-09-12 Dsm N.V. Composition de resine liquide durcissante
WO2005014679A1 (fr) * 2003-07-16 2005-02-17 Duga Uk Ltd Composes d'acrylate d'urethane a durcissement induit par la lumiere
US7715675B2 (en) 2003-07-18 2010-05-11 Corning Incorporated Optical fiber coating system and coated optical fiber
EP1997784A4 (fr) * 2006-03-23 2013-10-23 Furukawa Electric Co Ltd Module de fibre optique
CN111961382A (zh) * 2020-07-23 2020-11-20 珠海市斗门联邦彩色塑料印制有限公司 一种夜光涂料及其制备方法和含其的收缩标签
CN111961382B (zh) * 2020-07-23 2021-12-07 珠海市斗门联邦彩色塑料印制有限公司 一种夜光涂料及其制备方法和含其的收缩标签

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WO2001083393A3 (fr) 2002-03-28
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