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WO1997046495A1 - Composition de resine durcissable a l'etat liquide et fibres optiques en faisceau - Google Patents

Composition de resine durcissable a l'etat liquide et fibres optiques en faisceau Download PDF

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Publication number
WO1997046495A1
WO1997046495A1 PCT/NL1997/000322 NL9700322W WO9746495A1 WO 1997046495 A1 WO1997046495 A1 WO 1997046495A1 NL 9700322 W NL9700322 W NL 9700322W WO 9746495 A1 WO9746495 A1 WO 9746495A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
composition
anyone
polymer particles
Prior art date
Application number
PCT/NL1997/000322
Other languages
English (en)
Inventor
Zen Komiya
Tsuyoshi Hirai
Takashi Ukachi
Original Assignee
Dsm N.V.
Japan Synthetic Rubber Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dsm N.V., Japan Synthetic Rubber Co., Ltd. filed Critical Dsm N.V.
Priority to AU29821/97A priority Critical patent/AU2982197A/en
Publication of WO1997046495A1 publication Critical patent/WO1997046495A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • G02B6/4401—Optical cables
    • G02B6/4429—Means specially adapted for strengthening or protecting the cables
    • G02B6/4438—Means specially adapted for strengthening or protecting the cables for facilitating insertion by fluid drag in ducts or capillaries
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/104—Coating to obtain optical fibres
    • C03C25/106—Single coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/104—Coating to obtain optical fibres
    • C03C25/1065—Multiple coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a liguid curable resin composition for optical fibers exhibiting superior surface slip characteristics after cure, excellent curability, and superb durability, and to a bundle of a plurality of optical fibers, having an outer layer of bundling resin exhibiting superior surface slip characteristics and superb durability.
  • a resin coating is provided for protection and reinforcement of molten glass fiber immediately after spinning.
  • a known structure of the resin coating consists of a primary coating layer of a flexible resin which is applied to the surface of optical fiber and a secondary coating layer of a rigid resin which is provided over the primary coating layer.
  • a so-called optical fiber tape structural core is known in the art in the application of elemental optical fibers provided with resin coating.
  • the optical fiber tape structural core is made from several such elemental optical fibers, e.g. four or eight elemental optical fibers, by arranging these fibers in a plane and securing them with a binder to produce a tape structure with a rectangular cross section.
  • a method for producing a multi-core structure by bundling two or more such optical fiber tape structural cores is also known.
  • an eight-core structure is manufactured by covering two four-core optical fiber tape structures using a bundling material.
  • the resin composition for forming the primary coating is called a soft material; the resin composition for forming the secondary coating is called a hard material; the binder for preparing the optical fiber tape structural core from several elemental optical fiber is called a tape material; and the material for producing a multi-core structure by bundling two or more optical fiber tape structural cores is called a bundling material.
  • Air-blown fibers are also known.
  • the air-blown fibers are made by bundling several optical fibers into a cylinder and blowing the bundled optical fibers into a pipe, installed in advance, using pressurized air.
  • the bundling material used for this purpose is called an air-blown fiber bundling material.
  • an optical fiber cable containing a great number of optical fiber tape structural cores has been demanded.
  • laying of air-blown fibers in remote locations is desired along with expansion of the area wherein optical fiber cables are used.
  • a resin used as the coating material for such optical fibers must have characteristics of being a liquid at ordinary temperatures with high processability; of providing good productivity at a high curing rate; of having sufficient strength and superior flexibility; of exhibiting very little physical change during temperature changes over a wide range; of having superior thermal resistance and superior resistance to hydrolysis; of showing superior long term reliability with little physical changes over time; of showing superior resistance to chemicals such as acids and alkalis; of exhibiting low moisture and water absorption; of exhibiting superior light resistance; of exhibiting high resistance to oils; and of producing little hydrogen gas which adversely affects optical fiber characteristics.
  • An object of the present invention therefore is to provide a liquid curable resin composition for coating optical fibers satisfying the above-mentioned general requirements, exhibiting particularly superior surface slip characteristics after cure, a high curing rate, and a high strength, and suitable particularly for the manufacture of air-blown fibers.
  • a liquid curable resin composition comprising (a) a urethane (meth)acrylate, (b) a polyme ization initiator, and (c) polymer particles having an average particle diameter of 5 ⁇ m to 1 mm, and by a bundle comprising a plurality of coated glass optical fibers, the bundle having an outer layer of cured bundling resin, the bundling resin comprising
  • the urethane (meth)acrylate used in the present invention as the component (a) can be obtained by reacting a polyol , a diisocyanate, and a (meth)acrylate having a hydroxyl group, specifically, by reacting the isocyanate group of the diisocyanate with each of the hydroxyl groups of the polyol and the (meth)acrylate having a hydroxyl group.
  • the reaction can be carried out, for example, by the following methods: a method simultaneously reacting the polyol, the diisocyanate, and the (meth)acrylate having a hydroxyl group; a method reacting the polyol and the diisocyanate to obtain an intermediate, and reacting this intermediate with the (meth)acrylate having a hydroxyl group; a method of reacting the (meth)acrylate having a hydroxyl group and the diisocyanate, and then reacting the resulting compound with the polyol; a method of reacting the (meth)acrylate having a hydroxyl group and the diisocyanate, reacting the resulting compound with the polyol, then again reacting with the (meth)acrylate having a hydroxyl group.
  • polystyrene resin examples include aliphatic, alicyclic, or aromatic polyether diols, polyester diols, polycarbonate diols, and polycaprolactone diols. These polyols may be used either individually or in combination of two or more. Random polymerization, block polymerization, or graft polyme ization may be used for the polyme ization of each structural unit in these polyols with no specific limitations.
  • aliphatic polyether diols are polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and polyether diols obtained by the ring-opening copolymerization of two or more ionic-polymerizable cyclic compounds.
  • Examples of the ionic-polymerizable cyclic compounds include cyclic ethers such as ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyl-tetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorhydrine, glycidyl methacrylate, allyl glycidyl ether, allylglycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate.
  • polyether diols obtained by the ring-opening copolymerization of two or more ionic-polymerizable cyclic compounds include binary copolymers obtained by the combination of tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and
  • a cyclic imine such as ethyl imine
  • a cyclic lactone such as ⁇ -propiolactone or glycolic acid lactide
  • a cyclic siloxane such as dimethylcyclopolysiloxane.
  • polyether diols examples include PTMG650, PTMGIOOO, PTMG2000 (Mitsubishi Chemical Co., Ltd.); PPG400, PPG1000, EXCENOL 720, 1020, 2020 (Asahi Oline); PEG1000, UNISAFE DC1100, UNISAFE DC1800 (Nippon Oil and Fats Co., Ltd.); PPTG2000, PPTG1000, PTG400, PTGL2000 (Hodogaya Chemical Co., Ltd.); and Z-3001-4, Z-3001-5, PBG2000A, PBG2000B (Daiichi Kogyo Seiyaku Co., Ltd.).
  • alicyclic diols examples are an alkylene oxide addition diol to hydrogenated bisphenol A, an alkylene oxide addition diol to hydrogenated bisphenol F, and an alkylene oxide addition diol to 1,4-cyclohexane dimethanol are given.
  • aromatic polyether diols examples include an alkylene oxide addition diol to bisphenol A, alkylene oxide addition diol to bisphenol F, alkylene oxide addition diol to hydroquinone, alkylene oxide addition diol to naphthohydroquinone, and alkylene oxide addition diol to anthrahydroquinone.
  • aromatic polyether diols are commercially available under the trademarks, for example, of Uniol DA400, DA700, DA1000, and DA4000 (Nippon Oil and Fats Co.).
  • polyester diols include polyester diols obtained by the reaction of a polyhydric alcohol, and a polybasic acid.
  • polyhydric alcohols are ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexane diol, neopentyl glycol, 1,4-cyclohexane dimethanol, 3-methyl-l,5-pentane diol, 1,9-nonane diol, and 2-methyl-l,8-octane diol.
  • polybasic acid are phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid.
  • polyester diols Commercially available products of these polyester diols include, for example, Kurapole P-2010, PMIPA, PKA-A, PKA-A2, and PNA-2000 (Kuraray Co.).
  • polycarbonate polycarbonate of polytetrahydrofuran and polycarbonate of 1,6-hexane diol, and commercially available products, such as DN-980, DN-981, DN-982, DN-983 (Ninon Polyurethane) , PC-8000 (PPG of the US), and PC-THF-CD (BASF).
  • polycaprolactone diol examples include polycaprolactone diols obtained by the reaction of ⁇ -caprolactone and a diol, such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexane diol, neopentyl glycol, 1, -cyclohexane dimethanol, and 1,4-butane diol.
  • polycaprolactone diols are also commercially available under trademarks such as PLACCEL 205, 205AL, 212, 212AL, 220, 220AL (Daicell Co., Ltd.).
  • polyols other than those mentioned above are ethylene glycol, propylene glycol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, neopentyl glycol.
  • 1,4-cyclohexane dimethanol hydrogenated bisphenol A, hydrogenated bisphenol F, dimethylol compound of dicyclopentadiene, tricyclodecane dimethanol, pentacyclodecane dimethanol, ⁇ -methyl- ⁇ -valerolactone, polybutadiene with terminal hydroxy groups, hydrogenated polybutadiene with terminal hydroxy groups, castor oil-denatured diol, polydimethylsiloxane with terminal diols, and polydimethylsiloxane carbitol-denatured diols.
  • the molecular weight, as measured with GPC (gel permeation chromatography) with the use of polystyrene standards, of the polyol used for producing the urethane (meth)acrylate is usually 50 to 15,000, and preferably 100 to 8,000.
  • diisocyanate used for producing the urethane (meth)acrylate in the present invention are 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-cyclohexyl) isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, iso
  • diisocyanates 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and methylenebis(4-cyclohexylisocyanate) are particularly preferred.
  • diisocyanates may be used either individually or in combination of two or more.
  • compounds obtained by an addition reaction between compounds containing a glycidyl group such as alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth)acrylate, and (meth)acrylic acid can also be used.
  • a glycidyl group such as alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth)acrylate, and (meth)acrylic acid
  • (meth)acrylates having a hydroxyl group particularly desirable are 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate.
  • (meth)acrylates having a hydroxyl group may be used either individually or in combination of two or more.
  • the polyol, the diisocyanate, and the (meth)acrylate containing a hydroxy group are used preferably in a proportion such that for one equivalent of the hydroxyl group of the polyol, 1.1 to 3 equivalents of the diisocyanate group contained in the diisocyanate compounds and 0.2 to 1.5 equivalents of the hydroxyl group contained in the (meth)acrylate are used. It is desirable that the hydroxyl groups in the polyol and the (meth)acrylate be almost equivalent to the isocyanate groups in the diisocyanate compound.
  • a compound having a functional group which can be added to an isocyanate group isocyanate group
  • ⁇ -mercaptopropyltrimethoxy silane and ⁇ -aminopropyltrimethoxy silane are given as examples of the compound having such a functional group. Adhesion to materials such as glass can be improved by using such a compound.
  • These compounds can be used in an amount up to 10 parts by weight for 100 parts by weight of the total components for manufacturing the urethane (meth)acrylate.
  • a diamine may be added as an optional component.
  • Ethylenediamine, tetramethylenediamine, hexamethylenediamine, para-phenylenediamine, 4, '-diaminodiphenylmethane, and polyether diamine are given as examples of such a diamine.
  • the urethane (meth)acrylate obtained by the reaction of 1 mol of a diisocyanate and two mols of a (meth)acrylate containing a hydroxy group can be used in the present invention.
  • Such a urethane (meth)acrylate may be a reaction product of hydroxyethyl (meth)acrylate and 2,5- or 2,6-bis(isocyanatemethyl)-bicyclo[2.2.1]heptane, a reaction product of hydroxyethyl (meth)acrylate and and 2,4-tolylene diisocyanate, a reaction product of hydroxyethyl (meth)acrylate and isophorone diisocyanate, and a reaction product of hydroxypropyl (meth)acrylate and 2,4-tolylene diisocyanate.
  • These urethane (meth)acrylate can be used in an amount of less than 30 parts by weight for 100 parts by weight of the total amount of the urethane (meth)acrylates.
  • a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, n-butyl-tin-dilaurylate, triethylamine, l,4-diazabicyclo[2.2.2]octane, or
  • 2,6,7-trimethyl-l,4-diazabicyclo[2.2.2]octane is used, generally, in an amount of 0.01 to 1 part by weight for 100 parts by weight of the reaction raw materials.
  • the reaction temperature is normally in the range of 10 to 90°C, and preferably 30 to 80°C.
  • the urethane (meth)acrylate used in the present invention preferably has a weight average molecular weight as measured with GPC with the use of polystyrene standards, of 500 to 20,000. If the molecular weight is less than 500, this may cause a decrease in molecular weight between the cross-link points, resulting in cured products with insufficient flexibility and, occasionally, a large shrink stress when the composition is cured. If the molecular weight is larger than 20,000, the strength after cure may be insufficient.
  • the urethane (meth)acrylate is incorporated in the composition of the present invention in an amount preferably of 10 to 99 wt%, and particularly preferably 20 to 99 wt%.
  • the composition of the present invention is cured by heat and/or radiation.
  • a heat polymerization initiator or a radiation polymerization initiator can be used as the polymerization initiator (b) used in the present invention.
  • radiation means radiation from infrared light, visible light, ultraviolet light, X-rays, electron beams, ⁇ -rays, ⁇ -rays, and ⁇ -rays.
  • a radical polymerization initiator such as a peroxide or an azo compound is usually used when the liquid curable resin composition is cured by heat.
  • the radical polymerization initiator are benzoyl peroxide, t-butyloxybenzoate, and azobisisobutylonitrile.
  • a radiation polymerization initiator When the composition of the present invention is cured with radiation, a radiation polymerization initiator is used.
  • the radiation polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4 '-dimethoxybenzophenone, 4,4 '-diaminobenzophenone, Michler 's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal,
  • CGI1850 CGI1850, CG24-61 (Ciba Geigy) , Lucirin LR8728 (BASF), Darocure 1116, 1173 (Merck Co.), and Uvecryl P36 (UCB) .
  • the above-described heat polymerization initiator may be used together with the radiation polymerization initiator when the composition of the present invention is cured using both heat and radiation.
  • the polymerization initiators are used preferably in an amount of 0.1 to 10 wt%, and particularly preferably 0.5 to 7 wt%, in the composition of the present invention.
  • Particles of polymers such as polyolefin, acrylic resin, polyurethane, polyamide, polystyrene, silicone resin, styrene/divinylbenzene copolymer are given as examples of the polymeric particles which are used as component (c) in the composition of the present invention.
  • these resins are not fluorinated, as particles from fluorinated resins are very expensive, and tend to be incompatible with the urethane acrylate oligomer.
  • These polymer particles may be either cross-linked polymer particles or non-cross-linked polymer particles.
  • the cross-linked polymer particles have an advantage in that the polymer particles are not mutually soluble with the resin solution and the form of the polymer particles is hard to change.
  • acrylic resin such as poly(methyl methacrylate) are particularly preferred as the polymer particles. Because of the absence of unsaturated bonds in the polymer main chain, acrylic resin has excellent weather resistance. In addition, since acrylic resin can copolymerize with various cross-linking monomers in any optional proportion, highly cross-linked polymer particles can be obtained.
  • the polymer particles may be either particles produced by pulverizing a polymer or a polymer manufactured in the form of particles, and may be either sherical or non-spherical. These polymer particles are commercially available under the trademarks of Mipelon XM-220 (manufactured by Mitsui Petrochemical Co., Ltd.), poly(methyl methacrylate) globular fine particles (MB and MBX, manufactured by Sekisui Plastics Co., Ltd.), polystyrene particles (SBX, manufactured by Sikisui Plastics Co., Ltd.), high functional silicone powder (Torayfill, manufactured by Toray Dow Corning Co.), true globular functional fine particles polymer (Art Pearl, manufactured by Negami Kogyo Co., Ltd.), and the like.
  • Mipelon XM-220 manufactured by Mitsui Petrochemical Co., Ltd.
  • MB and MBX poly(methyl methacrylate) globular fine particles
  • SBX polystyrene particles
  • the specific gravity of the polymer particles is desirably the same or close to the specific gravity of the resin composition excluding the polymer particles (hereinafter referred to as "resin liquid"). Specifically, it is desirable that the difference between the specific gravity of the polymer particles and that of the resin liquid be in a range of between 0.3 to -0.3 g/ml. If the specific gravity of the polymer particles differs from that of the resin liquid markedly, the polymer particles may precipitate or float in a short period of time when the viscosity of the resin liquid decreases at high temperatures, thereby imparing storage stability of the composition.
  • the average particle diameter of these polymer particles is preferably in the range of 5 ⁇ m to 1 mm, and particularly preferably 10 ⁇ m to 500 ⁇ m.
  • the average particle diameter of the polymer particle is less than 5 ⁇ m, the surface slip characteristics of the cured products are insufficient; if more than 1 mm, it is difficult to disperse the polymer particles in the resin composition of the present invention in a stable manner.
  • the amount of polymer particles to be incorporated in the composition of the present invention should preferably be 0.1 to 30 wt%, and more preferably 0.5 to 20 wt%.
  • composition of the present invention may be incorporated to the extent that the characteristics of the composition are not adversely affected.
  • monomers possessing a (meth)acryloyl group or a vinyl group other than the urethane (meth)acrylate of above-mentioned component (a) are used.
  • Mono-functional monomers and poly-functional monomers are given as such monomers.
  • the following compounds can be given as examples of the mono-functional monomer: alicyclic structure-containing (meth)acrylate, such as isobornyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and cyclohexyl (meth)acrylate; (meth)acryloyl group-containing monomers, such as benzyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, (meth)acryloyl morpholine, 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)acryl
  • R 2 is a hydrogen atom or a methyl group
  • R 3 is an alkylene group having 2 to 6, preferably 2 to 4, carbon atoms
  • R 4 is a hydrogen atom or an alkyl group having 1 to 12, preferably 1 to 9, carbon atoms
  • m is an integer from 1 to 12, preferably 1 to 8;
  • R 2 has the same meaning as defined for formula (3), R 5 is an alkylene group having 2 to 8, preferably 2 to 5, carbon atoms; R 6 is a tetrahydrofurylgroup, and p is an integer from 1 to 8, preferably 1 to 4; and
  • R 7 is a phenyl group, optionally substituted with one alkyl group having 1 to 12, preferably 1 to 9, carbon atoms; and vinyl group-containing monomers such as N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl imidazole, vinyl pyridine, hydroxy butyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and N-vinyl carbazole.
  • vinyl group-containing monomers such as N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl imidazole, vinyl pyridine, hydroxy butyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and N-vinyl carbazole.
  • isobornyl (meth)acrylate and N-vinylpyrrolidone are preferred.
  • (meth)acryloyl group containing monomers such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene glycol di(meth)acrylate, tetra ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentylglycol di (meth)acrylate, trimethylolpropane trioxyethyl (meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, di(meth)acrylate of alkylene oxide addition di
  • reactive diluents may be used either individually or in combination of two or more, and incorporated in the composition of the present invention in an amount of, usually 80 wt% or less, and preferably 20 to 70 wt%.
  • the addition of the reactive diluents in this range ensures good coatability, an adequate curing rate, appropriate tenacity of cured products, and a low curing shrinkage.
  • polyester (meth)acrylate epoxy (meth)acrylate, polyamide (meth)acrylate, siloxane with a (meth)acryloyloxy group, fluorine-containing oligomer, silicon-containing oligomer, polysulfide oligomer, and the like can be given.
  • non-particle polymers are reactive polymers obtained by the reaction of a copolymer of glycidyl ( eth)acrylate and other vinyl group containing monomer and an acrylic acid; polyamide, polyamideimide, polyurethane, polybutadiene, polyether, polyester, pentadiene derivatives, styrene-butadiene-styrene block copolymer, styrene-ethylene-butene-styrene block terpolymer , styrene-isoprene-styrene block copolymer, petroleum resin, xylene resin, and ketone resin.
  • a copolymer of glycidyl ( eth)acrylate and other vinyl group containing monomer and an acrylic acid polyamide, polyamideimide, polyurethane, polybutadiene, polyether, polyester, pentadiene derivatives, styrene-butadiene-styrene block copo
  • amines may be used in the composition of the present invention to supress generation of hydrogen gas which causes transmission loss in optical fibers.
  • Diallylamine, diisopropylamine, diethylamine, diethylhexylamine, and the like are given as examples of such amines.
  • various additives may be included in the composition of the present invention as required.
  • additives include, for example, antioxidants, UV absorbers, photostabilizers, silane coupling agents, thermal polymerization inhibitors, leveling agents, surfactants, preservatives, plasticizers, lubricants, coloring agents, solvents, fillers, aging preventives, wettability improvers, and coating surface improvers.
  • antioxidants such as Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Geigy), Antigen P, 3C, FR, GA-80 (manufactured by Sumitomo Chemical Industries Co., Ltd.); UV absorbers, such as Tinuvin P, 234, 320, 326, 327, 328, 329, 213 (manufactured by Ciba Geigy), Seesorb 102, 103, 501, 202, 712, 704 (manufactured by Sypro Chemical Co. ) ?
  • photostabilizers such as Tinuvin 292, 144, 622LD (manufactured by Ciba Geigy ), Sanol LS770 (manufactured by Sankyo Chemical Co. ) , Sumisorb TM-061 (manufactured by Sumitomo Chemical Industries Co., Ltd.).
  • silane coupling agents are ⁇ -aminopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxy-silane, and ⁇ -acryloxypropyltrimethoxysilane, and commercially available products, such as SH6062, 6030 (manufactured by Toray Silicone Co., Ltd.), and KBE903, 603, 403 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the viscosity of the composition of the present invention is usually in the range of 200 to 20,000 cps, and preferably 2,000 to 15,000 cps, measured at 25°C.
  • composition of the present inventions after curing has a slip value of no greater than about 3 kgf/mm 2 , when tested as set forth herein.
  • shear slip value of the cured composition is between about 0.1 and 2 kgf/mm 2 .
  • Example 1 1,127 g of tricyclodecanedimethanol diacrylate, 1,453 g of 2,4-tolylene diisocyanate, 4.5 g of dibutyltin dilaurate, 1.5 g of 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor, and 0.5 g of phenothiazine were placed in a reaction vessel equipped with a stirrer. The mixture was cooled to 10°C over an ice-cooled bath and 1,266 g of hydroxyethyl acrylate was added while controlling the temperature at 20°C or lower. After the addition, the mixture was stirred for one hour at 10-20°C.
  • a composition of the present invention was prepared in the same manner as in Example 1, except that instead of 15 ⁇ m particles, cross-linked poly(methyl (meth)acrylate) particles with an average diameter of 30 ⁇ m, Art Pearl G-200(tm), manufactured by Negami Kogyo Co. were used as polymer particles.
  • a composition of the present invention was prepared in the same manner as in Example 1, except for using polyurethane particles (average diameter: 15 ⁇ m, Art Pearl C-400(tm), manufactured by Negami Kogyo Co.) as polymer particles, instead of 15 ⁇ m cross-linked poly(methylmethacrylate) particles.
  • polyurethane particles average diameter: 15 ⁇ m, Art Pearl C-400(tm), manufactured by Negami Kogyo Co.
  • a composition of the present invention was prepared in the same manner as in Example 1, except that polyurethane particles with an average diameter of 30 ⁇ m, Art Pearl C-200(tm), manufactured by Negami Kogyo Co.) were used as polymer particles, in stead of 15 ⁇ m corss- linked poly(methylmethacrylate) particles.
  • a composition was prepared in the same manner as in Example 1, except that no polymer particles were used.
  • the composition was applied to a glass plate using an applicator bar, to a thickness of 75 ⁇ m, followed by irradiation by UV light at 100 mJ/cm 2 in nitrogen atmosphere to provide a cured film with a thickness of 50 ⁇ m.
  • the cured film was peeled from the glass plate and allowed to stand at 23° and 50% RH for 24 hours. This film was used in the test.
  • Shear slip test A test specimen was attached to an aluminum sheet using a double-sided adhesive tape. Two sheets thus prepared were positioned so that the surfaces of the test specimens were in face to face contact and the sheets were fastened with a clip. The pressure at the surfaces of the test specimens when fastened with a clip was 0.241 kg/mm 2 . The two aluminum sheets were pulled apart at a pull-away speed of 50 mm/min to measure the force required for the sample sheets to slip. ⁇ Evaluation of strength of the cured product> 1.
  • the composition was applied to a glass plate using an applicator bar to a thickness of 150 ⁇ m, followed by irradiation by UV light at 1.0 J/cm 2 in air to provide a cured film with a thickness of 120 ⁇ m.
  • the cured film was peeled from the glass plate and allowed to stand at 23°C and 50% RH for 24 hours. This film was used in the test.
  • Measurement of modulus of elasticity in tension A strip of the test leaf with a width of 6 mm was prepared to measure modulus of elasticity in tension at 23°C according to JIS K7113. The tension at 2.5% stress was measured at a pulling rate of 1 mm/min to calculate the modulus of elasticity in tension.
  • the liquid curable resin composition for coating optical fibers of the present invention is particularly suitable as a taping material and a bundling material used for high integration fiber cables and air-blown fibers.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Paints Or Removers (AREA)

Abstract

Une composition de résine durcissable à l'état liquide destinée à revêtir des fibres optiques comprend: (1) un (méth)acrylate uréthanique; (B) un initiateur de polymérisation et (C) des particules polymères ayant un diamètre particulaire moyen compris entre 5 νm et 1 mm. La composition présente d'excellentes caractéristiques de glissement en surface, des caractéristiques de durcissement supérieures ainsi qu'une résistance suffisante, elle est très utile en tant que matériau destiné à la fabrication de câbles en fibre soufflée.
PCT/NL1997/000322 1996-06-07 1997-06-06 Composition de resine durcissable a l'etat liquide et fibres optiques en faisceau WO1997046495A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU29821/97A AU2982197A (en) 1996-06-07 1997-06-06 Liquid curable resin composition and bundled optical fibers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP8145712A JPH09324136A (ja) 1996-06-07 1996-06-07 光ファイバー被覆用液状硬化性樹脂組成物
JP8/145712 1996-06-07

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0860485A1 (fr) * 1997-02-20 1998-08-26 Dsm N.V. Composition liquide, durcissable de résine synthétique
WO2000039042A1 (fr) * 1998-12-23 2000-07-06 Owens Corning Systeme d'encollage non aqueux pour fibres de verre et polymeres moulable par injection
WO2003102035A1 (fr) * 2002-05-31 2003-12-11 Luvantix Co., Ltd. Composition de resine expansible et durcissable aux rayons ultraviolets
EP1396745A3 (fr) * 2002-09-03 2004-04-21 FITEL USA CORPORATION (a Delaware Corporation) Câbles à fibres optiques pour installations de microconduit
EP1484624A4 (fr) * 2002-03-13 2005-08-17 Fujikura Ltd Fibre optique de compensation de dispersion
WO2006036057A1 (fr) 2004-09-28 2006-04-06 Dsm Ip Assets B.V. Composition de gaine superieure en resine liquide durcissable par rayonnement pour fibres optiques
EP1477529A4 (fr) * 2002-01-25 2006-05-31 Sumitomo Bakelite Co Composition de composite transparent
WO2022107811A1 (fr) * 2020-11-19 2022-05-27 Japan Fine Coatings Co., Ltd. Composition pour former une couche de revêtement de fibre optique et couche durcie de celle-ci, fibre optique présentant une couche durcie et son utilisation
JP2022081377A (ja) * 2020-11-19 2022-05-31 日本特殊コーティング株式会社 光ファイバ被覆層形成用組成物及びその硬化層、並びに硬化層を有する光ファイバ及び光ファイバ被覆層形成用組成物の使用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6638616B2 (en) * 1999-10-15 2003-10-28 Dsm N.V. Radiation-curable compositions comprising oligomers having an alkyd backbone
JP2002003748A (ja) * 2000-06-26 2002-01-09 Dainippon Ink & Chem Inc 活性エネルギー線硬化型塗料組成物
JP4564834B2 (ja) 2004-09-24 2010-10-20 Ｊｓｒ株式会社 光ファイバアップジャケット用液状硬化性樹脂組成物
JP4952327B2 (ja) * 2007-03-27 2012-06-13 コニカミノルタビジネステクノロジーズ株式会社 電子写真用現像ローラの製造方法

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EP0106548A1 (fr) * 1982-09-20 1984-04-25 The Furukawa Electric Co., Ltd. Fibres optiques enrobées
EP0195387A1 (fr) * 1985-03-15 1986-09-24 Nippon Paint Co., Ltd. Fibres optiques revêtues
JPS6327504A (ja) * 1986-07-18 1988-02-05 Nippon Paint Co Ltd 放射エネルギ−線硬化性樹脂組成物
EP0345968A2 (fr) * 1988-05-28 1989-12-13 BICC Public Limited Company Fibres optiques revêtues
WO1991015434A1 (fr) * 1990-03-30 1991-10-17 Owens-Corning Fiberglas Corporation Composition de revetement pour fibres
US5182786A (en) * 1988-12-23 1993-01-26 Kansai Paint Co., Ltd. Active energy beam-curable composition containing particles and coated optical fiber
JPH05203847A (ja) * 1992-01-24 1993-08-13 Fujikura Ltd 光ファイバ

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EP0106548A1 (fr) * 1982-09-20 1984-04-25 The Furukawa Electric Co., Ltd. Fibres optiques enrobées
EP0195387A1 (fr) * 1985-03-15 1986-09-24 Nippon Paint Co., Ltd. Fibres optiques revêtues
JPS6327504A (ja) * 1986-07-18 1988-02-05 Nippon Paint Co Ltd 放射エネルギ−線硬化性樹脂組成物
EP0345968A2 (fr) * 1988-05-28 1989-12-13 BICC Public Limited Company Fibres optiques revêtues
US5182786A (en) * 1988-12-23 1993-01-26 Kansai Paint Co., Ltd. Active energy beam-curable composition containing particles and coated optical fiber
WO1991015434A1 (fr) * 1990-03-30 1991-10-17 Owens-Corning Fiberglas Corporation Composition de revetement pour fibres
JPH05203847A (ja) * 1992-01-24 1993-08-13 Fujikura Ltd 光ファイバ

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0860485A1 (fr) * 1997-02-20 1998-08-26 Dsm N.V. Composition liquide, durcissable de résine synthétique
US5986018A (en) * 1997-02-20 1999-11-16 Dsm N.V. Liquid curable resin compositions
WO2000039042A1 (fr) * 1998-12-23 2000-07-06 Owens Corning Systeme d'encollage non aqueux pour fibres de verre et polymeres moulable par injection
US6399198B1 (en) 1998-12-23 2002-06-04 Owens Corning Fiberglas Technology, Inc. Nonaqueous sizing system for glass fibers and injection moldable polymers
CZ299979B6 (cs) * 1998-12-23 2009-01-14 Owens Corning Bezvodá klížicí kompozice pro aplikaci na skelná vyztužující vlákna a vlákna pokrytá touto kompozicí
EP1477529A4 (fr) * 2002-01-25 2006-05-31 Sumitomo Bakelite Co Composition de composite transparent
AU2003211873B2 (en) * 2002-01-25 2008-05-22 Sumitomo Bakelite Co., Ltd. Transparent composite composition
EP1484624A4 (fr) * 2002-03-13 2005-08-17 Fujikura Ltd Fibre optique de compensation de dispersion
US7233728B2 (en) 2002-03-13 2007-06-19 Fujikura Ltd. Dispersion compensating optical fiber
KR100487026B1 (ko) * 2002-05-31 2005-05-10 주식회사 루밴틱스 자외선 경화형 발포체의 제조방법
WO2003102035A1 (fr) * 2002-05-31 2003-12-11 Luvantix Co., Ltd. Composition de resine expansible et durcissable aux rayons ultraviolets
EP1396745A3 (fr) * 2002-09-03 2004-04-21 FITEL USA CORPORATION (a Delaware Corporation) Câbles à fibres optiques pour installations de microconduit
WO2006036057A1 (fr) 2004-09-28 2006-04-06 Dsm Ip Assets B.V. Composition de gaine superieure en resine liquide durcissable par rayonnement pour fibres optiques
WO2022107811A1 (fr) * 2020-11-19 2022-05-27 Japan Fine Coatings Co., Ltd. Composition pour former une couche de revêtement de fibre optique et couche durcie de celle-ci, fibre optique présentant une couche durcie et son utilisation
JP2022081377A (ja) * 2020-11-19 2022-05-31 日本特殊コーティング株式会社 光ファイバ被覆層形成用組成物及びその硬化層、並びに硬化層を有する光ファイバ及び光ファイバ被覆層形成用組成物の使用

Also Published As

Publication number Publication date
JPH09324136A (ja) 1997-12-16
AU2982197A (en) 1998-01-05

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