WO1998032780A1 - Composition de resine liquide durcissable - Google Patents

Composition de resine liquide durcissable Download PDF

Info

Publication number
WO1998032780A1
WO1998032780A1 PCT/NL1998/000037 NL9800037W WO9832780A1 WO 1998032780 A1 WO1998032780 A1 WO 1998032780A1 NL 9800037 W NL9800037 W NL 9800037W WO 9832780 A1 WO9832780 A1 WO 9832780A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
composition
acrylate
composition according
resin composition
Prior art date
Application number
PCT/NL1998/000037
Other languages
English (en)
Inventor
Tsuyoshi Hirai
Toshikazu Kikuchi
Zen Komiya
Takashi Ukachi
Original Assignee
Dsm N.V.
Jsr Corporation
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., Jsr Corporation filed Critical Dsm N.V.
Priority to AU55789/98A priority Critical patent/AU5578998A/en
Publication of WO1998032780A1 publication Critical patent/WO1998032780A1/fr

Links

Classifications

    • 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
    • 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

Definitions

  • the present invention relates to a liquid curable resin composition, and more particularly, to a liquid curable resin composition exhibiting excellent coatability to ribbon matrixes due to the low viscosity, being able to cure fast, and capable of producing cured products with superior tearing characteristics due to the small elongation.
  • the resin composition is suitable for use as a material for bundling ribbon matrixes. Description of the related art:
  • a resin coating is provided for protection and reinforcement immediately after spinning molten glass fibers .
  • a known structure of the resin coating consists of a primary coating layer of a flexible resin which is coated on the surface of optical fibers and a secondary coating layer of a rigid resin which is provided over the primary coating layer.
  • a so-called optical fiber ribbon is known in the art in the application of coated optical fibers.
  • the optical fiber ribbon is made from several elemental optical fibers, e.g. four or eight optical fibers, by arranging these fibers in a plane and fixing them with a binder to produce a ribbon structure with a rectangular cross section.
  • a multiple core ribbon structure prepared by binding two or more optical fiber ribbons for example, a ribbon structure made from eight elemental fibers consisting of two ribbons, each made from four elemental optical fibers bound together, is also known.
  • the resin compositions for coating these optical fibers include a soft material used for producing the primary coating layer, a hard material used for producing the secondary coating layer, a ribbon matrix material for preparing optical fiber ribbons from several optical fibers, and a bundling material for producing multiple core ribbon structure consisting of several optical fiber ribbons.
  • the characteristics required for curable resins used as the bundling materials for optical fibers include: to be curable fast, to have a sufficient low viscosity to be coated to ribbon materials at a high speed, thereby providing excellent productivity, and to produce cured products with sufficient strength and superior flexibility, exhibiting very little physical change during temperature changes over a wide range, showing superior long term reliability with little physical changes over time, showing superior resistance to chemicals such as acids and alkalis, exhibiting low moisture and water absorption, and exhibiting superior surface characteristics and having a small coefficient of friction.
  • the characteristics of a bundling material to be comparatively easily released and separated from materials which are bound by this bundling material are demanded of the bundling materials not only used with optical fibers, but also used for other purposes.
  • An object of the present invention is therefore to provide a liquid curable resin composition, and particularly a liquid curable resin composition which can be rapidly cured, exhibits high productivity due to the low viscosity, and easily separated from articles which are bound by this resin composition without leaving adhered residue after separation.
  • a liquid curable resin composition comprising (A) a polyol polyurethane containing an ethylenically unsaturated group, (B) a polyfunctional compound containing three or more (meth) acryloyl groups, and (C) a compound containing N-vinyl groups in a proportion of 0.25 to 2 mols for one mol of the (meth) acryloyl group contained in the composition.
  • the polyol polyurethane containing ethylenically unsaturated group (Component (A) ) used in the present invention can be prepared by reacting a polyol, a diisocyanate, and a compound having an ethylenically unsaturated group, specifically, by reacting the isocyanate group of the diisocyanate with the hydroxyl group of the polyol and the compound having an ethylenically unsaturated group.
  • the reaction can be carried out, for example, by the following methods: a method of simultaneously reacting the polyol, the diisocyanate, and the compound having an ethylenically unsaturated group; a method of reacting the polyol and the diisocyanate to obtain an intermediate compound, and reacting this intermediate compound with the compound having an ethylenically unsaturated group; a method of reacting the diisocyanate and the compound with an ethylenically unsaturated group, and then reacting the resulting compound with the polyol; a method of reacting the diisocyanate and the compound with an ethylenically unsaturated group, reacting the resulting compound with the polyol, then again reacting with the compound with an ethylenically unsaturated group.
  • polystyrene resin examples include aliphatic polyether diols, alicyclic polyether diols, aromatic polyether diols, polyester diols, polycarbonate diols, polycaprolactone diols, and other polyols. These polyols may be used either individually or in combinations of two or more. The manner of polymerization of each constitutional unit in these polyols is not specifically limited and may be random polymerization, block polymerization, or graft polymerization.
  • aliphatic polyether diols among these polyols 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 compound include cyclic ethers such as ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3'- bischloromethyloxetane, tetrahydrofuran, 2- methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrine, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidylbenzo
  • polyether diol obtained by the ring-opening copolymerization of two or more types of these ionic-polymerizable cyclic compounds include binary copolymers and ternary copolymers, specifically, binary copolymers such as those obtained by the combination of tetrahydrofuran and propylene oxide, tetrahydrofuran and 2- methyltetrahydrofuran, tetrahydrofuran and 3- methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, and butene- 1-oxide and ethylene oxide; and ternary copolymers obtained by the combination of tetrahydrofuran, butene- 1-oxide, and ethylene oxide.
  • a cyclic imine such as ethylene imine
  • a cyclic lactone such as 3-propiolactone and glycolic acid lactide
  • a cyclic siloxane such as dimethylcyclopolysiloxane
  • aliphatic polether diols are commercially available under the trademarks, for example, of PTMG 650, PTMG 1000, PTMG 2000 (Mitsubishi Chemical Corp.); PPG 400, PPG 1000, EXCENOL 720, EXCENOL 1020, 2020, (Asahi Oline Co., Ltd.); PEG 1000, UNISAFE DC 1100, UNISAFE DC 1800 (Nippon Oil and Fats Co., Ltd.); PPTG 2000, PPTG 1000, PTG 400, PTGL 2000 (Hodogaya Chemical Co., Ltd.); and Z-3001-4, Z-3001-5, PBG 2000A, PBG 2000B, EO/BO 4000, EO/BO 2000 (Daiichi Kogyo Seiyaku Co., Ltd.).
  • Alkylene oxide adducts to hydrogenated bisphenol A, alkylene oxide adducts to hydrogenated bisphenol F, and alkylene oxide adducts to 1,4- cyclohexane diol are given as examples of alicyclic polyether diol.
  • Alkylene oxide addition diol to bisphenol A such as polyoxyethylene bisphenol A ether, 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 are given as examples of aromatic polyether diols.
  • the aromatic polyether diols are also commercially available under the trademarks, for example, of Uniol DA400, DA700, DA1000, and DA4000 (Nippon Oil and Fats Co., Ltd.).
  • Polyester diols obtained by the reaction of a polyhydric alcohol and a polyacidic base are given as examples of the polyester diol.
  • polyester diols which can be used include, for example, Kurapol P-2010, PMIPA, PKA-A, PKA-A2, PNA- 2000 (Kuraray Co., Ltd.).
  • a polycarbonate of polytetrahydrofuran and a polycarbonate of 1,6-hexane diol can be given as examples of the polycarbonate.
  • the polycarbonate can also be commercially available under the trademarks, for example, of DN-980, DN-981, DN-982, DN-983 (Nippon Polyurethane Industry Co., Ltd.), PC-8000 (PPG of the US) , and PC-THF-CD (BASF) .
  • the polycaprolactone diol are polycaprolactone diols obtained by the reaction of e-caprolactone and a diol.
  • Such a diol may be, for example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1, 2-polybutylene glycol, 1,6-hexane diol, neopentyl glycol, 1,4- cyclohexane dimethanol, and 1,4-butane diol.
  • These polycaprolactone diols can be also commercially available under the trademarks such as PLACCEL 205, 205AL, 212, 212AL, 220, 220AL (Daicel Chemical Industries, Ltd.).
  • polyol compounds which can be used include dimethylol compounds of 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, or dicyclopentadiene; tricyclodecane dimethanol, pentacyclopentadecane dimethanol, ⁇ -methyl- ⁇ -valerolactone, polybutadiene with terminal hydroxyl groups, hydrogenated polybutadiene with terminal hydroxyl groups, castor oil modified polyol, polydimethylsiloxane with terminal diols, and polydimethylsiloxane carbitol-modified polyols.
  • the number average molecular weight of the polyol for producing component (A) is usually 50- 15,000, and preferably 100-12,000.
  • the polyether polyols can produce polyurethane with particularly excellent durability and low-temperature characteristics .
  • diisocyanates used for producing component (A) of 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- cyclohexylisocyanate) , 2 , 2 , 4-trimethylhexamethylene diisocyanate,
  • diisocyanates 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and methylenebis (4-cyclohexylisocyanate) are particularly preferred.
  • diisocyanates may be used either individually or in combinations of two or more.
  • the compounds having an ethylenically unsaturated group used for producing the component (A) include (meth) acrylates containing a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) crylate, 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, (meth) acrylates represented by the following structural formulas (1) or (2) ,
  • R 1 is a hydrogen atom or a methyl group and n denotes an integer of 1-15.
  • these (meth) acrylates having a hydroxyl group particularly desirable are 2- hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
  • compounds obtained by the addition reaction of a compound containing a glycidyl group, such as, alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth) acrylate, and (meth) acrylic acid can also be used as the compound having an ethylenically unsaturated group .
  • These compounds having an ethylenically unsaturated group may be used either individually or in combination of two or more.
  • the proportion of the polyol, the diisocyanate, and the compound having an ethylenically unsaturated group used for preparing the component (A) is such that for one mol of the hydroxyl group of the polyol, 1.1-3 mols of the diisocyanate group contained in the diisocyanate compounds and 0.2-1.5 mols of the hydroxyl group contained in the hydroxyl group- containing (meth) acrylate are used.
  • a particularly preferred proportion is for one mol of the hydroxyl group of the polyol, 1.5-2 mols of the diisocyanate group contained in the diisocyanate compounds and 0.5- 1.0 mols of the hydroxyl group contained in the hydroxyl group-containing (meth) acrylate .
  • a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyl-tin- laurylate, triethylamine, 1, 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 10-90°C, preferably of 30-80°C.
  • the component (A) has a weight average molecular weight reduced to polystyrene of 500 to
  • weight average molecular weight is less than 500, flexibility of the cured product may be reduced due to a small molecular weight between cross- linking points and deformation due to shrinkage during curing may increase. If the molecular weight is larger than 20,000, on the other hand, the strength of the resin after cure may be insufficient.
  • the component (A) is incorporated in the composition in an amount preferably of 10-90% by weight, and more preferably 20-80% by weight.
  • the polyfunctional compound (B) contains three or more (meth) acrylate groups. Generally, the compound (B) will contain less than 10 (meth) acrylate groups, preferably less than 6.
  • the molecular weight is not critical, and will generally be between 300-2000.
  • the molecular weight is less than 1000.
  • the polyfunctional compound containing three or more (meth) acryloyl groups used as the component (B) in the present invention are trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol monohyroxypenta (meth) acrylate, tris (2- (meth) acryloxyethyl) -isocyanurate tri (meth) acrylate, and the like.
  • the component (B) can also be commercially available under the trademarks, for example, of FA731A (Hitachi Chemical Co., Ltd.); ARONIX M-315, M-350, M- 360, M-405, M-450 (Toagosei Chemical Industry Co., Ltd.); KAYARAD DPHA, D-310, D-320, D-330, DPCA-20,
  • DPCA-30, DPCA-60, DPCA-120 Nippon Kayaku Co., Ltd.
  • Viscoat 400 Osaka Organic Chemical Industry, Ltd.
  • Photomer 4172, 4149 Sun Nopco Co., Ltd.
  • ARONIX M-450, Viscoat 400, and Photomer 4149 are preferred.
  • the component (B) is incorporated in the composition in an amount preferably of 3-75% by weight, and more preferably 5-68% by weight. If less than 3% by weight, not only hardness of the cured products obtained from the resin composition is decreased, but also the rubbery elasticity is increased, resulting in difficulty in separating two bundled optical fiber ribbons due to elongation of the bundling material, when the composition is used as the bundling material for optical fiber ribbons. If the proportion of the component (B) is larger than 75% by weight, on the other hand, hardness of the cured products obtained from the resin composition is unduly increased, so that the bundling material is difficult to be broken and the resin composition exhibits too large shrinkage when cured. Adhesion to optical fiber ribbons is also impaired.
  • the compound (C) having a N-vinyl group may have one or more N-vinyl groups.
  • compound C has one N-vinyl group.
  • the molecular weight of compound (C) will be higher than 70, and generally lower than 1000.
  • the molecular weight and the viscosity of compound (C) are low, so compound (C) acts as a reactve diluent.
  • Suitable N-vinyl group comprising compounds include N-vinyl pyrrolidone, N-vinyl -carbazole, N-vinyl caprolactam, N-vinyl-formamide and reaction products of N-vinylformamide with e.g. isocyanate comprising compounds .
  • N-Vinyl pyrrolidone, N-vinyl caprolactam, and the like are preferred examples of the compound having an N-vinyl group used as the component (C) .
  • the amount of the compound having N-vinyl group is such that the proportion of the N-vinyl group is 0.25 to 2 mols for 1 mol of the (meth) acryloyl group contained in the composition. Preferably, the ratio is 0.35 or higher. It is also preferred to have less than 1 mole of N-vinyl group relative to the (meth) acryl group.
  • Either too large or too small an amount of the N-vinyl group for the (meth) acryloyl group in the composition may result in a retarded curing rate due to decrease in the alternate copolymerization of N-vinyl group and (meth) acryloyl group.
  • composition of the present invention preferably comprises other consituents.
  • a suitable additional compound is a urethane
  • (meth) acrylate compound produced by reacting 2 mols of a (meth) acrylate containing a hydroxyl group and one mol of diisocyanate can be added to the liquid curable resin composition of the present invention.
  • urethane (meth) acrylates are a reaction product of hydroxyethyl (meth) acrylate and 2 , 5-bis (isocyanate methyl) -bicyclo [2.2.1] heptane, a reaction product of hydroxyethyl (meth) acrylate 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,
  • urethane (meth) acrylate can be used in an amount preferably of 30 parts by weight or less for 100 parts by weight of the total amount of the polyol polyurethane (A) having an ethylenically unsaturated group and urethane (meth) acrylate .
  • the liquid curable resin composition of the present invention can be cured by heat or radiation.
  • the composition of the present invention usually contains a polymerization initiator.
  • a heat sensitive polymerization initiator and/or ligt sensitive polymerization initiator can be used as polymerization initiator.
  • Radiation here means radiation such as infrared light, visible light, ultraviolet light, X- rays, electron beams, ⁇ ?-rays, -rays, and ⁇ -rays.
  • ultraviolet light and/or visible light are used to cure the composition of the present invention.
  • a peroxide or an azo compound is usually used as a heat sensitive polymerization initiator.
  • Benzoyl peroxide, t- butyloxybenzoate, and azobisisobutylonitrile are given as specific examples.
  • a radiation sensitive polymerization initiator When the liquid curable resin composition of the present invention is cured by radiation, a radiation sensitive polymerization initiator is used.
  • Suitable examples of the radiation polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone , xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone,
  • the above-described heat polymerization initiators and radiation polymerization initiators may be used together.
  • the polymerization initiators are used in an amount of 0.1-10% by weight, preferably 0.5-7% by weight, in the composition.
  • other diluents and additives may be used in the liquid curable resin composition of the present invention to the extent that the effects of the present invention are not adversely affected.
  • Monomers containing (meth) acryloyl group or vinyl group other than the above-described monomers (B) and (C) can be used as a reactive diluent in the coating composition.
  • Such monomers include mono- functional and di-functional monomers.
  • the mono-functional monomers are alicyclic (meth) acrylates, such as isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl
  • (meth) acrylate dicyclopentenyl (meth) acrylate, 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) crylate, 2-hydroxybutyl
  • R 2 is a hydrogen atom or a methyl group
  • R 3 is an alkylene group containing 2 to 6, preferably 2 to 4 carbon atoms
  • R 4 is a hydrogen atom or an alkyl group containing 1 to 12, preferably 1 to 9, carbon atoms
  • m is an integer from 0 to 12, and preferably from 1 to 8.
  • CH 2 C(R 2 ) -C00(R 5 0) D -0- CH 2 -R 6 (4)
  • R 2 is the same as defined in formual (3) ;
  • R 5 is an alkylene group containing 2 to 8 , preferably 2 to 5, carbon atoms;
  • R 6 is a tetrahydrofuryl group; and
  • p is an integer from 1 to 8 , and preferably from 1 to .
  • CH 2 C (R 2 ) - COO (R 5 0) p -R 7 ( 5 )
  • R 2 , R 5 , and p are the same as defined in the formula (4) ; and R 7 is an aromatic group, preferably a phenyl group, optionally substituted with an alkyl group having 1-18 carbon atoms, preferably 1-9 carbon atoms ; and monomers containing a vinyl group other than N-vinyl group, such as hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether.
  • di-functional monomers examples include monomers containing (meth) acryloyl group such as 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, neopentyl glycol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, di (meth) acrylate of a diol which is an ethylene oxide adduct to bisphenol A, di (meth) acrylate of a diol which is an ethylene oxide adduct to hydrogenated bisphenol A, and epoxy (meth) acrylate which is a (meth) acrylate adduct to diglycidyl ether of bisphenol A; and vinyl group- containing monomers such as
  • tricyclodecanediyldimethyl di (meth) acrylate and diacrylate of a diol which is an alkylene oxide adduct to bisphenol A are particularly preferred.
  • reactive diluents may be added either individually or in combinations of two or more to the composition of the present invention in an amount, usually, of 1-80% by weight, preferably 10 to 70% by weight.
  • the addition of the reaction diluents in the amount in this range suitably controls the coatability and curing rate of the resin composition, toughness of the cured products, and reduces shrinkage during cure.
  • amines may be added to the liquid curable resin composition of the present invention to suppress generation of hydrogen gas which causes a transmission loss of optical fibers.
  • the amines which can be added include diarylamine, diisopropylamine, diethylamine, and diethylhexylamine .
  • antioxidants such as antioxidants, UV absorbers, photo-stabilizers, silane coupling agents, thermal polymerization inhibitors, leveling agents, surfactants, preservatives, plasticizers, lubricants, coloring agents, solvents, fillers, anti-oxidants, wettability improvers, and coatability improvers .
  • antioxidants which can be used are Irganox 1010, 1035, 1076, 1222 (Ciba Geigy) , Antigen P, 3C, FR, GA-80 (Sumitomo Chemical Industries Co., Ltd.), and the like.
  • UV absorbers Tinuvin P, 234, 320, 326, 327, 328, 329, 213 (Ciba Geigy), Seesorb 102, 103, 501, 202, 712, 704
  • photo-stabilizers which can be added include Tinuvin 292, 144, 622LD (manufactured by Ciba Geigy) , Sanol LS770 (manufactured by Sankyo Chemical Co.), and SUMISORB TM-061 (manufactured by Sumitomo Chemical Industries) .
  • silane coupling agents which can be given are ⁇ -aminopropyl- triethoxy silane, ⁇ -mercaptopropyltrimethoxy silane, ⁇ -methacryloxypropyltrimethoxy silane, and commercially available products such as SH6062, SH6030 (Toray Silicone Co.) and KBE903, KBE603, KBE403 (Shin-etsu Chemical Co. ) .
  • the viscosity of the liquid curable resin composition of the present invention is normally in the range of 200 to 10,000 cp at 25°C, and preferably 1,000 to 8, 000 cp at 25°C.
  • the liquid curable resin composition of the present invention preferably is used as bundling material in a construction to bind at least two ribbons comprising each at least two coated optical glass fibers bonded by a ribbon matrix material.
  • the coated optical glass fibers preferably are color coated, either by a thin UV-curable ink, or by coloring the secondary coating.
  • the bundle of ribbons will comprise 2-20 ribbons, preferably 2-10.
  • the ribbons generally will comprise 2-20 coated optical fibers, preferably 2-12.
  • the cured resin composition of the present invention has a Young's modulus of 5-50 kg/mm 2 . It is furthermore desirable, that the cured resin composition has an elongation at break of 70% or lower, preferably 50% or lower. The elongation at break generally will be higher than 3%, and preferably is higher than 10%.
  • the breaking strength of the cured composition preferably is higher than 0.5 kg/mm 2 , and more preferably higher than 1 kg/mm 2 . Generally, the breaking strength will be less than 10 kg/mm 2 , preferably less than 5 kg/mm 2 . It is desirable that the cured resin composition of the present invention has an adhesion to a ribbon matrix material in the range of 5 to 200 g/cm.
  • a composition was prepared in the same manner as in Example 2, except that no component (B) (trimethylolpropane ethoxy triacrylate) was added. Comparative Example 2
  • a composition was prepared in the same manner as in Example 2, except that no component (C) (N-vinyl pyrrolidone) was added.
  • liquid curable resin compositions prepared in Examples 1-2 and Comparative Examples 1-2 were evaluated by measuring the viscosity of the compositions, the Young's modulus, breaking strength, and elongation at break of the cured products, and the adhesion strength with a ribbon material, according to the following methods . The results are shown in Table 1.
  • the viscosity was measured at 25°C using a B- type viscometer manufactured by Tokyo Keiki Co., Ltd.
  • the liquid curable resin compositions were applied to glass plates using an applicator bar to a thickness of 125 mm and irradiated with UV light at 0.1 J/cm 2 or 1.0 J/cm 2 using a jet printer HMW (manufactured by Ore Manufacturing Co., Ltd.) in a nitrogen atmosphere, to obtain cured films with a thickness of 50 ⁇ m.
  • the films were peeled off from the glass plates and allowed to stand at 23 °C and 50% RH for 24 hours. The resulting films were used as test specimens.
  • test specimens were cut into stripes with a width of 6 mm to measure Young's modulus according to JIS K7113 at 23°C using Autograph AGS-1KND
  • compositions were applied to glass plates using an applicator bar to a thickness of 300 ⁇ m and irradiated with UV light at 1.0 J/cm 2 in air to obtain cured films with a thickness of 200 ⁇ m.
  • the films were peeled off from glass plates and allowed to stand at
  • test specimens were cut into stripes with a width of 6 mm to measure breaking elongation at break at 23 °C using Autograph AGS-1KND (manufactured by Shimazu Corp.), provided that conditions of a pulling rate of 1 mm/min and a bench mark distance of 25 mm were applied.
  • Autograph AGS-1KND manufactured by Shimazu Corp.
  • test specimens were cut into stripes with a width of 6 mm to measure breaking strength at 23 °C using Autograph AGS-1KND (manufactured by Shimazu).
  • An optical fiber material (R3139 manufactured by Japan Synthetic Rubber Co., Ltd.) was applied to glass plates using an applicator bar to a thickness of 300 ⁇ m and irradiated with UV light at 0.5 J/cm 2 in a nitrogen atmosphere to obtain cured films with a thickness of 200 ⁇ m.
  • the films were peeled off from the glass plates and allowed to stand at 23 °C and 50% RH for 24 hours. The resulting films were used as the test specimens.
  • the resin compositions prepared in the Examples and Comparative Examples were coated to one side of the test specimens using a spin coater (SPINNER 1H-2, manufactured by Mikasa Co., Ltd.) and irradiated with UV light at 0.1 J/cm 2 in a nitrogen atmosphere to obtain samples with a two layer structure, wherein the thickness of the resin compositions was 50 ⁇ m.
  • SPINNER 1H-2 manufactured by Mikasa Co., Ltd.
  • the samples were cut into stripes with a width of 1 cm to measure the adhesion strength at a pulling rate of 50 mm/min using Autograph AGS-IKND Type I (manufactured by Shimazu Corp.) .
  • the ratio o t e num er o mo s o e o a N-v ny groups and that of the total acryloyl groups in the resin composition The closer is this ratio to 1.0, the higher is the degree of the alternate copolymerization of the N-vinyl groups and that the acryloyl groups and, therefore, the higher the curing rate.
  • the liquid curable resin composition of the present invention exhibits a high curing rate, provides high productivity in optical fiber manufacturing due to the low viscosity, and produces cured products with superior tearing characteristics due to the small extensibility.
  • the resin composition is suitable for use as a bundling material and as a material for binding various other materials.

Landscapes

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

Abstract

Composition de résine liquide durcissable qui présente une vitesse de durcissement élevée, permet une grande productivité de par sa faible viscosité, et peut être enlevée facilement des objets auxquels elle est liée. Ladite composition est utile en tant que matériau pour la mise en faisceau de matériaux en ruban. Ladite composition de résine liquide thermodurcissable comporte un polyuréthanne de polyol contenant un groupe éthyléniquement insaturé, un composé polyfonctionnel contenant au moins trois groupes (méth)acryloyle et un composé contenant des groupes N-vinyle.
PCT/NL1998/000037 1997-01-23 1998-01-20 Composition de resine liquide durcissable WO1998032780A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU55789/98A AU5578998A (en) 1997-01-23 1998-01-20 Liquid curable resin composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9010595A JPH10204250A (ja) 1997-01-23 1997-01-23 液状硬化性樹脂組成物
JP9/10595 1997-01-23

Publications (1)

Publication Number Publication Date
WO1998032780A1 true WO1998032780A1 (fr) 1998-07-30

Family

ID=11754606

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1998/000037 WO1998032780A1 (fr) 1997-01-23 1998-01-20 Composition de resine liquide durcissable

Country Status (3)

Country Link
JP (1) JPH10204250A (fr)
AU (1) AU5578998A (fr)
WO (1) WO1998032780A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999008975A1 (fr) * 1997-08-15 1999-02-25 Dsm N.V. Composition de resine capable de durcir sous un rayonnement
EP1024382A2 (fr) * 1999-01-26 2000-08-02 Alcatel Elastomères polyoléfiniques thermoplastiques flexibles pour la protection des éléments de transmission dans un câble de télécommunications
US6579618B1 (en) 1997-08-15 2003-06-17 Dsm N.V. Coated optical fiber and radiation curable resin composition
WO2004033511A1 (fr) * 2002-10-08 2004-04-22 Dsm Ip Assets B.V. Composition de resine photodurcissable et matiere optique

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4789329B2 (ja) * 2000-04-03 2011-10-12 Ｊｓｒ株式会社 二層フィルム
JP2002188059A (ja) * 2000-12-20 2002-07-05 Jsr Corp 艶出し剤用組成物
KR101021577B1 (ko) * 2008-08-12 2011-03-16 에스에스씨피 주식회사 광경화형 코팅 조성물
JP5373750B2 (ja) * 2010-11-30 2013-12-18 三洋化成工業株式会社 紫外線硬化型樹脂組成物
CN108369324B (zh) 2015-12-01 2021-06-18 古河电气工业株式会社 光纤带芯线和光纤线缆

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2384008A1 (fr) * 1977-03-14 1978-10-13 Gaf Corp Composition de revetement a base de n-vinyl-2-pyrrolidone et d'un oligomere
EP0125710A2 (fr) * 1983-04-11 1984-11-21 International Standard Electric Corporation Revêtement durcissable par rayonnement U.V. pour des fibres optiques
US4844604A (en) * 1987-11-13 1989-07-04 Desoto, Inc. Optical fiber bundling material and bundled optical fibers
EP0326276A2 (fr) * 1988-01-25 1989-08-02 The Kendall Company Procédé de liaison de composants, par exemple pour la fabrication d'ensembles de projecteurs d'automobile et de compositions d'adhésifs pour cette application
GB2256874A (en) * 1991-06-07 1992-12-23 Sericol Ltd Photocurable compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2384008A1 (fr) * 1977-03-14 1978-10-13 Gaf Corp Composition de revetement a base de n-vinyl-2-pyrrolidone et d'un oligomere
EP0125710A2 (fr) * 1983-04-11 1984-11-21 International Standard Electric Corporation Revêtement durcissable par rayonnement U.V. pour des fibres optiques
US4844604A (en) * 1987-11-13 1989-07-04 Desoto, Inc. Optical fiber bundling material and bundled optical fibers
EP0326276A2 (fr) * 1988-01-25 1989-08-02 The Kendall Company Procédé de liaison de composants, par exemple pour la fabrication d'ensembles de projecteurs d'automobile et de compositions d'adhésifs pour cette application
GB2256874A (en) * 1991-06-07 1992-12-23 Sericol Ltd Photocurable compositions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999008975A1 (fr) * 1997-08-15 1999-02-25 Dsm N.V. Composition de resine capable de durcir sous un rayonnement
US6579618B1 (en) 1997-08-15 2003-06-17 Dsm N.V. Coated optical fiber and radiation curable resin composition
EP1024382A2 (fr) * 1999-01-26 2000-08-02 Alcatel Elastomères polyoléfiniques thermoplastiques flexibles pour la protection des éléments de transmission dans un câble de télécommunications
WO2004033511A1 (fr) * 2002-10-08 2004-04-22 Dsm Ip Assets B.V. Composition de resine photodurcissable et matiere optique

Also Published As

Publication number Publication date
AU5578998A (en) 1998-08-18
JPH10204250A (ja) 1998-08-04

Similar Documents

Publication Publication Date Title
US6191187B1 (en) Optical glass fiber coating compositions
US5787218A (en) Liquid curable urethane (meth)acrylate containing resin composition
EP0892822B1 (fr) Composition de resine liquide durcissable
EP0860485B1 (fr) Composition liquide, durcissable de résine synthétique
KR20010006365A (ko) 액상 경화성 수지 조성물
US20080254288A1 (en) Curable Liquid Resin Composition
AU705686B2 (en) Optical glass fiber coating composition
KR100508714B1 (ko) 방사선-경화성 수지 조성물
EP1095085A1 (fr) Composition de resine photodurcissable
US20080167432A1 (en) Curable Liquid Resin Composition
US5913004A (en) Optical glass fiber coating composition
JP4197216B2 (ja) 液状硬化性樹脂組成物およびその硬化物
WO1998032780A1 (fr) Composition de resine liquide durcissable
JPH09324136A (ja) 光ファイバー被覆用液状硬化性樹脂組成物
EP0968144A1 (fr) Composition de resine liquide durcissable destinee a une grosse fibre
WO1997014737A1 (fr) Composition liquide a base de resine durcissable
EP1320563B1 (fr) Composition de resine durcissable, liquide, et produits durcis
AU693855B2 (en) Liquid curable resin composition for optical fibers
JP4763244B2 (ja) 液状硬化性樹脂組成物
WO2002037143A2 (fr) Composition de resine polymerisable liquide comprenant un compose de silicone
JP3607748B2 (ja) 多層被覆
JP3292326B2 (ja) 液状硬化性樹脂組成物
JP4028288B2 (ja) 光ファイバ素線
JP2003147031A (ja) 液状硬化性樹脂組成物およびその硬化物
JPH11167202A (ja) 液状硬化性樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: CA

122 Ep: pct application non-entry in european phase