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WO1999052958A1 - Composition de resine durcissable par rayonnement - Google Patents

Composition de resine durcissable par rayonnement Download PDF

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Publication number
WO1999052958A1
WO1999052958A1 PCT/NL1999/000215 NL9900215W WO9952958A1 WO 1999052958 A1 WO1999052958 A1 WO 1999052958A1 NL 9900215 W NL9900215 W NL 9900215W WO 9952958 A1 WO9952958 A1 WO 9952958A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
composition according
polymerizable unsaturated
component
Prior art date
Application number
PCT/NL1999/000215
Other languages
English (en)
Inventor
Miyuki Ishikawa
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
Priority claimed from JP10121755A external-priority patent/JPH11116642A/ja
Application filed by Dsm N.V., Jsr Corporation filed Critical Dsm N.V.
Priority to KR1020007011327A priority Critical patent/KR20010042636A/ko
Publication of WO1999052958A1 publication Critical patent/WO1999052958A1/fr
Priority to US10/372,741 priority patent/US20030195271A1/en

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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
    • 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
    • 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
    • C08F290/062—Polyethers

Definitions

  • the present invention relates to a radiation curable resin composition, and particularly to a radiation curable resin composition suitable for use as a coating material for optical fibers.
  • optical fibers are fragile and easily broken, the optical fibers are usually coated with a coating material which is a radiation curable resin composition.
  • the transmission characteristics of optical fibers are known to be significantly affected by properties such as modulus of elasticity or the like of the primary coating material which is in direct contact with the optical fibers. Because the primary coating material absorbs a high lateral pressure, materials having a modulus of elasticity of 0.15 kg/mm or less, in terms of a secant modulus measured by JIS K 7127, have conventionally been used.
  • such a conventional radiation curable resin composition has a drawback when used as the primary coating material for optical fibers. That is, when the primary coating material is removed to connect an optical fiber with another optical fiber, a portion of resinous material is left on the optical fibers. The complete removal of such resinous material remaining requires time-consuming procedures, impairing the processability of the material .
  • one object of the present invention is to provide a radiation curable resin composition suitable for use as a primary coating material for optical fibers, which can form a cured coating with a low modulus of elasticity exhibiting a high breaking strength and small light transmission loss, and yet easily removed from optical fibers.
  • a radiation curable resin composition comprising:
  • the radiation curable resin composition which can produce a cured product having a total of at least two peaks or shoulders m a temperature range from -50 C to +35°C, preferably at least one peak or shoulder in a temperature range from -50°C to -20 C and at least one peak or shoulder in a temperature range from -20 C to +35 C, in a temperature dependency curve of loss tangent obtained from a temperature dependency measurement of a dynamic viscoelasticity ratio when cured by ultraviolet radiation at a dose of 1 J/cm m air.
  • the composition comprises: (A) 25 to 75 wt% of a polymer containing polymerizable unsaturated groups in an average amount of 1.2 per molecule, a urethane bond and a polyoxyalkylene structure in a molecular chain, and having an average molecular weight from 3,000 to 30,000,
  • Figure 1 shows a temperature dependency curve of loss tangent (plotted figure) of the cured - 4 -
  • Figure 2 shows a temperature dependency curve of loss tangent (plotted figure) of the cured product produced from the composition of obtained in Comparative Example 2.
  • peak means an apex of a convex curve in a limited area
  • shoulder means a shoulder or step in the same curve.
  • a shoulder is present in the loss tan ⁇ curve in case the derivative of the loss tangent curve shows a peak.
  • (meth) acrylic acid means acrylic acid and methacrylic acid inclusively.
  • (meth) acryloyl group means acryloyl group and methacryloyl group inclusively.
  • (meth) acrylate means acrylate and methacrylate inclusively.
  • the polymer used as the component (A) (hereinafter may also be called polymer (A) ) has polymerizable unsaturated groups in an average amount of 1.2 per one molecule, a urethane bond in the molecular chain, and a number average molecular weight from 3, 000 to 30, 000.
  • the polymerizable unsaturated group is a radically polymerizable ethylenically unsaturated group such as, for example, a (meth) acryloyl group.
  • the average number of polymerizable unsaturated groups in the polymer (A) is 1.2 or more, preferably 1.2-4, and more preferably 1.5- 2.5.
  • an individual molecule of the polymer in the component (A) may have one or more polymerizable unsaturated groups
  • the average number of such a group per molecule should be 1.2 or more. If the average number of polymerizable unsaturated groups per molecule is less than 1.2, the resulting composition exhibits inadequate curability. If the average number of the polymerizable unsaturated groups is more than 4, on the other hand, the cross-linking reaction becomes excessive, resulting in brittle cured products.
  • the polymer (A) has a number average molecular weight of 3,000-30,000, and preferably 5,000- 20,000. When the number average molecular weight is less than 3,000, cured products obtained from the composition tend to have poor elongation and low tenacity. When used as a coating material for the optical fibers, such a composition may result in a transmission loss of optical fibers. If the number average molecular weight is greater than 30,000, viscosity of the composition is excessively high so that the composition can be handled only with difficulty.
  • the polymer (A) contains an average of 1.2 or more, preferably 1.5-10, and more preferably 2-6, urethane bonds in a molecular chain. If the average number of urethane bonds is less than 1.2, tenacity of the cured products produced from the composition is poor. Such a composition tends to result transmission loss when used as a coating material for optical fibers.
  • the structure of the mam chain may comprise, for example, a polyether polyol urethane polymer, polyester polyol urethane polymer, polycaprolactone polyol urethane polymer, and the like. Either one type of these polymers may be used or two or more types may be used in combination in the polymer (A) . Of these polymers for the structure of the ma chain, comprising a polyether polyol urethane polymer is preferred. Either the entire mam chain is formed from the polyether polyol urethane polymer or a portion of the mam chain is formed from the polyether polyol urethane polymer.
  • the polymer of the component (A) which has such a polyether polyol -type urethane polymer as a basic structure can be prepared by reacting (a) a polyether polyol obtained by the ring-opening polymerization of an alkylene oxide (hereinafter referred to polyether polyol (a) ) , (b) a poly socyanate (hereinafter polyisocyanate (b) ) , and (c) a compound possessing an active hydrogen reactive with an isocyanate group and a polymerizable unsaturated group (hereinafter compound (c) ) .
  • polyether polyol obtained by the ring-opening polymerization of an alkylene oxide
  • polyisocyanate (b) ) a poly socyanate
  • compound (c) a compound possessing an active hydrogen reactive with an isocyanate group and a polymerizable unsaturated group
  • the polyether polyol (a) is a polyol, preferably a diol, having a polyoxyalkylene structure containing an oxyalkylene group with 2-10 carbon atoms as a repeating unit.
  • diols having such a polyoxyalkylene structure are polyglycol compounds such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyheptamethylene glycol, polyhexamethylene glycol, and polydecamethylene glycol, as well as polyether diols obtained by a ring-opening copolymerization of two or more ion-polymerizable cyclic compounds.
  • cyclic diols are given as examples of the ion-polymerizable cyclic compound: ethylene oxide, propylene oxide, butene-1 -oxide, isobutene oxide, 3 , 3-bis (chloromethyl) oxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3- methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyltetrahydrofuran, vinylcyclohexene oxide, phenyl glycidyl ether, butyl gly
  • polyether diols obtained by the ring-opening copolymerization of the above- mentioned ion-polymerizable cyclic compound and a cyclic imine such as ethyleneimine, a cyclic lactone such as p-propyolactone, a cyclic lactone such as glycolic acid lactide, or a cyclic siloxane such as dimethylcyclopolysiloxane can also be used.
  • ion-polymerizable cyclic compounds combinations of tetrahydrofuran and propylene oxide, tetrahydrofuran and 2 -methy11etrahydrofuran, tetrahydrofuran and 3 -methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, and propylene oxide and ethylene oxide can be given.
  • These two or more ion- polymerizable cyclic compounds may be bonded randomly in the resulting ring-opening copolymer.
  • the diols having such a polyoxyalkylene structure can be commercially available under the trademarks of, for example, PTMG1000 (Mitsubishi Chemical Corp.), PTMG2000 (same), PPG1000 (Asahi Oline Co., Ltd.), PPG2000 (same), EXCENOL2020 (same), EXCENOL1020 (same), PEG1000 (Nippon Oil and Fats Co., Ltd.), Unisafe DC 1100 (same), Unisafe DC 1800 (same), PPTG2000 (Hodogaya Chemical Co., Ltd.), PPTG1000 (same) , PTG400 (same) , and PTGL2000 (same) .
  • a diol and/or diamine which do not have a polyoxyalkylene structure may be used jointly with the polyether polyol (a) in the manufacture of the polyether polyol urethane polymer used as the component (A) .
  • the diol which does not have a polyoxyalkylene structure a polyester diol, polycaprolactone diol, polycarbonate diol, and the like can be given.
  • polyester diols obtained by the reaction of a polyhydric alcohol, such as ethylene glycol, propylene glycol, tetramethylene glycol, 1, 6-hexanediol , neopentyl glycol, or 1 , 4-cyclohexanedimethanol , and a polybasic acid, such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, or sebac c acid, can be given.
  • a polyhydric alcohol such as ethylene glycol, propylene glycol, tetramethylene glycol, 1, 6-hexanediol , neopentyl glycol, or 1 , 4-cyclohexanedimethanol
  • a polybasic acid such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, or sebac c acid
  • polycaprolactone diol polycaprolactone diols obtained by reacting ⁇ -caprolactone and a diol such as ethylene glycol, tetramethylene glycol, 1 , 6-hexaned ⁇ ol , neopentyl glycol, or 1 , 4-butaned ⁇ ol can be given.
  • a polycarbonate diol a polycarbonate diol of polytetrahydrofuran, a polycarbonate of 1,6- hexanediol, as well as products commercially available under the trademarks of DN-980 (Nippon Polyurethane
  • diammes such as ethylenediamme, tetramethylenediamme, hexamethylenediamme, p- phenylenediamme , 4,4' -diammodiphenylmethane , diammes including a hetero-atom, polyether diammes, and the like are given.
  • the polyisocyanate (b) is a compound having 2 to 6 isocyanate groups. Usually diisocyanate compounds are used. Specific examples of the diisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1, 5 -naphthalene diisocyanate, p-phenylene diisocyanate, 3,3' -dimethyl -4, 4 ' -diphenylmethane diisocyanate, 4, 4 ' -diphenylmethane diisocyanate, 3,3'- dimethylphenylene diisocyanate, 4 , 4 ' -biphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, methylenebis (4-cyclohexyl ⁇
  • (meth) acrylic compounds having a hydroxyl group are given.
  • (meth) acrylates such as 2 -hydroxyethyl (meth) acrylate, 2- hydroxypropyl (meth) acrylate,
  • 2-hydroxyoctyl (meth) acrylate pentaeryth ⁇ toltri (meth) acrylate, glyceroldi (meth) acrylate, dipentaeryth ⁇ tolmonohydroxypenta (meth) acrylate,
  • R is a hydrogen atom or methyl group
  • H 2 C C . -C-0-CH 2 CH 2 —-0-CCH 2 CH 2 CH 2 CH 2 CH 2 -—OH ( 2 )
  • R is the same as in the formula (1) and n is an integer of 1 to 5.
  • 2 -Hydroxyethyl (meth) acrylate can be given as a preferred compound among these (meth) acrylates .
  • compounds which do not have an active hydrogen nor a polymerizable unsaturated group can be given as compound (c 1 ) .
  • Specific examples are silane coupling agents such as ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, and alcohols such as methanol, isopropyl alcohol, ethanol, and butanol .
  • An alcohol is used to replace polymerizable unsaturated groups of the component (A) with non-polymerizable groups.
  • the silane coupling agents can be used not only for lowering the modulus of elasticity of the cured products, but also for increasing adhesion strength between the cured products and glass, or for making the surface of cured products slippery.
  • reaction of the polyether polyol (a) , polyisocyanate (b) , and compound (c) for example, the reaction of a diol compound, a diisocyanate compound, and a compound having an ethylenically unsaturated group can be preferably carried out using a urethanization catalyst such as copper naphthenate, - 12 -
  • the reaction is carried out at a temperature usually of 10-90°C, and preferably 30-80°C.
  • the component (A) may consist only of a polyether polyol-type urethane polymer or may contain a polyether polyol -type urethane polymer as a major component combined with other polymers belonging to the component (A) .
  • polyester polyol-type urethane polymer, polycaprolactone polyol-type urethane polymer, and the like can be given.
  • the proportion of a polyoxyalkylene structure contained the component (A) is preferably 50-98 wt%, more preferably 60-93 wt%, and most preferably 70-90 wt%. If the amount of the polyoxyalkylene structure m the component (A) is too small, the modulus of elasticity of the cured products increases at a low temperature, for example at a temperature less than 0°C. This tends to produce a transmission loss of optical fibers when the composition is used as a coating material for optical fibers.
  • the proportion of the component (A) in the composition of the present invention is usually 25-75 wt%, and preferably 40-70 wt%. If the proportion of the component (A) is too small, the elongation of the cured products is decreased; if too large, the viscosity of the composition increases. Handling of the material is impaired in either case.
  • Poly-functional monomers used as the component (B) of the present invention have two or more, usually 2-10, and preferably 2-6, polymerizable unsaturation groups.
  • a (meth) acryloyl group is desirable as the polymerizable unsaturation group.
  • composition of the present invention it is desirable for the composition of the present invention to contain a poly-functional monomer having a relatively low molecular weight for producing cured products with a high breaking strength, while exhibiting a low modulus of elasticity.
  • a poly-functional monomer should have a molecular weight of less than 800, preferably 70-800, and more preferably 100-650.
  • 1,6- hexanedioldiacrylate, 1, 9-nonanediolacrylate, triethylene glycol diacrylate, tricyclodecanedimethanol diacrylate, and trimethylolpropane alkoxy triacylate are desirable poly-functional monomers in view of the low modulus of elasticity and high breaking strength of the resulting cured products.
  • Particularly preferred polyfunctional monomers are 1, 6-hexanedioldiacrylate, 1 , 9-nonanedioldiacrylate, triethylene glycol diacrylate, and tricyclodecanedimethanol diacrylate. These monomers may be used either individually or in combinations of two or more as the component (B) .
  • poly-functional monomers are commercially available under the trademarks of, for example, HDDA, L-C9A (Daiichi Kogyo Seiyaku Co., Ltd.), Yupimer UV, SA1002, SA2007 (Mitsubishi Chemical Corp.), 3-EGA, 4-EGA, 9-EGA, 14-EGA (Kyoeisha Chemical Co., Ltd.), PHOTOMER4149 (Sunnopco Co., Ltd.), Viscoat 700 (Osaka Organic Chemical Industry Co., Ltd.), KAYARAD R- 604, DPCA-20, 30, 60, 120, HX-620, D-310, 330 (Nippon Kayaku Co., Ltd.), Aronix M-210, 215, 315, 325
  • the poly-functional monomer is included in the composition of the present invention as the component (B) in an amount of 0.1-10 wt%, and especially 0.5-5 wt%. If the proportion of the - 15 -
  • component (B) is too small, the breaking strength of the resulting cured products is low. If this proportion too large, the modulus of elasticity of the cured products is so high that elongation is decreased. Such a product is not suitable as a primary coating material for optical fibers.
  • a monomer having one polymerizable vinyl group and a molecular weight of 1,000 or less, preferably 70-800, is given as a typical example of the monomer having a polymerizable unsaturated group used as the component (C) in the present invention.
  • a form of (meth) acryloyl group such as an N-vinyl group, (meth) acrylamide group, vinyl ether group, or vinyl ester group, is given as an example. Of these, a form of (meth) acryloyl group is particularly preferred.
  • the component (C) functions as a reactive diluent in the composition of the present invention.
  • the component (C) it is desirable for the component (C) to be a liquid at room temperature. It is possible to adjust viscosity of the composition and modulus of elasticity of the cured products obtained from the composition by suitable selection of the types and amount of the compound, which is used as the component (C) . When two or more compounds are used as the component (C) , the mixture of these compounds only has to be liquid.
  • the following monomers are given as specific examples of the compounds used as component - 16 -
  • R 2 is a hydrogen atom or methyl group
  • R 3 is an alkylene group having 2-6, preferably 2-4, carbon atoms
  • R 4 is a hydrogen atom or an alkyl group having 1- 12, preferably 1-9, carbon atoms
  • q is an integer of 0-12, preferably 1-8
  • R is the same as defined in the formula (3), R is an alkylene group having 2-8, preferably 2-5, carbon atoms, and r is an integer of 1-8, and preferably 1-4, and - 18 -
  • H 2 C C r—C--OR 5 - -C —0-CH 2 - /
  • the component (C) it is desirable for the component (C) to include an N- vinyllactam such as N-vinyl- ⁇ -caprolactam (hereinafter described as N-vinylcaprolactam), and the like.
  • N-vinylcaprolactam N-vinylcaprolactam
  • the proportion of the N-vinyllactams in component (C) is from 3-20 wt%, and preferably 3-15 wt%.
  • N-vinylcapralactam is prefered
  • component (C) Inclusion of a compound with an alicyclic structure is desirable for the component (C) to increase water resistance, hot water resistance, acid - 19 -
  • isobornyl (meth) acrylate dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecanedimethanoldi (meth) acrylate, and the like are given. Of these, isobornyl acrylate and tricyclodecanedimethanoldiacrylate are preferred.
  • N- vmyllactam A combined use of the above-mentioned N- vmyllactam and the compound having an alicyclic structure as the component (C) is given as a preferred embodiment .
  • These compounds for the component (C) are commercially available under the trademarks such as Aronix M-102, M-lll, M-113, M-114, M-117 (Toagosei Co., Ltd.), KAYARAD TC110S, R629, R644 (Nippon Kayaku Co., Ltd.), and Viscoat 3700 (Osaka Organic Chemical Industry Co., Ltd.).
  • component (C) be incorporated in the composition of the present invention in an amount of 20-70 wt%, and preferably 25- 55 wt%.
  • Component (D) is particularly desirable that the component (C) be incorporated in the composition of the present invention in an amount of 20-70 wt%, and preferably 25- 55 wt%.
  • radiation active initiators which are used as component (D) in the composition of the present invention: 1-hydroxycyclohexyl phenyl ketone, 2,2- d ⁇ methoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraqumone , triphenylamme, - 20 -
  • Lucirin TPO LR8728 Lucirin TPO LR8953X (BASF)
  • These compounds for the component (D) may be used either individually or in combinations of two or more .
  • the proportion of the component (D) used in the composition of the present invention is usually the proportion of the component (D) used in the composition of the present invention.
  • a photosensitizer can be used together with the radiation-active initiator of the component (D) as - 21 -
  • the photosensitizers triethylamine, diethylamine, N-methyldiethanoleamine, ethanolamine, 4-dimethylaminobenzoic acid, 4 -ethyl dimethylaminobenzoate, 4-isoamyl dimethylaminobenzoate, and commercially available products such as UbecrylTM P102, 103, 104, 105 (UCB Co.), and the like can be given.
  • Additives other than the above-mentioned components (A) to (D) may be optionally added to the composition of the present invention. Included in such additives are antioxidants, UV absorbers, light stabilizers, silane coupling agents, aging preventives, thermal polymerization inhibitors, leveling agents, coloring matters, surfactants, preservatives, plasticizers, lubricants, solvents, fillers, wettability improvers, coating surface improvers, and the like.
  • antioxidants for example, phenol -type antioxidants, organic sulfur-type antioxidants, and the like are given. These are commercially available under the trademarks Irganox 1010, 1035, 1076, and 1222 (Ciba Specialty Chemicals Co., Ltd.), and the like.
  • UV absorbers benzotriaole-type UV absorbers, and the like can be given.
  • UV absorbers Tinuvin TM P, 234, 320, 326, 327, 328, 213 (Ciba Specialty
  • TM products Tmuvm 292, 144, 622LD (Ciba Specialty Chemicals Co., Ltd.), SanolTM LS-770, 765, 292, 2626, 1114, 744 (Sankyo Co., Ltd.), and the like can be given.
  • silane coupling agents ⁇ -aminopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane , and ⁇ -methacryloxypropyltrimethoxysilane, as well as commercially available products under the trademarks SH6062, SZ6030 (Toray-Dow Corning Silicone Co., Ltd.), KBE903, KBM803 (Shin-Etsu Silicone Co., Ltd.), and the like can be given.
  • aging preventives examples include phenol -type aging preventives, allyl amine-type aging preventives, and ketone amine-type aging preventives, as well as commercially available products under the trademarks Antigene W, S, P, 3C, 6C, RD-G, FR, AW (Sumitomo Chemical Industries Co., Ltd.), and the like can be given.
  • composition of the present invention can be prepared by blending the above-mentioned components (A) to (D) and the optional components at appropriate proportions.
  • the viscosity (at 25 C) of the composition of the present invention is in the range of 1,000- 20,000 cP, and preferably 1,500-15,000 cP, to ensure excellent coatability to optical fibers. Cured products
  • composition of the present invention is curable by irradiation with rays of an appropriate wavelenght
  • suitable radiation includes infrared radiation, visible rays, ultraviolet radiation, ⁇ -rays, ⁇ -rays, ⁇ -rays, and the like.
  • ultraviolet radiation which is prefered
  • the composition can be cured at an irradiation dose of 50
  • the irradiation dose is 50 mJ/cm or more, preferably 100 mJ/cm or more, the cured products exhibit a high breaking strength and a small amount of light transmission loss, in spite of a low modulus of elasticity. Generally, irradiation with 2 J/cm 2 less is preferred, and 1 J/cm or less is more preferred.
  • cured products obtained from the composition of the present invention by irradiation of ultraviolet light at a dose of 1 J/cm in air atmosphere those having (1) a secant modulus defined by the JIS K 7127 of 0.15 kg/mm 2 or less and (2) a tensile breaking strength, defined by the JIS K 7127, of 0.15 kg/mm or more exhibit superior workability when the coating is to be stripped from optical fibers, without leaving any residue on the fibers. Because such a coating material provides an advantage of easy optical fiber joining work, the material is ideal for use as a primary coating for optical fibers. It is preferred to have cured products having a secant modulus of 0.12 kg/mm or less. It is preferred to have cured products having a tensile breaking strenght of 0.18 kg/mm or more, in particular 0.21 kg/mm or more. - 24 -
  • the cured products obtained by irradiation with ultraviolet lights under the same conditions as mentioned above those having a total of two or more peaks or shoulders in the temperature range from -50°C to + 35 C temperature dependency curve obtained from the loss tangent from temperature dependency measurement of dynamic viscoelastic ty ratio, particularly, those having (a) at least one shoulder or peak in the temperature range from -50 C C to -20 C and (b) at least one shoulder or peak in the temperature range from -20°C to +35 C exhibit exceptionally superior workability when the coating is stripped from optical fibers.
  • Such a product is especially suitable as a primary coating material for optical fibers.
  • composition of the present invention is useful as a paint, surface reforming agent, printing ink, and the like. - 25 -
  • Mn number average molecular weight
  • the mixture was cooled with ice to 10°C or below while stirring. When the temperature was 10 C or below, 0.08 g of dibutyl tin dilaurate was added and the mixture was stirred for two hours while maintaining the temperature at 20-30°C.
  • ⁇ -mercaptopropyltrimethoxysilane (trademark: SH6062, manufactured by Toray-Dow Corning Silicone Co., Ltd.), which is a silane coupling agent, was added and the mixture was stirred for one hour at 40-50°C.
  • 1.15 g of 2 -hydroxyethylacrylate was added and the mixture was stirred for 30 minutes at 45-
  • Examples 1-7 Comparative Examples 1-2 10 g of laurylacrylate (component (C) ) , 17 g of nonylphenol EO-modified (4 mole modified) acrylate (trademark: M113, manufactured by Toagosei Co., Ltd., component (C) ) , 5 g of N-vinylcaprolactam (component (C) ) , 0.8 g of Irganox 1035 as an antioxidant, 2 g of 2 , 4 , 6-trimethylbenzoyl diphenylphosphine oxide, and 0.15 g of diethylamine were added to 65 g of the liquid urethane acrylate polymer (component (A) ) which was obtained in the Synthetic Example 1.
  • the resin solution I was used as is without adding a poly-functional monomer as the composition for Comparative Example 1.
  • Each liquid composition thus obtained in the Examples or Comparative Examples was applied to a sheet of glass using an applicator for producing a coating with a thickness of 250 ⁇ m.
  • the coating was irradiated with ultraviolet light from a 3.5 KW metal halide lamp (SMX- 3500/F-OS, manufactured by ORC Co., Ltd.) at a dose of - 28 -
  • JIS K7127 at a bench mark distance of 25 mm and a pulling rate of 1 mm/minute.
  • Dynamic viscoelasticity was measured using RHEOVIBRON MODEL RHEO-1021 (control unit) and RHEOVIBRON MODEL DDV-01FP (measuring unit) manufactured by Orientech Co., Ltd. at a heating rate of 2 C/min, bench mark distance of 30 mm, vibration frequency of 35 - 29 -
  • a four-core ribbon was nipped with a hot stripper S-214, manufactured by FURUKAWA ELECTRIC CO., LTD., for about 5 minutes at a temperature range of 85 ⁇ 2°C. Glass core fibers were extracted from the 4 -core ribbon to observe remains of the primary coating on extracted glass fibers. The coating removability was rated as "Excellent” when there were no remains of the primary coating material left on the surface of the glass fiber, "Good” when there was a small amount of remains, and "Bad” when the remains are significant.
  • compositions of Examples 1-7 have a viscosity of a desirable range as a primary coating for optical fibers.
  • the following findings are obtained from the results shown in Table 2.
  • Example 1 The cured product of Example 1 showed a high tensile breaking strength of 0.24 kg/mm , although the secant modulus was low (0.05 kg/mm ) . This cured product exhibited only one peak in the loss tangent temperature dependence curve. There were no other peaks or shoulders except for that one . - 3 1 -
  • Example 2 represents the composition having a tensile strength at break of 0.15 kg/mm 2 ; the loss tangent temperature dependence curve had one peak and one shoulder.
  • Example 3 has one peak at 5°C and one shoulder at -40°C as shown in Figure 1.
  • the secant modulus was low (0.06-0.10 kg/mm)
  • the products exhibited high tensile strength at break of 0.28-0.48 kg/mm 2 .
  • the loss tangent temperature dependence curves of these cured products showed one peak or shoulder in the temperature range from -50°C to -20 C C and another peak or shoulder in the temperature range from -20 C to +35 C.
  • the radiation curable composition of the present invention possesses favorable viscoelasticity and exhibits moderate resistance and deformation against external forces. Because of this, when used as a coating material, particularly a primary coating material, for optical fibers the products have a high breaking strength, while exhibiting a low modulus of elasticity, and showing superior light transmission characteristics with only a small amount of light transmission loss. In addition, removal of coating from optical fibers can be performed with extreme ease when optical fibers are joined together.

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Abstract

L'invention concerne une composition de résine durcissable par rayonnement convenant à une utilisation en tant que matériau de revêtement primaire pour fibres optiques, laquelle peut former un revêtement durci à faible module d'élasticité présentant une résistance élevée à la rupture et ayant une faible perte de transmission de lumière; la composition de revêtement comprend (A) un polymère contenant des groupes polymérisables insaturés en une quantité moyenne de 1,2 par molécule, une liaison uréthane dans une chaîne moléculaire, et présentant une masse moléculaire moyenne au nombre comprise entre 3000 et 30000, (B) un monomère polyfonctionnel ayant au moins deux groupes polymérisables insaturés, (C) un monomère ayant un groupe polymérisable insaturé et (D) un initiateur actif sous l'effet d'un rayonnement. Le module sécant du revêtement est inférieur à 0,15 kg/mm2, la résistance à la rupture est supérieure à 0,15 kg/mm2.
PCT/NL1999/000215 1997-08-15 1999-04-13 Composition de resine durcissable par rayonnement WO1999052958A1 (fr)

Priority Applications (2)

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KR1020007011327A KR20010042636A (ko) 1998-04-15 1999-04-13 방사선 경화성 수지조성물
US10/372,741 US20030195271A1 (en) 1997-08-15 2003-02-25 Coated optical fiber and radiation-curable resin composition

Applications Claiming Priority (2)

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JP98/121755 1998-04-15
JP10121755A JPH11116642A (ja) 1997-08-15 1998-04-15 放射線硬化性樹脂組成物

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1209132A1 (fr) * 2000-11-22 2002-05-29 Dsm N.V. Fibres optiques revêtues, composition de revêtement primaire, méthode de durcissement, et dispositif et méthode de mesure
US6579618B1 (en) 1997-08-15 2003-06-17 Dsm N.V. Coated optical fiber and radiation curable resin composition
US6852770B2 (en) * 2001-01-12 2005-02-08 Dsm Ip Assets, B.V. Radiation-curable composition and products coated therewith
US6916855B2 (en) 2000-11-22 2005-07-12 Dsm Ip Assets B.V. Radiation curable compositions
US7010206B1 (en) 2004-09-08 2006-03-07 Corning Incorporated Coated optical fiber and optical fiber coating system including a fast-gelling primary coating
US7067564B2 (en) 2000-11-22 2006-06-27 Dsm Ip Assets B.V. Coated optical fibers
US7706659B2 (en) 2000-11-22 2010-04-27 Dsm Ip Assets B.V. Coated optical fibers

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102858824B (zh) * 2010-11-19 2015-04-15 Dic株式会社 自由基固化性树脂组合物、使用其的被覆材料、土木建筑结构体及其施工方法
JP6369215B2 (ja) * 2014-08-13 2018-08-08 住友電気工業株式会社 光ファイバ心線及びその製造方法
WO2020175664A1 (fr) 2019-02-28 2020-09-03 関西ペイント株式会社 Composition de revêtement durcissable par rayonnement actinique, film de revêtement durci, article revêtu, et procédé de formation de film de revêtement
FR3108908B1 (fr) * 2020-04-01 2022-03-25 Arkema France Matériaux élastiques préparés à partir de compositions liquides durcissables

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4932750A (en) * 1982-12-09 1990-06-12 Desoto, Inc. Single-coated optical fiber
EP0407004A2 (fr) * 1989-06-27 1991-01-09 Borden, Inc. Matière d'enrobage durcissable par irradiation, rubans de fibres optiques les comprenant et procédé pour préparer de tels rubans de fibres optiques
WO1997019898A1 (fr) * 1995-11-28 1997-06-05 Dsm N.V. Composition de resine liquide photodurcissable
WO1999008975A1 (fr) * 1997-08-15 1999-02-25 Dsm N.V. Composition de resine capable de durcir sous un rayonnement

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4932750A (en) * 1982-12-09 1990-06-12 Desoto, Inc. Single-coated optical fiber
EP0407004A2 (fr) * 1989-06-27 1991-01-09 Borden, Inc. Matière d'enrobage durcissable par irradiation, rubans de fibres optiques les comprenant et procédé pour préparer de tels rubans de fibres optiques
WO1997019898A1 (fr) * 1995-11-28 1997-06-05 Dsm N.V. Composition de resine liquide photodurcissable
WO1999008975A1 (fr) * 1997-08-15 1999-02-25 Dsm N.V. Composition de resine capable de durcir sous un rayonnement

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6579618B1 (en) 1997-08-15 2003-06-17 Dsm N.V. Coated optical fiber and radiation curable resin composition
KR100854847B1 (ko) * 2000-11-22 2008-08-27 디에스엠 아이피 어셋츠 비.브이. 코팅된 광학섬유
WO2002042237A3 (fr) * 2000-11-22 2002-10-03 Dsm Nv Fibres optiques recouvertes
WO2002042237A2 (fr) * 2000-11-22 2002-05-30 Dsm N.V. Fibres optiques recouvertes
US6916855B2 (en) 2000-11-22 2005-07-12 Dsm Ip Assets B.V. Radiation curable compositions
US7067564B2 (en) 2000-11-22 2006-06-27 Dsm Ip Assets B.V. Coated optical fibers
EP1209132A1 (fr) * 2000-11-22 2002-05-29 Dsm N.V. Fibres optiques revêtues, composition de revêtement primaire, méthode de durcissement, et dispositif et méthode de mesure
US7706659B2 (en) 2000-11-22 2010-04-27 Dsm Ip Assets B.V. Coated optical fibers
US7865055B2 (en) 2000-11-22 2011-01-04 Dsm Ip Assets B.V. Coated optical fibers
US7886612B2 (en) 2000-11-22 2011-02-15 Dsm Ip Assets B.V. Coated optical fibers
US6852770B2 (en) * 2001-01-12 2005-02-08 Dsm Ip Assets, B.V. Radiation-curable composition and products coated therewith
US7010206B1 (en) 2004-09-08 2006-03-07 Corning Incorporated Coated optical fiber and optical fiber coating system including a fast-gelling primary coating
US7221842B2 (en) 2004-09-08 2007-05-22 Corning Incorporated Coated optical fiber and optical fiber coating system including a fast-gelling primary coating

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KR20010042636A (ko) 2001-05-25
CN1297460A (zh) 2001-05-30
CN1206280C (zh) 2005-06-15

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