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WO1998009923A1 - Composition de resine liquide photodurcissable - Google Patents

Composition de resine liquide photodurcissable Download PDF

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Publication number
WO1998009923A1
WO1998009923A1 PCT/NL1997/000499 NL9700499W WO9809923A1 WO 1998009923 A1 WO1998009923 A1 WO 1998009923A1 NL 9700499 W NL9700499 W NL 9700499W WO 9809923 A1 WO9809923 A1 WO 9809923A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
composition according
group
coating
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NL1997/000499
Other languages
English (en)
Inventor
Ikuno Higa
Zen Komiya
Takashi Ukachi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSR Corp
Koninklijke DSM NV
Original Assignee
Japan Synthetic Rubber Co Ltd
DSM NV
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 Japan Synthetic Rubber Co Ltd, DSM NV filed Critical Japan Synthetic Rubber Co Ltd
Priority to AU41387/97A priority Critical patent/AU4138797A/en
Publication of WO1998009923A1 publication Critical patent/WO1998009923A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08F290/064—Polymers containing more than one epoxy group per molecule
    • 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
    • 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
    • C08F290/061—Polyesters; Polycarbonates
    • 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 photo-curable liquid resin composition and, more particularly, to a photo-curable liquid resin composition possessing a low viscosity, exhibiting excellent stability during a long-term storage, and after curing has excellent characteristics and suitable for use as an optical fiber coating material.
  • 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 provided over the primary coating layer. Because the optical fiber coating process is carried out immediately after spinning molten glass fibers by drawing from a raw material, the coating material must have a high curing rate to expedite manufacture of optical fiber and to increase productivity. If the curing rate of the coating material is slow, the drawing speed in the manufacture of optical fiber is inevitably retarded, resulting in a low productivity.
  • An object of the present invention is therefore to provide a photo-curable liquid resin composition, suitable for coating optical fibers, having a low viscosity at room temperature, exhibiting excellent stability during a long-term storage and adequate adhesion to optical fibers, and after curing has excellent characteristics such as superior UV light resistance, heat resistance, yellowing resistance due to heat and light, and oil resistance, and producing only a slight amount of hydrogen.
  • a photo-curable liquid resin composition comprising, (A) a polymer containing at least one ethylenically unsaturated group and a backbone oligomer,
  • (C) a photopolymerization initiator (C) a photopolymerization initiator.
  • the object can be achieved also by a coated optical fiber, of which at least one of the coatings comprises a photo-cured composition, the composition is uncured form being formulated from components comprising
  • the monomer comprising a (meth)acrylate group and dioxane group used in suitable amounts gives the composition very desirable properties such as a low viscosity at room temperature in the uncured composition, and high adhesion to glass and low hydrogen production in the cured composition.
  • the photocurable composition of the present invention comprises at least three components: (A) a polymer, (B) a monomer and (C) an initiator.
  • the component (A) preferably comprises a polymer having (meth)acrylate group attached to a backbone oligomer.
  • the backbone oligomer preferably contains at least one polyether, polyolefin, polyester, polycarbonate or bisphenol group; mixtures of these polymer groups can be used, as well as groups that are (block) copolymers of said groups.
  • the backbone oligomer of component (A) comprises at least one structural unit selected from the following groups (l)-(4),
  • R 1 is an alkylene group having 2-6 carbon atoms
  • R 2 and R 3 individually represent a divalent organic group having 2-13 carbon atoms, and - ( R 4 -0- ) n -C-0 ) - ( 4 )
  • n is an integer of 1-50 and R 4 is an alkylene group having 2-6 carbon atoms or a divalent organic group of the following formula (5),
  • R 5 , R 6 , R 7 , and R 8 individually represent a hydrogen atom or an alkyl group having 1-8 carbon atoms.
  • Preferred alkylene groups having 2-6 carbon atoms which are represented by R 1 in formula (1) are the structural units shown by the following formulas (7-1) to (7-8).
  • m is an integer 3-10 and particularly preferably 5.
  • divalent organic groups represented by R 2 or R 3 divalent alkylene groups and arylene groups are preferred.
  • R 2 or R 3 are groups such as ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, phenylene, diphenylene, and bis(phenylenemethane) .
  • alkylene groups having 2-6 carbon atoms which are represented by R 4 in the formula (4) are the structural units shown by the above formulas (7-1) to (7-8). Of these, the structural units (7-1) and (7-3) are particularly preferred.
  • divalent organic group represented by R 4 of the formula (5) are (bis)phenylene- methane, 2 , 2 '-(bis)phenylenepropane, 2 ,2 '-(bis)phenylene- butane. Of these groups, the structural unit 2 , 2 '-
  • n is an integer of 1-50, and preferably 1-25.
  • the polymer comprises a backbone and an ethenenically unsaturated group, the latter preferably comprises an acrylate or methacrylate group.
  • An acrylate is most preferred because of the improved cure speed.
  • the following groups (8-1) to (8-5) are given as specific examples of the ethylenically unsaturated groups contained in the component (A).
  • CH 2 C ( R 12 ) -COCH 2 2 --CC--CCHH 22 OOCCHH 22 --CC--CCH 2 - ( 8-5 )
  • R 12 individually represent a hydrogen atom or a methyl group and R 13 is an alkylene group having 2-9 carbon atoms, and preferably alkylene groups having 2-5 carbon atoms, such as an ethylene group, propylene group, a tetramethylene group, and a pentamethylene group.
  • the groups (8-1) having one ethylenically unsaturated group, (8-2) having one ethylenically unsaturated group, (8-3) having two ethylenically unsaturated groups, and (8-4) having three ethylenically unsaturated groups are preferred, with the groups (8-1) and (8-2) being particularly preferred.
  • the structural units (1), (2), (3), (4) and the ethylenically unsaturated group which constitute the component (A) are preferably bonded via at least one bond selected from the group consisting of a urethane bond, a urea bond, an amide bond, an ester bond, and an ether bond.
  • the number average molecular weight (hereinafter abbreviated as Mn) of the component (A) is preferably 1,000-10,000, and more preferably 1,500-8,000.
  • the number of the ethylenically unsaturated groups contained in the component (A) is 1-20, preferably 1-10, and most preferably about 2-4, per molecule. Excellent curability of the composition, and favorable durability and flexibility of the cured products are obtained by keeping the proportion of the ethylenically unsaturated group in the above range.
  • These polymers containing an ethylenically unsaturated group may be used either individually or in combination of two or more as the component (A).
  • the proportion of the component (A) in the composition is preferably 10-75% by weight, and more preferably 30-70% by weight. Excellent coatability and processability of the composition, as well as superior flexibility, can be achieved by keeping the proportion of the component (A) in this range.
  • a process comprising reacting a diol (hereinafter referred to as diol (A)) containing at least one structural unit selected from the above formulas (1), (2), (3), and (4), and optionally a diol other than the diol (A), with a diisocyanate compound, to produce a polymer bonded by urethane bonds and having an isocyanate group, and then reacting the isocyanate group of this polymer with a compound having a hydroxyl group and the ethylenically unsaturated group represented by the formulas (8-1) to (8-5) (such a compound is hereinafter referred to as "specific unsaturated compound (A)), thereby introducing the ethylenically unsaturated group via the urethane bond and completing the manufacture of component (A).
  • diol (A) containing at least one structural unit selected from the above formulas (1), (2), (3), and (4), and optionally a diol other than the diol (A), with
  • a process comprising reacting the diol (A), and optionally a combination of the diol (A) and a diol compound other than the diol (A) or a diamine, with a diisocynate compound to produce a polymer bonded by urethane bonds, and optionally by urea bonds, and having an isocyanate group, and then reacting the isocyanate group of this polymer with the specific unsaturated compound (A), thereby introducing the ethylenically unsaturated group via the urethane bond and completing the manufacture of component (A).
  • a process comprising reacting a diisocyanate compound with the specific unsaturated compound (A) to produce a polymer bonded by urethane bonds and having an isocyanate group and ethylenically unsaturated groups, and reacting the isocyanate group of this polymer with the diol (A), and optionally a combination of the diol (A) and at least one compound selected from diol compounds other than the diol (A) and diamines, thereby producing urethane bonds, and optionally urea bonds and completing the manufacture of component (A).
  • a process comprising reacting the diol (A), and optionally a combination of the diol (A) and at least one compound selected from diol compounds other than the diol (A) and diamines, with a diisocynate compound to produce a polymer having at least two functional groups selected from hydroxyl group, primary amino group, and secondary amino group, and then reacting these functional groups with a compound having a carboxyl group, an epoxy group, or acid halide group and also having the ethylenically unsaturated group represented by the formulas (8-1) to (8-5), thereby producing ester bonds or amide bonds and completing the manufacture of component (A).
  • the products produced by these Processes 1 to 4 are urethane (meth)acrylate polymers which are suitable for use as the component (A).
  • the urethane (meth)acrylates are ideal components for providing superior mechanical characteristics such as strength and toughness required for a coating material for optical fibers in combination for with low or high Tg (for respectively, soft or hard mate ials ) .
  • Examples of the diol (A) containing the above structural unit (1) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyheptamethylene glycol, polyhexamethylene glycol, poly-2-methyltetramethylene glycol, ethylene oxide adduct to bisphenol A, butylene oxide adduct to bisphenol A, ethylene oxide adduct to bisphenol F, butylene oxide adduct to bisphenol F, ethylene oxide adduct to hydrogenated bisphenol A, butylene oxide adduct to hydrogenated bisphenol A, ethylene oxide adduct to hydrogenated bisphenol F, butylene oxide adduct to hydrogenated bisphenol F, and polyether diols obtained by the ring-opening copolymer ization of two or more types of ionic-polymer izable cyclic compounds.
  • Examples of the ionic-polymerizable cyclic compound used to produce these polyether diols include cyclic ethers such as ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetra-hydrofuran, dioxane, trioxane, tetraoxane, butadiene monoxide, and isoprene monoxide.
  • cyclic ethers such as ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetra-hydrofuran, dioxane, trioxane, tetraoxane, butadiene monoxide, and isoprene monoxide.
  • ionic-polymerizable cyclic compounds include tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, and ethylene oxide and butene-1-oxide.
  • the ring-opening copolymers of these two or more ionic-polymerizable cyclic compounds may be randomly bonded.
  • Examples of commercial available diols (A) having the structural unit shown by the formula (1) include PTMG 1000 and PTMG 2000 (Mitsubishi Chemical Co. , Ltd.); PPG 1000, PPG 2000, EXCENOL 2020, EXCENOL 1020 (Asahi Oline Co., Ltd.); PEG 1000, UNISAFE DC 1100, DA 400, DC 1800 (Nippon Oil and Fats Co., Ltd.); PPTG 2000, PPTG 1000, PTG 400, PTGL 2000 (Hodogaya Chemical Co.,
  • examples of the diol (A) having the structural unit of formula (2) include diols obtained by the reaction of ⁇ -caprolactone and a divalent diol, such as ethylene glycol, tetramethylene glycol, 1,6-hexane glycol, neopentylene glycol, or 1,4-butane diol.
  • diol (A) having the structural unit of formula (3) examples include polyester diols obtained by the reaction of a polyhydric alcohol, such as ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexane diol, neopentylene glycol, or
  • a polybasic acid such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, or sebacic acid.
  • Examples of the diol (A) having the structural unit of formula (4) include commercially available products, such as DN-980, DN-981, DN-982, DN-983, Nipporane N-982 (Nippon Polyurethane), and PC-8000 (PPG Industries Inc.).
  • diol compounds other than the diol (A) used in the Processes 1-4 examples include:
  • 1,4-cyclohexanedimethanol dimethylol compounds of dicyclopentadiene, tricyclodecanedimethanol , ⁇ -methyl- ⁇ -valerolactone, polybutadiene with terminal hydroxyl groups, hydrogenated polybutadiene with terminal hydroxyl groups, castor oil-denatured polyol, polydimethylsiloxane with terminal diols, and polydimethylsiloxane carbitol-denatured polyols.
  • examples of the diamine used in the Processes 2-4 above include, ethylene diamine, tetramethylene diamine, hexamethylene diamine, paraphenylene diamine, 4,4 '-diaminodiphenylmethane, diamines containing hetero atoms, and polyether diamines.
  • diisocyanate used in Processes 1-4 examples 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, dicyclohexylmethane diisocyanate, methylene bis(4-cyclohexylisocyanate) , hydrogenated diphenylmethane diisocyanate, 2 ,2 , 4-tri
  • examples of the (meth)acrylate compounds having a hydroxyl group as in the specific unsaturated compound(A) include.
  • examples of such (meth)acrylate compounds having hydroxyl group are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyoctyl (meth)acrylate, pentaerythritol tri (meth)acrylate, glycerine di (meth)acrylate, dipentaerythritolmonohydroxy penta (meth)aer late, 1, -butanediol mono(meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, 1 , 6-hexanediol mono(meth)acrylate, neopentylglycol mono(meth)acrylate, tr imethylolpropane di (meth)acrylate, trimethylolethane di (meth)acrylate, (meth)acrylates represented by the
  • CH 2 C - C-0-CH 2 -CH-CH 2 -0-R 20 (9-1) i ii i
  • R 14 O OH CH 2 C - C-0-CH 2 CH 2 - ( 0-CCH 2 CH 2 CH 2 CH 2 CH 2 ) D -OH ( 9-2 )
  • R 14 is a hydrogen atom or a methyl group
  • R 20 is a phenyl group
  • p is an integer from 1-5.
  • An example of commercially available products which can be used is ARONIX M113 (Toagosei Chemical Co., Ltd.).
  • Component (B) of the photo curable liquid curable resin composition is a compound comprising a (meth)acrylate and a dioxane group.
  • the compound constituting component (B) has a molecular wight of less than about 1400, but more than about 170. More in particular, the molecular weight of this compound is about 170-250.
  • the dioxane group preferably is a 1,3-dioxane or a 1,4-dioxane group, which may be substituted on one or more of the carbon atoms, and which is bound to the (meth)acrylate group via a C 1 _ i alkylene group. More in particular, a 1,3-dioxane group preferably is bound to the (meth)acrylate through a methylene bond at its 5 position. More in particular, this ethylenically unsaturated monomer is represented by the formula (6)
  • R 9 represents a hydrogen atom or a methyl group and R 10 represents a hydrogen atom or an alkyl group having 1-10 carbon atoms.
  • R 9 is a hydrogen
  • R 10 is methyl, ethyl, iso- or n-propyl.
  • R 10 is ethyl.
  • These monomers may be used either individually or in combination of two or more.
  • the proportion of the component (B) in the composition is preferably 5-40% by weight, and more preferably 10-30% by weight. In addition, it is desirable that the total of the components (A) and (B) in the liquid curable resin composition of the present invention be 30% by weight or more, and preferably 40% by weight or more.
  • the component (C) which is comprised in the liquid resin composition of the present invention include: 1-hydroxycyclohexyl phenyl ketone, 2 , 2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, tr iphenylamine,.
  • These compounds of the component (C) may be used either individually or in combination of two or more.
  • the proportion of the component (C) in the composition is preferably 0.1-10% by weight, and more preferably 1-5% by weight.
  • a photosensitizer may be optionally added in addition to these photopolymerization initiators.
  • photosensitizers examples include triethylamine, diethylamine, N-methyldiethanoleamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and isoamyl 4-dimethylaminobenzoate, and commercially available products such as Uvecryl P102, 103, 104, 105 (UCB).
  • Uvecryl P102, 103, 104, 105 Uvecryl P102, 103, 104, 105
  • At least one reactive diluent such as a mono-functional compound having one ethylenically unsaturated group in the molecule, but different from the component (B) (hereinafter referred to as mono-functional compound (D) ) or a poly-functional compound having two or more ethylenically unsaturated groups in the molecule (hereinafter referred to as poly-functional compound (E)).
  • the at least one reactive diluent preferably has a molecular weight of not more than 600, or a viscosity at room temperature of not more than about 300 mPa.s (measured as 100% diluent).
  • Examples of the mono-functional compounds (D) which can be incorporated in the composition include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl ( eth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)
  • (meth)acrylamide isobutoxymethyl (meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformaldehyde, N,N-dimethyl (meth)acrylamide, t-octyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate,
  • R 15 is a hydrogen atom or a methyl group
  • R 16 is an alkylene group containing 2 to 6, preferably 2 to 4 carbon atoms
  • R 17 is a phenyl group, optionally substituted with an alkyl group containing 1 to 12, preferably 1 to 9, carbon atoms
  • q is an integer from 0 to 12, and preferably from 1 to 8.
  • R 15 is the same as the R 15 of formula (11);
  • R l ⁇ is an alkylene group containing 2 to 8, preferably 2 to 5, carbon atoms; and r is an integer from 1 to 8, and preferably from 1 to 4, and R 21 is a tetrahydrofurfuryl group.
  • R 15 and R 18 are the same as the R 15 , R l ⁇ in formula (12); s is an integer from 1 to 15; and R 19 s are individually a hydrogen atom or a methyl group.
  • polyfunctional compounds (E) which can be incorporated into the composition include: tr imethylolpropane tri (meth)acrylate, pentaerythr itol tri(meth)acrylate, pentaerythr itol tetra(meth)acrylate, ethylene glycol di (meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di (meth)acrylate, 1, 4-butanediol di (meth)acrylate, 1, 6-hexanediol di (meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropanetrioxyethyl (meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri (meth)acrylate, tris (2-hydroxyethyl ) isocyanurate di (meth)acrylate, tricyclodecanedimethanol di (meth)acrylate, and epoxy (meth)
  • composition of the present invention contain at least one compound selected from these components (D) or components (E) in an amount of 1-40% by weight.
  • polymers or oligomers can be added to the compositions as additives.
  • Such polymers or oligomers include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivatives, styrene/butadiene/styrene block copolymer, styrene/ethylene/butene/styrene block copolymer, styrene/isoprene/styrene block copolymer, petroleum resin, xylene resin, ketone resin, fluorine-containing oligomer, silicone oligomer, polysulfide oligomer, and the like.
  • reactive oligomers prepared by copolymerizing styrene compounds, (meth)acryl compounds, (meth)acryl compounds with an epoxy group, and the like, and introducing an acryloyl group into the copolymer (e.g. AP-2150, B-3000 to B-3006 (Sin-Nakamura Chemical Co.)) may be incorporated in the composition.
  • an acryloyl group e.g. AP-2150, B-3000 to B-3006 (Sin-Nakamura Chemical Co.)
  • composition of the present invention may be formulated with various components, as required, such as antioxidants, UV absorbers, photo-stabilizers, silane coupling agents, aging preventives, thermal polymerization inhibitors, leveling agents, coloring matters, surface active agents, preservatives, plasticizers, lubricants, solvents, fillers, wettability improvers, and coated surface improvers.
  • antioxidants such as Irganox 1010, 1035, 1076, 1222 (Ciba Geigy), and the like.
  • UV absorbers examples include Tinuvin P234, P320, P326, P327, P328, P213 (Ciba Geigy), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400 (Sumitomo Chemical Industries Co., Ltd.).
  • Commercially available photo-stabilizers which can be added include Tinuvin 292, 144, 622LD (Ciba Geigy), and Sanol LS770, LS765, LS292, LS2626, LS1114, LS744 (Sankyo Co.).
  • silane coupling agents which can be used include ⁇ -aminopropyltr iethoxysilane, ⁇ -mercaptopropyltrimethoxy-silane, ⁇ -methacryloxypropyltrimethoxysilane, and commercial products such as SH6062, SZ6030 (Toray-Dow Corning Silicone Co.) and KBE903, KBM803 (Shin-etsu Silicone Co.).
  • Commercially available aging preventives include Antigene W, S, P, 3C, 6C, RD-G, FR, AW, and Sumiriser GA-80 (Sumitomo Chemical Co.).
  • the liquid curable resin composition of the present invention has a viscosity of 200 to 20,000 cP , and preferably 2,000 to 15,000 cP, at 25°C.
  • the liquid curable resin composition of the present invention When used as a secondary coating material of optical fiber or a bundling material for a optical fiber ribbon matrix, it is desirable that the Young's modulus after cure be 10 to 250 kg/mm 2 , particularly 40 to 150 kg/mm 2 . When used as a primary coating material for optical fiber, a desirable Young's modulus of the resin composition after cure is 0.05 to 0.3 kg/mm 2 .
  • the liquid curable resin composition of the present invention can be cured by heat and/or radiation on a substrate as to obtain a coated substrate, or to use the resin composition as a photo-curable adhesive.
  • the liquid curable coating composition can be used in a process for coating a pristine drawn optical fiber with a primary coating and/or a secondary coating according this invention, and curing the coating with radiation.
  • the liquid curable coating composition can also be used, in combination with suitable pigments or dyes, as an ink to color coated optical glass fibers.
  • a ribbon unit comprises generally 2-12 coated and colored optical fibers aligned in parallel.
  • the resin composition of the present invention can also be used as a bundling material as to bind a plurality of ribbons together.
  • the bundle of ribbons generally comprises 2-12 ribbons.
  • radiation means radiation of infrared light, visible light, ultraviolet light, X-rays, electron beam, ⁇ -rays, ⁇ -rays, ⁇ -rays, and the like.
  • the following components were charged into a vessel equipped with a stirrer: 9.7 g of tolylene diisocyanate, 85.5 g of a ring-opening polymer of ethylene oxide and butene oxide having Mn of 2,000, 0.024 g of 2 , 6-di-tert-butyl-p-cresol, and 0.008 g of tr icyclodecane dimethanol diacrylate (manufactured by Mitsubishi Chemical Co., Ltd.). The mixture was cooled with ice to 10°C or below while stirring. After the addition of 0.08 g of dibutyl tin dilaurate, the mixture was stirred for two hours while controlling the temperature at 20-30°C.
  • Cured resin samples were prepared by irradiating the resin compositions with UV light at a dose of 1000 mJ/cm 2 in the air using a 3.5 KW metal halide lamp (SMX-3500/F-OS, manufactured by ORC Co.). An amount of 1.0 g of these samples were accurately weighed. After extraction in methyl ethyl ketone for 12 hours using a Soxhlet extractor, the residue was dried under a vacuum of 10 mmHg at 60°C for 6 hours. The weight loss (%) was determined according to the following formula.
  • Cured films were prepared by coating the resin compositions to quartz plates using an applicator bar with a thickness of 150 mm to prepared films and irradiating the films with UV light at a dose of 100 mJ/cm 2 in a nitrogen gas stream using a 3.5 KW metal halide lamp
  • the cured films attached to the quartz plates were allowed to stand at 23°C and RH 50% for 24 hours to obtain test leaves.
  • the test leaves were cut into pieces with a 1 cm width.
  • the T-peel strength (g/cm) was measured for each test leaf at a cross head speed of 50 mm/min using a peel tester (Autograph AGS-1KND Type-1 , manufactured by Shimazu Manufacturing Co., Ltd.).
  • the photo-curable liguid resin composition for optical fibers of the present invention has a low viscosity at room temperatures, exhibits excellent stability during a long-term storage and adeguate adhesion to optical fibers, and produces cured products with excellent characteristics such as superior UV light resistance, heat resistance, resistance against becoming yellowed by heat and light, and oil resistance. In addition, the cured products generate only a slight amount of hydrogen gas.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de résine liquide photodurcissable comprenant (A) un polymère contenant un groupe éthyléniquement insaturé et une unité structurelle renfermant une liaison éther, une liaison ester ou une liaison éther ester; (B) un monomère contenant un groupe éthyléniquement insaturé représenté par la formule (I), dans laquelle R9 représente un atome d'hydrogène ou un groupe méthyle et R10 représente un atome d'hydrogène ou un groupe alkyle comportant 1 à 10 atomes de carbone; et (C) un initiateur de photopolymérisation. La composition présente une excellente stabilité durant un stockage prolongé, elle est facile à traiter quand elle est utilisée comme revêtement de fibres optiques et elle ne génère qu'une faible quantité d'hydrogène gazeux. Elle présente également une adhérence appropriée aux fibres optiques et d'excellentes caractéristiques telles que meilleure résistance aux UV, à la chaleur, au jaunissement par la chaleur et la lumière, et aux huiles.
PCT/NL1997/000499 1996-09-05 1997-09-01 Composition de resine liquide photodurcissable Ceased WO1998009923A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU41387/97A AU4138797A (en) 1996-09-05 1997-09-01 Photo-curable liquid resin composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP23499896A JP3756585B2 (ja) 1996-09-05 1996-09-05 光硬化性液状樹脂組成物
JP8/234998 1996-09-05

Publications (1)

Publication Number Publication Date
WO1998009923A1 true WO1998009923A1 (fr) 1998-03-12

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Country Status (3)

Country Link
JP (1) JP3756585B2 (fr)
AU (1) AU4138797A (fr)
WO (1) WO1998009923A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001049629A1 (fr) * 1999-12-30 2001-07-12 Corning Incorporated Revetement de fibre optique primaire a reticulation rapide
WO2003066749A1 (fr) * 2002-02-09 2003-08-14 W. & J. Leigh & Co., Revetements intumescents durcissables par rayonnement
EP1369723A4 (fr) * 2001-03-15 2008-04-09 Sumitomo Electric Industries Coeur rubane de fibre optique de type fendu

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4832021B2 (ja) * 2005-07-29 2011-12-07 Ｊｓｒ株式会社 液状硬化性樹脂組成物

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992006846A1 (fr) * 1990-10-19 1992-04-30 Dsm Desotech, Inc. Composition de resine liquide durcissable
WO1993021248A1 (fr) * 1992-04-20 1993-10-28 Dsm Desotech, Inc. Composition de resine liquide durcissable
WO1996011217A1 (fr) * 1994-10-11 1996-04-18 Dsm N.V. Composition d'enrobage pour fibres de verre optique
WO1997014737A1 (fr) * 1995-10-20 1997-04-24 Dsm N.V. Composition liquide a base de resine durcissable
WO1997019898A1 (fr) * 1995-11-28 1997-06-05 Dsm N.V. Composition de resine liquide photodurcissable

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992006846A1 (fr) * 1990-10-19 1992-04-30 Dsm Desotech, Inc. Composition de resine liquide durcissable
WO1993021248A1 (fr) * 1992-04-20 1993-10-28 Dsm Desotech, Inc. Composition de resine liquide durcissable
WO1996011217A1 (fr) * 1994-10-11 1996-04-18 Dsm N.V. Composition d'enrobage pour fibres de verre optique
WO1997014737A1 (fr) * 1995-10-20 1997-04-24 Dsm N.V. Composition liquide a base de resine durcissable
WO1997019898A1 (fr) * 1995-11-28 1997-06-05 Dsm N.V. Composition de resine liquide photodurcissable

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001049629A1 (fr) * 1999-12-30 2001-07-12 Corning Incorporated Revetement de fibre optique primaire a reticulation rapide
US6531522B1 (en) 1999-12-30 2003-03-11 Corning Incorporated Fast curing primary optical fiber coating
EP1369723A4 (fr) * 2001-03-15 2008-04-09 Sumitomo Electric Industries Coeur rubane de fibre optique de type fendu
WO2003066749A1 (fr) * 2002-02-09 2003-08-14 W. & J. Leigh & Co., Revetements intumescents durcissables par rayonnement

Also Published As

Publication number Publication date
AU4138797A (en) 1998-03-26
JPH1081705A (ja) 1998-03-31
JP3756585B2 (ja) 2006-03-15

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