WO2008120984A1 - Composition de résine liquide durcissable - Google Patents

Composition de résine liquide durcissable Download PDF

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Publication number
WO2008120984A1
WO2008120984A1 PCT/NL2008/050179 NL2008050179W WO2008120984A1 WO 2008120984 A1 WO2008120984 A1 WO 2008120984A1 NL 2008050179 W NL2008050179 W NL 2008050179W WO 2008120984 A1 WO2008120984 A1 WO 2008120984A1
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WO
WIPO (PCT)
Prior art keywords
meth
coating
acrylate
optical fiber
liquid resin
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Application number
PCT/NL2008/050179
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English (en)
Inventor
Hiroshi Yamaguchi
Satoshi Kamo
Takahiko Kurosawa
Original Assignee
Dsm Ip Assets B.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 Ip Assets B.V., Jsr Corporation filed Critical Dsm Ip Assets B.V.
Publication of WO2008120984A1 publication Critical patent/WO2008120984A1/fr

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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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • G02B6/4479—Manufacturing methods of optical cables
    • G02B6/448—Ribbon cables
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • G02B6/4479—Manufacturing methods of optical cables
    • G02B6/4486—Protective covering

Definitions

  • the present invention relates to a curable liquid resin composition which produces a cured product having low self-adhesiveness and a high stress relaxation rate.
  • a resin coating is provided over a glass fiber for protection and reinforcement immediately after the glass fiber is produced by spinning molten glass.
  • a structure is known in which a flexible primary coating layer is formed on a surface of the glass fiber and a more rigid secondary coating layer is applied over the primary coating layer.
  • a structure is also known in which, for example, four or eight resin-coated optical fibers are placed side by side in a plane and bundled with a bundling material to produce a ribbon-shaped coating layer having a rectangular section.
  • a resin composition for forming the primary coating layer is called a primary material
  • a resin composition for forming the secondary coating layer is called a secondary material
  • a material for bundling optical fibers is called a ribbon matrix material.
  • the secondary material or the ribbon matrix material is generally positioned in the outermost layer during the production process.
  • an optical fiber coated with the cured secondary material is stored in a state in which the optical fiber is wound around a bobbin, and is then unwound from the bobbin when applying an ink layer or forming a ribbon.
  • the optical fiber ribbon is also stored in a wound state so that portions of the ribbon are rubbed against each other when forming a cable. Since portions of the cured secondary material or the ribbon matrix materials come in contact in this manner, if the cured material has high adhesion, the optical fiber is not regularly wound around the bobbin and is not smoothly unwound, thereby hindering the production process. In order to prevent an irregular winding problem during winding or unwinding, the cured product must have low self-adhesiveness and a high stress relaxation rate.
  • the first aspect of the instant claimed invention is a radiation curable liquid resin composition
  • a radiation curable liquid resin composition comprising: (A) a urethane (meth)acrylate having a structure derived from polypropylene glycol with a number average molecular weight of about 4,000 or less;
  • (D) a polymerization initiator; wherein from about 50 to about 80 mass% of the component (C) is 2- ethylhexyl (meth)acrylate, and from about 50 to about 90 mass% of the component (D) is 1-hydroxycyclohexyl phenyl ketone.
  • the second aspect of the instant claimed invention is an optical fiber comprising the coating layer according to the first aspect of the instant claimed invention.
  • the third aspect of the instant claimed invention is an optical fiber ribbon comprising the coating layer according to the first aspect of the instant claimed invention.
  • the fourth aspect of the instant claimed invention is a process to coat an optical fiber with at least two radiation curable liquid resin compositions comprising a) providing an optical fiber; b) coating said optical fiber with a radiation curable coating, which is a primary coating, and optionally applying radiation to cure said primary coating; c) coating said optical fiber with a second radiation curable coating, which is a secondary coating, applied over the primary coating; d) applying radiation to cure said secondary coating; and optionally e) coating said optical fiber with a matrix radiation curable coating and applying radiation to cure said matrix radiation curable coating; wherein either the secondary coating or the optional matrix radiation curable coating is the composition of the first aspect of the instant claimed invention.
  • An object of the present invention is to provide a curable liquid resin composition which produces a cured product, used as a Secondary Coating or a Matrix Coating, where the product has low self-adhesiveness and a high stress relaxation rate.
  • the inventors of the present invention have found that the above object can be achieved by combining two types of specific urethane (me th) aery late s, a specific urethane (me th) aery late monomer, and a specific polymerization initiator. This finding has led to the completion of the present invention.
  • the cured product obtained by curing the curable liquid resin composition of the present invention exhibits low self adhesion, excellent surface sliding properties, a high stress-relaxation rate, and high strength to an external stress.
  • the urethane (me th) aery late used as the component (A) of the present invention has a structure derived from polypropylene glycol having a number average molecular weight of about 4,000 or less, and is produced by, for example, reacting a polypropylene glycol having a number average molecular weight of about 4,000 or less, a diisocyanate, and a hydroxyl-group-containing (meth) aery late.
  • the urethane (me th) aery late is produced by reacting isocyanate groups of the diisocyanate with hydroxyl groups of the polyol and the hydroxyl group -containing (meth)acrylate.
  • a method of reacting the polyol, the diisocyanate, and the hydroxyl group-containing (meth) aery late all together a method of reacting the polyol with the diisocyanate, and reacting the resulting product with the hydroxyl group -containing (meth)acrylate; a method of reacting the diisocyanate with the hydroxyl group -containing
  • the polyol used is a polypropylene glycol having a number average molecular weight of about 4,000 or less, and preferably from about 500 to about 4,000.
  • the number average molecular weight is determined by gel permeation chromatography (GPC method) as a polystyrene-reduced molecular weight.
  • the polypropylene glycol is commercially available as "PPG-400”, “PPGlOOO”, “PPG2000”, “PPG3000”, “EXCENOL 720", “EXCENOL 1020”, and “EXCENOL 2020” (manufactured by Asahi Glass Urethane Co., Ltd.), and the like.
  • diisocyanate 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5- naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'- diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'- biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis(2-isocyanateethyl)fumarate, 6-isopropyl-l,3-
  • 2,4-tolylene diisocyanate isophorone diisocyanate, xylylene diisocyanate, and methylenebis(4-cyclohexylisocyanate) are preferable.
  • These diisocyanates may be used either individually or in combination of two or more.
  • Examples of (meth)acrylates containing a hydroxyl group include 2- hydroxyethyl (meth) aery late, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (me th) aery late, 2-hydroxy-3-phenyloxypropyl (meth) aery late, 1,4-butanepolyol mono (meth) aery late, 2-hydroxyalkyl(meth)acryloyl phosphate, 4- hydroxycyclohexyl (meth) aery late, 1,6-hexanepolyol mono (meth) aery late, neopentyl glycol mono(meth)acrylate, trimethylolpropane di(meth) aery late, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and (meth)acrylates shown by the following formulas (1)
  • CH 2 C(R 1 )- COOCH 2 CH Z — (OCOCH 2 CH 2 CH 2 CH 2 GH 2 )- OH (1)
  • CH 2 C(R 1 )- COOCH 2 CH(OH)CH 2 -O — V ⁇ (2) wherein R 1 represents a hydrogen atom or a methyl group and n is an integer
  • a compound obtained by the addition reaction of (meth)acrylic acid and a glycidyl group -containing compound such as an alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth)acrylate may also be used.
  • a glycidyl group -containing compound such as an alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth)acrylate
  • hydroxyl group -containing (meth)acrylates 2 -hydroxy ethyl (meth)acrylate and 2- hydroxypropyl (me th) aery late are preferable.
  • hydroxyl group -containing (meth) aery late compounds may be used either individually or in combination of two or more.
  • (meth)acrylate are preferably used so that the isocyanate groups included in the diisocyanate and the hydroxyl groups included in the hydroxyl group- containing (meth) aery late are respectively 1.1 to 3 equivalents and 0.2 to 1.5 equivalents for one equivalent of the hydroxyl groups included in the polyol.
  • a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, trie thy lamine, l,4-diazabicyclo[2.2.2]octane, or 2,6,7- trimethyl-l,4-diazabicyclo[2.2.2]octane in an amount of 0.01 to 1 part by mass for 100 parts by mass of the reactants.
  • the reaction temperature is preferably 10 to 9O 0 C, and particularly preferably 30 to 80 0 C.
  • the hydroxyl group -containing (meth) aery late may be partially replaced with a compound having a functional group which can be added to an isocyanate group.
  • a compound having a functional group which can be added to an isocyanate group examples of such compound, y- mercaptotrimethoxysilane, ⁇ -aminotrimethoxysilane, or the like can be given. Use of these compounds improves adhesion to a substrate such as glass.
  • the urethane (meth)acrylate of component (A) is added to the curable liquid resin composition of the present invention in an amount of preferably from about 20 to about 50 mass%, and particularly preferably from about 25 to about 40 mass%.
  • the urethane (me th) aery late used as the component (B) of the present invention has a structure derived from polypropylene glycol having a number average molecular weight of more than about 4,000, and may be prepared by using polypropylene glycol having a number average molecular weight of more than about 4,000 instead of the polypropylene glycol having a number average molecular weight of about 4,000 or less used for preparing the urethane (me th) aery late of the component (A).
  • the urethane (me th) aery late of the component (B) is added to the curable liquid resin composition of the present invention in an amount of preferably from about 0.5 to about 7 mass%, and particularly preferably from about 1 to about 5 mass%.
  • urethane (meth)acrylates may optionally be added in addition to the urethane (meth) aery late (A) and the urethane (meth) aery late (B).
  • urethane (meth) aery late urethane (meth)acrylate which does not contain a polyol component and is obtained by reacting a diisocyanate compound and a hydroxyl group -containing (meth)acrylate compound can be given.
  • the diisocyanate compound and the hydroxyl group -containing (meth) aery late mentioned above as raw materials for synthesizing the component (A) may be preferably used as a diisocyanate compound and a hydroxyl group -containing (meth)acrylate used for synthesizing the ure thane (me th) aery late (B').
  • urethane (me th) aery late (B') other than the component (A) and the component (B) a reaction product of 2-hydroxyethyl (meth)acrylate and 2,4-tolylene diisocyanate at a molar ratio of 2:1, an equimolar reaction product of 2-hydroxypropyl (meth)acrylate, 2,4-tolylene diisocyanate, and 2-hydroxyethyl (meth)acrylate, and the like can be given.
  • the amount of the urethane (meth)acrylate (B') other than the component (A) and the component (B) to be added to the curable liquid resin composition of the present invention is preferably from about 20 to about 70 mass%, and particularly from about 30 to about 45 mass%.
  • monofunctional (meth)acrylates such as, for example, (meth)acrylates having an alkyl group such as butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth) aery late, pentyl (meth) aery late, amyl (meth) aery late, isoamyl (meth) aery late, hexyl (meth) aery late, heptyl (meth) aery late, octyl (meth) aery late, 2-ethylhexyl (meth)acrylate, iso-octyl (meth)acrylate, nonyl (meth) aery late, iso-nonyl (meth)acrylate, decyl (meth) aery late, iso-decyl (meth) aery late, undec
  • alkyl group such as butyl (meth)acrylate, is
  • (meth) aery late (meth)acrylates having an alicyclic structure such as isobornyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth) aery late, dicyclopentanyl (meth) aery late, dicyclopentenyl (meth) aery late, 4- butylcyclohexyl (meth) aery late , and cyclohexyl (meth)acrylate; (meth)acrylates having an aromatic ring such as benzyl (meth) aery late; and other (meth)acrylates such as 2-hydroxyethyl (meth) aery late, 2-hydroxypropyl (meth) aery late, 4-hydroxybutyl acrylate, stearyl (meth)acrylate, iso-stearyl (meth) aery late, tetrahydrofurfuryl (meth)acrylate, polyethylene glycol mono(meth)acrylate
  • the amount of the (meth) aery late monomer of the component (C) in the curable liquid resin composition of the present invention is preferably 20 to 50 mass%, and more preferably from about 25 to about 35 mass%.
  • a photopolymerization initiator or a heat polymerization initiator can be used as the polymerization initiator used as the component (D).
  • a heat polymerization initiator such as a peroxide or an azo compound can be used.
  • the heat polymerization initiator benzoyl peroxide, t-butyl-oxybenzoate, azobisisobutyronitrile, and the like can be given.
  • a photopolymerization initiator When curing the curable liquid resin composition of the present invention using light, a photopolymerization initiator is used.
  • a photosensitizer may optionally be added.
  • the photopolymerization initiator are 1-hydroxycyclohexyl phenyl ketone, 2,2- dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4- chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, l-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-l-one, 2-hydroxy-2- methyl-1-phen
  • from about 50 to about 90 mass%, and preferably from about 65 to about 90 mass% of the polymerization initiators of the component (D) is 1 -hydroxy cyclohexyl phenyl ketone. If the amount of 1- hydroxycyclohexyl phenyl ketone is less than about 50 mass%, surface curability (a sticking power) decreases, and if more than about 80 mass%, there is a tendency for the cure speed to decrease.
  • the polymerization initiator (D) is used in the curable liquid resin composition of the present invention in an amount of preferably from about 0.1 to about 10 mass%, and particularly preferably from about 0.3 to about 7 mass%.
  • the curable liquid resin composition of the present invention may further comprise a silicone compound having an average molecular weight of from about 1,500 to about 35,000 as a component (E).
  • the component (E) plays an important role in obtaining effects of improving peelability for removing the outermost layer optical fibers formed from the resin composition of the present invention from the adjacent layer thereof. If the average molecular weight of the component (E) is less than about 1,500, sufficient effects of improving peelability may not be obtained. If the average molecular weight of the component (D) exceeds about 35,000, the effects of improving peelability may be insufficient.
  • the average molecular weight is more preferably from about 1,500 to about 20,000, still more preferably from about 1,500 to about 20,000, and particularly preferably from about 3,000 to about 15,000.
  • the component (E) not include a polymerizable group such as an ethylenically unsaturated group. If the component (E) does not contain a polymerizable group, excellent peelability can be maintained even after subjecting the optical fibers to a heat history.
  • a polymerizable group such as an ethylenically unsaturated group.
  • the silicone compound polyether-modified silicone, alkyl- modified silicone, urethane acrylate-modified silicone, urethane -modified silicone, methylstyryl-modified silicone, epoxy polyether-modified silicone, alkylaralkyl polyether-modified silicone, and the like can be given. Of these, polyether-modified silicone is particularly preferable.
  • a polydimethylsiloxane compound in which at least one silicon atom is bonded to a group R 14 -(R 15 O) S -R 16 - (wherein R 14 represents a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms, R 15 represents an alkylene group having 2 to 4 carbon atoms (R 15 may have two or more different alkylene groups), R 16 represents an alkylene group having 2 to 12 carbon atoms, and s is an integer of 1 to 20) is preferably used.
  • R 15 in the above an ethylene group and a propylene group are preferable, with an ethylene group being particularly preferable.
  • the component (E) is added to the composition in an amount of preferably from about 0.1 to about 50 mass%, more preferably from about 0.5 to about 40 mass%, and particularly preferably from about 1 to about 20 mass% from the viewpoint of ensuring peelability, strength, and weather resistance of the outermost layer.
  • Additives such as antioxidant, coloring agents, UV absorbers, light stabilizers, heat polymerization inhibitors, leveling agents, surfactants, preservatives, plasticizers, lubricants, solvents, fillers, aging preventives, wettability improvers, and coating surface improvers may be added to the curable liquid resin composition of the present invention in addition to the above-described components.
  • antioxidants As examples of the antioxidants, “Irganox 1010”, “Irganox 1035”, “Irganox 1076”, and “Irganox 1222” (manufactured by Ciba Specialty Chemicals Co., Ltd), “Antigene P”, “Antigene 3C”, “Antigene FR”, and “Antigene GA-80” (manufactured by Sumitomo Chemical Industries Co., Ltd.), and the like can be given.
  • UV absorbers As examples of the UV absorbers, “Tinuvin P”, “Tinuvin 234", “Tinuvin 320”, “Tinuvin 326”, “Tinuvin 327”, “Tinuvin 328”, “Tinuvin 329”, and “Tinuvin 213” (manufactured by Ciba Specialty Chemicals Co., Ltd.), “Seesorb 102”, “Seesorb 103”, “Seesorb 501”, “Seesorb 202”, “Seesorb 712", and “Seesorb 704" (manufactured by Sypro Chemical Co., Ltd.), and the like can be given.
  • oligomers, polymers, or additives may optionally be included in the composition of the present invention insofar as the characteristics of the composition are not impaired.
  • polyester (meth)acrylate, epoxy (meth)acrylate, polyamide (me th) aery late, siloxane polymers having a (meth)acryloyloxy group, glycidyl methacrylate, and the like can be given.
  • the viscosity of the curable liquid resin composition of the present invention at 25 0 C is preferably from about 0.1 to about 10 Pa s, more preferably from about 1 to about 8 Pa s, and particularly preferably from about 2 to about 6 Pa s.
  • An aspect of the instant claimed invention is a process to coat an optical fiber with at least two curable liquid resin compositions comprising a) providing an optical fiber; b) coating said optical fiber with a radiation curable coating, which is a primary coating, and optionally applying radiation to cure said primary coating; c) coating said optical fiber with a second radiation curable coating, which is a secondary coating, applied over the primary coating; and d) applying radiation to cure said secondary coating; and optionally e) coating said optical fiber with a matrix radiation curable coating and applying radiation to cure said matrix radiation curable coating, wherein either the secondary coating or the optional matrix radiation curable coating is the composition of Claim 1.
  • the one or more radiation curable liquid resin compositions may include a Primary Coating, a Secondary Coating and an Ink Coating. Primary Coatings, Secondary
  • optical fibers into a ribbon configuration is standardized based on either industry standard or government standard or both depending upon where the optical fiber is manufactured and used. People of ordinary skill in the art of optical fibers know what type of ribbon configurations are acceptable in what jurisdiction.
  • composition of the present invention when used either as a Secondary Coating or as a Matrix coating may be cured by applying heat or radiation. It is preferable under most circumstances to cure by applying radiation. Radiation used herein refers to infrared rays, visible light, ultraviolet rays, X-rays, electron beams, ⁇ -rays, ⁇ -rays, ⁇ -rays, and the like.
  • the product of the process is either a coated optical fiber (if the composition of the instant claimed invention is used as a Secondary Coating) or an "optical fiber ribbon" (if the composition of the instant claimed invention is used as a Matrix Coating) which is one or more optical fibers arranged in a ribbon configuration.
  • the Young's modulus of the product obtained after curing is preferably from about 100 to about 2,500 MPa.
  • the Young's modulus of the cured product is preferably from about 0.5 to about 3 MPa.
  • the stress relaxation time which is defined as the time required for the stress to decrease to 37% of the initial stress, is usually about 10 minutes or less, preferably five minutes or less, and particularly preferably three minutes or less.
  • 2,4-tolylene diisocyanate 0.012 g of 2,6-di-t-butyl-p-cresol, and 0.039 g of dibutyltin dilaurate.
  • the mixture was cooled with ice to 1O 0 C or below while stirring.
  • 30.65 g of a ring-opening polymer of propylene oxide having a number average molecular weight of 1,000 the mixture was allowed to react for two hours with stirring while controlling the liquid temperature at 35 0 C or less.
  • 7.12 g of hydroxyethyl acrylate was added dropwise and the mixture was stirred for a further three hours at 70 to 75 0 C.
  • the reaction was terminated when the residual isocyanate content was reduced to 0.1 wt% or less to obtain a urethane acrylate with a structure having hydroxyethyl acrylate bonded to both ends of propylene oxide via 2,4- tolylene diisocyanate.
  • the resulting urethane acrylate is referred to as "UA-I”.
  • a reaction vessel equipped with a stirrer was charged with 1.59 g of 2,4- tolylene diisocyanate, 0.012 g of 2,6-di-t-butyl-p-cresol, and 0.039 g of dibutyltin dilaurate.
  • the mixture was cooled with ice to 1O 0 C or below while stirring.
  • 1.06 g of hydroxyethyl acrylate dropwise while controlling the temperature at 2O 0 C or less the mixture was allowed to react for one hour while stirring.
  • a reaction vessel equipped with a stirrer was charged with 41.4 g of 2,4- tolylene diisocyanate, 0.02 g of 2,6-di-t-butyl-p-cresol, 0.08 g of dibutyltin dilaurate, and 0.008 g of phenothiazine.
  • the mixture was cooled to 2O 0 C with stirring.
  • 27.6 g of 2-hydroxyethyl acrylate dropwise the mixture was allowed to react for one hour while stirring and controlling the temperature at 25 0 C or lower.
  • 30.9 g of 2- hydroxypropyl acrylate the mixture was reacted at about 60 0 C with stirring.
  • urethane acrylate which is an equimolar reaction product of 2,4-tolylene diisocyanate, 2-hydroxyethyl acrylate, and 2- hydroxypropyl acrylate.
  • the resulting urethane acrylate is referred to as "UA- 3".
  • Synthesis Example 4 synthesis 2 of urethane (meth)acrylate (B')
  • a reaction vessel equipped with a stirrer was charged with 42.9 g of 2,4- tolylene diisocyanate, 0.02 g of 2,6-di-t-butyl-p-cresol, 0.08 g of dibutyltin dilaurate, and 0.008 g of phenothiazine.
  • the mixture was cooled to 2O 0 C with stirring. After the addition of 57.1 g of 2-hydroxyethyl acrylate dropwise, the mixture was allowed to react for one hour at room temperature while stirring and controlling the temperature at 25 0 C or lower.
  • the reaction was terminated when the residual isocyanate concentration was 0.1 wt% or less to obtain a urethane acrylate having a structure with 2-hydroxypropyl acrylate bonded to both ends of 2,4-tolylene diisocyanate.
  • the resulting urethane acrylate is referred to as "UA-4".
  • the curable liquid resin composition was applied to a glass plate using a 250 ⁇ m thickness applicator bar and cured by applying ultraviolet rays at a dose of 1 J/cm 2 in air to obtain a test film.
  • the film was cut into a strip-shaped sample having an extension part width of 6 mm and a length of 25 mm.
  • the sample was subjected to a tensile test at a temperature of 23 0 C and a humidity of 50%.
  • the Young's modulus was calculated from the tensile strength at a strain of 2.5% and a tensile rate of 1 mm/min.
  • Breaking strength and breaking elongation of the test sample were measured using a tensile tester ("AGS-50G” manufactured by Shimadzu Corp.). Tensile rate 50 mm/min
  • the adhesive of the cured products of the compositions obtained in Examples and Comparative Examples was evaluated.
  • the liquid composition was applied to a sliding glass plate using a 381 ⁇ m thickness applicator.
  • the applied liquid composition was irradiated with ultraviolet rays at a dose of 0.1 J/cm 2 in a nitrogen atmosphere to obtain a cured film with a thickness of about 200 ⁇ m.
  • the cured film on the sliding glass plate was allowed to stand for 24 hours at a temperature of 23 0 C and a humidity of 50%.
  • a sample in the shape of a strip having an extension part with a width of 10 mm was prepared from the cured film.
  • An adhesion test of the sample was carried out according to JIS Z0237 using a tensile tester. The adhesion was determined from the tensile strength at a tensile rate of 50 mm/min.
  • SH28PA dimethylpolysiloxane polyoxyalkylene copolymer (manufactured by

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Abstract

L'invention concerne une composition de résine liquide durcissable qui comprend : (A) un uréthane (méth)acrylate qui possède une structure dérivée de polypropylèneglycol présentant une masse moléculaire moyenne en nombre d'environ 4000 ou moins; (B) un uréthane (méth)acrylate qui possède une structure dérivée d'un polypropylèneglycol présentant une masse moléculaire moyenne en nombre supérieure à environ 4000; (C) un monomère de (méth)acrylate; et (D) un initiateur de polymérisation. Dans ladite composition, une quantité comprise entre environ 50 et environ 80 % en masse du composant (C) est représentée par du 2-éthylhexyl (méth)acrylate, et une quantité comprise entre environ 50 et environ 90 % en masse du composant (D) est représentée par de la 1-hydroxycyclohexylphénylcétone. Cette composition, lorsqu'elle est durcie, permet d'obtenir un produit durci présentant une faible autoadhérence et un taux de relaxation de contrainte élevé. Ladite composition est apte à être utilisée en tant que revêtement secondaire ou en tant que revêtement matriciel pour des fibres optiques.
PCT/NL2008/050179 2007-03-29 2008-03-28 Composition de résine liquide durcissable WO2008120984A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2479197A1 (fr) * 2009-09-18 2012-07-25 DIC Corporation Composition de résine durcissable au rayonnement actinique, et produits et films traités correspondants
WO2017151380A1 (fr) * 2016-03-04 2017-09-08 Dow Global Technologies Llc Composition d'uréthane acrylate durcissable
EP3978976A4 (fr) * 2019-05-28 2022-07-27 Sumitomo Electric Industries, Ltd. Fil de coeur de bande de fibre optique, câble de fibre optique et procédé de fabrication de fil de coeur de bande de fibre optique

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5022752B2 (ja) * 2007-03-29 2012-09-12 Ｊｓｒ株式会社 液状硬化性樹脂組成物
JP2010106122A (ja) * 2008-10-29 2010-05-13 Dyflex Corp ウレタンアクリレート樹脂組成物、塗工剤、ウレタンアクリレート樹脂組成物の製造方法
JP6106253B1 (ja) * 2015-12-04 2017-03-29 株式会社フジクラ 光ファイバテープ、光ファイバテープの製造方法、及び間欠固定型光ファイバテープの連結部の形成に用いられる紫外線硬化樹脂組成物
JP2020204687A (ja) * 2019-06-17 2020-12-24 住友電気工業株式会社 光ファイバテープ心線、光ファイバケーブルおよび光ファイバテープ心線の製造方法
JP7338299B2 (ja) 2019-07-30 2023-09-05 株式会社レゾナック 光硬化性粘着剤組成物および粘着シート

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001047824A1 (fr) * 1999-12-24 2001-07-05 Dsm N.V. Compositions de gainage de fibres optiques
WO2005026228A1 (fr) * 2003-09-17 2005-03-24 Dsm Ip Assets B.V. Composition de resine liquide polymerisable
WO2005087874A1 (fr) * 2004-03-15 2005-09-22 Dsm Ip Assets B.V. Composition de resine liquide durcissante
JP2006036989A (ja) * 2004-07-29 2006-02-09 Jsr Corp 液状硬化性樹脂組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001047824A1 (fr) * 1999-12-24 2001-07-05 Dsm N.V. Compositions de gainage de fibres optiques
WO2005026228A1 (fr) * 2003-09-17 2005-03-24 Dsm Ip Assets B.V. Composition de resine liquide polymerisable
WO2005087874A1 (fr) * 2004-03-15 2005-09-22 Dsm Ip Assets B.V. Composition de resine liquide durcissante
JP2006036989A (ja) * 2004-07-29 2006-02-09 Jsr Corp 液状硬化性樹脂組成物

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2479197A1 (fr) * 2009-09-18 2012-07-25 DIC Corporation Composition de résine durcissable au rayonnement actinique, et produits et films traités correspondants
EP2479197A4 (fr) * 2009-09-18 2013-09-11 Dainippon Ink & Chemicals Composition de résine durcissable au rayonnement actinique, et produits et films traités correspondants
US8754180B2 (en) 2009-09-18 2014-06-17 Dic Corporation Active-energy-ray-curable resin composition, cured product thereof, and film
WO2017151380A1 (fr) * 2016-03-04 2017-09-08 Dow Global Technologies Llc Composition d'uréthane acrylate durcissable
CN109104865A (zh) * 2016-03-04 2018-12-28 陶氏环球技术有限责任公司 可固化氨基甲酸酯丙烯酸酯组合物
EP3423508B1 (fr) 2016-03-04 2022-04-27 Dow Global Technologies Llc Composition d'uréthane acrylate durcissable
EP3978976A4 (fr) * 2019-05-28 2022-07-27 Sumitomo Electric Industries, Ltd. Fil de coeur de bande de fibre optique, câble de fibre optique et procédé de fabrication de fil de coeur de bande de fibre optique

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