WO2007032386A1 - Composition de résine liquide durcissable pour gaine de fibre optique - Google Patents

Composition de résine liquide durcissable pour gaine de fibre optique Download PDF

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Publication number
WO2007032386A1
WO2007032386A1 PCT/JP2006/318150 JP2006318150W WO2007032386A1 WO 2007032386 A1 WO2007032386 A1 WO 2007032386A1 JP 2006318150 W JP2006318150 W JP 2006318150W WO 2007032386 A1 WO2007032386 A1 WO 2007032386A1
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Prior art keywords
meth
mass
acrylate
optical fiber
resin composition
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PCT/JP2006/318150
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English (en)
Japanese (ja)
Inventor
Hiroshi Yamaguchi
Satoshi Kamo
Masanobu Sugimoto
Takeo Shigemoto
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Jsr Corporation
Dsm Ip Assets B.V.
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Publication of WO2007032386A1 publication Critical patent/WO2007032386A1/fr

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    • 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
    • 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
    • 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
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • Liquid curable resin composition for optical fiber up jacket Liquid curable resin composition for optical fiber up jacket
  • the present invention relates to a liquid curable resin composition for an up jacket which is used after being applied to the surface of an optical fiber.
  • glass fibers are hot melt-spun and coated with a resin coating for the purpose of protection and reinforcement.
  • This process is called drawing, and as a resin coating, a structure in which a flexible primary coating layer is first provided on the surface of an optical fiber and a highly rigid secondary coating layer is provided outside thereof is known. Yes.
  • a structure in which a plurality of these optical fiber strands coated with a resin coating are arranged on a plane and hardened with a binding material to provide a tape-like coating layer is known.
  • the resin composition for forming the primary coating layer is a soft material
  • the resin composition for forming the secondary coating layer is a node material
  • a tape-shaped coating layer is formed.
  • the resin composition for this purpose is referred to as a tape material.
  • the outer diameter of the optical fiber is usually about 250 ⁇ m, but for the purpose of improving the workability by manual work, the outer diameter is further covered with another resin layer to make the outer diameter 500-900. Increased to about m.
  • a resin coating layer is usually referred to as an upjacket layer. Since the upjacket layer itself does not require optical properties, transparency is not particularly required, and it may be colored to impart visual discrimination. An important feature of the upjacket layer is that it can be peeled off easily and without damaging the underlying coating layer and the secondary coating layer when the optical fiber is connected.
  • the curable resin used as a coating material for optical fibers including such an upjacket layer has excellent coatability and can be drawn at high speed; has sufficient strength and flexibility; heat resistance Excellent in weather resistance; excellent in resistance to acids, alkalis, etc .; excellent in oil resistance; low in water absorption and hygroscopicity; low in hydrogen gas generation; in liquid form Properties such as good storage stability are required.
  • the upjacket layer is the upper layer.
  • the upper jacket layer and the lower primary coating layer and the secondary coating layer are firmly adhered to each other, so that when the tape layer is peeled off and the optical fiber is exposed, the upjacket layer is damaged or the optical fiber is broken.
  • the upjacket layer was peeled from the strands, it was often possible to break the primary coating layer and the secondary coating layer. For this reason, there has been a problem that the workability of the optical fiber connection work has deteriorated.
  • the liquid curable resin composition for up jackets with improved peelability includes three types of polysiloxane compounds (Patent Document 1) and a resin material.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-287717
  • Patent Document 2 Japanese Patent Laid-Open No. 9-324136
  • Patent Document 3 Japanese Patent Laid-Open No. 2000-273127
  • the peelability of the upjacket layer formed from the above composition was not sufficient.
  • the upper jacket layer is often heated to about 80 to 120 ° C. during the coating process of the cable layer in which thermoplastic resin is frequently used. There was a problem that the peelability of the layer was lowered.
  • An object of the present invention is to provide a liquid curable resin composition for an optical fiber up jacket which is excellent in function as an optical fiber coating material and excellent in peelability from an adjacent coating layer.
  • the present inventor blended various components into a liquid curable resin composition containing urethane (meth) acrylate, and the function of the cured product as an optical fiber coating layer and peelability.
  • a silicone compound having a certain molecular weight by adding a silicone compound having two or more ethylenically unsaturated groups at a specific ratio in a compound having an ethylenically unsaturated group. And found that this purpose can be achieved.
  • the present invention relates to a total amount of 100% by mass of the following components (A), (B) and (C):
  • liquid curable resin composition for an optical fiber upjacket wherein 80% by mass or more of the total amount of component (B) is a compound having two or more ethylenically unsaturated groups.
  • the present invention also provides an optical fiber upjacket layer comprising a cured product of the liquid curable resin composition for an optical fiber upjacket.
  • the present invention provides an optical fiber up jacket wire having the optical fiber up jacket layer.
  • the optical fiber upjacket layer obtained from the resin composition of the present invention has functions such as sufficient strength and weather resistance, has good peelability, and has a high temperature of about 80 to 120 ° C. Even after exposure, the workability of optical fiber connection work is improved because the decrease in peelability is small.
  • FIG. 1 is a diagram showing a conceptual diagram of a tensile testing machine.
  • FIG. 2 is a conceptual diagram of the behavior of the coating removal stress when the upjacket layer is pulled out.
  • the urethane (meth) acrylate which is the component (A) of the present invention is produced, for example, by reacting a polyol, a diisocyanate and a hydroxyl group-containing (meth) acrylate. That is, it is produced by reacting the isocyanate group of the diisocyanate with the hydroxyl group of the polyol and the hydroxyl group of the hydroxyl group-containing (meth) acrylate.
  • component (A) is a hydroxyl group-containing (meth) attale toy salt per mole of diisocyanate. It can also be produced by reacting 2 moles of the compound.
  • urgent urethane (meth) acrylates include the reaction product of hydroxyethyl (meth) acrylate and 2,4-tolylene diisocyanate, and hydroxy ethyl (meth) acrylate and 2, 5 (Or 2, 6) —Bis (isocyanatomethyl) -bicyclo [2.2.1] heptane reactant, hydroxyethyl (meth) ataryl
  • this reaction for example, a method in which a polyol, diisocyanate, and a hydroxyl group-containing (meth) acrylate are charged together and reacted; a method in which a polyol and a diisocyanate are reacted, and then a hydroxyl group-containing (meth) acrylate is reacted; A method of reacting a diisocyanate and a hydroxyl group-containing (meth) acrylate and then reacting with a polyol in the following manner; reacting a diisocyanate and a hydroxyl group-containing (meth) acrylate, then reacting with a polyol, and finally a hydroxyl group-containing ( Examples thereof include a method of reacting (meth) acrylate.
  • polyols preferably used here include polyether polyols, polyether polyols, polycarbonate polyols, poly-strength prolataton polyols and other polyols.
  • the polymerization mode of each structural unit of these polyols is not particularly limited and may be any of random polymerization, block polymerization, and graft polymerization.
  • polyether polyols are obtained by ring-opening copolymerization of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, or two or more ion-polymerizable cyclic compounds.
  • aliphatic polyether polyols examples include ethylene oxide, propylene oxide, butene 1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3 —Methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, buroxetane, burte
  • examples thereof include cyclic ethers such as trahydrofuran, butylcyclohexene oxide, phenol glycidyl ether, butyl glycidy
  • cyclic imines such as ethyleneimine
  • cyclic ratatonic acids such as ⁇ -propiolatatatone and glycolic acid lactide
  • dimethylcyclopolysiloxanes can also be used.
  • Specific combinations of the above two or more ion-polymerizable cyclic compounds include, for example, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene.
  • terpolymers of oxide, propylene oxide and ethylene oxide, butene 1-oxide and ethylene oxide, tetrahydrofuran, butene-1-oxide, and ethylene oxide may be bonded at random or may have a block-like bond.
  • These aliphatic polyether polyols are, for example, PTMG650, PTMG1000, PTMG2000 (above, manufactured by Mitsubishi Igaku), PPG-400, PPG1000, PPG2000, PPG3000, EXCENOL720, 1020, 2020 (above, made by Asahi Glass Urethane ), PEG1000, Useful DC1100, DC1800 (above, made by Nippon Oil & Fats), PPTG2000, PPTG1000, PTG400, PTGL2000 (above, made by Hodogaya Chemical), Z—3001—4, Z—3001—5 , PBG2000 A, PBG2000B (Daiichi Kogyo Seiyaku Co., Ltd.) etc.
  • polyether polyol for example, a polyol with alkylene oxide of bisphenol A, a polyol with alkylene oxide of bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol.
  • a polyol with alkylene oxide hydrogenated bisphenol F polyol with alkylene oxide, polyol with hydroquinone alkylene oxide, polyol with naphthoquinone alkylene oxide, anthra hydroquinone with alkylene oxide
  • Caropolyol, 1,4-cyclohexanepolyol and its polyols with alkylene oxide tricyclodecane polyol, tricyclodecane dimethanol, pentacyclopentadecane Ol, cyclic polyethers such pentacyclopentadecanedimethanol poly Oars.
  • bisphenol A alkylene oxide-attached caropolyol and tricyclodecane dimethanol are preferred.
  • polystyrene resin examples include a polyol with a alkylene oxide, a polyol with an alkylene oxide of bisphenol F, and an alkylene oxide addition polyol of a 1,4-cyclohexane polyol.
  • polyester polyol examples include a polyester polyol obtained by reacting a dihydric alcohol and a dibasic acid.
  • dihydric alcohol examples include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6 hexane polyol, neopentyl glycol, 1,4-cyclohexane dimethanol, 3 methyl-1,5 pentane polyol, 1,9-nonane polyol, 2-methyl-1,8 octane polyol and the like.
  • dibasic acid examples include dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid.
  • dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid.
  • commercially available products such as Kurapol P-2010, PMIPA, PKA-A, PKA-A2, PNA-2000 (manufactured by Kuraray Co., Ltd.) are available.
  • polycarbonate polyol examples include polycarbonate of polytetrahydrofuran and polycarbonate of 1,6 hexane polyol.
  • DN-980, 981, 982, 983 above, Nippon Polyurethane
  • PC-8000 manufactured by PPG, USA
  • PC-THF-CD manufactured by BASF
  • poly-strength prolatatone polyol for example, ⁇ -strength prolatatone and, for example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene
  • poly-strength polyols obtained by reacting divalent polyols such as darikonole, 1,6 hexane polyol, neopentyl glycol, 1,4-cyclohexane dimethanol, and 1,4 butane polyol.
  • These polyols are sold on the market such as Plaxel 205, 205A, 212, 212AL, 220, 220AL (manufactured by Daisenolei Agricultural Industry). It can be done manually.
  • polystyrene resin examples include ethylene glycol, propylene glycol, 1,4 butane polyol, 1,5 pentane polyol, 1,6 hexane polyol, neopentyl glycol, 1,4-cyclohexane dimethanol.
  • Dicyclopentadiene dimethylol compound Dicyclopentadiene dimethylol compound, tricyclodecane dimethanol, / 3-methyl- ⁇ -valerolataton, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol, polydimethylsiloxane-terminated polyol compound, polydimethylsiloxane And carbitol-modified polyol.
  • diamines such as ethylene diamine, tetramethylenediamine, hexamethylene diamine, norephedylene diamine, 4,4'-diaminodiphenylmethane, diamines containing heteroatoms, polyether diamines, and the like. Are listed.
  • polyether polyols particularly aliphatic polyether polyols are preferred.
  • polypropylene glycol or polypropylene glycol which is preferably a copolymer of butene monooxide and ethylene oxide, is particularly preferred.
  • These polyols are commercially available, such as PPG-400, PPG1000, PPG2000, PPG3000, EXCEN OL720, 1020, and 2020 (above, manufactured by Asahi Glass Urethane).
  • Diols which are copolymers of butene 1-oxide and ethylene oxide, are commercially available such as EOZBO50 0, EO / BO1000, EO / BO2000, EO / BO3000, EOZBO4000 (above, Daiichi Kogyo Seiyaku). .
  • the number average molecular weight of poly-nore is preferably 400-1000, particularly preferably 500-800.
  • the number average molecular weight is determined by gel permeation chromatography (GPC method) using polystyrene as the molecular weight standard.
  • diisocyanate examples include 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 1,3 xylylene diisocyanate, 1,4 xylylene diisocyanate ⁇ 1,5 naphthalene diisocyanate , M-Phenolenediocyanate, ⁇ Huelen Diisocyanate, 3, 3'-Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-Diphenylmethane diisocyanate, 3,3'-Dimethylphenol-diisocyanate, 4, 4 ' -Biphenol-diisocyanate, 1,6 hexane diisocyanate, isophorone diisocyanate, methylene bis (4 cyclohexyl isocyanate), 2, 2, 4 trimethyl hexamethylene diisocyanate, bis (2 isocyanate) (Netetyl) fumarate, 6 isopropyl
  • diisocyanates may be used alone or in combination of two or more.
  • hydroxyl group-containing (meth) atalylate examples include, for example, 2-hydroxyethyl (meth) atalyl
  • R 1 represents a hydrogen atom or a methyl group
  • n is a number of 1 to 15
  • (Meth) acrylate and the like represented by Also alkyl glycidyl ether, R A compound obtained by an addition reaction between a glycidyl group-containing compound such as rylglycidyl ether and glycidyl (meth) acrylate and a (meth) acrylic acid can also be used.
  • a glycidyl group-containing compound such as rylglycidyl ether and glycidyl (meth) acrylate and a (meth) acrylic acid
  • hydroxyl group-containing (meth) atalylates in particular, 2-hydroxyethyl (meth) atalylate, 2
  • hydroxyl group-containing (meth) acrylate compounds can be used alone or in combination of two or more.
  • the use ratio of the polyol, diisocyanate and hydroxyl group-containing (meth) acrylate is such that the isocyanate group contained in the diisocyanate is 1.1 to 3 equivalents and the hydroxyl group-containing (meth) acrylate is contained in one equivalent of the hydroxyl group contained in the polyol. It is preferable that the hydroxyl group of the rate is 0.2 to 1.5 equivalents.
  • a part of the hydroxyl group-containing (meth) atalylate can be replaced with a compound having a functional group that can be added to the isocyanate group.
  • a compound having a functional group that can be added to the isocyanate group For example, ⁇ -mercaptotrimethoxysilane, ⁇ -aminotrimethoxysilane and the like can be mentioned. By using these compounds, adhesion to a substrate such as glass can be enhanced.
  • the urethane (meth) acrylate which is the component ( ⁇ )
  • the compound having an ethylenically unsaturated group a polymerizable monofunctional compound or a polymerizable polyfunctional compound can be used.
  • monofunctional compounds include bull group-containing ratatam such as ⁇ -bulurpyrrolidone, ⁇ -bull force prolatatam, isobolol (meth) atarylate, bolol (meth) atalylate, Tricyclode force-( Aliphatic structure-containing (meth) atalylate such as (meth) acrylate, dicyclopental (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, allyloyl morpholine, bur Examples include imidazole and bullpyridine.
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 is 2 to 6 carbon atoms, preferably an 2-4 ⁇ alkylene group
  • R 4 is 1 to 12 hydrogen atoms or carbon atoms
  • r represents a number of 0 to 12, preferably 1 to 8
  • R 5 represents a hydrogen atom or a methyl group
  • R ° represents an alkylene group having 2 to 8, preferably 2 to 5 carbon atoms
  • R 7 represents a hydrogen atom or a methyl group
  • p is preferably a number from 1 to 4.
  • R 8 , R 9 , R 1Q and R 11 are independent of each other, H or CH, and q is an integer of 1 to 5.
  • burata group-containing ratata such as N-vinylpyrrolidone and N-birucaprolatatam, isovolyl (meth) acrylate, and lauryl acrylate are preferred.
  • Examples of the polymerizable polyfunctional compound include trimethylolpropane tri (meth) acrylate, trimethylol propane trioxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, triethylene glycol.
  • R 12 and R 13 are each independently a hydrogen atom or a methyl group, and n is a number from 1 to 100]
  • compounds represented by the above formula (7) such as ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tricyclodecane dimethylol diatalylate, ethylene oxide Bisphenol A with di- (meth) acrylate, tris (2-hydroxyethyl) cyano cyanate tri (meth) acrylate, and tripropylene glycol di (meth) acrylate are preferred. Of these, tripropylene glycol di (meth) acrylate is particularly preferred.
  • These (B) compounds having an ethylenically unsaturated group are usually mixed in an amount of 1 to 70% by mass with respect to 100% by mass of the total amount of components (A), (B) and (C). Preferably it is 5-50 mass%, Most preferably, it is 10-40 mass%. If it is less than 1% by mass, the curability may be impaired, and if it exceeds 70% by mass, the coating shape changes due to low viscosity and the coating is not stable.
  • the compound has an ethylenically unsaturated group of (B) 80% by mass or more of the total amount of compounds having an ethylenically unsaturated group and a force of 2 or more.
  • the amount of the compound having 2 or more ethylenically unsaturated groups is 80% by mass or more, the thermal expansion coefficient (linear expansion coefficient) of the cured product of the composition decreases, and the upjacket layer has a temperature of about 80 to 120 ° C. Even when the heat history is given, good peelability can be obtained.
  • the compound having two or more ethylenically unsaturated groups is more preferably 90% by mass or more, particularly preferably 100% by mass.
  • the liquid curable resin composition of the present invention contains a polymerization initiator as the component (C).
  • a polymerization initiator a thermal polymerization initiator or a photoinitiator can be used.
  • thermosetting a thermal polymerization initiator such as a peroxide or an azo compound is usually used.
  • a thermal polymerization initiator such as a peroxide or an azo compound.
  • benzoyl peroxide, t-butyl-oxybenzoate, azobisisobutyrate-tolyl and the like can be mentioned.
  • the liquid curable resin composition of the present invention is photocurable, it is preferable to use a photopolymerization initiator and, if necessary, further use a photosensitizer.
  • the photopolymerization initiator include 1-hydroxycyclohexyl phenol ketone, 2,2-dimethoxy-2-phenol-phenphenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3- Methylacetophenone, 4-chlorobenzoic benzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1 (4 isopropyl phenol) -Hydroxy) 2-hydroxy-2-methylpropane 1-one, 2-hydroxy 2-methyl-1
  • the thermal polymerization initiator and the photopolymerization initiator may be used in combination.
  • the polymerization initiator is blended in an amount of 0.1 to 10% by mass, particularly 0.3 to 7% by mass, with respect to 100% by mass of the total amount of components (A), (B) and (C).
  • the polymerization initiator is blended in an amount of 0.1 to 10% by mass, particularly 0.3 to 7% by mass, with respect to 100% by mass of the total amount of components (A), (B) and (C).
  • the liquid curable resin composition of the present invention further contains a silicone compound having an average molecular weight of 1,500 to 35,000 as component (D).
  • the component (D) is important in obtaining the effect of improving the peelability from the adjacent layers of the optical fiber upjacket layer formed using the resin composition of the present invention.
  • the average molecular weight of component (D) is less than 1,500, sufficient peelability improvement effect cannot be obtained, and when the average molecular weight exceeds 35,000, peelability improvement effect becomes insufficient. More preferably, the average molecular weight is 1,500 to 20,000, more preferably 1,500 to 20,000, particularly 3,000 to 15,000!
  • component (D) preferably does not have a polymerizable group such as an ethylenically unsaturated group. Since component (D) does not have a polymerizable group such as an ethylenically unsaturated group, good peelability can be maintained even when a thermal history is applied.
  • silicone compound examples include polyether-modified silicone, alkyl-modified silicone, urethane acrylate-modified silicone, urethane-modified silicone, methylstyryl-modified silicone, epoxy polyether-modified silicone, and alkylaralkyl poly. Ether-modified silicones and the like. Of these, polyether-modified silicones are particularly preferred. That's right.
  • the polyether-modified silicone at least one group in Kei atom of R 14 - (R 1 5 ⁇ ) -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 be a mixture of two or more alkylene groups), R 16 represents an alkylene group having 2 to 12 carbon atoms, and s is 1 A polydimethylsiloxane compound having a number of ⁇ 20) bonded thereto is preferred. Of these, R 15 is preferably an ethylene group or a propylene group, particularly preferably an ethylene group.
  • those having no polymerizable group such as ethylenically unsaturated group include, for example, SH28PA; dimethylpolysiloxane polyoxyalkylene copolymer, Toray Dow Cowing Co., Ltd., Paintad 19, 54; Dimethylpolysiloxane polyoxyalkylene copolymer, Toray Dow Co., Ltd., FM0411; Silaplane, Chisso, SF8428; Dimethylpolysiloxane polyoxyalkylene copolymer (containing side chain OH), Toray Dow COUNGING, BYK UV3510 (Big Chemi.
  • silicone compounds having an ethylenically unsaturated group include Tego Rad 2300, 2200N, and Tego Chemie.
  • the blending amount of the component (D) is 0 with respect to 100% by mass of the total amount of the components (A), (B), and (C) from the viewpoint of the peelability of the upjacket layer and the strength and weather resistance. 1 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 20% by mass.
  • a flame retardant may be added to the liquid curable resin composition of the present invention.
  • the flame retardant is not particularly limited as long as it is a known flame retardant, and examples thereof include halogen-based (bromine, chlorine-based), phosphorus-based, nitrogen-based, and silicone-based flame retardants. .
  • brominated flame retardants include tetrabromobisphenol A (TBBPA), decabromodiphenol-oxide, oxosubsuccinyl mocyclododecane, tribromophenol, ethylene bistetrabromophthalimide, TBBPA polycarbonate oligomer, brominated polystyrene, TB BPA epoxy oligomer, TBBPA bisbromopropyl ether, ethylene bispenta bromodiphenol, pentabromobenzenoleate, hexabromobenzene, bromine And aromatic triazine.
  • TBBPA tetrabromobisphenol A
  • decabromodiphenol-oxide decabromodiphenol-oxide
  • oxosubsuccinyl mocyclododecane tribromophenol
  • ethylene bistetrabromophthalimide TBBPA polycarbonate oligomer
  • brominated polystyrene TB BPA epoxy
  • Examples of the phosphoric flame retardant include phosphoric acid ester, halogen-containing phosphoric acid ester, polyphosphoric acid ammonium, red phosphoric acid type, phosphaphenanthrene type and the like.
  • Specific examples of the phosphoric acid ester include triisopropyl phosphate, tris (2-capped isopropyl) phosphate, cresyl diphenyl phosphate, tricresyl phosphate and the like.
  • Examples of the chlorine-based flame retardant include chlorinated paraffin, perchlorocyclopentadecane, and chlorendic acid.
  • the blending amount of (E) flame retardant is preferably 1 to 50% by weight with respect to 100% by weight of the total amount of components (A), (B) and (C). It is preferable that the amount of -50% by mass, more preferably 5-20% by mass. If it is less than 1% by mass, the flame retardant effect is insufficient, and if it exceeds 50% by mass, the flame retardant may bleed out from the cured product or adversely affect the elastic properties of the upjacket layer. Nah ...
  • the liquid curable resin composition of the present invention contains a polyol compound having a molecular weight of 1500 or more as the component (F).
  • a polyol compound having a molecular weight of 1500 or more as the component (F).
  • the effect of improving the peelability from the adjacent layers of the optical fiber upjacket layer formed using the resin composition of the present invention can be further improved.
  • the molecular weight of component (F) is less than 1500, there is a problem in terms of durability in transferring to the ink layer, which is preferable.
  • the polyol compound has a molecular weight of 1500 to 10,000, and more preferably ⁇ 2000 to 8,000.
  • polyolefin compound of component (F) examples include polyether polyols, polyester polyols, polycarbonate polyols, poly-strength prolataton polyols, and other polyols.
  • the polymerization mode of each structural unit of these polyols is not particularly limited and may be any of random polymerization, block polymerization, and graft polymerization.
  • polyether polyol for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, or two or more kinds of ionic polymerizations.
  • aliphatic polyether polyols obtained by ring-opening copolymerization of a functional cyclic compound.
  • the ion polymerizable cyclic compound include ethylene oxide and propylene.
  • a polyether polyol obtained by ring-opening copolymerization of the above ion polymerizable cyclic compound with a cyclic imine such as ethyleneimine, a cyclic ratatonic acid such as j8-propiolatatone or glycolic acid lactide, or dimethyl cyclopolysiloxane can also be used.
  • combinations of the two or more ion polymerizable cyclic compounds include tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, Examples thereof include terpolymers of propylene oxide and ethylene oxide, butene 1-oxide and ethylene oxide, tetrahydrofuran, butene-1-oxide, and ethylene oxide.
  • the ring-opening copolymer of these ion-polymerizable cyclic compounds may be bonded at random or may be bonded in a block form.
  • These aliphatic polyether polyols are, for example, PTMG2000 (Mitsubishi Chemical), PPG2000, PPG3000, EXCENOL2020 (above, Asahi Glass Urethane), DC1800 (Enomoto Yushi), PPTG2000, PTGL2000 (above, Hodogaya Available from the market) such as PBG2000A, PB G2000B (Daiichi Kogyo Seiyaku).
  • polyether polyol for example, bisphenol A alkylene polyol-containing polyol, bisphenol F alkylene oxide-containing polyol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol.
  • cyclic polyether polyols such as all, tricyclodecane polyol, tricyclodecane dimethanol, pentacyclopentadecane polyol, and pentacyclopentadecane dimethanol.
  • examples of the cyclic polyether polyol include xylene oxide addition polyol, bisphenol F alkylene carbonate addition polyol, 1,4-cyclohexane polyol addition alkylene oxide polyol, and the like. These polyols may be linear molecules or have a branched structure. These may be used in combination.
  • polyol having a branched structure such as an alkyl group typified by a methyl group or an ethyl group, has a hydroxyl group at the end of each branched chain, and the molecular weight of the polyol is branched. It is preferable to contain a polyol having a value divided by the number of hydroxyl groups at the chain ends of 500 to 2000 (hereinafter also referred to as “polyol having a branched structure”).
  • polystyrene resin As a specific example of the polyol having a branched structure, a polyol obtained by ring-opening polymerization of at least one kind selected from ethylene oxide, propylene oxide, and butylene oxide, such as glycerin, or sorbitol, is particularly preferable.
  • polypropylene glycol and copolymers of butene 1-oxide and ethylene oxide are preferred!
  • the value obtained by dividing the molecular weight of the polyol by the number of hydroxyl groups at the end of the branched chain is preferably 500 to 2000, and more preferably 1000 to 1500.
  • the number average molecular weight of the polyol itself is 1500 to 12000, more preferably 2000 to 10,000, especially 2500 to 8000 intensifiers as polystyrene-reduced molecular weight determined by gel permeation chromatography.
  • the polyol having a branched structure is preferably one having 3 to 6 branched chain terminal hydroxyl groups in one molecule! /.
  • polystyrene resin examples include PPG2000, PPG3000, EXCENOL2020 (above, Asahi Glass Urethane Co., Ltd.); Diol, which is a copolymer of butene 1-oxide and ethylene oxide, is EOZBO2000, EO / BO3000, EOZBO4000. It can be obtained as a commercial product such as (Daiichi Kogyo Seiyaku Co., Ltd.).
  • polyols having a branched structure include, for example, “Sanix TP-400”, “Sanix GL-3000”, “Sanix GP-250” manufactured by Daiichi Kogyo Seiyaku, Asahi Glass Urethane, Sanyo Chemical Industries, Ltd. ”,“ Sanix GP-400 ”,“ Sanix GP-600 ”,“ Sanix Nicks GP-1000, Sanix GP-3000, Sanix GP-3700M, Sax GP-4000, Sanix GEP-2800, New Paul TL4500N.
  • the blending amount of the component (F) is 10 with respect to 100% by mass of the total amount of the components (A), (B) and (C) from the viewpoint of the peelability of the upjacket layer and the strength and weather resistance.
  • liquid curable resin composition of the present invention various additives, for example, an antioxidant, a colorant, an ultraviolet absorber, and a light stabilizer, are optionally added within a range not impairing the characteristics of the present invention.
  • the liquid curable resin composition of the present invention is a force that is cured by heat and Z or radiation.
  • radiation refers to infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, ⁇ rays, j8 Line, ⁇ -ray, etc.
  • the cured product of the liquid curable composition of the present invention preferably exhibits a yang ratio of 200 MPa to 500 MPa.
  • a cable layer made of thermoplastic resin can be provided in contact with the outside of the optical fiber upjacket layer.
  • a reaction vessel equipped with a stirrer is charged with tetraethylene nouryl ether ether acrylate 15.381 g, 2,6 di-tert-butyl p-taresol 0.015 g, toluene diisocyanate 7.80 g, dibutyltin dilaurate 0.023 g, These were cooled with ice until the liquid temperature became 20 to 15 ° C. with stirring. Hydroxyethyl talylate 6. OOg was added, and the mixture was stirred and reacted for 2 hours while controlling the liquid temperature to be 35 ° C or lower.
  • HEA represents a structure derived from hydroxyethyl acrylate
  • TDI represents a structure derived from toluene diisocyanate
  • DA400 represents polyethylene bis having a number average molecular weight of 400.
  • a structure derived from phenol A ether is shown
  • PTMG2000 shows a structure derived from polytetramethylene glycol having a number average molecular weight of 2000.
  • UA-3 contains 32.2 parts by mass, 16.1 parts by mass, and 16.1 parts by mass of urethane (meth) ate acrylate having a structure represented by the following formulas (11) to (13), respectively. Is a mixture.
  • HEA represents a structure derived from hydroxyethyl acrylate
  • HP A represents a structure derived from hydroxypropyl acrylate
  • TDI is derived from toluene diisocyanate
  • PPG1000 shows a structure derived from polypropylene glycol having a number average molecular weight of 1000.
  • Each component having the composition shown in Table 1 was charged into a reaction vessel equipped with a stirrer and stirred for 1 hour while controlling the liquid temperature at 50 ° C. to obtain a liquid curable resin composition.
  • liquid curable resin compositions obtained in the examples and comparative examples were cured by the following method to prepare test pieces, and the following evaluations were performed. The results are also shown in Table 1.
  • Linear expansion coefficient A liquid curable resin composition is applied onto a glass plate using an applicator bar with a thickness of 250 ⁇ m, and this is cured by irradiating it with ultraviolet rays of UZcm 2 energy in the air, and a film for measuring the linear expansion coefficient.
  • a strip-shaped sample was prepared from this film so as to have a width of 3 mm and a length of 20 mm, and the linear expansion coefficient was measured with a linear expansion coefficient measuring device (manufactured by SEIKO Instruments: SSCZ520 0).
  • a sheet of the same resin having a thickness of 1 mm was prepared from a flame retardant polyethylene resin pellet containing sodium hydroxide and magnesium using a hot press (press conditions: press pressure 60 kgfZcm 2 , 180 ° CX 3 minutes).
  • An up-jacket wire was sandwiched between flame-retardant polyethylene resin sheets and pressed with a hot press (press conditions: press pressure lkgfZcm 2 , 180 ° CX 1 min) to produce a pseudo cable, which was used as a measurement sample.
  • Fig. 1 As shown in Fig. 1, hold 3cm from the end of the above-mentioned pseudo cable with a hot stripper (Furukawa Electric Co., Ltd.) and pull it at a speed of 50mZmin using a tensile tester (Shimadzu Corporation).
  • the coating removal stress (maximum stress shown in Fig. 2) during drawing was measured. Measurements were made immediately after the production of the pseudo cable (referred to as “coating removal stress immediately after production”) and after standing for 7 days in an environment at 85 ° C and relative humidity of 85% (referred to as “coating removal stress after high temperature and high humidity test”). ) Went to each.
  • SH28PA dimethylpolysiloxane polyoxyalkylene copolymer, manufactured by Toray Industries, Inc.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)

Abstract

La présente invention concerne une composition de résine liquide durcissable pour gaines de fibres optiques qui a d'excellentes fonctions requises pour des matériaux de revêtement pour fibres optiques et possède une excellente amovibilité de la couche de revêtement adjacente. La composition de résine liquide durcissable pour gaines de fibres optiques comprend (A) de 30 à 90 % en masse de (méth)acrylate d’uréthane ayant une structure dérivée de polypropylène glycol ayant une masse moléculaire moyenne en nombre de 400 à 1 000 déterminée par chromatographie par perméation de gel, (B) de 1 à 70 % en masse d’un ou plusieurs composés ayant un ou plusieurs groupes éthyléniquement insaturés, (C) de 0,1 à 10 % en masse d’un initiateur de polymérisation, (D) de 1 à 50 % en masse d’un composé siliconé ayant une masse moléculaire moyenne de 1 500 à 35 000, et (F) de 10 à 50 % en masse d’un composé polyol ayant une masse moléculaire supérieure ou égale à 1 500, chaque quantité étant sur la base de la somme des ingrédients (A), (B) et (C), où au moins 80 % en masse de l'ingrédient (B) correspond à un composé ayant deux ou plusieurs groupes éthyléniquement insaturés.
PCT/JP2006/318150 2005-09-15 2006-09-13 Composition de résine liquide durcissable pour gaine de fibre optique WO2007032386A1 (fr)

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JP2005268863 2005-09-15
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JP2006-052261 2006-02-28

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CN113999516A (zh) * 2021-11-10 2022-02-01 广东电网有限责任公司 一种减振材料及其制备方法和应用

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JP2008250075A (ja) * 2007-03-30 2008-10-16 Jsr Corp 光ファイバテープ
CN115975495B (zh) * 2022-12-23 2024-04-26 澳达树熊涂料(惠州)有限公司 一种高透防下陷双组份透明底漆及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61111943A (ja) * 1984-10-31 1986-05-30 Nitto Electric Ind Co Ltd 光学ガラスフアイバ用被覆材料
JP2005301237A (ja) * 2004-03-15 2005-10-27 Jsr Corp 液状硬化性樹脂組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61111943A (ja) * 1984-10-31 1986-05-30 Nitto Electric Ind Co Ltd 光学ガラスフアイバ用被覆材料
JP2005301237A (ja) * 2004-03-15 2005-10-27 Jsr Corp 液状硬化性樹脂組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113999516A (zh) * 2021-11-10 2022-02-01 广东电网有限责任公司 一种减振材料及其制备方法和应用

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