WO2010018995A2 - 광경화형 코팅 조성물 - Google Patents
광경화형 코팅 조성물 Download PDFInfo
- Publication number
- WO2010018995A2 WO2010018995A2 PCT/KR2009/004503 KR2009004503W WO2010018995A2 WO 2010018995 A2 WO2010018995 A2 WO 2010018995A2 KR 2009004503 W KR2009004503 W KR 2009004503W WO 2010018995 A2 WO2010018995 A2 WO 2010018995A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating composition
- photocurable coating
- acrylate
- weight
- optical fiber
- Prior art date
Links
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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- 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
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/326—Polyureas; Polyurethanes
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02214—Optical fibres with cladding with or without a coating tailored to obtain the desired dispersion, e.g. dispersion shifted, dispersion flattened
- G02B6/02285—Characterised by the polarisation mode dispersion [PMD] properties, e.g. for minimising PMD
-
- 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
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02395—Glass optical fibre with a protective coating, e.g. two layer polymer coating deposited directly on a silica cladding surface during fibre manufacture
Definitions
- the present invention relates to a photocurable coating composition for an optical fiber, and more particularly, even when an optical fiber is manufactured by a non-spinning process in an optical fiber manufacturing process, an optical fiber having a low PMD (Polarization Mode Dispersion) value can be manufactured.
- the present invention relates to a burnable coating composition and an optical fiber to which the same is applied.
- the diameter of one strand of the optical fiber is 0.1 to 1mm and is drawn out one by one, so the quality is very sensitive to change depending on the minute retardation or the difference in tensile force generated during manufacturing.
- polymer coating materials such as primary and secondary materials, ink materials, and ribbon materials
- characteristics of the coating materials and curing technologies have been developed.
- polymer materials for optical fiber coatings have recently been required to increase the working speed, technology development has been focused only on improving the curing speed.Non-spinning of optical fiber coating materials is required for quality improvement and process improvement. Technical research on the function of coating materials to be applied to the process is not actively conducted.
- PMD Polarization Mode Dispersion
- low PMD values are an important factor in transmission systems such as long-range, multi-channel and data.
- the PMD generation of optical fibers can be divided into two types: the optical fiber itself and the external impact during the cabling process.
- Optical fiber itself can be divided into specific ratio of core part and cladding part of quartz fiber of optical fiber, bubble of core part, residual stress of cladding part, oval of coating, etc.
- an object of the present invention is to obtain an optical fiber having a low PMD value even in the non-spinning process in the optical fiber extraction process, by the photocurable coating composition and the photocurable coating composition without distortion of the optical fiber in the rib matrix It is to provide a coated optical fiber.
- the photocurable coating composition according to the present invention for achieving the above object comprises a photopolymerized urethane acrylate oligomer, a reactive monomer, a photoinitiator and an amine additive, and at the time of optical fiber manufacturing in a non-spinning process, PMD (Polarization Mode Dispersion) is characterized in that less than 0.1ps / ⁇ km.
- the photocurable coating composition of the present invention the photopolymerizable urethane acrylate oligomer is 30 to 90% by weight, the reactive monomer is 5 to 60% by weight, the photoinitiator 1 to 15% by weight, the amine additive is 0.01 to 0.5 It is characterized by having a proportion by weight.
- the photocurable coating composition of the present invention contain a silane monomer and a stabilizer or a mixture thereof in a proportion of 0.5 to 5% by weight.
- the optical fiber coated with the photocurable coating composition according to the present invention exhibits low shrinkage characteristics, thereby minimizing stress that may occur during optical fiber manufacturing, and in particular, even when the optical fiber is manufactured by a non-spinning process, A breakthrough effect with a PMD value can be obtained.
- the photocurable coating composition according to an embodiment of the present invention is synthesized from a composition comprising a polyol copolymer, a polyisocyanate, an acrylate alcohol, a urethane reaction catalyst, and a polymerization inhibitor, so that the polyester and the polyether polyol monomer are appropriately copolymerized. It is characterized by including the urethane type acrylate oligomer (A) whose number average molecular weight (Mw.) Is 15,000-25,000.
- the post-curing shrinkage (%) of the photocurable coating resin composition in which the oligomer, the reactive monomer (B), the photoinitiator (C), the amine additive (D), and the other additive (E) is appropriately combined is 0.5 to 1 It is characterized by.
- the photopolymerized urethane acrylate oligomer (A) used in the present invention is (i) polyol copolymer, (ii) polyisocyanate, (iii) acrylate alcohol, (iv) urethane reaction catalyst and ( v) synthesized from a composition comprising a polymerization inhibitor, preferably consisting of a polyether polyol and a polyester polyol in a 10:30 to 70:90 weight ratio and having a number average molecular weight (Mw.) in the range of 15,000 to 25,000. desirable.
- a polymerization inhibitor preferably consisting of a polyether polyol and a polyester polyol in a 10:30 to 70:90 weight ratio and having a number average molecular weight (Mw.) in the range of 15,000 to 25,000. desirable.
- the photopolymerizable urethane acrylate oligomer (A) is preferably used in an amount of 30 to 90% by weight of the photocurable coating resin composition. If it is less than 30% by weight, there is a problem of loss due to micro bending and steam generation due to heat of ultraviolet energy during the process due to an increase in the cure shrinkage of the resin composition. This can happen.
- composition for synthesizing the oligomer (A) are as follows.
- the polyol copolymer (i) used in the present invention has a molecular weight of 100 to 10,000 and preferably includes repeating units of -CH 2 CH 2 O- or -CH 2 CH (CH 2 CH 3 ) O-.
- Preferred examples of the polyol copolymer (i) include a polyester polyol, a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, and a ring-opening tetrahydrofuran Tetrahydrofuran propyleneoxide ring opening copolymer, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,5- pentanediol), 1,6-hexanediol, 1,6-hexandiol, neopentyl glycol, 1,4-cyclohexane dimethanol, bisphenol-A It is preferable to use 1 or more types from the group which consists of a type diol.
- polyether polyol or ring-opening tetrahydrofuran propylene oxide copolymer and 70 to 90% by weight of the polyester polyol may be used in combination.
- the polyol polymer is preferably used 30 to 75% by weight of the photopolymerizable urethane acrylate oligomer composition.
- Preferred examples of the polyisocyanate (ii) used in the present invention include 2,4-tolyenediisocyanate, 2,6-tolyenediisocyanate, 1,3-xylenediisocyanate (1,3-xylene diisocyanate), 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexanediisocyanate, isophorone di Isocyanate (isophoronediisocyanate (IPDI)) and mixtures thereof.
- the polyisocyanate (ii) is preferably used in an amount of 10 to 40% by weight of the photopolymerizable urethane acrylate oligomer (A).
- the acrylate alcohol (iii) used in the present invention includes one or more (meth) acrylates and hydroxy groups, and preferred examples thereof are 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenyloxypropyl (meth) Acrylate, 4-hydroxybutyl acrylate, neopentyl glycomono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 1-6 hexanediol mono (meth) acrylate, pentaerythritol penta (meth ) Acrylate, dipentaerythritol penta (meth) acrylate, and mixtures thereof.
- the acrylate alcohol (iii) is preferably used in an amount of 10 to 35% by weight of the photopolymerizable urethane acrylate oligomer (A).
- the urethane reaction catalyst (iv) used in the present invention is a catalyst added in a small amount during the urethane reaction, and examples thereof include copper naphthlenate, cobalt naphthenate, zinc naphate, and n-butyltinlaurate. ), Tristhylamine, 2-methyltriethylene diamide and mixtures thereof.
- the reaction catalyst (iv) is preferably used in an amount of 0.01 to 1% by weight of the photopolymerizable urethane acrylate oligomer (A).
- Preferred examples of the polymerization inhibitor (V) used in the present invention include hydroquinone (hydrpoquione), hydroquinone monomethyl ether, para-benzoquinone, phenothiazine and mixtures thereof, and the photopolymerized urethane acrylate It is preferable to use in an amount of 0.01 to 1% by weight of the oligomer (A).
- the photopolymerized urethane acrylate oligomer (A) can be synthesized from the respective components as follows. After the polyol copolymer (i), optionally the polyester compound, and the polymerization inhibitor (v) are put in the reactor, the vacuum is reduced for 30 minutes to 1 hour, and water is removed to prevent side reactions of water and isocyanate. After maintaining the water-removed mixture at a temperature of 40 to 65 ° C. for 30 minutes to 1 hour, polyisocyanate (ii) was added in a split form and stirred at 200 to 300 rpm to obtain 1 of the total weight of the urethane reaction catalyst (iv). Add about 3 At this time, the fever is severe, so be careful.
- the temperature is maintained at 50 to 75 ° C. until the -OH peak disappears on the FT-IR.
- the reaction time is about 2 to 3 hours.
- acrylate alcohol (ii) is added. At this time, too much heat is necessary to pay attention.
- the temperature was raised to 60 to 80 ° C., and the remaining amount of the urethane reaction catalyst (iv) was added to react until the -NCO peak disappeared on the FT-IR to obtain a photopolymerized urethane acrylate oligomer (A). .
- the reactive monomer (B) used in the present invention is used as a diluent for matching the working viscosity with the photopolymerizable urethane acrylate oligomer (A) having a polymer structure, a low molecular weight monomer is preferable.
- the reactive monomer comprising at least one acrylate group, methacrylate group or vinyl group is used in an amount of 5 to 60% by weight of the total weight of the coating resin composition.
- the reactive monomer may have one or more acrylate groups, methacrylate groups or vinyl groups in its molecular structure, and monomers having 1 to 3 or more various functional groups may be used.
- Preferred examples thereof include phenoxyethyl acrylate, phenoxyethylene glycol acrylate, phenoxy tetraethylene glycol acrylate, phenoxy hexaethylene glycol acrylate, isobornyl acrylate (IBOA), isobornyl methacrylate, N-vinyl Pyrrolidone (N-VP), N-vinylcaprolactam (N-VC), Acryloyl Morpholine (ACMO), bisphenol ethoxylate diacrylate, ethoxylate phenol monoacrylate, polyethylene glycol Polyethyleneglycol 400 diacrylate, tripropylene glycol diacrylate, trimethyl propane triacrylate (TMPTA), polyethylene glycol diacrylate, ethylene oxide addition triethyl propane triacrylate (ethyleneoxide-addition triethylolpropantri acrylate; EO -TMPTA), pentaerythritol tetraacrylate (PETA), 1,4-butanedi
- a monomer that exhibits an effect of increasing the adhesion may be further used.
- the photoinitiator (C) used in the present invention since the optical fiber coating is made to maintain a fast line speed of 1,500m / min or more, it is added to maintain the fast curing speed of the resin itself.
- the photoinitiator (C) receives ultraviolet energy to form free radicals and attack the double bonds in the resin to induce polymerization.
- Irgacure # 184 (hydroxycyclohexylphenylketone) manufactured by Ciba Geigy
- Igacure # 907 (2-methyl-1 [4- (methyl Thio) phenyl] -2-morpholino-propan-1-one (2-methyl-1 [4- (methylthio) phenyl] -2-morpholino-propan-1-one
- Igacure # 500 (hydroxy Ketones and benzophenones
- Igacure # 651 (benzildimethylketone)
- Darocure # 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1- one)
- Tarocure TPO (2,4,6-trimethylbenzoyl-diphenylphosophin oxide)
- Darocure CGI # 1800 bisacyl phosphine oxide
- Darocure CGI # 1700 bisacyl phosphine oxide and hydroxyket
- the amine additive used in the present invention is added to prevent polymerization of the photocurable coating resin by high temperature and light before curing, to prevent hydrogen gas generation after curing, and to prevent transmission loss of the optical fiber and to give fast curing rate characteristics at high speed withdrawal. do. Preferred examples thereof include diallylamine, diisoproylamine, diethylamine, diethylhexylamine, triethlyamine, methyldiethanolamine, and N-methyldiethanolamine. , Ethanol amine, diethanol amine is selected from the group consisting of.
- the amine additive (D) is used in an amount of 0.01 to 0.5% by weight of the optical fiber coating resin composition.
- the photocurable coating resin composition of the present invention contains a silane monomer, a stabilizer or a mixture thereof in order to prevent the adhesion between the coating layer and the glass to be reduced.
- the silane monomers, stabilizers or mixtures thereof (E) are used in amounts of 1 to 5% by weight of the total weight of the coating resin composition.
- silane monomer not only increases the adhesion between the coating layer and the glass but also fundamentally lowers the water absorption of the resin composition.
- silane monomers include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri (methoxyethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, and gamma-glycidoxy, from Chisso, Japan.
- Propylmethoxysilane, gamma-aminopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane and mixtures thereof can be used.
- Stabilizers play a role in improving the thermal and oxidative stability and storage stability of the coating resin composition
- representative oxidizing agents include Irganox 1010, Iganox 1035, Iganox 1076, and mixtures thereof of Ciba. Can be mentioned.
- the shrinkage ratio after curing exhibits a low shrinkage characteristic of 0.05 to 1%, thereby minimizing the impact from inside and outside the optical fiber, thereby minimizing the impact from the non-spinning process. It is possible to produce an optical fiber having a low PMD value.
- the urethane (meth) acrylate oligomer having an average urethane bond number of 4 according to the input ratio and a NCO concentration of 0.1-0.3% of the urethane prepolymer before 2-hydroxyethyl acrylate was synthesized.
- the coating resin composition according to the present invention was blended as shown in Table 1 below.
- Miramer PU220 is Aliphatic difunctional Urethane Acrylate Oligomer (Mw.4,800) from Miwon.
- M-164 is Ethoxylated (4) Nonylphenol Acrylate from Miwon Corporation.
- NPF-041 is a highly concentrated Propyleneoxide (4) Nonylphenol Acrylate.
- NVC Basf's N-Vinylcaprolactam.
- SR-506 is Sartomer's Isobornyl acrylate.
- SR-339 is Sartomer's 2-Phenoxyethyl acrylate.
- M-2100 is Miwon's Ethoxylated (10) Bisphenol A diacrylate.
- Darocure TPO is a 2,4,6-Trimethylbenzoyl diphenyl phospine oxide marketed by CIBA.
- Irganox1076 is Octadecyl-3- (3,5-di-tert.butyl-4-hydroxyphenyl) -propionate sold by CIBA.
- S-810 is a ⁇ -mecaptopropyl trimethoxysilane available from CHISSO.
- Diethylamine is commercially available from JUNSEI.
- the viscosity of the composition was measured in a range of 50 to 90% torque at 25 ° C., using spindle 31 using a Brookfield Viscometer (Brookfield DV III +) according to ASTM D-2196.
- the film of the cured composition was separated from the glass plate, cut into a width of 13 mm using a dedicated blade cutter (JDC cutter), and stored in a desiccator having a temperature of 23 degrees and a relative humidity of 50% or less for one day and then Instron 4443 UTM. After measuring 2.5% secant modulus for each light amount by pulling at a speed of 25 mm / min, the amount of light at the point of 95% (Ultimate of 95% Secant Modulus) of the maximum achievable secant modulus was defined as the curing rate.
- composition prepared in the above example on a glass plate of 20 ⁇ 20 cm size, push it with a bar coater, put it in a fixed frame into which nitrogen is injected (nitrogen flow rate 40lpm), and 600Watt 9mm of fusion yarn (model: DRS10 / 12-QN).
- a film having a thickness of 600 ⁇ m was prepared by irradiating and curing the light with a speed of 30 fpm and 1.0 J / cm 2 using D-bulb. The cured film was cut to about 15 mm in length and about 10 mm in width to prepare a measurement sample.
- the prepared samples were mounted in DMTA IV (Dynamic mechanical temperature analysis manufacturer: Rheometry) and the measured geometrical values were entered.
- the temperature conditions at the time of measurement were cooled to about -100 ° C and then raised to 2 ° C / min until the temperature reached about 60 ° C.
- the test frequency used was 1.0 radians / second.
- Tg glass transition temperature
- the resin composition of the above example or comparative example was applied to the quartz glass fibers as the primary coating agent using an optical fiber drawing device (manufactured by Nextrom Co., Ltd), and then the secondary coating agent (Efiron manufactured by SSCP corp.) LS 2171) was applied thereon and cured simultaneously.
- the glass fiber has a diameter of 125 ⁇ m, and a primary coating agent and a secondary coating agent were applied thereon to be 250 ⁇ m after curing. Curing was performed using a UV lamp (DRS10 / 12-part, 600watt manufactured by Fusion), withdrawal speed was 1500mpm.
- the process is a non-spinning process, and the cladding-noncircularity of the optical fiber is preferably 0.3 to 0.5.
- the optical fiber obtained by the above method was stored for 3 days at a temperature of 23 ° C. and a relative humidity of 50% or less. After making the optical fiber in the bundle (Free Tension Fiber), it was measured according to the Interferometric method with a PMD 4000 (manufactured by PE.fiberoptics Co., Ltd) equipment, the results are shown in Table 2. .
- the optical fiber PMD is generally a standard of 0.2 or less (ITU-T G-652, 657), more specifically 0.1 or less, as a criterion for indicating the reliability characteristics of the optical fiber. As shown in Comparative Examples 1 to 4 of Table 2, the optical fiber PMD value using the coating resin composition for the optical fiber with high shrinkage may be high as 0.1 or more, which may cause difficulty in long distance and large capacity transmission.
- the PMD of the optical fiber using the low shrinkage coating resin composition of the optical fiber of Examples 1 to 6 according to the present invention has a very low PMD value of 0.1 or less, and enables a long-distance and large capacity transmission system. The same post process can be overcome.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
Abstract
Description
올리고머 | 실시예1 | 실시예2 | 실시예3 | 실시예4 | 실시예5 | 실시예6 | 비교예1 | 비교예2 | 비교예3 | 비교예4 | |
합성실시예1(Mw. 25,000) | 50 | 48 | 48 | ||||||||
합성실시예2(Mw. 22,000) | 57 | 63 | |||||||||
합성실시예3(Mw. 18,000) | 41 | ||||||||||
합성비교예1(Mw. 5,500) | 65 | 56 | |||||||||
Miramer PU220(Mw.4,800) | 60 | 55 | |||||||||
모노머 | M-164 | 25 | 32 | 42 | 28 | 45 | 25 | 45 | 30 | 40 | |
NPF-041 | 27 | ||||||||||
NVC | 3 | 5 | 5 | 5 | |||||||
SR-506 | 12 | 6 | 10 | 6 | |||||||
SR-339 | 18 | 6 | 5 | ||||||||
광개시제 | Darocure TPO | 2 | 3 | 3 | 2 | 2 | 2 | 3 | 2 | 2 | 3 |
첨가제 | Irganox 1076 | 2 | 3 | 3 | 2 | 2 | 2 | 3 | 2 | 2 | 3 |
S-810 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | |
Diethylamine | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
실시예1 | 실시예2 | 실시예3 | 실시예4 | 실시예5 | 실시예6 | 비교예1 | 비교예2 | 비교예3 | 비교예4 | |
점도 (cps) | 5,451 | 5,770 | 7,250 | 3,216 | 5,661 | 5,092 | 7,558 | 3,009 | 3,124 | 2,919 |
2.5% 시컨트 모듈러스 (kgf/mm2) | 0.12 | 0.09 | 0.11 | 0.17 | 0.15 | 0.13 | 0.23 | 0.16 | 0.13 | 0.19 |
경화속도 (Joul/cm2) | 0.4 | 0.4 | 0.25 | 0.15 | 0.19 | 0.38 | 0.11 | 0.13 | 0.31 | 0.28 |
유리 접착력 (N) | 1.29 | 2.77 | 1.76 | 1.39 | 1.21 | 1.0 | 1.59 | 1.79 | 3.56 | 1.31 |
유리 전이 온도 (˚C) | -18 | -16 | -24 | -21 | -34 | -22 | -13 | -23 | -15 | -13 |
경화 후 수축률 (%) | 0.61 | 0.78 | 0.67 | 0.85 | 0.67 | 0.98 | 3.04 | 3.74 | 5.12 | 4.59 |
PMD (ps/√km) | 0.052 | 0.063 | 0.045 | 0.086 | 0.071 | 0.089 | 0.135 | 0.157 | 0.307 | 0.28 |
Claims (18)
- 광중합형 우레탄 아크릴레이트 올리고머, 반응성 모노머, 광개시제 및 아민 첨가제를 포함하며,넌-스피닝(Non-spinning) 공정으로 광섬유 제조시에, PMD(Polarization Mode Dispersion)값이 0.1ps/√km이하인 것을 특징으로 하는 광경화형 코팅 조성물.
- 제1항에 있어서,상기 광경화형 코팅 조성물의 경화 후 수축률이 0.5 ~ 1%인 것을 특징으로 하는 광경화형 코팅 조성물.
- 제1항에 있어서,2.5% 시컨트 모듈러스(secant modulus)가 0.05 ~ 0.3 kgf/mm2인 것을 특징으로 하는 광경화형 코팅 조성물.
- 제1항에 있어서,유리면과 코팅면과의 접착력이 1 ~ 5 N인 것을 특징으로 하는 광경화형 코팅 조성물.
- 제1항에 있어서,최대 달성 가능 시컨트 모듈러스의 95%를 달성하기 위한 광량이 0.5J/cm2이하인 것을 특징으로 하는 광경화형 코팅 조성물.
- 제1항에 있어서,상기 광중합형 우레탄 아크릴레이트 올리고머는 30 내지 90 중량%, 상기 반응성 모노머는 5 내지 60 중량%, 상기 광개시제는 1 내지 15 중량%, 상기 아민 첨가제는 0.01 내지 0.5 중량%의 비율을 가지는 것을 특징으로 하는 광경화형 코팅 조성물.
- 제6항 있어서,상기 광중합형 우레탄 아크릴레이트 올리고머는 15,000g/㏖ 내지 25,000g/㏖의 수평균 분자량(Mw.)을 가지는 것을 특징으로 하는 광경화형 코팅 조성물.
- 제6항 있어서,상기 광중합형 우레탄 아크릴레이트 올리고머는 폴리올 공중합체, 폴리이소시아네이트, 아크릴레이트 알코올, 우레탄 반응촉매 및 중합금지제를 포함하는 조성물로부터 합성된 것을 특징으로 하는 광경화형 코팅 조성물.
- 제8항에 있어서,상기 폴리올 공중합체는 분자량이 100 내지 10,000이며, -CH2CH2O- 또는 -CH2CH(CH2CH3)O-의 반복단위를 포함하는 것을 특징으로 하는 광경화형 코팅 조성물.
- 제8항에 있어서,상기 폴리올 공중합체는, 폴리에테르 폴리올 또는 링 개환 테트라하이드로퓨란 프로필렌 옥사이드 공중합체 10내지 30중량%와 폴리에스터 폴리올 70내지 90중량%의 혼합물인 것을 특징으로 하는 광경화형 코팅 조성물.
- 제8항에 있어서,상기 폴리이소시아네이트는, 2,4-톨릴렌다이이소시안네이트(2,4-tolylenediisocyanate), 2,6-톨릴렌다이이소시안네이트, 1,3-크실렌다이이소시아네이트(1,3-xylene diisocyanate), 1,4-크실렌다이이소시아네이트, 1,5-나프탈렌이소시아네이트(1,5-naphthalene diisocyanate), 1,6-헥산다이이소시아네이트(1,6-hexanediisocyanate), 이소포론디이소시아네이트(isophoronediiso- cyanate;IPDI) 및 이들의 혼합물로 이루어진 군으로부터 선택되는 하나 이상의 화합물인 것을 특징으로 하는 광경화형 코팅 조성물.
- 제8항에 있어서,상기 아크릴레이트 알코올은 하나 이상의 메타아크릴레이트 및 히드록시기를 포함하는 것을 특징으로 하는 광경화형 코팅 조성물.
- 제6항에 있어서,상기 반응성 모노머는 하나 이상의 아크릴레이트기, 메타아크릴레이트기 또는 비닐기를 포함하는 것을 특징으로 하는 광경화형 코팅 조성물.
- 제13항에 있어서,상기 반응성 모노머는, 페녹시에틸아크릴레이트, 페녹시에틸렌글리콜아크릴레이트, 페녹시테트라에틸렌글리콜아크릴레이트, 페녹시헥사에틸렌글리콜아크릴레이트, 이소보닐아크릴레이트, 이소보닐메타아크릴레이트, N-비닐피롤리돈, N-비닐카프로락탐,아크릴로일모르폴린, 비스페놀 에톡실레이트 디아크릴레이트, 에톡실레이트 페놀 모노아크릴레이트, 폴리에틸렌글리콜 400 디아크릴레이트, 트리프로필렌글리콜 디아크릴레이트, 트리메틸 프로판 트리아크릴레이트, 폴리에틸렌글리콜 디아크릴레이트, 에틸렌 옥사이드 부가형 트리에틸프로판 트리아크릴레이트, 펜타에리스리톨 테트라아크릴레이트, 1,4-부탄디올 디아크릴레이트, 1,6-헥산디올 디아크릴레이트, 에톡실레이티드 펜타에리스리톨 테트라아크릴레이트, 에톡실레이티드 노닐페놀 아크릴레이트, 2-페녹시에틸 아크릴레이트, 에톡실레이티드 비스페놀 A 디아크릴레이트, 알콕실레이티드 노닐페놀 아크릴레이트, 알콕실레이티드 3관능성 아크릴레이트 에스터, 메탈릭 디아크릴레이트, 3관능성 아크릴레이트 에스터, 3관능성 메타크릴레이트 에스터 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 광경화형 코팅 조성물.
- 제6항에 있어서,상기 아민 첨가제는 디알릴아민, 디이소프로필아민, 디에틸아민, 디에틸헥실아민, 트리에틸아민, N-메틸디에탄올아민, 에탄올아민, 디에탄올아민 및 이들의 혼합물로 이루어진 군으로부터 선택된 하나 이상인 것을 특징으로 하는 광경화형 코팅 조성물.
- 제6항에 있어서,실란계 모노머 및 안정제를 더 포함하는 것을 특징으로 하는 광경화형 코팅 조성물.
- 제16항에 있어서,상기 실란계 모노머 및 안정제는 0.5 내지 5 중량 %의 비율로 포함되는 것을 특징으로 하는 광경화형 코팅 조성물.
- 제1항 내지 제17항의 광경화형 코팅 조성물로 코팅되며, 넌-스피닝(Non-Spinning) 공정으로 제조된 광섬유.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09806857A EP2316896A2 (en) | 2008-08-12 | 2009-08-12 | Photocurable coating composition |
CN2009801410833A CN102177211A (zh) | 2008-08-12 | 2009-08-12 | 可光致固化的涂料组合物 |
US13/058,734 US20110135269A1 (en) | 2008-08-12 | 2009-08-12 | Photocurable coating composition |
JP2011522906A JP2011530642A (ja) | 2008-08-12 | 2009-08-12 | 光硬化型コーティング組成物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2008-0078822 | 2008-08-12 | ||
KR1020080078822A KR101021577B1 (ko) | 2008-08-12 | 2008-08-12 | 광경화형 코팅 조성물 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2010018995A2 true WO2010018995A2 (ko) | 2010-02-18 |
WO2010018995A3 WO2010018995A3 (ko) | 2010-07-08 |
Family
ID=41669485
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2009/004503 WO2010018995A2 (ko) | 2008-08-12 | 2009-08-12 | 광경화형 코팅 조성물 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20110135269A1 (ko) |
EP (1) | EP2316896A2 (ko) |
JP (1) | JP2011530642A (ko) |
KR (1) | KR101021577B1 (ko) |
CN (1) | CN102177211A (ko) |
WO (1) | WO2010018995A2 (ko) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101001656B1 (ko) * | 2008-08-26 | 2010-12-15 | 에스에스씨피 주식회사 | 광중합형 수지 조성물 및 이를 사용하여 제조되는 광섬유 |
KR101272857B1 (ko) | 2011-06-07 | 2013-06-11 | 주식회사 블루폴리텍 | 도로 피복용 도료 조성물 |
EP2855147A1 (en) | 2012-05-31 | 2015-04-08 | Corning Incorporated | Stiff interlayers for laminated glass structures |
JP6530754B2 (ja) | 2013-08-30 | 2019-06-12 | コーニング インコーポレイテッド | 軽量、高剛性ガラスラミネート構造 |
KR101807900B1 (ko) * | 2013-09-27 | 2017-12-12 | 주식회사 엘지화학 | 도너 필름용 광경화성 수지 조성물 및 도너 필름 |
WO2015046720A1 (ko) * | 2013-09-30 | 2015-04-02 | 주식회사 엘지화학 | 편광판 |
CN105244081B (zh) | 2013-10-16 | 2019-03-26 | 日立化成株式会社 | 劣化抑制方法、膜及其制造方法以及层叠体 |
JP6672584B2 (ja) * | 2014-11-13 | 2020-03-25 | 住友電気工業株式会社 | 光ファイバ心線 |
US10350861B2 (en) | 2015-07-31 | 2019-07-16 | Corning Incorporated | Laminate structures with enhanced damping properties |
US20210055171A1 (en) * | 2018-01-29 | 2021-02-25 | University Of Louisville Research Foundation, Inc. | Stretchable optical fibers for strain-sensitive textiles |
FR3108908B1 (fr) * | 2020-04-01 | 2022-03-25 | Arkema France | Matériaux élastiques préparés à partir de compositions liquides durcissables |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3068284B2 (ja) * | 1991-10-04 | 2000-07-24 | 帝人株式会社 | 帯電防止性合成樹脂成形品 |
JP3334152B2 (ja) * | 1992-03-30 | 2002-10-15 | 大日本インキ化学工業株式会社 | 光ファイバー被覆用樹脂組成物 |
JPH10231340A (ja) * | 1996-12-20 | 1998-09-02 | Takeda Chem Ind Ltd | 光硬化性樹脂組成物およびその製造方法 |
US6075065A (en) * | 1996-12-20 | 2000-06-13 | Takeda Chemical Industries, Ltd. | Photocurable resin composition and a method for producing the same |
JPH10204250A (ja) * | 1997-01-23 | 1998-08-04 | Jsr Corp | 液状硬化性樹脂組成物 |
JP2002338641A (ja) | 2001-05-18 | 2002-11-27 | Shin Etsu Chem Co Ltd | 液状放射線硬化型樹脂組成物、光ファイバ用被覆組成物、及び光ファイバ |
KR100571475B1 (ko) * | 2002-05-13 | 2006-04-17 | 주식회사 루밴틱스 | 광섬유 리본 코팅용 난연성 수지 조성물 |
KR100596492B1 (ko) * | 2003-11-28 | 2006-07-04 | 주식회사 루밴틱스 | 광섬유 인라인 코팅용 광경화형 고분자 수지 조성물 |
JP2005292510A (ja) * | 2004-03-31 | 2005-10-20 | Dainippon Printing Co Ltd | 帯電防止層を有する反射防止フィルム |
JP2006251424A (ja) * | 2005-03-11 | 2006-09-21 | Jsr Corp | 液状硬化性樹脂組成物 |
-
2008
- 2008-08-12 KR KR1020080078822A patent/KR101021577B1/ko active IP Right Grant
-
2009
- 2009-08-12 JP JP2011522906A patent/JP2011530642A/ja active Pending
- 2009-08-12 WO PCT/KR2009/004503 patent/WO2010018995A2/ko active Application Filing
- 2009-08-12 US US13/058,734 patent/US20110135269A1/en not_active Abandoned
- 2009-08-12 CN CN2009801410833A patent/CN102177211A/zh active Pending
- 2009-08-12 EP EP09806857A patent/EP2316896A2/en not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
"Radiometer: UV Power PUCK, UVA", EIT CO., LTD., pages: 320 - 390 |
Also Published As
Publication number | Publication date |
---|---|
JP2011530642A (ja) | 2011-12-22 |
KR101021577B1 (ko) | 2011-03-16 |
US20110135269A1 (en) | 2011-06-09 |
KR20100020154A (ko) | 2010-02-22 |
WO2010018995A3 (ko) | 2010-07-08 |
CN102177211A (zh) | 2011-09-07 |
EP2316896A2 (en) | 2011-05-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2010018995A2 (ko) | 광경화형 코팅 조성물 | |
US7906566B2 (en) | Curable liquid resin composition | |
US6961508B2 (en) | Coated optical fibers | |
WO2010024563A2 (ko) | 광중합형 수지 조성물 및 이를 사용하여 제조되는 광섬유 | |
KR100952908B1 (ko) | 경화 폴리머 코팅 광섬유 | |
EP1189848B1 (en) | Liquid curable resin composition and cured products | |
US4908297A (en) | Coating compositions | |
KR101018357B1 (ko) | 우수한 고온 내수성을 갖는 광경화형 코팅 조성물 | |
JP2008527420A (ja) | 被覆光ファイバおよび光ファイバの被覆に好適な硬化性組成物 | |
EP0860485A1 (en) | Liquid curable resin composition | |
US7105583B2 (en) | Radiation-curable compositions for optical fiber coating materials | |
RU2320590C2 (ru) | Оптическое волокно с отвержденным полимерным покрытием | |
JP3211893B2 (ja) | 光ファイバ被覆用紫外線硬化型樹脂組成物 | |
US20030119998A1 (en) | Free radical-curable composition for optical fiber coating materials | |
JPH04296377A (ja) | 光ファイバテープ用紫外線硬化型バインダー樹脂組成物 | |
KR20120092944A (ko) | 광섬유용 광경화형 코팅 조성물 및 광섬유 | |
KR100626509B1 (ko) | 광섬유 코팅재용 방사선-경화가능한 조성물 | |
US20240010553A1 (en) | Composition for forming coating layer of optical fiber and cured layer thereof, optical fiber having cured layer, and use thereof | |
JPH04132724A (ja) | 光ファイバ被覆用紫外線硬化型樹脂組成物 | |
JP3134268B2 (ja) | 光ファイバ被覆用紫外線硬化型樹脂組成物 | |
KR20100106287A (ko) | 우수한 고온 내수성을 갖는 광섬유 | |
JPH06313022A (ja) | 紫外線硬化型樹脂組成物 | |
KR20000059764A (ko) | 광섬유 리본코팅용 자외선 경화형 수지 조성물 | |
JPH10287445A (ja) | ポリフェニルアルキルシロキサン添加剤を含有する放射線硬化性光学ガラス繊維被覆組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980141083.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09806857 Country of ref document: EP Kind code of ref document: A2 |
|
ENP | Entry into the national phase |
Ref document number: 2011522906 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13058734 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 707/KOLNP/2011 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009806857 Country of ref document: EP |