CN112662303A - Highly water-resistant resin composition for optical fiber coating - Google Patents
Highly water-resistant resin composition for optical fiber coating Download PDFInfo
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- CN112662303A CN112662303A CN202011104949.8A CN202011104949A CN112662303A CN 112662303 A CN112662303 A CN 112662303A CN 202011104949 A CN202011104949 A CN 202011104949A CN 112662303 A CN112662303 A CN 112662303A
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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
- 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
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- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- 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
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- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
- C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
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Abstract
The present invention relates to a highly water-resistant resin composition which can be effectively used for coating an optical fiber, and in the present invention, the resin composition is prepared by mixing (H) and water2O) fluorinated polyol having minimized Ether bond structure (Ether Linkage, -C-O-C-) of oxygen bond with high affinity as a base material, synthesizing a photocurable urethane oligomer, and preparing a resin composition using the photocurable urethane oligomer synthesized in this manner, thereby providing high water resistance of the tree for optical fiber coatingA grease composition having remarkably improved water resistance against moisture penetration while satisfying low refractive properties basically required for optical fiber cladding, is effectively applied to high-power optical fiber lasers.
Description
Technical Field
The present invention relates to a highly water-resistant resin composition which can be effectively used for coating an optical fiber, and in the present invention, the resin composition is prepared by mixing (H) and water2O) fluorinated polyol in which Ether bond structure (Ether Linkage, -C-O-C-) having oxygen bond of high affinity is minimized as a base material, synthesizing a photo-curable urethane oligomer, and preparing a resin composition using the photo-curable urethane oligomer synthesized in this manner, thereby providing a resin composition for optical fiber coating with high water resistance, which has significantly improved water resistance against moisture penetration while satisfying low refractive property basically required for optical fiber coating and is effectively applied to a high-power optical fiber laser.
Background
In recent years, among resin compositions for optical fiber coating, a photo-curable resin composition using ultraviolet rays is widely used, and when such a photo-curable resin is used, the reaction time is relatively short, the energy efficiency is high, the curing can be performed at a lower temperature, and the whole process equipment and equipment can be simplified, compared to the existing thermosetting resin, thereby improving the production efficiency.
Examples of such a photocurable resin composition for optical fiber coating include resin compositions shown in korean patent laid-open publication No. 500191 (ultraviolet-curable optical fiber-coating resin composition) and korean patent laid-open publication No. 1003002 (resin composition for optical fiber coating). Although such prior photocurable resin compositions exhibit low refractive properties suitable for optical fiber coating and relatively good impact resistance, the fluorinated polyol as a base material of these resin compositions comprises a plurality of Ether bond structures (Ether Linkage, -COC-) due to which the Ether bond structures are involved with water (H)2O) oxygen bond having high affinity, and thus it is easily impregnated with moisture in the case of being exposed to a high-temperature and high-humidity environment for a long time for optical fiber coating, the impregnated moisture is accumulated at the interface between the core of the optical fiber made of glass fiber and the cladding of the optical fiber made of resin composition and functions to separate the core and the cladding, thereby hindering the light of the optical fiberThe optical performance becomes an important factor that degrades the long-term reliability of the optical fiber.
More specifically, the optical fiber coating is a factor that plays a role of guiding light transmitted through the optical fiber core, and in this case, a factor that determines the range of incident angles of light that can be effectively guided is the number of openings of the coating, which is determined by the refractive index of the constituent resin composition. Therefore, it is important to keep the refractive index characteristic of the cladding constant to stably maintain the output of the optical fiber. However, the change of the refractive index of the resin composition having low refractive index characteristic applied to the coating of the optical fiber according to the temperature is relatively large, and particularly, in the case of the recently actively developed KW-class or higher optical fiber laser, the temperature of the optical fiber itself transmitting the high-power laser light is rapidly increased, and in order to prevent the temperature increase of the optical fiber itself, it has recently been devised to wind the laser optical fiber around a cylinder or a cooling pad equipped with a temperature reducing device for use. That is, the optical fiber for a laser coated with a clad layer made of a resin composition having a low refractive index characteristic is designed to be tightly wound around a cylinder or a cooling pad equipped with a temperature reducing means, so that heat generated by high-power laser light transmitted through the optical fiber is radiated from the surface of the cylinder or the cooling pad equipped with a temperature reducing means, and the temperature of the optical fiber itself can be kept constant.
However, in this process, since the temperature lowering device is always kept in a low temperature state, moisture contained in the air is often condensed due to a temperature difference from the ambient air. In this case, as described above, the organic solvent (H) is composed of a plurality of organic solvents (H)2O) an ether bond structure (-C-O-C-) having an oxygen bond with high affinity, condensed moisture is relatively easily absorbed into the cladding and accumulated on the interface between the core and the cladding of the optical fiber, and thus the cladding is separated (delaminations), resulting in loss of optical and physical functions of the cladding.
In the conventional case, even in the case of using a coating made of a resin composition containing a plurality of ether bonds (-C-O-C-), most of them are mainly applied to a low-capacity, low-power fiber laser, and therefore, in this case, since the output capacity is not so high, the temperature of the optical fiber itself does not rise so high, and therefore, a cooling device does not need very high performance, and the amount of moisture condensed due to a temperature difference is small, and the deterioration of the performance of the optical fiber due to the permeation of moisture does not become a great problem.
However, recently, a coating made of such a low refractive index resin composition is beginning to be applied to a high power fiber laser, and as described above, the amount of moisture condensed around the optical fiber increases due to the temperature difference between the temperature reducing device and the ambient air, and therefore, deterioration of the optical fiber performance due to moisture permeation by the resin composition has become a major factor of system operation failure, and a countermeasure therefor is urgently required.
[ patent document ]
(patent document 0001)1 Korean patent grant No. 500191 (name: resin composition for ultraviolet-curing optical fiber coating, grant No. 2005.06.30)
(patent document 0002)2 Korean patent grant publication No. 1003002 (name: resin composition for optical fiber coating, grant date: 12/15/2010)
Disclosure of Invention
The present invention is intended to solve the above problems, and an object of the present invention is to provide a highly water-resistant resin composition to be effectively applied to optical fiber coating, which will contain water (H)2O) fluorinated polyol having minimized Ether bond structure (Ether Linkage, -C-O-C-) of oxygen bond with high affinity as a base material, synthesizing a photo-curable urethane oligomer, and preparing a resin composition using the photo-curable urethane oligomer synthesized in this manner, thereby providing a highly water-resistant resin composition for optical fiber coating having significantly improved water resistance against moisture penetration while satisfying low refractive properties basically required for optical fiber coating and effectively applied to high-power fiber lasers
In accordance with the above object, the present invention provides a resin composition for coating an optical fiber with high water resistance, which is synthesized with a polyisocyanate and an acrylate monomer by a urethane reaction using a fluorinated polyol having the structure of the following [ chemical formula 1], to synthesize a photo-curable urethane oligomer with high water resistance, and to the photo-curable urethane oligomer thus synthesized, a photo-curable monomer and a photoinitiator for adjusting viscosity are added.
[ chemical formula 1]
Here, M, N and P are the number of repetitions of each repeating unit, M and N are 1 to 100, and P has a range of 1 to 10.
[ Effect of the invention ]
The high water-resistant resin composition for optical fiber coating according to the present invention effectively reduces the content of hydrophilic ether bond (-C-O-C-) contained in the existing resin composition for optical fiber coating, has remarkably improved water resistance against moisture penetration while satisfying the low refractive performance basically required for optical fiber coating, shows excellent performance in an environmental test of 5000 hours performed at a humidity of 85% and an operating temperature of 85 ℃ which is a standard for long-term reliability of optical fibers or optical devices and a high-temperature high-pressure steam 72 hour test of 125 ℃ and 2 atmospheres, and shows excellent performance effectively applicable to high-power fiber lasers.
Drawings
Fig. 1 is a graph showing the results of a high-temperature, high-humidity, high-Pressure Cooker (Pressure Cooker) test performed on an optical fiber coated with a high-water-resistant resin composition according to the present invention and a photocurable resin composition according to the related art, respectively, as cladding materials.
Detailed Description
Hereinafter, specific constituent components of the above-described high water resistance resin composition for coating an optical fiber according to the present invention and a process for preparing the same will be described in more detail by preferred examples.
To prepare the highly water-resistant resin composition for coating an optical fiber of the present invention, first, water (H) is added2O) fluorinated polyol with minimized ether linkage (-COC-) having oxygen linkage of high affinity as substrate by urethane reactionThe polyisocyanate and the acrylate monomer are synthesized to synthesize the photo-curable urethane oligomer having high water resistance, and at this time, a (meth) acrylate monomer having a hydroxyl group (OH-) or a (meth) acrylate monomer having an isocyanate group (NCO-) may be used as the synthesized acrylate monomer, respectively, and a specific synthesis method thereof is as follows.
(1) Synthesis of photocurable urethane oligomer: urethane (urethane) oligomer A
In one embodiment of the present invention, a urethane oligomer a having the structure of the following [ chemical formula 2] is synthesized by adding (i) a fluorine-based polyol copolymer, (ii) a polyisocyanate (polyisocynate), (iii) a (meth) acrylate monomer having a hydroxyl group (OH-), (iv) a urethane polymerization catalyst, and (v) a polymerization inhibitor having the structure of the following [ chemical formula 1 ].
[ chemical formula 1]
Here, M, N and P are the number of repetitions of each repeating unit, M and N are 1 to 100, and P has a range of 1 to 10.
[ chemical formula 2]
Herein, R is1Is an aromatic or aliphatic hydrocarbon radical having 2 to 20 carbon atoms, R2Each independently an aromatic or aliphatic hydrocarbon group containing 1 to 6 (meth) acrylate groups having 2 to 20 hydrocarbons, and L is the number of repetitions of the repeating unit, having a range of 1 to 10.
In this case, (i) a fluorine-based polyol copolymer used for synthesizing the urethane oligomer a: (ii) polyisocyanate: iii) a molar ratio of (meth) acrylate monomers having a hydroxyl group (OH-) to 1: 2: 2, when L ═ 2, 2: 3: 2, and 3 when L ═ 3: 4: 2 and synthesizing.
Specific components constituting the urethane oligomer a according to one embodiment of the present invention are as follows.
(i) Fluorine-containing polyol copolymer
As described above [ chemical formula 1]The fluorine-based polyol copolymer comprises- [ CF (CF)3)CF2-O]-or- [ CF2]As the repeating unit, for example, when M is 4, N is 4, and P is 5, the molecular weight of the fluorine-based polyol Mw is 1,820g/mole, and the content of oxygen (-O-) of an ether bond structure contained in the fluorine-based polyol copolymer is 10.5% by weight.
Currently commercially available is "perfluoropolyether diol (molecular weight Mw 1,208 g/mole)" from Synquest Laboratory.
(ii) Polyisocyanate (polyisocynate)
Examples of materials that may be used as the polyisocyanate include 2, 4-tolylene diisocyanate (2, 4-tolylene diisocyanate), 2, 6-tolylene diisocyanate (2, 6-tolylene diisocyanate), 1, 3-xylylene diisocyanate (1, 3-xylylene diisocyanate), 1, 4-xylylene diisocyanate (1, 4-xylylene diisocyanate), 1,5-naphthalene diisocyanate (1,5-naphthalene diisocyanate), 1, 6-hexamethylene diisocyanate (1, 6-hexamethylene diisocyanate), isophorone diisocyanate (isophorone diisocyanate), mixtures thereof, and the like.
(iii) (meth) acrylate monomer having hydroxyl group (OH-)
Examples of the (meth) acrylate monomer having a hydroxyl group (OH-) include 2-hydroxyethyl (meth) acrylate (2-hydroxyhexyl (meth) acrylate), 2-hydroxypropyl (meth) acrylate (2-hydroxypropyl (meth) acrylate), 2-hydroxybutyl (meth) acrylate (2-hydroxyhydroxypropyl acrylate), 2-hydroxypropyl acrylate (2-hydroxypropylacrylate), 2-Hydroxy 3-phenoxypropyl (meth) acrylate (2-Hydroxy-3-phenoxypropyl (meth) acrylate), 2-Hydroxy 3-acryloyloxypropylmethacrylate (2-Hydroxy-3-phenoxypropyl methacrylate), 2-hydroxybutyl acrylate (4-hydroxybutyl acrylate), neopentyl glycol (mono (methacrylate) (neopentyl glycol) methacrylate (2-hydroxyglycidyl methacrylate), and the like, 4-hydroxycyclohexyl (meth) acrylate (4-hydroxycyclohexyl (meth) acrylate), 1,6-hexanediol mono (meth) acrylate (1, 6-hexanediolo (meth) acrylate), pentaerythritol penta (meth) acrylate), dipentaerythritol penta (meth) acrylate, and mixtures thereof.
(iv) Carbamate polymerization catalyst
The urethane polymerization catalyst used in the present invention is a catalyst added in a small amount during the urethane reaction, and preferred examples thereof may be selected from copper naphthenate (copper naphthenate), cobalt naphthenate (cobalt naphthenate), zinc naphthenate (zinc naphthenate), n-dibutyltin dilaurate (n-dibutyltinaurate), triethylamine (trishylamine), 2-methyltriethylenediamine (2-methyltriethylenediamine), and mixtures thereof.
(v) Polymerization inhibitor
As the polymerization inhibitor, a generally commercially available one can be used, and for example, it may be selected from butylhydroxytoluene, hydroquinone (hydroquinone), hydroquinone monomethyl ether (hydroquinone), p-benzoquinone (para-benzoquinone), phenothiazine (phenothiazine), and a mixture thereof.
The above-mentioned constituent components of the urethane oligomer a according to the present example can be synthesized by the following method.
1) In the glass reactor, a condenser, a temperature measuring device, a nitrogen Purge (Purge) tube, and an agitator were installed, and (i) a fluorine-based polyol copolymer was added, the temperature was maintained at 45 ℃ to 65 ℃ under a vacuum of 760mmHg or less, and the pressure was reduced for a sufficient time (for example, 20 minutes to 1 hour) to remove moisture. After that, the water remaining in the reactor was completely removed by nitrogen Bubbling (Bubbling) for 30 minutes.
2) Adding (ii) a polyisocyanate to the (i) fluorine-based polyol copolymer from which moisture has been removed. (iii) stirring at 200rpm to 300rpm while maintaining the temperature at 45 ℃ to 65 ℃ using a Heating Mantle for temperature control (Heating Mantle), and adding 50 to 80% by weight of (iv) urethane polymerization catalyst (100 to 1,000ppm of the total reactants) based on the total weight of the catalyst used. The reactor was cooled with cooling water so that the temperature of the reactants did not rise above 95 ℃ due to the generation of heat of reaction. After the generation of heat was completed, the reaction was carried out for 2 to 3 hours while maintaining at 50 to 85 ℃.
3) After the reaction is completed, (iii) a (meth) acrylate monomer having a hydroxyl group (OH-) and (v) a polymerization inhibitor are added, and then stirring is performed at 200rpm to 300rpm, while cooling the reactor with cooling water so that the temperature of the reactants does not rise above 85 ℃ due to the generation of reaction heat. After the generation of heat was completed, while maintaining at 60 to 85 ℃, the remaining catalyst was added to carry out the reaction until the-NCO peak on IR disappeared, thereby completing the synthesis.
The urethane oligomer A synthesized according to this example had a viscosity at 25 ℃ of 1,000 to 1,000,000cPs, preferably 4,000 to 50,000cPs (Brookfield viscometer, Brookfield DV III +), and a refractive index of 1.4 or less, preferably 1.32 to 1.37.
(2) Synthesis of photocurable urethane oligomer: urethane oligomer B
In another embodiment of the present invention, a urethane oligomer B having a structure of the following [ chemical formula 3] is synthesized by adding (i) a fluorine-based polyol copolymer having a structure of the following [ chemical formula 1], (ii) a polyisocyanate (polyisocynate), (iii) a (meth) acrylate monomer having an isocyanate group (NCO-), (iv) a urethane polymerization catalyst, and (v) a polymerization inhibitor.
[ chemical formula 3]
Herein, R is1Is an aromatic or aliphatic hydrocarbon radical having 2 to 20 carbon atoms, R2Each independently an aromatic or aliphatic hydrocarbon containing 1 to 6 (meth) acrylate groups having 2 to 20 hydrocarbonsAnd K is the number of repetitions of the repeating unit, and has a range of 1 to 10.
In this case, (i) a fluorine-based polyol copolymer used for synthesizing the urethane oligomer B: (ii) polyisocyanate: iii) a molar ratio of (meth) acrylate monomers having an isocyanate group (NCO-) to 1: 0: 2,2 when K ═ 1: 1: 2, and 3 when K ═ 2: 2: 2 and synthesizing.
Specific components constituting the urethane oligomer B according to another embodiment of the present invention are as follows.
(i) Fluorine-containing polyol copolymer
As described above [ chemical formula 1]The fluorine-based polyol copolymer comprises- [ CF (CF)3)CF2-O]-or- [ CF2]As the repeating unit, for example, when M is 4, N is 4, and P is 5, the molecular weight of the fluorine-based polyol Mw is 1,820g/mole, and the content of oxygen (-O-) of an ether bond structure contained in the fluorine-based polyol copolymer is 10.5% by weight.
Currently commercially available is "perfluoropolyether diol (molecular weight Mw 1,208 g/mole)" from Synquest Laboratory.
(ii) Polyisocyanate (polyisocynate)
Examples of materials that may be used as the polyisocyanate include 2, 4-tolylene diisocyanate (2, 4-tolylene diisocyanate), 2, 6-tolylene diisocyanate (2, 6-tolylene diisocyanate), 1, 3-xylylene diisocyanate (1, 3-xylylene diisocyanate), 1, 4-xylylene diisocyanate (1, 4-xylylene diisocyanate), 1,5-naphthalene diisocyanate (1,5-naphthalene diisocyanate), 1, 6-hexamethylene diisocyanate (1, 6-hexamethylene diisocyanate), isophorone diisocyanate (isophorone diisocyanate), mixtures thereof, and the like.
(iii) (meth) acrylate monomer having isocyanate group (NCO-)
Examples of the (meth) acrylate monomer having an isocyanate group (NCO-) may be selected from 2-isocyanatoethyl methacrylate (2-isocyanatoethylmethacrylate), 2- (2-isocyanatoethoxy) ethyl methacrylate (2- (2-isocyanatoethoxy) ethylmethacrylate), 2-isocyanatoethyl acrylate (2-isocyanatoethylacrylate), 1-bis (acryloyloxymethyl) ethyl isocyanate (1,1-bis (acryloyloxymethyl) ethylisocyanate), and mixtures thereof, commercially available as karrenz MOI, karrenz MOI-EG, karrenz AOI, karrenz BEI, and the like, from Showa Denko corporation.
(iv) Carbamate polymerization catalyst
The urethane polymerization catalyst used in the present invention is a catalyst added in a small amount during the urethane reaction, and preferred examples thereof may be selected from copper naphthenate (copper naphthenate), cobalt naphthenate (cobalt naphthenate), zinc naphthenate (zinc naphthenate), n-dibutyltin dilaurate (n-dibutyltinaurate), triethylamine (trishylamine), 2-methyltriethylenediamine (2-methyltriethylenediamine), and mixtures thereof.
(v) Polymerization inhibitor
As the polymerization inhibitor, a generally commercially available one can be used, and for example, it may be selected from butylhydroxytoluene, hydroquinone (hydroquinone), hydroquinone monomethyl ether (hydroquinone), p-benzoquinone (para-benzoquinone), phenothiazine (phenothiazine), and a mixture thereof.
The above-mentioned constituent components of the urethane oligomer B according to the present example can be synthesized by the following method.
1) In the glass reactor, a condenser, a temperature measuring device, a nitrogen Purge (Purge) tube, and an agitator were installed, and (i) a fluorine-based polyol copolymer was added, the temperature was maintained at 45 ℃ to 65 ℃ under a vacuum of 760mmHg or less, and the pressure was reduced for a sufficient time (for example, 20 minutes to 1 hour) to remove moisture. After that, the water remaining in the reactor was completely removed by nitrogen Bubbling (Bubbling) for 30 minutes.
2)(When K is 1 or more) Adding (ii) a polyisocyanate to the (i) fluorine-based polyol copolymer from which moisture has been removed. Using a Heating Mantle for temperature control (Heating Mantle) while maintaining the temperature at 45 ℃ to 65 ℃Under the state, stirring was performed at 200rpm to 300rpm, and 50 to 80 wt% of (iv) urethane polymerization catalyst (100 to 1,000ppm of the total reactants) was added based on the total weight of the catalyst used. The reactor was cooled with cooling water so that the temperature of the reactants did not rise above 95 ℃ due to the generation of heat of reaction. After the generation of heat was completed, the reaction was carried out for 2 to 3 hours while maintaining at 50 to 85 ℃.
3) After the reaction of 1) or 2) is completed, (iii) a (meth) acrylate having an isocyanate group and (v) a polymerization inhibitor are added, and then stirring is performed at 200rpm to 300rpm while cooling the reactor with cooling water so that the temperature of the reactants does not rise to 85 ℃ or more due to the generation of reaction heat. After the generation of heat was completed, the remaining catalyst was added while maintaining at 60 ℃ to 85 ℃ (total amount of catalyst was added when K ═ 0). After the catalyst was added, the reaction was carried out until the-NCO peak on IR disappeared, thereby completing the synthesis.
The urethane oligomer B synthesized according to this example had a viscosity at 25 ℃ of 1,000 to 1,000,000cPs, preferably 4,000 to 50,000cPs (Brookfield viscometer, Brookfield DV III +), and a refractive index of 1.4 or less, preferably 1.32 to 1.37.
In the present invention, a photocurable resin composition for coating an optical fiber having high water resistance is prepared by using as a base material a urethane oligomer a or a urethane oligomer B synthesized by the above-described method, or a urethane oligomer obtained by mixing the urethane oligomer a and the urethane oligomer B, and adding a photocurable monomer and a photoinitiator for adjusting viscosity, wherein the weight ratio of the urethane oligomer and the photocurable monomer used is such that the weight ratio of the urethane oligomer is 20 to 99% by weight of the total weight of the resin composition excluding the added photoinitiator, and the weight ratio of the photocurable monomer is the remaining 1 to 80% by weight. In addition, various additives such as a leveling agent or an antioxidant may be added to the resin composition thus prepared as needed.
The specific components of the highly water-resistant resin composition for coating an optical fiber prepared according to the present invention are as follows.
(A) Urethane oligomer
In the highly water-resistant resin composition for coating an optical fiber according to the present invention, the urethane oligomer a having the structure of the above-mentioned [ chemical formula 2] or the urethane oligomer B having the structure of the above-mentioned [ chemical formula 3] may be used, or the urethane oligomer a and the urethane oligomer B may be used in a mixture, and the mixing weight ratio in the mixing may be freely set in a range of 1 to 99% by weight based on the urethane oligomer a depending on the use application of the resin composition.
(B) Photo-curing monomer
In the high water resistance resin composition for optical fiber coating according to the present invention, various photocurable monomers commonly used in photocurable resin compositions may be used as the added photocurable monomer to adjust the viscosity of the resin composition, and may be, for example, 2,2,2-trifluoroethyl acrylate (2,2,2-trifluoroethylmethacrylate), 2,2,2-trifluoroethyl methacrylate (2,2,2-trifluoroethylmethacrylate), 2,2,3,3,3, 3-pentafluoropropyl acrylate (2,2,3,3,3-pentafluoropropylmethacrylate), 2,2,3,3,3, 3-pentafluoropropylmethacrylate (2,2,3,3,3-pentafluoropropylmethacrylate), 2- (perfluorobutyl) ethyl acrylate (2- (perfluorobutyl) methacrylate), or 2- (perfluorobutyl) ethyl methacrylate, 3- (perfluorobutyl) -2-hydroxypropyl acrylate (3- (perfluorobutyl) -2-hydroxypropyl methacrylate), 3- (perfluorobutyl) -2-hydroxypropyl methacrylate (3- (perfluorobutyl) -2-hydroxypropyl methacrylate), ethyl 2- (perfluorooctyl) acrylate (2- (perfluorohexyl) ethyl methacrylate), ethyl 2- (perfluorohexyl) methacrylate (2- (perfluorohexyl) ethyl methacrylate), 3-perfluorohexyl-2-hydroxypropyl acrylate (3-perfluorohexyl-2-hydroxypropyl acrylate), 3-perfluorohexyl-2-hydroxypropyl methacrylate (3-perfluorohexyl-2-hydroxypropyl methacrylate), ethyl 2- (perfluorooctyl) methacrylate (2- (perfluorooctyl) 2-hydroxypropyl methacrylate), and ethyl 2- (perfluorooctyl) acrylate (2- (perfluorooctyl) methacrylate) 3-perfluorooctyl-2-hydroxypropyl acrylate (3-perfluorooctyl-2-hydroxypropyl methacrylate), 3-perfluorooctyl-2-hydroxypropyl methacrylate (3-perfluorooctyl-2-hydroxypropyl methacrylate), ethyl 2- (perfluorodecyl) acrylate (2- (perfluorodecyl) ethyl methacrylate), ethyl 2- (perfluorodecyl) methacrylate (2- (perfluorodecyl) hydroxyethyl acrylate), ethyl 2- (perfluoro-3-methylbutyl) acrylate (2- (perfluorobutyl-3-methylbutyl) ethyl acrylate), ethyl 2- (perfluoro-3-methylbutyl) methacrylate (2- (perfluorobutyl-3-methylbutyl) hydroxyethyl acrylate), 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate (3- (perfluorobutyl-2-hydroxypropyl) methacrylate), and mixtures thereof, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate (3- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate), ethyl 2- (perfluoro 5-methylhexyl) acrylate (2- (perfluoro-5-methylhexyl) ethyl methacrylate), ethyl 2- (perfluoro 5-methylhexyl) methacrylate (2- (perfluoro-5-methylhexyl) ethyl methacrylate), 3- (perfluoro 5-methylhexyl) hydroxypropyl acrylate (3- (perfluoro-5-methylhexyl) -2-hydroxypropyl methacrylate), 3- (perfluoro 5-methylhexyl) -2-hydroxypropyl methacrylate (3- (perfluoro-5-methylhexyl) -2-hydroxypropyl methacrylate), ethyl 2- (perfluoro-7-methyloctyl) acrylate (2-hydroxypropyl-7-methyl-octyl) methacrylate (3- (perfluoro-5-methyl-hexyl) -2-hydroxypropyl methacrylate) ethylmethacrylate), 2- (perfluoro-7-methyloctyl) ethylmethacrylate (2-perfluor-7-methyloctyl) ethylmethacrylate), 3- (perfluoro-7-methyloctyl) hydroxypropylacrylate (3-perfluor-7-methyloctyl) -2-hydroxypropylmethacrylate), 3- (perfluoro-7-methyloctyl) -2-hydroxypropylmethacrylate (3-perfluor-7-methyloctyl) -2-hydroxypropylmethacrylate), 1H, 3H-propyltetrafluroacrylate (1H,1H, 3H-trifluoromethylacrylate), 1H, 3H-propyltetrafluroacrylate (1H,1H,5H-octafluoropentyl acrylate (1H,1H, 5H-perfluoropentyl) methacrylate (1H,1H, 5H-perfluoropentyl) acrylate, 1H,1H,5H octafluoropentyl methacrylate (1H,1H,5Hoctafluoropentyl methacrylate), 1H,1H, 7H-dodecylfluoroheptyl acrylate (1H,1H,7H-dodecafluoroheptyl acrylate), 1H,1H,7H-dodecafluoroheptyl acrylate (1H,1H,7H-dodecafluoroheptyl methacrylate), 1H,1H,9H-hexadecafluorononyl methacrylate (1H,1H,9H-hexadecafluorononyl acrylate), 1H,1H,9H-hexadecafluorononyl methacrylate (1H, 1H-hexadecafluorononyl methacrylate), 1H-1- (trifluoromethyl) trifluoroethyl acrylate (1H-1- (trifluoromethyl) trifluoroethyl methacrylate), 1H-1- (trifluoromethyl) trifluoroethyl methacrylate (1H-1- (trifluoromethyl) trifluoroethyl) methacrylate (1H-1H, 1H-1- (trifluoromethyl) trifluoroethyl) 1H, 1H-1- (trifluoromethyl) trifluoroethyl methacrylate (1H-1- (trifluoromethyl) trifluoroethyl) methacrylate (1H, 1H-1-dodecafluoroheptyl acrylate (1H, 1H-1-trifluoroethyl acrylate (1H, 1-trifluoromethyl) and 1-, 1H,3H-hexafluorobutyl acrylate (1H-1- (trifluoromethylmethyl) trifluoromethylacrylate), 1H,3H-hexafluorobutyl methacrylate (1H,1H, 3H-hexafluorobutylmethacrylate), and the like.
In addition, it goes without saying that various types of photocurable monomers obtained by synthesizing a fluorinated polyol and an acrylate through a urethane reaction may be used according to the choice of the user.
(C) Photoinitiator
The photoinitiator used in the present invention is a photoinitiator generally used in conventional photopolymerization, and for example, Irgacure #184 (hydroxycyclohexyl phenyl ketone), Irgacure #907 (2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone (2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-one), Irgacure #500 (hydroxy-ketones and benzophenones), Irgacure #651 (benzyldimethyl ketone)), Dacure #1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone)) from Ciba Geigy may be used, and may be selected from those available from the group consisting of, Darocure CGI #1800 (bisacylphosphine oxide) and CGI #1700 (bisacylphosphine oxide and benzophenone) are preferably used in an amount of about 0.1 to 5 wt% based on the total weight of the resin composition.
(D) Additive agent
In addition, the high water-resistant resin composition for optical fiber coating according to the present invention may include conventional additives such as a leveling agent, a slip agent, a stabilizer, an antioxidant, etc. to improve thermal and oxidative stability, storage stability, surface characteristics, flow characteristics, process characteristics, etc., as the leveling agent, DC-190 of Dow-Corning Co., 2100, 2200, 2300, etc. of Tego Co., Ltd. may be used, DC-56, 57 of Dow-Corning Co., Ltd. may be used as the slip agent, a tertiary amine such as diethylethanolamine and trihexylamine, a hindered amine, an organic phosphate, a hindered phenol, or a mixture thereof may be used as the stabilizer, 3, 5-di-t-4-butylhydroxytoluene (3, 5-di-t-4-butylhydroxytoluene; BHT), etc. may be used as the antioxidant, at this time, the additive is added to the resin composition in an amount ranging from 0.1 to 10% by weight based on the total weight of the resin composition.
Hereinafter, the characteristics of the high water resistance resin composition according to the present invention are confirmed in more detail by comparing the specific physical properties of the high water resistance resin composition according to the present invention having the above-described configuration with the existing resin composition for coating an optical fiber.
[ preparation examples ]
Preparation of highly Water-resistant resin composition for optical fiber coating according to the present invention
Preparation example 1: preparation of photocured urethane oligomer A
In a 1L flask, 362.4g of Synquest Laboratory Co.A Perfluoropolyether Diol (Mw 1,208g/mole) was charged, and then a vacuum pump was connected to the reactor to remove moisture (H) contained in the charged polyol while maintaining a temperature of 45 to 65 ℃ using a Heating Mantle (Heating Mantle)2O) for 1 hour. After that, the water remaining in the reactor was completely removed by nitrogen Bubbling (Bubbling) for another 30 minutes. Here, in performing the above-described moisture removal process, a sufficient amount of nitrogen gas was supplied to the reactor by bubbling throughout the process to remove oxygen gas in the reactor and prevent moisture and oxygen gas from penetrating into the connection portion with the condenser. Thereafter, 88.8g of isophorone diisocyanate (IPDI) (Diol: IPDI molar ratio 3: 4) and 0.1g of dibutyltin n-Dilaurate (DBTL) were added to carry out a reaction, and after the generation of heat was completed, the reaction was carried out while maintaining 75 to 80 ℃ until the NCO peak on FT-IR was not changed. Thereafter, 0.1G of butylhydroxytoluene was added, and 44.9G of G-201P (2-hydroxy 3-acryloyloxypropyl) available from Daikin Co., Ltd. was added dropwise while maintaining the temperature at 85 ℃Methacrylate) and 0.75g of hydroquinone Monomethyl Ether (MEHQ). After the generation of heat was completed, the reaction was carried out while maintaining at 80 ℃ to 90 ℃ until the NCO peak on FT-IR disappeared.
The photo-curable urethane oligomer a synthesized in preparation example 1 was measured to have a viscosity of 580,800cPs and a refractive index of 1.362 at 25 ℃.
Preparation example 2: preparation of photocured urethane oligomer B
In a 1L flask, 362.4g of Synquest Laboratory Co.A Perfluoropolyether Diol (Mw 1,208g/mole) was charged, and then a vacuum pump was connected to the reactor to remove moisture (H) contained in the charged polyol while maintaining a temperature of 45 to 65 ℃ using a Heating Mantle (Heating Mantle)2O) for 1 hour. After that, the water remaining in the reactor was completely removed by nitrogen Bubbling (Bubbling) for another 30 minutes. Here, in performing the above-described moisture removal process, a sufficient amount of nitrogen gas was supplied to the reactor by bubbling throughout the process to remove oxygen gas in the reactor and prevent moisture and oxygen gas from penetrating into the connection portion with the condenser. Thereafter, 0.1g of butylhydroxytoluene was added, and 71.7g of Karenz BEI (1,1-bis (acryloyloxymethyl) ethyl isocyanate) and 0.75g of hydroquinone Monomethyl Ether (MEHQ) were added dropwise while maintaining 85 ℃. After the generation of heat was completed, the reaction was carried out while maintaining at 80 ℃ to 90 ℃ until the NCO peak on FT-IR disappeared.
The photo-curable urethane oligomer B synthesized in preparation example 2 was measured to have a viscosity of 1,850cPs and a refractive index of 1.350 at 25 ℃.
Using the urethane oligomer a and the urethane oligomer B synthesized in the above-described preparation examples 1 and 2 as base materials, a photocurable resin composition for coating an optical fiber was prepared as in the following preparation examples 3 and 4.
Preparation example 3: preparation of photocurable resin composition for optical fiber coating
In 75 wt% of the photocurable urethane oligomer a prepared according to preparation example 1, as a photocurable monomer for adjusting the viscosity of the resin composition, 22.4 wt% of 2- (perfluorooctyl) ethyl methacrylate (2- (perfluorooctyl) ethyl methacrylate) and 1.1 wt% of M300(trimethyl propane triacylate) of Miwon were added, and as a photoinitiator, 1.5 wt% of Irgacure #184 of Ciba Specialty Chemicals was added, thereby preparing a photocurable resin composition for optical fiber coating.
Preparation example 4: preparation of photocurable resin composition for optical fiber coating
To 97.4 wt% of the photocurable urethane oligomer B prepared according to preparation example 2, as a photocurable monomer for adjusting the viscosity of the resin composition, 1.1 wt% of M300 (trimetylolpropane triacrylate) by Miwon was added, and as a photoinitiator, 1.5 wt% of Irgacure #184 by Ciba Specialty Chemicals was added, thereby preparing a photocurable resin composition for coating an optical fiber.
[ comparative example ]
Preparation of resin composition for optical fiber coating according to prior art
In comparative examples 1 to 4 below, a conventional resin composition for coating an optical fiber, which is based on a conventional photopolymerizable oligomer and disclosed in the above-mentioned korean patent laid-open publication No. 1003002 (resin composition for coating an optical fiber), was prepared.
As described in the specification of patent No. 1003002, a resin composition for coating an optical fiber having the following chemical formula 4 is used in a conventional resin composition for coating an optical fiber]A urethane oligomer synthesized based on a fluorinated polyol having the structure of [ chemical formula 4] below]In the case of the fluorinated polyol of the structure (1), the repeating unit includes- [ CF2-CF2-O]-or- [ CF2-O]-。
[ chemical formula 4]
Herein, R is3Each is independentis-CH on its origin2O-or-CH2(OCH2CH2)nO- (n is an integer of 1 to 3), and p and q are the number of repeating units.
For example, in the case of D10/H of Solvay Solexis Co, used in the aforementioned patent No. 1003002, R is3is-CH2O-, p is 9, q is 7, and the molecular weight Mw is 1,528g/mole, in which case the content of oxygen (-O-) having an ether bond structure contained in D10/H which is a fluorinated polyol having a conventional chemical formula structure is 19.9% by weight, which is in accordance with the present invention having the above-mentioned [ chemical formula 1] structure]The fluorinated polyol of (2) has an oxygen (-O-) content of the ether bond structure about two times higher than that of the fluorinated polyol of (1).
Comparative example 1: preparation of Photocurable urethane oligomers according to the prior art
In a 1L flask, 458.4g of fluorinated polyol D10/H (Mw 1,528g/mole) of Solvay Solexis was charged, and then a vacuum pump was connected to the reactor to remove moisture (H) contained in the charged polyol while maintaining a state of 45 to 65 ℃ using a Heating Mantle (Heating Mantle)2O) for 1 hour. After that, the water remaining in the reactor was completely removed by nitrogen Bubbling (Bubbling) for another 30 minutes. At this time, also in the above-mentioned moisture removal treatment, a sufficient amount of nitrogen gas was supplied to the reactor by bubbling throughout the treatment to remove oxygen gas in the reactor and prevent moisture and oxygen gas from penetrating into the connection portion with the condenser. Thereafter, 88.8g of isophorone diisocyanate (IPDI) (Diol: IPDI molar ratio 3: 4) and 0.1g of dibutyltin n-Dilaurate (DBTL) were added to carry out a reaction, and after the generation of heat was completed, the reaction was carried out while maintaining 75 to 80 ℃ until the NCO peak on FT-IR was not changed. Thereafter, 0.1G of butylhydroxytoluene was added, and 44.9G of Daikin G-201P (2-hydroxy 3-acryloyloxypropyl methacrylate) and 0.75G of hydroquinone Monomethyl Ether (MEHQ) were added dropwise while maintaining 85 ℃. After the generation of heat was completed, the reaction was carried out while maintaining at 80 ℃ to 90 ℃ until the NCO peak on FT-IR disappeared.
The photo-curable urethane oligomer synthesized in comparative example 1 was measured to have a viscosity of 169,400cPs and a refractive index of 1.362 at 25 ℃.
Comparative example 2: preparation of photocured urethane oligomer B
In a 1L flask, 458.4g of fluorinated polyol D10/H (Mw 1,528g/mole) of Solvay Solexis was charged, and then a vacuum pump was connected to the reactor to remove moisture (H) contained in the charged polyol while maintaining a state of 45 to 65 ℃ using a Heating Mantle (Heating Mantle)2O) for 1 hour. After that, the water remaining in the reactor was completely removed by nitrogen Bubbling (Bubbling) for another 30 minutes. At this time, also in the above-mentioned moisture removal treatment, a sufficient amount of nitrogen gas was supplied to the reactor by bubbling throughout the treatment to remove oxygen gas in the reactor and prevent moisture and oxygen gas from penetrating into the connection portion with the condenser. Thereafter, 0.1g of butylhydroxytoluene was added, and 71.7g of Karenz BEI (1,1-bis (acryloyloxymethyl) ethyl isocyanate) and 0.75g of hydroquinone Monomethyl Ether (MEHQ) were added dropwise while maintaining 85 ℃. After the generation of heat was completed, the reaction was carried out while maintaining at 80 ℃ to 90 ℃ until the NCO peak on FT-IR disappeared.
The photo-curable urethane oligomer synthesized in comparative example 2 was measured to have a viscosity of 1,680cPs at 25 c and a refractive index of 1.351.
Conventional photocurable resin compositions for coating optical fibers were prepared as in comparative examples 3 and 4 below, using the photocurable urethane oligomers according to the prior art synthesized in comparative examples 1 and 2 as substrates.
Comparative example 3: preparation of photocurable resin composition for optical fiber coating according to the prior art
In 75 wt% of the photocurable urethane oligomer prepared according to comparative example 1, as a photocurable monomer for adjusting the viscosity of the resin composition, 22.4 wt% of 2- (perfluorooctyl) ethyl methacrylate (2- (perfluorooctyl) ethyl methacrylate) and 1.1 wt% of M300(trimethyl propane triacylate) of Miwon was added, and as a photoinitiator, 1.5 wt% of Irgacure #184 of Ciba Specialty Chemicals was added, thereby preparing a photocurable resin composition for optical fiber coating according to the prior art.
Comparative example 4: preparation of photocurable resin composition for optical fiber coating according to the prior art
To 97.4 wt% of the photocurable urethane oligomer prepared according to comparative example 2, 1.1 wt% of M300 (trimethyolpropane triacrylate) by Miwon was added as a photocurable monomer for adjusting the viscosity of the resin composition, and 1.5 wt% of Irgacure #184 by Ciba Specialty Chemicals was added as a photoinitiator, thereby preparing a photocurable resin composition for coating an optical fiber according to the prior art.
[ test examples ]
Evaluation of physical Properties of resin composition for optical fiber coating
a) Refractive index
The refractive index of the composition at 25 ℃ under a light source of 589nm was measured according to ASTM D54250 using an Abber refractometer ATAGO 3T.
b) Viscosity (Viscosity)
The viscosity of the compositions was measured according to ASTM D-2196 using a Brookfield viscometer (Brookfield DV III +, spindle 63) at 25 ℃ with a torque in the range of 50% to 90%.
c) Glass transition temperature (Tg)
In order to know the glass transition temperature characteristics of the composition, a glass transition temperature (Tg) value was measured by analyzing a heat flux difference according to temperature of an Ultraviolet (UV) cured film using a dsc (differential Scanning calorimeter) (ASTM D3418).
d) Water Transmission Rate (Water Vapor Transmission Rate)
In order to find the moisture permeability characteristics of the composition, the moisture permeability was measured in g/m on an Ultraviolet (UV) cured film using a moisture permeability analyzer2WVTR (Water Vapor Transmission Rate) in units of day (grams of water permeated per square meter per day). The equipment used is Systhech Illinois 7001, at 37.8 deg.C,The cured film having a thickness of 800 μm was measured under a humidity of 90.01% and a pressure of 760 mmHg.
e) Fiber optic high temperature high humidity Pressure Cooker (Pressure Cooker) test
In order to know the water resistance characteristics of the composition, the photo-curable low refractive resin composition prepared by the above preparation examples and comparative examples was first coated to a thickness of 30 μm, and then the photo-curable high refractive resin composition for secondary coating used in a general optical fiber was coated to a thickness of 30 μm, and the thus-coated dummy optical fiber having a glass core size of 125 μm was put into a Pressure Cooker (Pressure Cooker) together with water, and the temperature was raised to 125 ℃ so that the vapor Pressure reached 2 atm. After a certain time, the Optical fiber exposed to the high temperature and high pressure steam was dried in air for 30 minutes to remove surface moisture, and then the Optical Loss (Optical Loss) of the Optical fiber was measured.
Test example 1: refractive index and viscosity measurement results of resin composition
The composition components and measured refractive indices and viscosities of the high water resistance resin compositions according to the present invention prepared according to preparation examples 3 and 4 and the photocurable resin compositions according to the prior art prepared according to comparative examples 3 and 4 are shown in the following [ table 1 ].
[ TABLE 1]
Refractive index and viscosity of resin composition
As shown in [ table 1], the high water resistance resin composition according to the present invention has a low refractive index in a very similar range to that of the photocurable resin composition according to the prior art, and has a viscosity in a range of 2,000 to 8,000cPs suitable for optical fiber coating use.
Test example 2: glass transition temperature (Tg) measurement results of resin composition according to DSC Data
To the high water resistance resin compositions according to the present invention prepared according to preparation examples 3 and 4 and the photo-curable resin compositions according to the prior art prepared according to comparative examples 3 and 4, after being cured by irradiation with ultraviolet rays, glass transition temperatures were measured by DSC analysis, and are shown in the following [ table 2 ].
[ TABLE 2]
Glass transition temperature (Tg) of the resin composition according to DSC Data
As shown in [ table 2], the high water resistance resin composition according to the present invention has a relatively high glass transition temperature, which reduces the Diffusion Rate of moisture (Diffusion Rate), compared to the photo-curable resin composition according to the related art, whereby relatively high durability can be ensured under high temperature/high humidity environment.
Test example 3: water Vapor Transmission Rate (WVTR) measurement result
To the high water resistance resin compositions according to the present invention prepared according to preparation examples 3 and 4 and the photo-curable resin compositions according to the prior art prepared according to comparative examples 3 and 4, after curing by irradiation of ultraviolet rays, measured in g/m2The Water permeability (Water Vapor Transmission Rate) in units of day (Water Vapor Transmission grams per square meter) is shown below [ Table 3]]In (1).
WVTR comparison of resin compositions based on moisture Transmission
As shown in [ table 3], the high water resistance resin composition according to the present invention showed significantly reduced moisture transmittance, and showed a WVTR value reduced by 44% or more at most, as compared to the photo-curable resin composition according to the prior art.
Test example 4: light (es)Test results of fiber high temperature and high humidity Pressure Cooker (Pressure Cooker)
Optical loss of the optical fiber was measured by using the high water-resistant resin composition according to the present invention prepared according to preparation example 3 and the photo-curable resin composition according to the prior art prepared according to comparative example 3 as optical fiber coating materials, adding to a pressure cooker together with water, raising the temperature to 125 ℃ to make the vapor pressure reach 2 atm, and after a certain time, drying the optical fiber exposed to high temperature and high pressure vapor in the air for 30 minutes to remove surface moisture, and shown in fig. 1.
As shown in fig. 1, the optical loss value of the optical fiber coated with the highly water-resistant resin composition according to the present invention as a coating material shows a good optical loss value within the measurement error range even after 20 hours in the above-mentioned high-temperature, high-pressure and high-humidity pressure cooker test, whereas in the case of the optical fiber coated with the photocurable resin composition according to the prior art as a coating material, the coating film is peeled off due to moisture permeation, thus extending the duration of the pressure cooker test, and thus, the optical loss rapidly increases after 2 to 4 hours.
As described above, the high water resistant resin composition for optical fiber coating according to the present invention has viscosity and low refractive index characteristics suitable for use in optical fiber coating, and at the same time, exhibits a higher glass transition temperature and thus a lower moisture transmittance compared to the high water resistant resin composition for optical fiber coating according to the related art, and thus can ensure relatively excellent durability under high temperature, high pressure and high humidity environments, and thus can be effectively applied to a high power optical fiber laser or the like in which moisture condensed around an optical fiber increases due to a higher temperature difference between a temperature reducing device and ambient air.
The constitution of the present invention has been described above by way of examples and preparation examples, but these show only some examples of preferred embodiments of the present invention, the present invention is not limited thereto, and various changes and modifications made by those skilled in the art to which the present invention pertains are within the technical spirit of the present invention without departing from the gist of the present invention described in the claims of the claims.
Claims (12)
1. A highly water-resistant resin composition for coating an optical fiber, comprising:
(i) a photocurable urethane oligomer synthesized using a fluorinated polyol having the structure of the following chemical formula 1 as a base material;
(ii) a photo-curable monomer; and
(iii) a photo-initiator,
[ chemical formula 1]
Here, M, N and P are the number of repetitions of each repeating unit,
m and N are in the range of 1 to 100,
p has a range of 1 to 10.
2. The highly water-resistant resin composition for coating an optical fiber according to claim 1,
the photo-curable urethane oligomer has a structure of the following chemical formula 2,
[ chemical formula 2]
Herein, R is1Is an aromatic or aliphatic hydrocarbon group having 2 to 20 carbon atoms,
R2each independently an aromatic or aliphatic hydrocarbon group containing 1 to 6 (meth) acrylate groups having 2 to 20 hydrocarbons,
l is the number of repetitions of the repeating unit, having a range of 1 to 10.
3. The highly water-resistant resin composition for coating an optical fiber according to claim 1,
the photo-curable urethane oligomer has a structure of the following chemical formula 3,
[ chemical formula 3]
Herein, R is1Is an aromatic or aliphatic hydrocarbon group having 2 to 20 carbon atoms,
R2each independently an aromatic or aliphatic hydrocarbon group containing 1 to 6 (meth) acrylate groups having 2 to 20 hydrocarbons,
k is the number of repetitions of the repeating unit, having a range of 1 to 10.
4. The highly water-resistant resin composition for coating an optical fiber according to claim 1,
the photo-curable urethane oligomer is a mixture of a urethane oligomer having a structure of the following chemical formula 2 and a urethane oligomer having a structure of the following chemical formula 3,
[ chemical formula 2]
Herein, R is1Is an aromatic or aliphatic hydrocarbon group having 2 to 20 carbon atoms,
R2each independently an aromatic or aliphatic hydrocarbon group containing 1 to 6 (meth) acrylate groups having 2 to 20 hydrocarbons,
l is the number of repetitions of the repeating unit, having a range of 1 to 10,
[ chemical formula 3]
Herein, R is1Is an aromatic or aliphatic hydrocarbon group having 2 to 20 carbon atoms,
R2each of which isIndependently an aromatic or aliphatic hydrocarbon group containing 1 to 6 (meth) acrylate groups having 2 to 20 hydrocarbons,
k is the number of repetitions of the repeating unit, having a range of 1 to 10.
5. The highly water-resistant resin composition for coating an optical fiber according to claim 1,
the photo-curable urethane oligomer is included in a weight ratio of 20 to 99 wt% of the total weight of the resin composition excluding the photo-initiator.
6. The highly water-resistant resin composition for coating an optical fiber according to claim 1,
the photoinitiator is included in a weight ratio of 0.1 to 5 wt% based on the total weight of the resin composition.
7. The highly water-resistant resin composition for coating an optical fiber according to claim 1,
in the resin composition, at least one additive selected from the group consisting of a leveling agent, a slip agent, a stabilizer, and an antioxidant is further included.
8. The highly water-resistant resin composition for coating an optical fiber according to claim 7,
the additive is included in a weight ratio of 0.1 to 10 wt% based on the total weight of the resin composition.
9. The highly water-resistant resin composition for coating an optical fiber according to claim 1,
the photocurable monomer is selected from the group consisting of 2,2,2-trifluoroethylacrylate (2,2,2-trifluoroethylacrylate), 2,2,2-trifluoroethylmethacrylate (2,2,2-trifluoroethylmethacrylate), 2,2,3,3,3-pentafluoropropylacrylate (2,2,3,3,3-pentafluoropropylacrylate), 2,2,3,3,3-pentafluoropropylmethacrylate (2,2,3,3,3-pentafluoropropylmethacrylate), 2- (perfluorobutyl) ethyl acrylate (2- (perfluorobutyl) hydroxyethyl acrylate), 2- (perfluorobutyl) ethyl methacrylate (2- (perfluorobutyl) hydroxypropyl) methacrylate), 3- (perfluorobutyl) -2-hydroxypropyl acrylate (3- (perfluorobutyl) -2-hydroxypropyl acrylate), and 2- (perfluorobutyl) -2-hydroxypropyl acrylate (3- (perfluorobutyl) -2-hydroxypropyl-acrylate (2- (perfluorobutyl) -2-hydroxypropyl) -2- (perfluorobutyl) -3- (perfluorobutyl) -2-hydroxypropyl) methacrylate, Ethyl 2- (perfluorooctyl) acrylate (2- (perfluorohexyl) ethylmethacrylate), ethyl 2- (perfluorohexyl) methacrylate (2- (perfluorohexyl) ethylmethacrylate), 3-perfluorohexyl-2-hydroxypropylacrylate (3-perfluorohexyl-2-hydroxypropylmethacrylate), 3-perfluorohexyl-2-hydroxypropylmethacrylate (3-perfluorohexyl-2-hydroxypropylmethacrylate), ethyl 2- (perfluorooctyl) acrylate (2- (perfluorooctyl) ethylmethacrylate), ethyl 2- (perfluorooctyl) methacrylate (2- (perfluorooctyl) ethylmethacrylate), 3-perfluorooctyl-2-hydroxypropylacrylate (3-perfluorooctyl) ethylmethacrylate), 3-perfluorooctyl-2-hydroxypropylacrylate (3-perfluorooctyl-2-hydroxypropylacrylate), 3-perfluorooctyl-2-hydroxypropylacrylate (3-perfluorooctyl-2-hydroxypropylmethacrylate), and 3-perfluorooctyl-2-hydroxypropylacrylate (3-perfluorooctyl-2-hydroxypropylmethacrylate), Ethyl 2- (perfluorodecyl) acrylate (2- (perfluorodecyl) ethyl methacrylate), ethyl 2- (perfluorodecyl) methacrylate (2- (perfluorodecyl) ethyl methacrylate), ethyl 2- (perfluoro-3-methylbutyl) acrylate (2- (perfluoro-3-methylbutyl) ethyl methacrylate), 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate (3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate), 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate (3- (perfluoro-3-methyl) -2-hydroxypropyl acrylate), Ethyl 2- (perfluoro-5-methylhexyl) acrylate (2- (perfluoro-5-methylhexyl) ethyl methacrylate), ethyl 2- (perfluoro-5-methylhexyl) methacrylate (2- (perfluoro-5-methylhexyl) ethyl methacrylate), 3- (perfluoro-5-methylhexyl) hydroxypropyl acrylate (3- (perfluoro-5-methylhexyl) -2-hydroxypropylmethacrylate), ethyl 2- (perfluoro-7-methyloctyl) acrylate (2-perfluoro-7-methylictyl) methacrylate), ethyl 2- (perfluoro-7-methyloctyl) methacrylate (2-perfluoro-7-methylisoctyl) methacrylate, 3- (perfluoro-7-methyloctyl) hydroxypropyl acrylate (3-perfluor-7-methyloctyl) -2-hydroxypropylmethacrylate), 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate (3-perfluor-7-methyloctyl) -2-hydroxypropylmethacrylate), 1H,3H-tetrafluoropropyl acrylate (1H,1H,3H-tetrafluoropropylmethacrylate), 1H,3H-tetrafluoropropylmethacrylate (1H,1H,3H-tetrafluoropropylmethacrylate), 1H,5H-octafluoropentyl acrylate (1H,1H,5H-octafluoropentyl acrylate), 1H,5H-octafluoropentyl methacrylate (1H,1H,5H-octafluoropentyl methacrylate), 1H,5H octafluoropentyl methacrylate (1H,1H,5H-octafluoropentyl methacrylate), 1H, 5H-heptafluoropentyl methacrylate (1H,1H, 5H-dodecafluoropentyl H, 1H-dodecyl H, 7H-1H-dodecyl-1H, 7-dodecyl-H, 1H, 7-dodecyl-H, 1H,7H-dodecafluoroheptylacrylate, 1H,1H,7H-dodecafluoroheptylacrylate (1H,1H,7H-dodecafluoroheptylacrylate), 1H,1H, 9H-hexadecafluoronylmethacrylate (1H,1H,9H-hexadecafluorononylacrylate), 1H,1H,9H-hexadecafluorononylmethacrylate (1H,1H,9H-hexadecafluorononylmethacrylate), 1H-1- (trifluoromethyl) trifluoroethylacrylate (1H-1- (trifluoromethylmethacrylate), 1H-1- (trifluoromethylmethacrylate) methyl trifluoroethylacrylate (1H-1- (trifluoromethylmethacrylate), 1H-1- (trifluoromethylacrylate), 1H-1- (trifluoromethylmethacrylate) trifluoroethylacrylate (1H-1- (trifluoromethylmethacrylate), 1H-1- (trifluoromethylacrylate), 1H-1- (trifluoromethylmethacrylate) trifluoroethylmethacrylate), 1H-1- (3H-hexafluoromethacrylate), 1H, 3H-hexafluoroarylacrylate) and mixtures of two or more thereof.
10. The highly water-resistant resin composition for coating an optical fiber according to claim 1,
the photoinitiator is any one selected from the group consisting of Irgacure #184 (hydroxycyclohexylphenylketone), Irgacure #907 (2-methyl-1 [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone (2-methyl-1- [4- (meth) phenyl ] -2-morpholino-propan-1-one), Irgacure #500 (hydroxyketone and benzophenone), Irgacure #651 (benzyldimethylketone), Darocure #1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone (2-hydroxy-2-methyl-1-phenyl-propan-1-one)), Darocure #1800 (bisacylphosphine oxide) and bis (acylphosphine oxide) 1700 (bisacylphosphine oxide) and bis (naphthoyl phosphine oxide) 1700 One or a combination of two or more.
11. The highly water-resistant resin composition for coating an optical fiber according to claim 2,
the photocurable urethane oligomer is synthesized from:
(i) a fluorine-based polyol having a structure of chemical formula 1;
(ii) polyisocyanates (polyisocynate);
(iii) a (meth) acrylate monomer having a hydroxyl group (OH-);
(iv) a urethane polymerization catalyst; and
(v) and (4) a polymerization inhibitor.
12. The highly water-resistant resin composition for coating an optical fiber according to claim 3,
the photocurable urethane oligomer is synthesized from:
(i) a fluorine-based polyol having a structure of chemical formula 1;
(ii) polyisocyanates (polyisocynate);
(iii) a (meth) acrylate monomer having an isocyanate group (NCO-);
(iv) a urethane polymerization catalyst; and
(v) and (4) a polymerization inhibitor.
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| KR10-2019-0127988 | 2019-10-15 |
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| CN113355017A (en) * | 2021-05-06 | 2021-09-07 | 武汉长盈鑫科技有限公司 | Low-refractive-index optical fiber coating resin with high glass transition temperature |
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Citations (3)
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| US5026814A (en) * | 1988-09-15 | 1991-06-25 | Ausimont S.R.L. | Fluorinated polyurethanes endowed with improved mechanical properties, containing rubber-like polyoxyperfluoroalkylene-structure blocks and hydrogenated rigid blocks |
| WO2010021476A2 (en) * | 2008-08-19 | 2010-02-25 | 에스에스씨피 주식회사 | Photopolymerizable oligomer, photopolymerizable resin composition containing the same, and optical fiber |
| CN108350141A (en) * | 2015-09-16 | 2018-07-31 | 科巨希化学股份有限公司 | (methyl) acrylamide oligourethane and actinic energy ray curable resion composition containing the oligomer |
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| KR100500191B1 (en) | 2002-09-10 | 2005-07-14 | 에스에스씨피 주식회사 | Uv-curable resin composition for cladding layer of optical fiber |
| KR101003002B1 (en) | 2008-06-30 | 2010-12-22 | 에스에스씨피 주식회사 | Resin Composition for Optical Fiber Cladding |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026814A (en) * | 1988-09-15 | 1991-06-25 | Ausimont S.R.L. | Fluorinated polyurethanes endowed with improved mechanical properties, containing rubber-like polyoxyperfluoroalkylene-structure blocks and hydrogenated rigid blocks |
| WO2010021476A2 (en) * | 2008-08-19 | 2010-02-25 | 에스에스씨피 주식회사 | Photopolymerizable oligomer, photopolymerizable resin composition containing the same, and optical fiber |
| CN108350141A (en) * | 2015-09-16 | 2018-07-31 | 科巨希化学股份有限公司 | (methyl) acrylamide oligourethane and actinic energy ray curable resion composition containing the oligomer |
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| CN113355017A (en) * | 2021-05-06 | 2021-09-07 | 武汉长盈鑫科技有限公司 | Low-refractive-index optical fiber coating resin with high glass transition temperature |
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