KR101051287B1 - Photopolymerization oligomer, photopolymerization resin composition and optical fiber containing the oligomer - Google Patents

Abstract

The present invention provides an optical fiber having a photopolymerizable oligomer and a photopolymerizable resin composition comprising the oligomer and a cladding portion formed by the resin composition, which can be cured at a low ultraviolet light amount due to a very high curing rate and exhibit high strength after UV curing. The present invention relates to a photopolymerizable resin composition comprising a photopolymerizable oligomer, a photopolymerizable monomer having carbon fluoride and containing (meth) acrylate groups at its ends, a photopolymerizable monomer containing two or more polyfunctional acrylate groups, and a photoinitiator. Characterized in that it comprises a.

Description

Photopolymerizable oligomers, photopolymerizable resin compositions and optical fibers including the oligomers TECHNICAL FIELD

The present invention provides an optical fiber having a photopolymerizable oligomer and a photopolymerizable resin composition comprising the oligomer and a cladding portion formed by the resin composition, which can be cured at a low ultraviolet light amount due to a very high curing rate and exhibit high strength after UV curing. It is about.

Recently, the coating method using UV-curable fluororesin has a shorter reaction time, higher energy efficiency, does not require high temperature during curing, and can simplify equipment and equipment. Has many advantages, and research on this is being actively conducted.

On the other hand, the optical fiber is slightly different depending on the application, but generally consists of a core portion having a high transmittance and a cladding portion having a lower refractive index than the core portion, and transmits light.

In indoor optical fibers and short-range special optical fibers, a technique of replacing the cladding portion with a polymer instead of glass is performed for the flexibility of the fiber in a special design, for example, when the diameter of the core portion is thick, and also the cladding layer Techniques for forming the second cladding layer on the outside are also being developed.

In this case, in order to transmit light preferably, a polymer for forming a second cladding layer having a lower refractive index than the cladding layer is required. Thus, many studies have been conducted to develop a resin composition for cladding to implement a low refractive index.

For example, US Pat. Nos. 4,558,082 and 4,663,185 disclose silicone acrylate polymer resins, and US Pat. No. 4,469,724 includes modulus by incorporating a ring structure within a photopolymerizable chain. Techniques of improved cis or trans fluorinated acrylates and thermoset cis or trans fluorinated epoxy are disclosed. In addition, U.S. Patent No. 4,508,916 discloses a photopolymerized perfluorinated acrylate resin, and U.S. Patent No. 4,617,350 discloses a thermoplastic resin having a refractive index in the range of 1.37 to 1.48 that can be used for optical applications, including optical fibers. Is disclosed.

However, such a conventional cladding resin has a problem in that it is difficult to pull out the optical fiber due to the high amount of ultraviolet light, and the strength is low, and has a problem in the related applications.

The technical problem to be solved by the present invention can be easily cured even in a low UV light amount, exhibits high strength after UV curing, can be applied in various applications, optical polymerization oligomer, photopolymer resin composition and optical fiber having a cladding formed using the same To provide.

The photopolymerizable oligomer according to the present invention for solving the above technical problem, has a structure of formula (1).

Where

Each R ¹ is independently CH ₂ O or —CH ₂ (OCH ₂ CH ₂ ) _a O—, wherein a is an integer from 1 to 3,

R ² is an aromatic or aliphatic hydrocarbon group having 6 to 20 carbon atoms,

R ³ are each independently a meta (acrylate) group having 2 to 40 carbon atoms,

n is (1) to (5),

m is (2) to (6), where m = n + 1,

p is (2)-(20) and p / q has a range of 0.8-2.5.

Further, the photopolymerizable resin composition of the present invention includes the photopolymerizable oligomer, a photopolymerizable monomer having a fluorocarbon and containing a (meth) acrylate group at a terminal, a photopolymerizable monomer containing two or more polyfunctional acrylate groups, and a photoinitiator. It is characterized by including.

Finally, the optical fiber of the present invention is characterized by having a cladding portion formed using the photopolymerizable resin composition.

The photopolymerizable oligomer and the resin composition according to the present invention can implement numerical aperture according to the refractive index, exhibit high strength after UV curing, do not break even from external impact, and have a high curing speed even at low light amount, so as a cladding material of glass or plastic optical fiber. It can be usefully used.

Photopolymerizable resin composition according to an embodiment of the present invention, (a) a photopolymerizable oligomer having the structure of formula (1), (b) a photopolymerizable monomer having a carbon fluoride, containing a (meth) acrylate group at the terminal (c) a photopolymerizable monomer containing two or more polyfunctional (meth) acrylates, (d) a photoinitiator, and (e) a polymerization inhibitor or an antioxidant.

Hereinafter, each component is demonstrated.

(a) photopolymerization oligomer

The photopolymerizable oligomers used in the present invention include (i) fluorinated polyol copolymers, (ii) polyisocyanates, (iii) methacrylates with hydroxy, (iv) polycondensation catalysts, and (v) polymerization Synthesis with inhibitor

According to the invention, the molar ratio of (i) fluorine-based polyol copolymer: (ii) polyisocyanate: (iii) hydroxy-containing (meth) acrylate is (i) component: (ii) component is 1: 1 to 1: 3, and (i) component: (iii) the component is preferably 0.6: 2 to 20: 2, the amount of the (iv) component and (v) component is 0.01 to 0.01 based on 100% by weight of the component (i) It is preferable that 1 weight% is included.

The components constituting the photopolymerizable oligomer are as follows.

(i) Fluorinated Polyol Copolymer

Fluorinated polyol copolymers include -CF ₂ CF ₂ -or -CF ₂ CF ₂ O- as repeating units, preferred examples of which are 1H, 1H, 9H-hexadecafluorononanol (1H, 1H, 9H-hexadecafluorononanol ), Hexafluoro-2-methylisopropanol, 1,1,1,3,3,3-hexafluoro-2-propanol (1,1,1,3,3,3- hexafluoro-2-propanol), hexafluoro-2- (p-tolyl) isopropanol, 4,5,5,6,6,6-hexafluoro-4- (Trimethyl) -1-hexanol (4,5,5,6,6,6-hexafluoro-4- (trimethyl) -1-hexanol), 4,5,5,6,6,6-hexafluoro -4- (trifluoromethyl) -2-hexen-1-ol (4,5,5,6,6,6-hexafluoro-4- (trifluoromethyl) -2-hexene-1-ol), 3,3 , 4,4,5,5,6,6-octafluoro-1,6-hexanediol (3,3,4,4,5,5,6,6-octafluoro-1,6-hexanediol), 1H, 1H, 5H-octafluoro-1-pentanol (1H, 1H, 5H-octafluoro-1-pentanol), 1H, 1H-pentadecafluoro-1-octanol (1H, 1H-pentadecafluoro-1- octanol), 2,3,4,5,6-pentafluorobenzyl alcohol (2,3,4,5,6-pentafluorobenzyl alcohol), pentafluorobutanol-2, 4,4,5,5,5-pentafluoropentanol (4,4,5,5 , 5-pentafluoropentanol), pentafluoropropionaldehyde hydrate and mixtures thereof, and commercially obtainable thereof are Z-Dol (Solvay Solexis), Z-Dol TX (Solva Solixis), Fluorolink D (Solva Solixis), Fluorolink D10 / H (Solva Solixis), Fluorolink D10 (Solva Solixis), Fluorolink T, Fluorolink T10 (Solva Solixis), Fluorolink E (Solva Solixis), Fluorolink E10 / H (Solva Solixis), Fluorolink E10 (Solva Solixis), Zonyl TA-L (Dupont) and Zonyl TA-N (Dupont).

(ii) polyisocyanate

Polyisocyanates include 2,4-tolyenediisocyanate, 2,6-tolyenediisocyanate, and 1,3-xylenediisocyanate 1,4-xylenediisocyanate, 1,5-naphthalenediisocyanate, 1,6-hexanediisocyanate, isophorone di Isocyanates (isophoronediisocyanate) and mixtures thereof.

(iii) (meth) acrylate with hydroxy

Hydroxy-containing (meth) acrylates include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxy propyl methacrylate (2- hydroxypropyl methacrylate), 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-serylbutyl acrylate Dimethacrylate (grycerin dimethacrylate), 2-hydroxy-3-acryloyloxy propyl methacrylate, 2-hydroxy 3-phenoxy propyl acrylate (2-hydroxy 3-phenoxy propyl acrylate), 2-acryloyloxy ethyl 2-hydroxy ethyl phthalate, pentaerythritol triacrylate (pentaerythrito triacrylate, trishydroxyethyl isocyanurate diacrylate, trishydroxyethyl isocyanurate dimethacrylate, pentaerythritol diacrylate monostearate monostearate), pentaerythritol dimethacrylate monostearate, and the like.

(iv) polycondensation catalysts

The polycondensation catalyst used in the present invention is a catalyst added in a small amount during the urethane reaction, and examples thereof include copper naphthenate, cobalt naphthenate, zinc naphthate, and n-dibutyl. N-dibutyltindilaurate, tristhylamine, 2-methyltriethylenediamide, and mixtures thereof.

(v) polymerization inhibitor

Polymerization inhibitors may be used conventionally, for example, butyl hydroxy toluene, hydroquinon, hydroquinonmonomethyl ether, para-benzoquinone, phenothiazine ) And mixtures thereof.

The photopolymerizable oligomer (a) can be synthesized from the respective components as follows:

The fluorine-based polyol copolymer (i) and the polymerization inhibitor (v) are placed in a reactor to remove moisture by, for example, 10 minutes to 1 hour at a pressure of 760 mmHg or less. The water-free mixture was maintained at 40 to 65 ° C., and then polyisocyanate (ii) was added to the mixture and stirred at 200 to 300 rpm, based on the total catalyst (iv) weight using the polycondensation catalyst (iv). It is added in an amount of 10 to 50% by weight. After the exotherm, the reaction was maintained at 50 to 85 ° C. for 2 to 3 hours. After completion of the reaction, (meth) acrylate (iii) having a hydroxy group was added, and after completion of exotherm, the temperature was raised to 60 to 90 ° C., and the remaining catalyst was added to react until the -NCO peak disappeared on the IR. ) Can be obtained.

According to the present invention, in order to lower the viscosity of the photopolymerizable oligomer, the above components may be, for example, an acrylate or methyl acrylate containing a hydrocarbon or fluorocarbon group having 4 to 12 carbon atoms (eg, perfluorooctylethyl acrylate, Perfluorooctylethyl methacrylate) or solvents such as ketones, ether acetates and carbonates.

According to the present invention, the photopolymerizable oligomer of the general formula (1) having a bifunctional group or more (meth) acrylate introduced into the sock end may improve the numerical aperture due to the low refractive index.

The photopolymerizable oligomer has a viscosity at 25 ° C. of 1,000 cPs to 10,000,000 cPs, preferably 4,000 cPs to 50,000 cPs (Brookfield DV III +) and a refractive index of 1.5 or less, preferably 1.32 to 1.43. Do.

The content of the photopolymerizable oligomer may be 20 to 90% by weight based on the total weight of the resin composition for optical fiber cladding.

(b) a photopolymerizable monomer having carbon fluoride and containing a (meth) acrylate group at its terminal;

The resin composition for optical fiber cladding according to the present invention is a photopolymerizable monomer having carbon fluoride and containing a (meth) acrylate group at its end. Monomers commonly used, for example, 2,2,2-trifluoroethyl acrylate (2,2,2-trifluoroethyl acrylate), 2,2,2-trifluoroethyl methacrylate (2,2,2-trifluoroethyl methacrylate), 2,2,3,3,3-pentafluoropropyl acrylic Rate (2,2,3,3,3-pentafluoropropyl acrylate), 2,2,3,3,3-pentafluoropropyl methacrylate (2,2,3,3,3-pentafluoropropyl methacrylate), 2- (Perfluorobutyl) ethyl acrylate (2- (perfluorobytyl) ethyl acrylate), 2- (perfluorobytyl) ethyl methacrylate, 3- (perfluorobutyl)- 2-hydroxypropyl acrylate (3- (perfluorobytyl) -2-hydroxypropyl acrylate), 3- (perfluorobutyl) -2-hydroxypropyl methacrylate (3- (perfluo robytyl) -2-hydroxypropyl methacrylate), 2- (perfluorohexyl) ethyl acrylate, 2- (perfluorohexyl) ethyl methacrylate (2- (perfluorohexyl) ethyl methacrylate ), 3-perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate (3-perfluorohexyl-2-hydroxypropyl acrylate) methacrylate), 2- (perfluorooctyl) ethyl acrylate, 2- (perfluorooctyl) ethyl methacrylate, 2-perfluorooctyl) ethyl methacrylate 3-perfluorooctyl-2-hydroxypropyl acrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2- ( Perfluorodecyl) ethyl acrylate (2- (perfluorodecyl) ethyl acrylate), 2- (perfluorodecyl) Ethyl methacrylate (2- (perfluorodecyl) ethyl methacrylate), 2- (perfluoro-3-methylbutyl) ethyl acrylate), 2- (perfluoro-3) -Methylbutyl) ethyl methacrylate (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 methacrylate (3-perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate), 2- (perfluoro-5 -Methylhexyl) ethyl acrylate (2- (perfluoro-5-methylhexyl) ethyl acrylate), 2- (perfluoro-5-methylhexyl) ethyl methacrylate (2- (perfluoro-5-methylhexyl) ethyl methacrylate) 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate (3-perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate), 3- (perfluoro-5-methylhexyl)- 2-hydroxypropyl metaa Relate (3-perfluoro-5-methylhexyl) -2-hydroxypropyl methacrylate), 2- (perfluoro-7-methyloctyl) ethyl acrylate), 2- (purple Fluoro-7-methyloctyl) ethyl methacrylate (2-perfluoro-7-methyloctyl) ethyl methacrylate, 3-perfluoro-7-methyloctyl) -2-hydroxypropyl acrylate (3-perfluoro-7 -methyloctyl) -2-hydroxypropyl acrylate), 3-perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 1H, 1H, 3H-tetrafluoropropyl acrylate (1H, 1H, 3H-tetrafluoropropyl acrylate), 1H, 1H, 3H-tetrafluoropropyl methacrylate (1H, 1H, 3H-tetrafluoropropyl methacrylate), 1H, 1H, 5H-octa Fluoropentyl acrylate (1H, 1H, 5H-octafluoropentyl acrylate), 1H, 1H, 5H-octafluoropentyl methacrylate (1H, 1H, 5H-octafluoropentyl methacrylate), 1H, 1H, 7H-dodecafluoro Methyl acrylate (1H, 1H, 7H-dodecafluoroheptyl acrylate), 1H, 1H, 7H-dodecafluoroheptyl methacrylate (1H, 1H, 7H-dodecafluoroheptyl methacrylate), 1H, 1H, 9H-hexadecafluorononyl Acrylate (1H, 1H, 9H-hexadecafluorononyl acrylate), 1H, 1H, 9H-hexadecafluorononyl methacrylate (1H, 1H, 9H-hexadecafluorononyl methacrylate), 1H-1- (trifluoromethyl) trifluoro Rhothyl acrylate (1H-1- (trifluoromethyl) trifluoroethyl acrylate), 1H-1- (trifluoromethyl) trifluorodecyl methacrylate (1H-1- (trifluoromethyl) trifluoroethyl methacrylate), 1H, 1H, 3H Fluorine-based monomers such as hexafluorobutyl acrylate (1H, 1H, 3H-hexafluorobutyl acrylate) and 1H, 1H, 3H-hexafluorobutyl methacrylate (1H, 1H, 3H-hexafluorobutyl methacrylate). Can be.

(c) photopolymerizable monomers containing two or more polyfunctional (meth) acrylates

The resin composition for optical fiber cladding according to the present invention is a photopolymerizable monomer containing two or more polyfunctional (meth) acrylates. Monomers commonly used, for example, ethyleneglycol diacrylate, ethyleneglycol. Ethyleneglycol dimethacrylate, diethyleneglycol diacrylate, ethyleneglycol dimethacrylate, triethyleneglycol diacrylate, Triethyleneglycol dimethacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, polyethylene glycol molecular weight 200 diacrylate ( PEG (polyehtyleneglycol) 200 diacrylate ), Polyethylene glycol molecular weight 200 dimethacrylate (PEG (polyehtyleneglycol) 200 dimethacrylate), polyethylene glycol molecular weight 400 diacrylate (PEG (polyehtyleneglycol) 400 diacrylate), polyethylene glycol molecular weight 400 dimethacrylate ( Poly (ethylene glycol) 600 dimethacrylate (PEG), polyethylene glycol molecular weight 600 diacrylate (PEG (polyehtylene glycol) 600 diacrylate, polyethylene glycol molecular weight 600 dimethacrylate (PEG) 1000 diacrylate (PEG (polyehtyleneglycol) 1000 diacrylate), polyethylene glycol molecular weight 1000 dimethacrylate (PEG (polyehtyleneglycol) 1000 dimethacrylate), polypropylene glycol molecular weight 400 diacrylate (PPG (polypropyleneglycol) 400 diacrylate) Polypropylene glycol molecular weight 400 dimethacrylate (PPG (pol ypropyleneglycol) 400 dimethacrylate), 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butane Diol diacrylate (1,4-butanediol diacrylate), 1,4-butanediol dimethacrylate (1,4-butanediol dimethacrylate), 1,6-hexanediol diacrylate (1,6-hexanediol diacrylate), 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol diacrylate 1,9-nonanediol dimethacrylate, 1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate , Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate acrylate), polytetramethyleneglycol diacrylate, polytetramethyleneglycol dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol Tetramethacrylate (pentaerythritol tetramethacrylate), dipentaerythritol hexaacrylate (dipentaerythritol hexamethaacrylate), dipentaerythritol hexamethaacrylate, glycerin diacrylate, glycerin dimethacrylate (glycerin dimethacrylate), trimethylopropane benzoate acrylate, trimethylopropane benzoate methacrylate, dimethylol tricyclodecane diacrylate hylol tricyclo decane diacrylate, dimethylol tricyclo decane dimethacrylate, 2,2-bis (4- (acryloxyethoxy) phenyl) cropane (2,2-bis (4- acryloxyethoxy) phenyl) propane), 2,2-bis (4- (methacryloxyethoxy) phenyl) cropane (2,2-bis (4-methacryloxyethoxy) phenyl) propane), 2,2-bis (4- (Acryloxydiethoxy) phenyl) cropane (2,2-bis (4-acryloxydiethoxy) phenyl) propane), 2,2-bis (4- (methacryloxydiethoxy) phenyl) cropane (2, 2-bis (4-methacryloxydiethoxy) phenyl) propane), 2,2-bis (4- (acryloxypolyethoxy) phenyl) cropane (2,2-bis (4-acryloxypolyethoxy) phenyl) propane), 2, 2-bis (4- (methacryloxypolyethoxy) phenyl) propane (2,2-bis (4-methacryloxypolyethoxy) phenyl) propane), trishydroxyethyl isocyanurate triacrylate, Trishydroxyethyl iso Trishydroxyethyl isocyanurate trimethacrylate, ring-opened caprolactone dipentaerythritol hexaacrylate (hexaacrylate of caprolactone modified dipentaerythritol), ring-opened caprolactone dipentaerythritol hexamethacrylate (hexamethacrylate of caprolactone modified dipentaerythritol, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated bisphenol A diacrylate (2) ethoxylated (2) bisphenol A diacrylate, ethoxylated (2) bisphenol A dimethacrylate, (2) bisphenol A dimethacrylate, ethoxylated (3) bisphenol A diacrylate (3) bisphenol A diacrylate), ethoxylated (3) bisphenol A Ethoxylated (3) bisphenol A dimethacrylate, ethoxylated (4) bisphenol A diacrylate, ethoxylated (4) bisphenol A diacrylate, ethoxylated (4) bisphenol A dimethacrylate ( ethoxylated (4) bisphenol A dimethacrylate, ethoxylated (8) bisphenol A diacrylate, ethoxylated (8) bisphenol A diacrylate, ethoxylated (8) bisphenol A dimethacrylate A dimethacrylate), ethoxylated (10) bisphenol A diacrylate, ethoxylated (10) bisphenol A dimethacrylate, ethoxylated (10) bisphenol A dimethacrylate Ethoxylated (30) bisphenol A diacrylate, ethoxylated (30) bisphenol a dimethacrylate (30) bisphenol A dimethacrylate).

(d) photoinitiators

Photoinitiators used in the present invention are conventional materials, such as commercially available Irgacure 184 (1-hydroxy cyclohexyl phenyl ketone) from Ciba Geigy, divalent Cure 1173 (2-hydroxy 2-methyl 1-phenyl 1-propanone), Darocur (MBF) (methylbenzoyl formate ), agacure 752 (oxy phenyl acetic acid 2- (2-oxo 2-phenyl acetoxy ethoxy) ethyl ester) Oxy phenyl acetic 2- (2-hydroxy ethoxy) ethyl ester), Igacure 651 (alpha, alpha-dimethoxy alpha-phenylacetophenone ( alpha, alpha-dimethoxy alpha-phenylacetophenone)), Igacure 369 (2-benzyl 2 (dimethylamino) 1- (4- (4-morpholinyl) phenyl) 1- Tanone (2-benzyl 2- (dimethylamino) 1- (4- (4-morpholinyl) phenyl) 1-butanone)), Igacure 907 (2-methyl 1- (4- (methylthio) phenyl) 2- ( 4-morpholinolinyl) 1-propanone (2-methyl 1- (4-methylthio) phenyl0 2- (4-morpholinyl) 1-propanone)), Darocure Tipio (TPO) (diphenyl (2,4 , 6-trimethylbenzoyl) phosphine oxide (Diphenyl (2,4,6 trimethylbenzoyl) phosphine oxide), Igacure 810 (vhtmvls oxide, phenyl bis (2,4,6 trimethyl benzoyl) (phosphine oxide, phenyl bis (2 , 4,6 trimethyl benzoyl)), Igacure 784 (bis (ita 5-2,4-cyclopentadien 1-yl) bis (2,6-difluoro 3- (1H-pyrrole 1-yl) Phenyl) titanium (bis (eta 5-2,4-cyclopentadien 1-yl) bis (2,6-difluoro 3- (1H-pyrrol 1-yl) phenyl) titanium), Igacure 250 (idodium, (4 -Methylphenyl) (4- (2-methylpropyl) phenyl)-, hexafluoro phosphate (1-) (iodonium, (4-methylphenyl) (4- (2-methylpropyl) phenyl)-, hexafluorophosphate (1-)) , Darocure BP ( BP) (benzophenone), Darocure CGI # 1800 (bisacyl phosphine oxide) and CGI # 1700 (bisacylphosphine oxide and hydroxy ketone) One or more selected from the group consisting of can be used. The photoinitiator may include 0.1 to 10% by weight based on the total weight of the composition.

(e) polymerization inhibitors or antioxidants

In addition, the photopolymerizable resin composition of the present invention, in addition to the above-described components, in order to improve thermal and oxidative stability, storage stability, surface properties, flow characteristics and process characteristics, for example, leveling agent, slip agent or stabilizer, etc. It may include a conventional additive of, the leveling agent, such as DC-190 of Dow-Corning and 2100, 2200, 2300 of Tego, etc., the slip agent of DC-56, 57, stabilizer May be used a third amine such as diethylethanolamine and trihexylamine, hindered amine, organic phosphate, hindered phenol, mixtures thereof and the like. The additive may comprise 0.1 to 10% by weight relative to the total weight of the composition.

The method of manufacturing the photopolymerizable resin composition of the present invention is as follows.

A photopolymerizable oligomer (a), a photopolymerizable monomer (b) having a fluorocarbon and containing (meth) acrylate groups at its terminals, a photopolymerizable monomer (c) containing two or more polyfunctional (meth) acrylate groups, The photoinitiator (d) and the polymerization inhibitor and the antioxidant (e) are added to the reactor and reacted with stirring at a uniform speed of 1000 rpm or more using a dispersion impeller at a temperature of 15 to 50 ° C. and a humidity of 60% or less. If the reaction temperature is less than 15 ° C, the viscosity of the oligomer (a) rises, a process problem occurs, and if the temperature exceeds 50 ° C, the photoinitiator (d) forms a radical to cause a curing reaction. If the reaction humidity exceeds 60%, the resulting resin composition generates bubbles during the subsequent coating process, and a side reaction occurs in which unreacted substances react with moisture in the air, and the stirring speed is 1,000 rpm. If less than, the formulation may not be made well.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention, but the scope of the present invention is not limited thereto.

Manufacturing example

Preparation Example 1 to 4: Preparation of the photopolymerization oligomer (a)

According to the kind of fluorine-type polyol copolymer and the kind of (meth) acrylate which has polyisocyanate and hydroxy, it can synthesize | combine as follows.

Preparation Example 1

669 g of fluorolink D10 / H (Solvey Solexis) and 206 g of isophorone diisocyanate (IPDI) (fluorolink D10 / H: IPDI molar ratio = 1: 2) were added to a 1-L flask, and the temperature was raised to 70 ° C. Then 0.6 g of n-dibutyltinlaurylate (DBTL) are added. After the exotherm is completed, the reaction is maintained at 80 to 90 ° C until the NCO peak on the FT-IR is unchanged. 0.4 g of hydroquinone monomethyl ether (HQMME) was added thereto and maintained at 85 ° C., followed by dropwise addition of 124 g of 2-hydroxyethyl acrylate. After the exotherm is completed, the reaction is maintained at 80 to 90 ° C until the NCO peak on the FT-IR disappears.

Production Example 2

526 g of fluorolink D10 / H (Solvey Solexis) and 173 g of isophorone diisocyanate (IPDI) (fluorolink D10 / H: IPDI molar ratio = 1: 2) were charged to a 1 L flask, and the temperature was raised to 70 ° C. Then 0.6 g of n-dibutyltinlaurylate (DBTL) are added. After the exotherm is completed, the reaction is maintained at 80 to 90 ° C until the NCO peak on the FT-IR is unchanged. 100 g of perfluorooctylethyl acrylate fluoromonomer and 0.4 g of hydroquinone monomethyl ether (HQMME) were added thereto and maintained at 85 ° C., followed by 200 g of 2-hydroxy 3-acryloyl propyl methacrylate. Dropping After the exotherm is completed, the reaction is maintained at 80 to 90 ° C until the NCO peak on the FT-IR disappears.

Production Example 3

626 g of fluorolink E10 (Solvey Solexis) and 234 g of isophorone diisocyanate (IPDI) (fluorolink E10: IPDI molar ratio = 1: 2) were added to a 1 L flask, and the temperature was raised to 70 ° C, followed by n-die. 0.6 g of butyltinlaurylate (DBTL) are added. After the exotherm is completed, the reaction is maintained at 80 to 90 ° C until the NCO peak on the FT-IR is unchanged. 0.4 g of hydroquinone monomethyl ether (HQMME) was added thereto, maintained at 85 ° C., and 140 g of 2-hydroxyethyl acrylate was added dropwise thereto. After the exotherm is completed, the reaction is maintained at 80 to 90 ° C until the NCO peak on the FT-IR disappears.

Preparation Example 4

548 g of fluorolink D10 / H (Solvey Solexis) and 205 g of isophorone diisocyanate (IPDI) (fluorolink D10 / H: IPDI molar ratio = 1: 2) were charged to a 1-L flask, and the temperature was raised to 70 ° C. Then 0.6 g of n-dibutyltinlaurylate (DBTL) are added. After the exotherm is completed, the reaction is maintained at 80 to 90 ° C until the NCO peak on the FT-IR is unchanged. 0.4 g of hydroquinone monomethyl ether (HQMME) was added thereto and maintained at 85 ° C., and then 247 g of 2-hydroxy 3-acryloyl propyl methacrylate was added dropwise thereto. After the exotherm is completed, the reaction is maintained at 80 to 90 ° C until the NCO peak on the FT-IR disappears.

Comparative Examples 1 to 4: Preparation of the resin composition for optical fiber cladding according to the refractive index

Comparative Example 1

54% by weight of the oligomer prepared in Preparation Example 1, 35% by weight of perfluorooctylethyl methacrylate, 7% by weight of TMPTA (trimethylolpropane triacrylate), Irgacure (184) 2% by weight of Ciba Special Chemicals, 1% by weight of Darocur TPO, 0.5% by weight of Benzophenone and additives 3,5-di-tertiary-4-butylhydroxy toluene (3 , 5-di-tertiary-4-butylhydroxy toluene (BHT) was added to prepare a resin composition for ultraviolet curable optical fiber cladding.

Comparative Example 2

63% by weight of oligomer prepared in Preparation Example 3, 27% by weight of perfluorooctylethyl methacrylate, 6% by weight of TMPTA, 2% by weight of Irgacure # 184 (Ciba Special Chemicals) , 1% by weight of Darocur TPO, 0.5% by weight Benzophenone and additives 3,5-di-tertiary-4-butylhydroxy toluene (3,5-di-tertiary-4-butylhydroxy toluene; BHT) was added to prepare a resin composition for ultraviolet curable optical fiber cladding.

Comparative Example 3

72% by weight of oligomer prepared in Preparation Example 3, 3% by weight of TMPTA, 12% by weight of HDDA, PEG400DA (polyethylene glycol 400 diacrylate) 10% by weight, Irgacure (Irgacure) # 184 (Ciba Special Chemicals) 2% by weight, 1% by weight of Darocur TPO, 0.5% by weight of Benzophenone and 3,5-di-tertiary-4-butylhydroxy Toluene (3,5-di-tertiary-4-butylhydroxy toluene; BHT) 0.5% by weight is added to prepare a resin composition for ultraviolet curable optical fiber cladding.

Comparative Example 4

70 wt% oligomer prepared in Preparation Example 3, 4 wt% TMPTA, 8 wt% HDDA, 5 wt% ethoxylated 10 bisphenol A diacrylate, PEG400DA (polyethylene glycol molecular weight 400 9% by weight of diethyl (polyethylene glycol 400 diacrylate), 2% by weight of Irgacure # 184 (Ciba Special Chemicals), 1% by weight of Darocur TPO, Resin composition for ultraviolet curable optical fiber cladding by adding 0.5% by weight of Benzophenone and 0.5% by weight of 3,5-di-tertiary-4-butylhydroxy toluene (BHT) additive To prepare.

Examples 1 to 7: Preparation of the resin composition for optical fiber cladding according to the refractive index

Example 1

20 wt% of the oligomer prepared in Preparation Example 1, 41 wt% of the oligomer prepared in Preparation Example 2, 29.5 wt% of perfluorooctylethyl methacrylate, 5.5 wt% of TMPTA, Irgacure # 184 (Ciba Specialty) 2% by weight of Ciba Special Chemicals, 1% by weight of Darocur TPO, 0.5% by weight of Benzophenone, and additives 3,5-di-tertiary-4-butylhydroxy toluene (3, 0.5 wt% of 5-di-tertiary-4-butylhydroxy toluene (BHT) was added to prepare a resin composition for UV-curable optical fiber cladding.

Example 2

62% by weight of oligomer prepared in Preparation Example 2, 29% by weight of perfluorooctylethyl methacrylate, 5% by weight of TMPTA, 2% by weight of Irgacure # 184 (Ciba Special Chemicals) , 1% by weight of Darocur TPO, 0.5% by weight Benzophenone and additives 3,5-di-tertiary-4-butylhydroxy toluene (3,5-di-tertiary-4-butylhydroxy toluene; BHT) was added to prepare a resin composition for ultraviolet curable optical fiber cladding.

Example 3

66 weight% oligomer prepared in Preparation Example 2, 20 weight% perfluorooctylethyl methacrylate, 7 weight% TMPTA, HDDA (1,6-hexanediol diacrylate) 3% by weight, 2% by weight of Irgacure # 184 (Ciba Special Chemicals), 1% by weight of Darocur TPO, 0.5% by weight of Benzophenone and additives 3,5- 0.5 wt% of di-tertiary-4-butylhydroxy toluene (BHT) is added to prepare a resin composition for ultraviolet curable optical fiber cladding.

Example 4

60.5% by weight of the oligomer prepared in Preparation Example 4, 31.5% by weight of perfluorooctylethyl methacrylate, 4% by weight of TMPTA, 2% by weight of Irgacure # 184 (Ciba Special Chemicals) , 1% by weight of Darocur TPO, 0.5% by weight Benzophenone and additives 3,5-di-tertiary-4-butylhydroxy toluene (3,5-di-tertiary-4-butylhydroxy toluene BHT) is added to prepare a resin composition for ultraviolet curable optical fiber cladding.

Example 5

20% by weight of oligomer prepared in Preparation Example 1, 50% by weight of oligomer prepared in Preparation Example 2, 14% by weight of perfluorooctylethyl methacrylate, 9% by weight of TMPTA, 3% by weight of HDDA, Irgacure # 184 (Ciba Special Chemicals) 2% by weight, 1% by weight of Darocur TPO, 0.5% by weight Benzophenone and 3,5-di-tertiary-4-butylhydric 0.5 weight% of hydroxy toluene (3,5-di-tertiary-4-butylhydroxy toluene; BHT) is added, and the resin composition for ultraviolet curable optical fiber cladding is manufactured.

Example 6

15 wt% oligomer prepared in Preparation Example 1, 54 wt% oligomer prepared in Preparation Example 2, 12 wt% TMPTA, 10 wt% HDDA, ethoxylate 10 bisphenol A diacrylate (ethoxylated 10 bisphenol A diacrylate) 10 % By weight, 2% by weight of Irgacure # 184 (Ciba Special Chemicals), 1% by weight of Darocur TPO, 0.5% by weight of Benzophenone, and 3,5-die of additives 0.5 wt% of tertiary-4-butylhydroxy toluene (BHT) was added to prepare a resin composition for ultraviolet curable optical fiber cladding.

Example 7

15 wt% oligomer prepared in Preparation Example 1, 49 wt% oligomer prepared in Preparation Example 2, 11 wt% TMPTA, 11 wt% HDDA, ethoxylate 10 bisphenol A diacrylate (ethoxylated 10 bisphenol A diacrylate) 10 % By weight, 2% by weight of Irgacure # 184 (Ciba Special Chemicals), 1% by weight of Darocur TPO, 0.5% by weight of Benzophenone, and 3,5-die of additives 0.5 wt% of tertiary-4-butylhydroxy toluene (BHT) was added to prepare a resin composition for ultraviolet curable optical fiber cladding.

Test Method : Evaluation of Physical Properties of Resin Composition for Optical Fiber Cladding

a) refractive index

The refractive index at 589 nm is measured at 25 ° C. using an Abbe refractometer ATAGO 3T.

b) viscosity

Viscosity is measured in the range of 50-90% torque using spindle 31 using a Brookfield Viscometer (Brookfield DV III +).

c) refractive index after curing

After the silicon wafer is fixed on the spin coater, the resin composition is dropped and spin-coated at about 5000 rpm for 30 seconds to prepare a 10 μm thick specimen. The specimen was cured by irradiating a light quantity of 25 J / cm ² using 300 W D-bulb manufactured by Fusion Company. This specimen is fixed to the prism of Sairon's Prism Coupler SPA 4000, finds the contacts and matches them with a 852 nm laser light source, scans them by rotating them from -5 degrees to 5 degrees and measures the refractive index after curing. .

d) 2.5% secant modulus

Apply the composition prepared in the above example on a glass plate, and fix the bar coater to 7 mil thickness, and then push it to harden by irradiating the light amount of 2.5, 5, 25 J / cm ² using 600 W D-bulb of Fusion Corp. A film of thickness is produced. The film of the cured composition was separated from the glass plate, cut to 13 mm in width using a dedicated blade, and 2.5% secant modulus was measured using Instron's 4443 UTM.

Test Example 1

The refractive index and viscosity of the photopolymerizable oligomers prepared in Preparation Examples 1 to 4 were measured and shown in Table 1 below.

TABLE 1

Manufacturing 1 Manufacture 2 Manufacturing 3 Manufacturing 4 Refractive index (589 nm) 1.386 1.397 1.409 1.385 Viscosity (Measured Temperature) 50882 (40 degrees) 17295 (54 degrees) 18586 (54 degrees) 53437 (54 degrees) Organoleptic 2 4 2 4

As shown in Table 1, the refractive index and viscosity can be adjusted according to the type of fluorine-based polyol copolymer and the type of (meth) acrylate having polyisocyanate and hydroxy.

Test Example 2

Refractive index, viscosity and secant modulus according to the components of the photopolymerizable resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were measured, and are shown in Tables 2 and 3 below.

Table 2

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Refractive Index (589 nm) 1.389 1.405 1.432 1.441 Viscosity (25 degrees) 1381 8517 5551 4961 Cured Index (852 nm) 1.397 1.413 1.442 1.452 2.5% secant modulus (MPa) 285 294 352 412

TABLE 3

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Refractive Index (589 nm) 1.391 1.396 1.405 1.408 1.408 1.432 1.441 Viscosity (25 degrees) 4318 5559 5042 5287 6821 5429 6831 Cured Index (852 nm) 1.399 1.404 1.413 1.422 1.415 1.443 1.452 2.5% secant modulus (MPa) 365 415 519 571 528 758 807

As can be seen in Tables 2 to 3, Examples 1 to 7 compound of the present invention comprising a photopolymerizable oligomer of Formula 1 prepared in Preparation Examples 1, 2, 4 has a low refractive index from 1.391 to 1.441, Appropriate viscosity for fiber extraction from 4318 to 6821 cPs, and high 2.5% secant modulus from 360 to 807 MPa.

On the other hand, the resin compositions for optical fiber cladding of Comparative Examples 1 to 4, which include conventional photopolymerizable oligomers prepared in Preparation Examples 1 and 3, are adjustable in the same refractive index region and exhibit viscosity, but 2.5% sec in the same refractive index region. It can be seen that the modulus is significantly lower than the present invention.

Table 4

Light quantity (J / cm ² ) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 2.5 133 129 159 170 5 193 174 208 236 25 285 294 352 412

Table 5

Light quantity (J / cm ² ) Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 2.5 209 288 352 348 357 550 720 5 237 328 408 429 405 614 739 25 365 415 519 571 528 758 807

Table 6

Modulus ratio according to light quantity Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 2.5 / 25 47% 44% 45% 41% 5/25 68% 59% 59% 57%

TABLE 7

Modulus ratio according to light quantity Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 2.5 / 25 57% 69% 68% 61% 68% 73% 89% 5/25 65% 79% 79% 75% 77% 81% 92%

As can be seen in Tables 4 to 7, Examples 1 to 7 compounds of the present invention comprising a photopolymerizable oligomer of Formula 1 prepared in Preparation Examples 1, 2, 4 has a low of 2.5 to 5 J / cm ² Compared with modulus cured at light quantity and modulus cured at 25 J / cm ² light quantity, it showed a fast curing rate.

On the other hand, the resin compositions for optical fiber cladding of Comparative Examples 1 to 4, including the conventional photopolymerizable oligomers prepared in Preparation Examples 1 and 3, are cured at a low light amount of 2.5 to 5 J / cm ² , but the amount of light in the same refractive index region. It can be seen that the change in modulus according to the present invention is significantly lower than that of the present invention.

Claims (21)

A photopolymerized oligomer having the structure of formula (1). <Formula 1>

Where Each R ¹ is independently CH ₂ O or —CH ₂ (OCH ₂ CH ₂ ) _a O—, wherein a is an integer from 1 to 3, R ² is an aromatic or aliphatic hydrocarbon group having 6 to 20 carbon atoms, R ³ are each independently a meta (acrylate) group having 2 to 40 carbon atoms, n is (1) to (5), m is (2) to (6), where m = n + 1 p is (2)-(20) and p / q has a range of 0.8-2.5. The method of claim 1, The photopolymerizable oligomer is (i) a fluorinated polyol copolymer, (ii) polyisocyanate, (iii) a (meth) acrylate having a hydroxide group, (iv) a polycondensation catalyst and (v) a polymerization inhibitor. Photopolymerized oligomer, characterized in that synthesized from. The method of claim 2, The (meth) acrylate having a hydroxide group is a photopolymerization type characterized in that it is a mixture of a (meth) acrylate having a bifunctional or higher hydroxyl group and a (meth) acrylate having a hydroxide group other than the bifunctional group. Oligomers. delete The method of claim 2, The fluorine-based polyol copolymer is a photopolymerizable oligomer, characterized in that it has a repeating unit of -CF ₂ CF ₂ -or -CF ₂ CF ₂ O-. The method of claim 5, wherein the fluorine-based polyol copolymer, 1H, 1H, 9H-hexadecafluorononanol (1H, 1H, 9H-hexadecafluorononanol), hexafluoro-2-methylisopropanol, 1,1,1,3,3,3- Hexafluoro-2-propanol (1,1,1,3,3,3-hexafluoro-2-propanol), hexafluoro-2- (p-tolyl) isopropanol (hexafluoro-2- (p-tolyl) isopropanol ), 4,5,5,6,6,6-hexafluoro-4- (trimethyl) -1-hexanol (4,5,5,6,6,6-hexafluoro-4- (trimethyl)- 1-hexanol), 4,5,5,6,6,6-hexafluoro-4- (trifluoromethyl) -2-hexen-1-ol (4,5,5,6,6,6- hexafluoro-4- (trifluoromethyl) -2-hexene-1-ol), 3,3,4,4,5,5,6,6-octafluoro-1,6-hexanediol (3,3,4 , 4,5,5,6,6-octafluoro-1,6-hexanediol), 1H, 1H, 5H-octafluoro-1-pentanol (1H, 1H, 5H-octafluoro-1-pentanol), 1H, 1H-pentadecafluoro-1-octanol (1H, 1H-pentadecafluoro-1-octanol), 2,3,4,5,6-pentafluorobenzyl alcohol (2,3,4,5,6-pentafluorobenzyl alcohol), pentafluorobutanol-2, 4,4,5,5,5-pentafluoropentanol (4,4,5 alcohol) , 5,5-pentafluoropentanol), pentafluoropropionaldehyde hydrate, Z-Dol (Solvay Solexis), Z-Dol TX (Solva Solixis), Fluorolink ) D (Solvay Solix), Fluorolink D10 / H (Solvay Solix), Fluorolink D10 (Solvay Solix), Fluorolink T, Fluorolink T10 (Solvay Solix), Fluorolink Lolink E (Solvay Solix), Fluorolink E10 / H (Solvay Solix), Fluorolink E10 (Solvay Solix), Zonyl TA-L (Dupont), Zonyl Photopolymerizable oligomer, characterized in that any one or a mixture of two or more selected from the group consisting of TA-N (Dupont). The method of claim 2, wherein the polyisocyanate is 2,4-tolyenediisocyanate, 2,6-tolyenediisocyanate, 1,3-xylenediisocyanate, 1, 4-xylene diisocyanate (1,4-xylenediisocyanate), 1,5-naphthalened diisocyanate (1,5-naphthalenediisocyanate), 1,6-hexane diisocyanate (1,6-hexanediisocyanate), isophoronediisocyanate Photopolymerized oligomer, characterized in that any one or a mixture of two or more selected from the group consisting of. The method of claim 1, The photopolymerization oligomer further comprises a diluent for lowering the viscosity of the photopolymerization oligomer. The method of claim 8, wherein the diluent, Photopolymerizable oligomer, characterized in that the acrylate or methyl acrylate monomer containing a hydrocarbon or fluorocarbon group having 4 to 12 carbon atoms.  The method of claim 8, wherein the diluent, A photopolymerizable oligomer, characterized in that the solvent is selected from ketones, ether acetates and carbonates. The method of claim 1, The photopolymerizable oligomer, characterized in that the viscosity at 25 ℃ is 1,000 cPs to 10,000,000 cPs. The method of claim 1, A photopolymer type oligomer having a refractive index of 1.38 to 1.46. The photopolymerizable resin composition containing the photopolymerization oligomer of any one of Claims 1-3 or 5-12. delete The method of claim 13, The photopolymerizable resin composition has a 2.5% secant modulus of 50 to 1000 MPa. The method of claim 13, Additives are further added in a ratio of 0.1 to 10% by weight relative to the total resin composition weight, The additive is a photopolymerizable resin composition, characterized in that any one or a mixture of two or more selected from leveling agents, defoamers, stabilizers or antioxidants. delete The optical fiber which has a cladding part formed using the photopolymerizable resin composition of Claim 13. delete delete delete