KR101003002B1 - Resin Composition for Optical Fiber Cladding - Google Patents

Abstract

The present invention provides a photopolymerizable oligomer containing a (meth) acrylate group at a sock end, a photopolymerizable monomer type A containing a (meth) acrylate group at a sock end, and a (meth) acrylate group at one end thereof. It relates to a resin composition for optical fiber cladding comprising at least one photopolymerizable monomer selected from photopolymerizable monomer type B to contain and (c) a photoinitiator. The resin composition for optical fiber cladding according to the present invention can realize a high numerical aperture due to a low refractive index, exhibit high strength after UV curing, and thus can be usefully used as a cladding material of glass or plastic optical fiber due to strong external impact.

Description

Resin composition for optical fiber cladding {RESIN COMPOSITION FOR CLADDING LAYER OF OPTICAL FIBER}

The present invention relates to a resin composition for optical fiber cladding having a low refractive index, which enables high numerical aperture and exhibits high strength after UV curing.

Recently, the coating method using UV-curable fluorine resin has 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.

The optical fiber has a slight difference 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 photocurable 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 photocurable 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 may exhibit a high refractive index by exhibiting a low refractive index, but has a disadvantage in that it is difficult to apply due to a low strength, which may damage even a small external impact.

Accordingly, an object of the present invention is to provide a resin composition for optical fiber cladding, which is possible to implement a high numerical aperture because the refractive index is low, and exhibits high strength after UV curing, and is also resistant to external impact.

According to the above object, in the present invention, (a) a photopolymerizable oligomer having a structure of formula (1), (b) a photopolymerizable monomer type A having a structure of formula (2) and a photopolymerizable monomer type B having a structure of formula (3) It provides a resin composition for optical fiber cladding comprising at least one photopolymerizable monomer selected from (c) and a photoinitiator:

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 10 carbon atoms,

R ⁴ is a hydrocarbon group or fluorocarbon group having 2 to 20 carbon atoms,
l, m, n, p, and q are the number of iterations for each repeating unit,

l is 1 to 6,

m is 1 to 5,

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

p is 2 to 20,

The ratio of p to q (p / q) ranges from 0.8 to 2.5.

The resin composition for optical fiber cladding according to the present invention can realize a high numerical aperture due to a low refractive index, and exhibit high strength after UV curing, and thus can be usefully used as a cladding material of glass or plastic optical fiber because it is resistant to external impact.

The resin composition for optical fiber cladding of the present invention comprises (a) a photopolymerizable oligomer of formula (1) having a bifunctional or more (meth) acrylate group introduced therein and (b) a bifunctional or more (meth) acrylate group introduced into the sock end. And at least one photopolymerizable monomer selected from photopolymerizable monomer type A of formula (2) and photopolymerizable monomer type (B) having a structure of formula (3) having a bifunctional or higher (meth) acrylate group introduced at one end thereof.

In Chemical Formulas 1 to 3, preferably R ¹ is -CH ₂ (OCH ₂ CH ₂ ) _a O-, wherein a is an integer of 1 to 3, R ⁴ is a hydrocarbon or carbonization of 2 to 10 carbon atoms It is a fluorine group.

Hereinafter, each component is demonstrated.

(a) photopolymerization oligomer

The photopolymerizable oligomers (a) used in the present invention are (i) fluorine-based polyol copolymers, (ii) polyisocyanates, (iii) (meth) acrylates having isocyanate groups, (iv) polycondensation catalysts and (v) ) Was synthesized as a polymerization inhibitor.

According to the invention, the molar ratio of (i) fluorine-based polyol copolymer: (ii) polyisocyanate is from 1: 0.3 to 1: 2.2, and (i) fluorine-based polyol copolymer: (iii) of (meth) acrylate having an isocyanate group. The molar ratio is preferably 0.3: 1 to 10: 1. In addition, the (iv) polycondensation catalyst and the (v) polymerization inhibitor can be used in an effective amount, for example, it is preferable to use in an amount of 0.01 to 1 parts by weight based on 100 parts by weight of the fluorine-based polyol copolymer.

The components constituting the photopolymerizable oligomer (a) 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-methyl-isopropanol, 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 Rho-4- (trimethyl) -1-hexanol (4,5,5,6,6,6-hexa fluoro-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), pentafluoro-2-butanol, 4,4,5,5,5-pentafluoropentanol (4,4 , 5,5,5-pentafluoropentanol), pentafluoropropionaldehyde hydrate and mixtures thereof, and commercially obtainable Z-Dol (Solvay Solexis), Z-Dol TX (Solva Solixis), Fluorolink D (Solva Solixis), Fluorolink D10 / H (Solva Solixis), Fluorolink D10 (Solva Solixis), Fluoro Fluorolink T, fluorolink T10 (Solvay Solix), fluorolink E (Solvay Solix), fluorolink E10 / H (Solvay Solix), fluorolink E10 (Solvay Solix), 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) acrylates having isocyanate groups

(Meth) acrylates having isocyanate groups are 2-isocyanatoethyl methacrylate (2-isocyanatoethyl methacrylate), 2- (2-isocyanatoethoxy) ethyl methacrylate (2- (2-isocyanatoethyoxy) ethyl methacrylate), 2-isocyanatoethyl acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and mixtures thereof Commercially obtainable are Karenz MOI (Showa Denko), Karenz MOI-EG (Showa Denko), Karenz AOI (Showa Denko) and Karenz BEI (Showa Denko). Cosa).

(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, hydroquinone, 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 an isocyanate group is added, and after completion of exotherm, the temperature is raised to 60 to 90 ° C., and the remaining catalyst is added to react until the -NCO peak disappears 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 acrylate or methyl acrylate containing a hydrocarbon or fluorocarbon group having 4 to 12 carbon atoms (for example, perfluorooctylethyl acrylate, purple Dilution using a monomer of urooctylethyl methacrylate) or a solvent such as ketone, ether acetate and carbonate.

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 1.4 or less, preferably 1.32 to 1.39. 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) photopolymerizable monomer

The photopolymerizable monomer used in the present invention may use at least one selected from photopolymerizable monomer type A of formula 2 and photopolymerizable monomer type B of formula 3, which may improve secant modulus.

Photopolymerization monomer type A

The photopolymerizable monomer type A used in the present invention may be synthesized from (i) a fluorine-based polyol copolymer, (ii) an (meth) acrylate having an isocyanate group, (iii) a polycondensation catalyst and (iv) a polymerization inhibitor, The synthesis method may be prepared by the same method as the photopolymerizable oligomer (a) except that no polyisocyanate is used.

At this time, the molar ratio of (i) fluorine-based polyol copolymer: (ii) (meth) acrylate having an isocyanate group is preferably 1: 0.1 to 5, preferably 1: 0.5 to 3.5. The amount of the (iii) polycondensation catalyst and (iv) polymerization inhibitor is preferably 0.01 to 1 part by weight based on 100 parts by weight of the fluorine-based polyol copolymer.

The photopolymerizable monomer type A has a viscosity at 25 ° C. of 100 cPs to 10,000 cPs (Brookfield DV III +) and a refractive index of 1.43 or less, preferably 1.31 to 1.42.

Photopolymerization monomer type B

The photopolymerizable monomer type B used in the present invention can be synthesized from (i) fluorine alcohol, (ii) (meth) acrylate with isocyanate group, (iii) polycondensation catalyst and (iv) polymerization inhibitor.

At this time, the molar ratio of (i) fluorine alcohol: (ii) (meth) acrylate having an isocyanate group is preferably 1: 0.1 to 5, preferably 1: 0.1 to 2.5. The amount of the (iii) polycondensation catalyst and (iv) polymerization inhibitor is preferably 0.01 to 1 part by weight based on 100 parts by weight of the fluorine alcohol.

Fluorinated alcohols include 2,2,2-trifluoro ethanol, 2-fluoro ethanol, 1,1,1,3,3,3-hexafluoro Rho-2-propanol (1,1,1,3,3,3-hexafluoro-2-propanol), 2,2,3,3,3-pentafluoro-1-propanol (2,2,3,3 , 3-pentafluoro-1-propanol), 2,2,3,3, -tetrafluoro-1-propanol (2,2,3,3-tetrafluoro-1-propanol), 1,1,1-trifluoro Ro-2-propanol (1,1,1-trifluoro-2-propanol), 1,3-difluoro-2-propanol, perfluoro-tert-butyl Perfluoro-tert-butyl alcohol, 1,1,1,3,3,4,4,4-octafluoro-2-butanol (1,1,1,3,3,4,4,4- octafluoro-2-butanol), 2,2,3,3,4,4,4-heptafluoro-1-butanol (2,2,3,3,4,4,4-heptafluoro-1-butanol), 2,2,3,4,4,4-hexafluoro-1-butanol (2,2,3,4,4,4-hexafluoro-1-butanol), 1,1,1,3,3,3 Hexafluoro-2-methyl-propanol (1,1,1,3,3,3-hexafluoro-2-methyl-propanol), 2-trifluoromethyl-2-propanol ), 2,2,3, 3,4,4,5,5, -octafluoro-1-pentanol (2,2,3,3,4,4,5,5-octafluoro-1-pentanol), 4,4,5,5 , 5-pentafluoro-1-pentanol (4,4,5,5,5-pentafluoro-1-pentanol), pentafluorophenol, 2,3,5,6-tetrafluorophenol ( 2,3,5,6-tetrafluorophenol), 2,3,4-trifluorophenol, 2,3,5-trifluorophenol , 2,3,6-trifluorophenol (2,3,6-trifluorophenol), 2,3-difluorophenol (2,3-difluorophenol), 2,4-difluorophenol (2,4- difluorophenol), 2,5-difluorophenol, 2,6-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol , 3,5-difluorophenol, 3-fluorophenol, 3-fluorophenol, 4-fluorophenol, 3,3,4,4,5,5,6,6,6-nonnafluoro-1-hexanol (3,3,4,4,5,5,6,6,6-nonafluoro-1-hexanol ), 2-fluoro-3- (trifluoromethyl) phenol (2- fluoro-3- (trifluoromethyl) phenol), 2-fluoro-5- (trifluoromethyl) phenol, 2,3,4,5-tetrafluorobenzyl alcohol (2,3,4,5-tetrafluorobenzyl alcohol), 2,3,6-trifluorobenzyl alcohol (2,3,6-trifluorobenzyl alcohol), 2,4,5-trifluorobenzyl alcohol (2,4 , 5-trifluorobenzyl alcohol), 3,4,5-trifluorobenzyl alcohol (3,4,5-trifluorobenzyl alcohol), α, α, α-trifluoro-o-cresol (α, α, α-trifluoro -o-cresol), α, α, α-trifluoro-m-cresol (α, α, α-trifluoro-m-cresol), α, α, α-trifluoro-p-cresol (α, α , α-trifluoro-p-cresol), 3- (trifluoromethoxy) phenol, 4- (trifluoromethoxy) phenol, 4,4, 5,5,6,6,7,7,7-nonafluoro-1-heptanol (4,4,5,5,6,6,7,7,7-nonafluoro-1-heptanol), 2, 2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol (2,2,3,3,4,4, 5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octa nol), 3,5-bis (trifluoromethyl) phenol (3,5-bis (trifluoromethyl) phenol), 2-fluoro-3- (trifluoromethyl) benzyl alcohol (2-fluoro-3- ( trifluoromethyl) benzyl alcohol), 2-fluoro-6- (trifluoromethyl) benzyl alcohol (2-fluoro-6- (trifluoromethyl) benzyl alcohol), 2,2,3,3,4,4,5,5 , 6,6,7,7,8,8,9,9,9-hepta-decafluoro-1-nonanol (2,2,3,3,4,4,5,5,6,6, 7,7,8,8,9,9,9-hepta-decafluoro-1-nonanol) and 2,2,3,3,4,4,5,5,6,6,7,7,8,8 , 9,9-hexadecafluoro-1-nonanol (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1 -nonanol).

The photopolymerizable monomer type B can be synthesized from the respective components as follows:

After the fluorine-based alcohol is put into the reactor, water is removed by reducing the pressure to about 760 mmHg or less for about 10 minutes to 1 hour. The water-free mixture was maintained at 40 to 65 ° C., and then (meth) acrylate having an isocyanate group was added to the mixture, followed by stirring at 200 to 300 rpm, and 10 to 50 wt% based on the total catalyst using the polycondensation catalyst. Add in the amount of. After the exotherm is terminated, the remaining catalyst is added and the remaining catalyst is added to react until the -NCO peak disappears on the IR, thereby obtaining a photopolymerizable monomer type B type.

The photopolymerizable monomer type B preferably has a viscosity at 25 ° C. of 100 cPs to 10,000 cPs (Brookfield DV III +) and a refractive index of 1.45 or less, preferably 1.40 to 1.44.

The resin composition for optical fiber cladding of the present invention may include 1 to 79% by weight of one or more photopolymerizable monomers selected from photopolymerizable monomer type A or B with respect to the total weight of the resin composition for optical fiber cladding.

In addition, the resin composition for optical fiber cladding according to the present invention is a monomer commonly used in addition to the photopolymerizable monomer type A or B, for example, 2,2,2-trifluoroethyl acrylate (2,2,2-trifluoroethyl acrylate), 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate (2,2,3, 3,3-pentafluoropropyl acrylate), 2,2,3,3,3-pentafluoropropyl methacrylate (2,2,3,3,3-pentafluoropropyl methacrylate), 2- (perfluorobutyl) ethyl acrylic 2- (perfluorobutyl) ethyl acrylate), 2- (perfluorobutyl) ethyl methacrylate, 2- (perfluorobutyl) -2-hydroxypropyl acrylate ( 3- (perfluorobutyl) -2-hydroxypropyl acrylate), 3- (perfluorobutyl) -2-hydroxypropyl methacrylate (3- (perfluorobutyl) -2-hydroxypropyl methacrylate), 2- (perflu Orohexyl) ethyl acrylate (2- (perfluorohexyl) ethyl acrylate), 2- (perfluorohexyl) ethyl methacrylate), 3-perfluorohexyl-2-hydroxypropyl 3-perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2- (perfluorooctyl) ethyl acrylate (2- (perfluorooctyl) ethyl acrylate), 2- (perfluorooctyl) ethyl methacrylate), 3-perfluorooctyl-2-hydroxypropyl acrylate (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 metha crylate), 2- (perfluoro-3-methylbutyl) ethyl acrylate (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), 3- (perfluoro -5-methylhexyl) -2-hydroxypropyl acrylate (3-perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl methacryl (3-perfluoro-5-methylhexyl) -2-hydroxypropyl methacryl ate), 2- (perfluoro-7-methyloctyl) ethyl acrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate (2- perfluoro-7-methyloctyl) ethyl methacrylate), 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl acrylate, 3-perfluoro 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-octafluoropentyl acrylate (1H, 1H, 5H-octafluoropentyl acrylate ), 1H, 1H, 5H-octafluoropentyl methacrylate (1H, 1H, 5H-octafluoropentyl methacrylate), 1H, 1H, 7H-dodecafluoroheptyl acrylate (1H, 1H, 7H-dodecafluoroheptyl acrylate), 1H, 1H, 7H- Decafluoroheptyl methacrylate (1H, 1H, 7H-dodecafluoroheptyl methacrylate), 1H, 1H, 9H-hexadecafluorononyl acrylate (1H, 1H, 9H-hexadecafluorononyl acrylate), 1H, 1H, 9H-hexadeca Fluorononyl methacrylate (1H, 1H, 9H-hexadecafluorononyl methacrylate), 1H-1- (trifluoromethyl) trifluoroethyl acrylate (1H-1- (trifluoromethyl) trifluoroethyl acrylate), 1H-1- ( Trifluoromethyl) trifluoroethyl methacrylate (1H-1- (trifluoromethyl) trifluoroethyl methacrylate), 1H, 1H, 3H-hexafluorobutyl acrylate (1H, 1H, 3H-hexafluorobutyl acrylate), 1H, 1H And a fluorine monomer such as 3H-hexafluorobutyl methacrylate (1H, 1H, 3H-hexafluorobutyl methacrylate).

(c) photoinitiators

Photoinitiators used in the present invention are conventional materials, such as commercially available Irgacure # 184 (hydroxycyclohexylphenylketone) from Ciba Geigy, Igacure # 907 ( 2-methyl-1 [4- (methylthio) phenyl] -2-morpholino-propan-1-one (2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1- one)), Igacure # 500 (hydroxy-ketones and benzophenone), Igacure # 651 (benzyldimethyl-ketone), Darocure # 1173 (2-hydric) 2-hydroxy-2-methyl-1-phenyl-propan-1-one, Darocure CGI # 1800 (bisacyl phosphine oxide)) and CGI # 1700 (bisacylphosphine oxide and benzophenone) may be used. The photoinitiator may include 0.1 to 10% by weight based on the total weight of the composition.

(d) other additives

In addition, the resin composition for optical fiber cladding of the present invention, in addition to the components described above, in order to improve thermal and oxidative stability, storage stability, surface characteristics, flow characteristics and process characteristics, for example, leveling agent, slip agent, stabilizer Or it may include a conventional additives such as antioxidants, the leveling agent is DC-190 of Dow-Corning and 2100, 2200, 2300, such as Tego, D-Corning DC-56, 57, as stabilizers, tertiary amines such as diethylethanolamine and trihexylamine, hindered amines, organic phosphates, hindered phenols, mixtures thereof, and as oxidant control agents, for example, 3,5-di-tertiary- 4-butylhydroxy toluene (3,5-di-tertiary-4-butylhydroxy toluene; BHT) and the like can be used. The additive may comprise 0.1 to 10% by weight relative to the total weight of the composition.

The method for producing the resin composition for glass or plastic optical fiber cladding of the present invention is as follows:

A photopolymerized oligomer (a), a photopolymerized monomer (b), a photoinitiator (c) and other additives (d) were added to the reactor and 1000 rpm using a dispersion impeller at a temperature of 15 to 50 ° C. and a humidity of 60% or less. The reaction is carried out while stirring at the above uniform speed. 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 (c) forms a radical to cause a curing reaction. When the reaction humidity exceeds 60%, the resulting resin composition generates bubbles during the subsequent coating process, and side reactions in which unreacted substances react with moisture in the air occur, and the stirring speed is less than 1,000 rpm. It may not be well blended.

The resin composition prepared as described above can realize a high numerical aperture due to a low refractive index, exhibit high strength after UV curing, and thus can be usefully used as a material of the cladding portion of glass or plastic optical fiber due to strong external impact. In particular, transmission of radio waves, microwaves, infrared rays, visible light, ultraviolet light, X-rays or gamma rays; Illumination or display from light sources, including natural and artificial light sources; And high power laser transmission, medical field, optical device or optical sensor field.

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.

Example

Preparation Examples 1 to 4: Preparation of Photopolymerization Oligomer (a)

According to the molar ratio of a fluorine-type polyol copolymer and polyisocyanate, it can synthesize | combine as follows.

Preparation Example 1

260 g of fluorolink E (Solvey Solexis) was added to a 1 L flask, and the temperature was raised to 60 ° C., and 0.1 g of n-dibutyltinlaurylate (DBTL) was added, and 13 g of isophorone diisocyanate (IPDI) Rolink E: IPDI molar ratio = 2: 1) was dripped. After the exotherm, the reaction was maintained at 80 to 90 ° C until the NCO peak on the FT-IR disappeared. 100 g of perfluorooctylethyl acrylate fluoromonomer and 0.1 g of butyl hydroxy toluene were added thereto and maintained at 85 ° C., and then 28 g of 1,1-bis (acryloyloxymethyl) ethyl isocyanate was added dropwise thereto. When the exotherm was completed, the reaction was maintained at 80 to 90 ° C until the NCO peak on the FT-IR disappeared.

Production Example 2

The same procedure as in Preparation Example 1 was conducted except that the molar ratio of Fluorolink E: IPDI was 3: 2.

Preparation Example 2-1

The molar ratio of Fluorolink E to IPDI was 3: 2, and perfluorooctylethyl acrylate was used in the same manner as in Preparation Example 1, except that perfluorooctylethyl acrylate was used instead of perfluorooctylethyl acrylate fluoromonomer.

Production Example 3

The same procedure as in Preparation Example 1 was conducted except that the molar ratio of Fluorolink E: IPDI was 4: 3.

Preparation Example 4

The same procedure as in Preparation Example 1 was carried out except that the molar ratio of Fluorolink E: IPDI was 5: 4.

Preparation Example 6 Preparation of Photopolymerizable Monomer Type B

92 g of 1H, 1H, 5H-octafluoro-1-pentanol was added to a 1 L flask, and the temperature was raised to 60 ° C., followed by addition of 0.05 g of n-dibutyltinlaurylate (DBTL), followed by 1,1-bis ( 109 g of acryloyloxymethyl) ethyl isocyanate was added dropwise. After the exotherm was completed, 0.05 g of butyl hydroxy toluene was added and maintained at 60 to 80 ° C until the NCO peak on the FT-IR disappeared.

Preparation Example 5 Preparation of Photopolymerizable Monomer Type A

150 g of fluorolink D10 / H (Solvey Solexis) was added to a 1 L flask, and the temperature was raised to 60 ° C., and 0.1 g of n-dibutyltin laurylate (DBTL) was added, followed by 1,1-bis (acrylo) 51 g of oxymethyl) ethyl isocyanate was added dropwise. After the exotherm was completed, 0.1 g of butyl hydroxy toluene was added and maintained at 80 to 90 ° C until the NCO peak on the FT-IR disappeared.

Examples 1 to 6: Preparation of Resin Composition for Optical Fiber Cladding

Example 1

72 wt% of the oligomer prepared in Preparation Example 2, 10 wt% of the monomer type A prepared in Preparation Example 5, 12.8 wt% of perfluorooctylethyl methacrylate, 3 wt% of TMPTA, and Irgacure # 184 ( 2 wt% Ciba Special Chemicals and 0.2 wt% additive (3,5-di-tertiary-4-butylhydroxy toluene (BHT) Was added to prepare a resin composition for ultraviolet curable optical fiber cladding.

Example 2

Resin composition for UV-curable optical fiber cladding was added by adding 72% by weight of the oligomer prepared in Preparation Example 2, 25.8% by weight of monomer type A prepared in Preparation Example 5, 2% by weight of Igacure # 184 and 0.2% by weight of an additive (BHT). Was prepared.

Example 3

72 wt% oligomer prepared in Preparation Example 3, 22.8 wt% of monomer type A prepared in Preparation Example 5, 3 wt% of trimethylol propane triacrylate (TMPTA), 2 wt% of Igacure # 184, and additives (BHT) 0.2 wt% was added to prepare a resin composition for ultraviolet curable optical fiber cladding.

Example 4

72 wt% of the oligomer prepared in Preparation Example 3, 15.8 wt% of the monomer type A prepared in Preparation Example 5, 10 wt% of the monomer type B prepared in Preparation Example 6, 2 wt% of Igacure # 184, and the additive (BHT) 0.2 wt% was added to prepare a resin composition for ultraviolet curable optical fiber cladding.

Example 5

72 wt% of the oligomer prepared in Preparation Example 2-1, 19.8 wt% of the monomer type A prepared in Preparation Example 5, 6 wt% of the monomer type B prepared in Preparation Example 6, 2 wt% of Igacure # 184, and the additive ( BHT) was added 0.2% by weight to prepare a resin composition for ultraviolet curable optical fiber cladding.

Example 6

76 wt% of the oligomer prepared in Preparation Example 2-1, 16.8 wt% of Monomer Type A prepared in Preparation Example 5, 5 wt% of Monomer Type B prepared in Preparation Example 6, 2 wt% of Igacure # 184, and the additive ( BHT) was added 0.2% by weight to prepare a resin composition for ultraviolet curable optical fiber cladding.

Comparative Example 1

72 wt% of the oligomer prepared in Preparation Example 1, 22.8 wt% of perfluorooctylethyl acrylate, 3 wt% of TMPTA, 2 wt% of Igacure # 184, and 0.2 wt% of an additive (BHT) were added to the ultraviolet curable optical fiber cladding. The resin composition for was prepared.

Comparative Example 2

72 wt% of the oligomer prepared in Preparation Example 2, 22.8 wt% of perfluorooctylethyl acrylate, 3 wt% of TMPTA, 2 wt% of Igacure # 184, and 0.2 wt% of an additive (BHT) were added to the ultraviolet curable optical fiber cladding. The resin composition for was prepared.

Comparative Example 3

72 wt% of the oligomer prepared in Preparation Example 3, 22.8 wt% of perfluorooctylethyl acrylate, 3 wt% of TMPTA, 2 wt% of Igacure # 184, and 0.2 wt% of an additive (BHT) were added to the ultraviolet curable optical fiber cladding. The resin composition for was prepared.

Comparative Example 4

72 wt% of the oligomer prepared in Preparation Example 4, 22.8 wt% of perfluorooctylethyl acrylate, 3 wt% of TMPTA, 2 wt% of Igacure # 184, and 0.2 wt% of an additive (BHT) were added to the ultraviolet curable optical fiber cladding. The resin composition for was prepared.

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

a) refractive index

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

b) viscosity

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

c) refractive index after curing

After fixing the silicon wafer on the spin coater, the resin composition was 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 Corporation. The specimen is fixed to the prism of Sairon's Prism Coupler SPA 4000, finds contacts and matches them with a 632.8, 852, and 1550 nm laser light source, scans and rotates from -5 degrees to 5 degrees, then cures. The refractive index was measured.

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 irradiate and harden by irradiating the light quantity of 25 J / cm ² using 600 W D-bulb of Fusion company to make a 100 μm thick film. Produced. The film of the cured composition was separated from the glass plate, cut to a width of 13 mm using a dedicated blade, and 2.5% secant modulus was measured using Instron 4443 UTM.

Test Example 1

The refractive indices and the viscosities of the photopolymerizable oligomers and photopolymerizable monomer types A and B prepared in Preparation Examples 1 to 6 were measured and shown in Table 1 below.

As shown in Table 1, due to the molecular weight according to the molar ratio of fluorolink E and IPDI of Preparation Examples 1 to 4, the viscosity increased and the refractive index decreased. However, it can be seen that the refractive index is not significantly reduced compared to the rate of viscosity increase.

Test Example 2

Refractive index, viscosity and secant modulus according to the components of the resin composition for optical fiber cladding prepared in Comparative Examples 1 to 4 were measured and shown in Table 2 below.

Test Example 3

The refractive index and the numerical aperture of the resin compositions for optical fiber claddings prepared in Comparative Examples 1 to 4 and Examples 5 or 6 were measured and shown in Table 3.

Test Example  4

Refractive index, viscosity and secant modulus according to the components of the resin composition for optical fiber cladding prepared in Examples 1 to 6 were measured and shown in Table 4 below.

As can be seen in Tables 2 to 4, the compound of the present invention comprising the photopolymerizable oligomer of Formula 1 prepared in Preparation Examples 1 to 4 and the photopolymerizable monomer prepared in Preparation Examples 5 or 6 has a refractive index of Not only did it show a low numerical aperture, but also 2.5% secant modulus was much better than 25 MPa. On the contrary, the resin compositions for optical fiber cladding of Comparative Examples 1 to 4, which contain the photopolymerizable oligomers of Chemical Formula 1 prepared in Preparation Examples 1 to 4 but include conventional photopolymerizable monomers, may exhibit high numerical aperture due to low refractive index. However, 2.5% secant modulus was significantly lower than the present invention.

Claims (19)

at least one photopolymerizable monomer selected from (a) a photopolymerizable oligomer having a structure of Formula 1, (b) a photopolymerizable monomer type A having a structure of Formula 2 and a photopolymerizable monomer type B having a structure of Formula 3, and (c) Resin composition for optical fiber cladding containing photoinitiator: Formula 1

Formula 2

Formula 3

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 10 carbon atoms, R ⁴ is a hydrocarbon group or fluorocarbon group having 2 to 20 carbon atoms, l, m, n, p, and q are the number of iterations for each repeating unit, l is 1 to 6, m is 1 to 5, n is 2 to 6, where n = m + 1, p is 2 to 20, The ratio of p to q (p / q) ranges from 0.8 to 2.5. The method of claim 1, at least one photopolymerized type selected from (a) 20 to 90% by weight of a photopolymerizable oligomer having a structure of Formula 1, (b) a photopolymerizable monomer type A having a structure of Formula 2 and a photopolymerizable monomer type B having a structure of Formula 3 A resin composition for optical fiber cladding comprising 1 to 79% by weight of monomer and (c) 0.1 to 10% by weight of photoinitiator. The method of claim 1, The photopolymerizable oligomers are synthesized from (i) fluorinated polyol copolymers, (ii) polyisocyanates, (iii) (meth) acrylates having isocyanate groups, (iv) polycondensation catalysts and (v) polymerization inhibitors. Resin composition for optical fiber cladding, characterized in that. The method of claim 1, A photopolymerizable monomer type A is synthesized from (i) a fluorinated polyol copolymer, (ii) an (meth) acrylate having an isocyanate group, (iii) a polycondensation catalyst, and (iv) a polymerization inhibitor. Composition. The method of claim 1, A photopolymerizable monomer type B is synthesized from (i) a fluorine alcohol, (ii) an (meth) acrylate having an isocyanate group, (iii) a polycondensation catalyst, and (iv) a polymerization inhibitor. The method of claim 1, A resin composition for optical fiber cladding, wherein the photopolymerizable oligomer has a viscosity at 25 ° C. of 1,000 cPs to 10,000,000 cPs (Brookfield DV III +). The method of claim 1, A resin composition for optical fiber cladding, wherein the photopolymerizable monomer type A or type B has a viscosity at 25 ° C. of 100 cPs to 10,000 cPs (Brookfield DV III +). The method according to any one of claims 3 to 5, A resin composition for optical fiber cladding, further comprising diluting at least one component by further using an acrylate or methyl acrylate monomer containing a hydrocarbon or fluorocarbon group having 4 to 12 carbon atoms. The method according to any one of claims 3 to 5, Resin composition for optical fiber cladding, characterized in that one or more components are further diluted using a solvent. The method according to claim 3 or 4, Fluorinated polyol copolymers include 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-hexen-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, pentafluoro-2-butanol, 4,4,5,5 , 5-pentafluoropentanol (4,4,5,5,5-pentafluoropentanol), pentafluoropropionaldehyde hydrate, Z-Dol (Solvay Solexis), Z- Dol TX (Solvay Solix), Fluorolink D (Solvay Solix), Fluorolink D10 / H (Solvay Solix), Fluorolink D10 (Solvay Solix), Fluorolink T, Fluorolink T10 (Solva Solixis), Fluorolink E (Solva Solixis), Fluorolink E10 / H (Solva Solixis), Fluorolink E10 (Solva Solixis), Zonyl ( Zonyl) TA-L (Dupont), Zonyl TA-N (Dupont) and a resin composition for optical fiber cladding, characterized in that selected from the group consisting of. The method of claim 3, Polyisocyanate is 2,4-tolyenediisocyanate, 2,6-tolyenediisocyanate, 1,3-xylenediisocyanate 1,4-xylenediisocyanate, 1,5-naphthalenediisocyanate, 1,6-hexanediisocyanate, isophorone di Resin composition for optical fiber cladding, characterized in that it is selected from the group consisting of isocyanates (isophoronediisocyanate) and mixtures thereof. The method according to any one of claims 3 to 5, (Meth) acrylates having isocyanate groups are 2-isocyanatoethyl methacrylate, 2- (2-isocyanatoethoxy) ethyl methacrylate (2- (2-isocyanatoethyoxy) ethyl methacrylate), 2-isocyanatoethyl acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and mixtures thereof Resin composition for optical fiber cladding, characterized in that selected from the group consisting of. The method of claim 5, Fluorinated alcohol is 2,2,2-trifluoroethanol, 2-fluoroethanol, 1,1,1,3,3,3-hexafluoro- 2-propanol (1,1,1,3,3,3-hexafluoro-2-propanol), 2,2,3,3,3-pentafluoro-1-propanol (2,2,3,3,3 -pentafluoro-1-propanol), 2,2,3,3, -tetrafluoro-1-propanol, 2,2,3,3-tetrafluoro-1-propanol, 1,1,1-trifluoro- 2-propanol (1,1,1-trifluoro-2-propanol), 1,3-difluoro-2-propanol, perfluoro-t-butyl alcohol (perfluoro tert-butyl alcohol), 1,1,1,3,3,4,4,4-octafluoro-2-butanol (1,1,1,3,3,4,4,4-octafluoro-2 -butanol), 2,2,3,3,4,4,4-heptafluoro-1-butanol (2,2,3,3,4,4,4-heptafluoro-1-butanol), 2,2 , 3,4,4,4-hexafluoro-1-butanol (2,2,3,4,4,4-hexafluoro-1-butanol), 1,1,1,3,3,3-hexafluoro Ro-2-methylpropanol (1,1,1,3,3,3-hexafluoro-2-methylpropanol), 2-trifluoromethyl-2-propanol, 2,2, 3,3,4,4,5,5 , -Octafluoro-1-pentanol (2,2,3,3,4,4,5,5-octafluoro-1-pentanol), 4,4,5,5,5-pentafluoro-1- Pentanol (4,4,5,5,5-pentafluoro-1-pentanol), pentafluorophenol, 2,3,5,6-tetrafluorophenol (2,3,5,6-tetrafluorophenol ), 2,3,4-trifluorophenol, 2,3,5-trifluorophenol, 2,3,6-trifluoro Rophenol (2,3,6-trifluorophenol), 2,3-difluorophenol, 2,4-difluorophenol, 2,5-difluoro Rophenol (2,5-difluorophenol), 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol (3,5-difluorophenol), 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 3,3,4,4,5 , 5,6,6,6-nonnafluoro-1-hexanol (3,3,4,4,5,5,6,6,6-nonafluoro-1-hexanol), 2-fluoro-3- (Trifluoromethyl) phenol (2-fluoro-3- (trifluoromethyl) phenol), 2-fluoro-5- (trifluoromethyl) phenol (2-fluoro-5- (trifluoromethyl) phenol), 2,3,4,5-tetrafluorobenzyl alcohol (2,3 , 4,5-tetrafluorobenzyl alcohol), 2,3,6-trifluorobenzyl alcohol (2,3,6-trifluorobenzyl alcohol), 2,4,5-trifluorobenzyl alcohol (2,4,5-trifluorobenzyl alcohol) alcohol), 3,4,5-trifluorobenzyl alcohol (3,4,5-trifluorobenzyl alcohol), α, α, α-trifluoro-o-cresol (α, α, α-trifluoro-o-cresol ), α, α, α-trifluoro-m-cresol (α, α, α-trifluoro-m-cresol), α, α, α-trifluoro-p-cresol (α, α, α-trifluoro p-cresol), 3- (trifluoromethoxy) phenol, 4- (trifluoromethoxy) phenol, 4,4,5,5, 6,6,7,7,7-nonafluoro-1-heptanol (4,4,5,5,6,6,7,7,7-nonafluoro-1-heptanol), 2,2,3, 3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol (2,2,3,3,4,4,5,5, 6,6,7,7,8,8,8-pentadecafluoro-1-octanol), 3,5 Bis (trifluoromethyl) phenol (3,5-bis (trifluoromethyl) phenol), 2-fluoro-3- (trifluoromethyl) benzyl alcohol (2-fluoro-3- (trifluoromethyl) benzyl alcohol), 2-fluoro-6- (trifluoromethyl) benzyl alcohol, 2,2,3,3,4,4,5,5,6,6,7 , 7,8,8,9,9,9-hepta-decafluoro-1-nonanol (2,2,3,3,4,4,5,5,6,6,7,7,8, 8,9,9,9-hepta-decafluoro-1-nonanol) and 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexa Decafluoro-1-nonanol (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1-nonanol) Resin composition for optical fiber cladding, characterized in that selected from. The method of claim 1, A resin composition for optical fiber cladding, wherein the resin composition has a numerical aperture of 0.4 or more and 2.5% secant modulus of 25 MPa or more. The method of claim 1, A resin composition for optical fiber cladding, further comprising a leveling agent, an antifoaming agent, a stabilizer or an antioxidant. The optical fiber containing the resin composition for optical fiber cladding of Claim 1 in a cladding part. The method of claim 16, Optical fiber, which is used to transmit radio waves, microwaves, infrared rays, visible light, ultraviolet rays, X-rays or gamma rays. The method of claim 16, Optical fiber, characterized in that used as a light source or used for illumination or display. The method of claim 16, Optical fiber characterized in that it is used in the field of high power laser transmission, medical field, optical device or optical sensor.