D1451 radiation curable supercoatings for single mode optical fiber

1. A method of making a single-mode optical fiber that has a primary coating layer that is in contact with the outer surface of the optical fiber and a secondary coating layer that is in contact with the outer surface of the primary coating layer, the method comprising the steps of:

forming the primary coating layer by curing a composition selected from the group of formula compositions wherein the composition of the Primary Coating layer, prior to curing, is obtained by curing a composition selected from the group consisting of formulations compositions (i), (ii), (iii), (iv), (v) and (vi); wherein said formulations compositions (i), (ii), (iii), (iv), (v) and (vi) are defined as follows:

(i) 58.50 wt. % of an oligomer prepared by reaction of: 51.68 wt. % of polypropylene glycol, MW=4200, 0.09 wt. % of 2,6-di-tert-butyl-p-cresol, 4.76 wt. % of isophorone diisocyanate, 0.03 wt. % of dibutyl tin dilaurate, and 1.94 wt. % of 2-hydroxyethyl acrylate;

1.50 wt. % of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide;

0.60 wt. % of hindered phenol antioxidant;

0.10 wt. % of bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate;

34.05 wt. % of ethoxylated nonyl phenol acrylate;

1.00 wt. % of bisphenol A ethoxylated diacrylate;

3.00 wt. % of 2-phenoxyethyl acrylate;

0.75 wt. % of trimethylolpropane tri(3-mercaptopropionate);

and 0.50 wt. % of y-mercaptopropyltrimethoxysilane;

(ii) 50.01 wt. % of an oligomer prepared by reaction of: 45.78 wt. % of polypropylene glycol, MW=4200, 0.01 wt. % of acrylic acid, 99%, 0.04 wt. % of 2,6-di-tert-butyl-4-methylphenol, 2.92 wt. % of monomeric toluene diisocyanate, and 1.24 wt. % of 2-hydroxyethyl acrylate;

0.50 wt. % of hindered phenol antioxidant;

46.29 wt. % of ethoxylated (4) nonyl phenol acrylate, MW=450;

0.91 wt. % of bisphenol A ethoxylated diacrylate;

0.10 wt. % of bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate;

1.20 wt. % of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide;

0.0 wt. % of 2,4,6 trimethylbenzoyldiphenylphocphine oxide type photoinitiator;

and 0.99 wt. % of y-mercaptopropyltrimethoxysilane;

(iii) 65.00 wt. % of an oligomer prepared by reaction of: 57.47 wt. % of polypropylene glycol, MW=4200, 0.1 wt. % of 2,6-di-tert-butyl-4-methylphenol, 5.25 wt. % of isophorone diisocyanate, 0.03 wt. % of dibutyl tin dilaurate, and 2.15 wt. % of 2-hydroxyethyl acrylate;

21.55 wt. % of ethoxylated (4) nonyl phenol acrylate, MW=450;

9 wt. % of 2-phenoxyethyl acrylate;

1 wt. % of bisphenol A ethoxylated diacrylate;

1.5 wt. % of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide;

0.0 wt. % of 2,4,6 trimethylbenzoyldiphenylphosphine oxide type photoinitiator;

0.6 wt. % of hindered phenol antioxidant;

0.1 wt. % of bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate;

and 1.25 wt. % of y-mercaptopropyltrimethoxysilane;

(iv) 55.91 wt. % of an oligomer prepared by reaction of: 3.38 wt. % of 2,4-toluene diisocyanate, 0.05 wt. % of 2,6-di-tert-butyl-p-cresol, 0.01 wt. % of acrylic acid, 1.46 wt. % of 2-hydroxyethyl acrylate, 50.10 wt. % of polypropylene glycol, MW=4200, and 0.03 wt. % of dibutyltin dilaurate, 40.29 wt. % ethoxylated nonyl phenol acrylate;

1.50 wt. % of bisphenol A ethoxylate diacrylate;

1.70 wt. % of 2,4,6-trimethylbenzoyldiphenylphosphine oxide type photoinitiator;

0.50 wt. % of hindered phenol antioxidant;

0.10 wt. % of bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate;

and 0.90 wt. % of y-mercaptopropyltrimethoxysilane;

(v) 47.56 wt. % of an oligomer prepared by reaction of: 91.54 wt. %, by weight of the oligomer, of polypropylene glycol, MW=4200, 0.02 wt. %, by weight of the oligomer, of acrylic acid, 99%, 0.08 wt. %, by weight of the oligomer, of 2,6-di-tert-butyl-4-methyl phenol, 5.83 wt. %, by weight of the oligomer, of monomeric toluene diisocyanate, 0.05 wt. %, by weight of the oligomer, of dibutyltin dilaurate, and 2.48 wt. %, by weight of the oligomer, of 2-hydroxyethyl acrylate;

0.85 wt. % of ethoxylated bisphenol A acrylate;

44.09 wt. % of ethoxylated nonyl phenol acrylate;

5.00 wt. % of 2,4,6-trimethylbenzoyl ethoxy phenyl phosphine oxide;

1.00 wt. % of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide;

0.47 wt. % of hindered phenol antioxidant;

0.09 wt. % of bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate;

and 0.94 wt. % of ˜, -mercaptopropyltrimethoxysilane;

and (vi) 47.05 wt. % of an oligomer prepared by reaction of: 91.54 wt. %, by weight of the oligomer, of polypropylene glycol, MW=4200, 0.02 wt. %, by weight of the oligomer, of acrylic acid, 99%, 0.08 wt. %, by weight of the oligomer, of 2,6-di-tert-butyl-4-methyl phenol, 5.83 wt. %, by weight of the oligomer, of monomeric toluene diisocyanate, 0.05 wt. %, by weight of the oligomer, of dibutyltin dilaurate, and 2.48 wt. %, by weight of the oligomer, of 2-hydroxyethyl acrylate;

0.84 wt. % of ethoxylated bisphenol A acrylate;

43.62 wt. % of ethoxylated nonyl phenol acrylate;

5.00 wt. % of 2,4,6-trimethylbenzoyl ethoxy phenyl phosphine oxide;

2.00 wt. % of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide;

0.47 wt. % of hindered phenol antioxidant;

0.09 wt. % of bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate;

and 0.93 wt. % of 7-mercaptopropyltrimethoxysilane; and

forming the secondary coating layer by curing a composition selected from the group of formula compositions wherein the composition of the Secondary Coating layer, prior to curing, is obtained by curing a composition selected from the group consisting of the formulations of group compositions (a), (b), (c) and (d); wherein said formulations compositions (a), (b), (c) and (d) are defined as follows:

(a) 28.78 wt. % of an oligomer prepared by reaction of: 21.26 wt. %, by weight of the oligomer, of an 80/20 blend of the 2,4- and 2,6-isomer of toluene diisocyanate, 0.05 wt. %, by weight of the oligomer, of 2,6-di-tert-butyl-4-methyl phenol, 14.18 wt. %, by weight of the oligomer, of 2-hydroxyethyl acrylate, 0.05 wt. %, by weight of the oligomer, of dibutyltin dilaurate, and 64.46 wt. %, by weight of the oligomer, of polypropylene glycol, MW=1000;

38.42 wt. % of difunctional bisphenol A-based epoxy acrylate oligomer;

7.2 wt. % of isobornyl acrylate;

8.15 wt. % of 2-phenoxyethyl acrylate;

5.76 wt. % of tripropylene glycol diacrylate;

4.27 wt. % of 1,6-hexanediol diacrylate;

2.43 wt. % of a blend, wherein said blend consists essentially of 35 wt. % of aromatic acid acrylate half ester and 65 wt. % of ethoxylated trimethylolpropane triacrylate;

1 wt. % of 2,4,6-trimethylbenzoyldiphenylphosphine oxide type photoinitiator;

0 wt. % of bis(2,4,6 trimethylbenzoyl)phenylphosphine oxide;

3 wt. % of 1-hydroxycyclohexyl-phenyl ketone;

0.5 wt. % of hindered phenol antioxidant;

0.33 wt. % of a blend, wherein said blend consists essentially of 40 to 70 wt. % of dimethyl, methyl(propyl(poly(ethylene oxide) (propylene oxide))acetate)siloxane, 30 to 60 wt. % of poly(ethylene oxide propylene oxide) monoallyl ether acetate, and less than 9 wt. % of polyether polyol acetate;

and 0.17 wt. % of dimethyl, methyl(propyl(poly(ethylene oxide))acetate) siloxane;

(b) 30.00 wt. % of an oligomer prepared by reaction of: 21.26 wt. %, by weight of the oligomer, of an 80/20 blend of the 2,4- and 2,6-isomer of toluene diisocyanate, 0.05 wt. %, by weight of the oligomer, of 2,6-di-tert-butyl-4-methyl phenol, 14.18 wt. %, by weight of the oligomer, of 2-hydroxyethyl acrylate, 0.05 wt. %, by weight of the oligomer, of dibutyltin dilaurate, and 64.46 wt. %, by weight of the oligomer, of polypropylene glycol, MW=1000;

40.00 wt. % of epoxy diacrylate;

7.5 wt. % of isobornyl acrylate;

8.5 wt. % of 2-phenoxyethyl acrylate;

6 wt. % of tripropylene glycol diacrylate;

4.5 wt. % of 1,6-hexanediol diacrylate;

0.5 wt. % of hindered phenol antioxidant;

0.0 wt. % of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide;

0.5 wt. % of 2,4,6-trimethylbenzoyldiphenylphosphine oxide type photoinitiator;

2 wt. % of 1-hydroxycyclohexyl-phenyl ketone;

0.33 wt. % of a blend, wherein said blend consists essentially of a blend of 40 to 70 wt. % of dimethyl, methyl(propyl(poly(ethylene oxide) (propylene oxide))acetate)siloxane, 30 to 60 wt. % of poly(ethylene oxide propylene oxide) monoallyl ether acetate, and less than 9 wt. % of polyether polyol acetate;

and 0.17 wt. % of dimethyl, methyl(propyl(poly(ethylene oxide))acetate) siloxane;

(c) 20.27 wt. % of an oligomer prepared by reaction of: 21.26 wt. %, by weight of the oligomer, of an 80/20 blend of the 2,4- and 2,6-isomer of toluene diisocyanate, 0.05 wt. %, by weight of the oligomer, of 2,6-di-tert-butyl-4-methyl phenol, 14.18 wt. %, by weight of the oligomer, of 2-hydroxyethyl acrylate, 0.05 wt. %, by weight of the oligomer, of dibutyltin dilaurate, and 64.46 wt. %, by weight of the oligomer, of polypropylene glycol, MW=1000;

50.00 wt. % of epoxy diacrylate;

1.06 wt. % of 2,4,6-trimethylbenzoyldiphenylphosphine oxide type photoinitiator;

0.80 wt. % of 1-hydroxycyclohexyl phenyl ketone;

0.50 wt. % of 2,6-di-tert-butyl-4-methylphenol;

1.06 wt. % of a blend of 70 wt. % of oligo[2-hydroxy-2-methyl-1-[4(1-methyl-vinyl)phenyl]propanone] and 30 wt. % of 2-hydroxy-2-methyl-1-phenylpropanone;

15.00 wt. % of tripropylene glycol diacrylate;

9.80 wt. % of 1,6-hexanediol diacrylate;

0.50 wt. % of ethoxylated (4) nonyl phenol acrylate, MW=450;

0.68 wt. % of a blend, wherein said blend consists essentially of 40 to 70 wt. % of dimethyl, methyl(propyl(poly(ethylene oxide) (propylene oxide))acetate)siloxane, 30 to 60 wt. % of poly(ethylene oxide propylene oxide) monoallyl ether acetate, and less than 9 wt. % of polyether polyol acetate;

and 0.33 wt. % of dimethyl, methyl(propyl(poly(ethylene oxide))acetate) siloxane;

and (d) 28.1 wt. % of an oligomer prepared by reaction of: 21.26 wt. %, by weight of the oligomer, of an 80/20 blend of the 2,4- and 2,6-isomer of toluene diisocyanate, 0.05 wt. %, by weight of the oligomer, of 2,6-di-tert-butyl-4-methyl phenol, 14.18 wt. %, by weight of the oligomer, of 2-hydroxyethyl acrylate, 0.05 wt. %, by weight of the oligomer, of dibutyltin dilaurate, and 64.46 wt. %, by weight of the oligomer, of polypropylene glycol, MW=1000;

37.4 wt. % of a difunctional bisphenol A-based epoxy acrylate oligomer;

5.2 wt. % of 1,6-hexanediol diacrylate;

10.3 wt. % of ethoxylated 4 bisphenol A diacrylate;

14.75 wt. % of 2-phenoxyethyl acrylate;

0.75 wt. % of 2,4,6-trimethylbenzoyldiphenylphosphine oxide type photoinitiator;

2.5 wt. % of 1-hydroxcyclohexyl phenyl ketone;

0.5 wt. % of hindered phenol antioxidant;

and 0.33 wt. % of a blend, wherein said blend consists essentially of 40 to 70 wt. % of dimethyl, methyl(propyl(poly(ethylene oxide) (propylene oxide))acetate)siloxane, 30 to 60 wt. % of poly(ethylene oxide propylene oxide) monoallyl ether acetate, and less than 9 wt. % of polyether polyol acetate;

and 0.17 wt. % of dimethyl, methyl(propyl(poly(ethylene oxide))acetate) siloxane.