D1381 supercoatings for optical fiber

Abstract

The invention provides an optical fiber coated with a Supercoating, wherein the Supercoating comprises at least two layers, wherein the first layer is a Primary Coating that is in contact with the outer surface of the optical fiber and the second layer is a Secondary Coating in contact with the outer surface of the Primary Coating, wherein the cured Primary Coating on the optical fiber has the following properties after initial cure and after one month aging at 85° C. and 85% relative humidity: A) a % RAU of from about 84% to about 99%; B) an in-situ modulus of between about 0.15 MPa and about 0.60 MPa; and C) a Tube Tg, of from about −25° C. to about −55° C.; wherein the cured Secondary Coating on the optical fiber has the following properties after initial cure and after one month aging at 85° C. and 85% relative humidity: A) a % RAU of from about 80% to about 98%; B) an in-situ modulus of between about 0.60 GPa and about 1.90 GPa; and C) a Tube Tg, of from about 50° C. to about 80° C.

1 - 10 . (canceled) 
     
     
         11 . A process to coat a glass optical fiber with a Supercoating, comprising the steps of
 (i) operating a glass drawing tower to produce a glass optical fiber;   (ii) coating said glass optical fiber with the Supercoating of claim  1 ;   (iii) applying radiation to said Supercoating to cure said Supercoating;   wherein said glass drawing tower is operated at a line speed of between about 750 m/min and about 2,100 m/min;   wherein said Supercoating comprises a Radiation Curable Primary Coating and a Radiation Curable Secondary Coating and wherein said Radiation Curable Primary Coating is applied directly to the optical fiber and then the Radiation Curable Secondary Coating is applied directly to the Radiation Curable Primary Coating;   wherein radiation may be applied sequentially, first to the Radiation Curable Primary Coating and then to the Radiation Curable Secondary Coating, known as wet on dry application; or the radiation may be applied concurrently to the Radiation Curable Primary Coating and to the Radiation Curable Secondary Coating, known as wet on wet application;   wherein the cured Primary Coating on the optical fiber has the following properties after initial cure and after one month aging at 85° C. and 85% relative humidity:
 A) a % RAU of from about 84% to about 99%; 
 B) an in-situ modulus of between about 0.15 MPa and about 0.60 MPa; and 
 C) a Tube Tg, of from about −25° C. to about −55° C.; 
   wherein the cured Secondary Coating on the optical fiber has the following properties after initial cure and after one month aging at 85° C. and 85% relative humidity:
 A) a % RAU of from about 80% to about 98%; 
 B) an in-situ modulus of between about 0.60 GPa and about 1.90 GPa; and 
 C) a Tube Tg, of from about 50° C. to about 80° C.; 
   wherein said Radiation Curable Primary Coating is selected from the group consisting of a radiation curable Primary Coating composition comprising:
 A) an oligomer; 
 B) first diluent monomer; 
 C) a second diluent monomer; 
 D) a third diluent monomer; 
 E) a first light stabilizer; 
 F) a first photoinitiator; 
 G) a second photoinitiator; 
 H) an antioxidant; 
 I) a second light stabilizer; and 
 J) an adhesion promoter; 
   wherein said oligomer is the reaction product of
 i) hydroxyl-containing acrylate; 
 ii) an isocyanate; 
 iii) a polyether polyol; 
 iv) a polymerization inhibitor; 
 v) a catalyst; and 
 vi) a diluent; 
   wherein said oligomer has a number average molecular weight of from at least about 4000 g/mol to less than or equal to about 15,000 g/mol;   wherein said catalyst is selected from the group consisting of copper naphthenate; cobalt naphthenate; zinc naphthenate; triethylamine; triethylenediamine; 2-methyltriethyleneamine; dibutyl tin dilaurate; metal carboxylates, including, but not limited to: organobismuth catalysts such as bismuth neodecanoate, CAS 34364-26-6; zinc neodecalnoate, CAS 27253-29-8; zirconium neodecanoate, CAS 39049-04-2; and zinc 2-ethylhexanoate, CAS 136-53-8; sulfonic acids, including but not limited to dodecylbenzene sulfonic acid, CAS 27176-87-0; and methane sulfonic acid, CAS 75-75-2; amino or organo-base catalysts, including, but not limited to: 1,2-dimethylimidazole, CAS 1739-84-0; and diazabicyclo[2.2.2]octane, CAS 280-57-9; and triphenyl phosphine; alkoxides of zirconium and titanium, including, but not limited to zirconium butoxide, (tetrabutyl zirconate) CAS 1071-76-7; and titanium butoxide, (tetrabutyl titanate) CAS 5593-70-4; and ionic liquid phosphonium, imidazolium, and pyridinium salts, such as, but not limited to, trihexyl(tetradecyl)phosphonium hexafluorophosphate, CAS No. 374683-44-0; 1-butyl-3-methylimidazolium acetate, CAS No. 284049-75-8; and N-butyl-4-methylpyridinium chloride, CAS No. 125652-55-3; and tetradecyl(trihexyl)phosphonium chloride; and   wherein a cured film of said radiation curable Primary Coating composition has a peak tan δ Tg of from about −25° C. to about −55° C.; and a modulus of from about 0.85 MPa to about 1.10 MPa;   and a radiation curable Primary Coating composition comprising:
 A) an oligomer; 
 B) a diluent monomer; 
 C) a photoinitiator; 
 D) an antioxidant; and 
 E) an adhesion promoter; 
   wherein said oligomer is the reaction product of:
 i) a hydroxyethyl acrylate; 
 ii) an aromatic isocyanate; 
 iii) an aliphatic isocyanate; 
 iv) a polyol; 
 v) a catalyst; and an 
 vi) inhibitor, 
   wherein said oligomer has a number average molecular weight of from at least about 4000 g/mol to less than or equal to about 15,000 g/mol; and   wherein said catalyst is selected from the group consisting of dibutyl tin dilaurate; metal carboxylates, including, but not limited to: organobismuth catalysts such as bismuth neodecanoate, CAS 34364-26-6; zinc neodecanoate, CAS 27253-29-8; zirconium neodecanoate, CAS 39049-04-2; and zinc 2-ethylhexanoate, CAS 136-53-8; sulfonic acids, including but not limited to dodecylbenzene sulfonic acid, CAS 27176-87-0; and methane sulfonic acid, CAS 75-75-2; amino or organo-base catalysts, including, but not limited to: 1,2-dimethylimidazole, CAS 1739-84-0; and diazabicyclo[2.2.2]octane (DABCO), CAS 280-57-9 (strong base); and triphenyl phosphine; alkoxides of zirconium and titanium, including, but not limited to zirconium butoxide, (tetrabutyl zirconate) CAS 1071-76-7; and titanium butoxide, (tetrabutyl titanate) CAS 5593-70-4; and ionic liquid phosphonium, imidazolium, and pyridinium salts, such as, but not limited to, trihexyl(tetradecyl)phosphonium hexafluorophosphate, CAS No. 374683-44-0; 11-butyl-3-methylimidazolium acetate, CAS No. 284049-75-8; and N-butyl-4-methylpyridinium chloride, CAS No. 125652-55-3; and tetradecyl(trihexyl)phosphonium; and wherein a cured film of said radiation curable Primary Coating composition has a peak tan delta Tg of from about −25° C. to about −45° C. and a modulus of from about 0.50 MPa to about 1.2 MPa; and   wherein said Radiation Curable Secondary Coating is selected from the group consisting of   a Radiation Curable Secondary Coating comprising:
 A) a Secondary Coating Oligomer Blend, which is mixed with 
 B) a first diluent monomer; 
 C) a second diluent monomer; 
 D) optionally, a third diluent monomer; 
 E) an antioxidant; 
 F) a first photoinitiator; 
 G) a second photoinitiator; and 
 H) optionally a slip additive or a blend of slip additives; 
   wherein said Secondary Coating Oligomer Blend comprises:
 α) an Omega Oligomer; and 
 β) an Upsilon Oligomer; 
   wherein said Omega Oligomer is synthesized by the reaction of
 α1) a hydroxyl-containing (meth)acrylate; 
 α2) an isocyanate; 
 α3) a polyether polyol; and 
 α4) tripropylene glycol; in the presence of 
 α5) a polymerization inhibitor; and 
 α6) a catalyst; to yield the Omega Oligomer; 
   wherein said catalyst is selected from the group consisting of copper naphthenate, cobalt naphthenate, zinc naphthenate, triethylamine, triethylenediamine, 2-methyltriethyleneamine, dibutyl tin dilaurate; metal carboxylates, including, but not limited to: organobismuth catalysts such as bismuth neodecanoate; zinc neodecanoate; zirconium neodecanoate; zinc 2-ethylhexanoate; sulfonic acids, including but not limited to dodecylbenzene sulfonic acid, methane sulfonic acid; amino or organo-base catalysts, including, but not limited to: 1,2-dimethylimidazole and diazabicyclooctane; triphenyl phosphine; alkoxides of zirconium and titanium, including, but not limited to Zirconium butoxide and Titanium butoxide; and Ionic liquid phosphonium salts; and tetradecyl(trihexyl)phosphonium chloride; wherein said β) Upsilon Oligomer is an epoxy diacrylate; and   a Radiation Curable Secondary Coating composition, wherein said composition comprises
 A) a Secondary Coating Oligomer Blend; which is mixed with 
 B) a first diluent; 
 C) a second diluent; 
 D) an antioxidant; 
 E) a first photoinitiator; 
 F) a second photoinitiator; and 
 G) optionally a slip additive or a blend of slip additives; 
   wherein said Secondary Coating Oligomer Blend comprises:
 α) an Alpha Oligomer; 
 β) a Beta Oligomer; 
 γ) a Gamma Oligomer; 
   wherein said Alpha Oligomer is synthesized by the reaction of
 α1) an anhydride; with 
 α2) a hydroxyl group containing acrylate; and the reaction product of α1) and 
 α2) is then reacted further with 
 α3) an epoxy; in the presence of 
 α4) a first catalyst; 
 α5) a second catalyst; 
   wherein said first catalyst is selected from the group consisting of a triarylphosphine catalyst, such as triphenylphosphine (TPP) or tritolylphosphine, and   wherein said second catalyst is selected from the group consisting of a tertiary amine catalyst, such as the triethylene triamine catalyst 1,4-diazabicyclo[2.2.2]octane (DABCO) and α6) an polymerization inhibitor; to yield the Alpha Oligomer;   wherein said Beta Oligomer is synthesized by the reaction of
 β1) a hydroxyl group containing acrylate; 
 β2) a diisocyanate; and 
 β3) a polyether polyol; in the presence of 
 β4) a catalyst; 
   wherein said β4) catalyst is selected from the group consisting of copper naphthenate, cobalt naphthenate, zinc naphthenate, triethylamine, triethylenediamine, 2-methyltriethyleneamine, dibutyl tin dilaurate; metal carboxylates, including, but not limited to: organobismuth catalysts such as bismuth neodecanoate, CAS 34364-26-6; zinc neodecanoate, CAS 27253-29-8; zirconium neodecanoate, CAS 39049-04-2; and zinc 2-ethylhexanoate, CAS 136-53-8; sulfonic acids, including but not limited to dodecylbenzene sulfonic acid, CAS 27176-87-0; and methane sulfonic acid, CAS 75-75-2; amino or organo-base catalysts, including, but not limited to: 1,2-dimethylimidazole, CAS 1739-84-0; and diazabicyclo[2.2.2]octane, CAS 280-57-9; and triphenyl phosphine; alkoxides of zirconium and titanium, including, but not limited to zirconium butoxide, (tetrabutyl zirconate) CAS 1071-76-7; and titanium butoxide, (tetrabutyl titanate) CAS 5593-70-4; and ionic liquid phosphonium, imidazolium, and pyridinium salts, such as, but not limited to, trihexyl(tetradecyl)phosphonium hexafluorophosphate, CAS No. 374683-44-0; 1-butyl-3-methylimidazolium acetate, CAS No. 284049-75-8; and N-butyl-4-methylpyridinium chloride, CAS No. 125652-55-3; and tetradecyl(trihexyl)phosphonium; and   wherein said Gamma Oligomer is an epoxy diacrylate.   
     
     
         12 . The process of  claim 11  wherein the glass drawing tower is operated at a line speed of about 2,100 m/min.