Transparent thermoplastic blend of a cycloolefin copolymer and a thermoplastic polyurethane

Abstract

A blend of a cycloolefin copolymer and a thermoplastic urethane having similar indices of refraction is transparent. The cycloolefin copolymer is derived from norbornene and other monomers such that it has a processing range compatible with the thermoplastic urethane. The urethane component preferably has a polyether intermediate. A thermoplastic urethane compatibilizing agent is utilized desirably having a hydrocarbon intermediate portion. The compositions can be made to have desirable electrical dissipative properties for static control applications.

1 . A clear thermoplastic composition, comprising: 
 a blend of cycloolefin copolymer and a thermoplastic polyurethane, said cycloolefin copolymer and said thermoplastic polyurethane, independently, having an index of refraction of from about 1.48 to about 1.58.    
     
     
         2 . A clear thermoplastic composition according to  claim 1 , wherein said cycloolefin copolymer is derived from at least one polycyclic olefin monomer and from at least one acylic 1-olefin monomer and wherein the amount of said acylic 1-olefin monomer is from about 45 to about 85 mole percent based upon the total moles of said acylic 1-olefin monomer and said polycyclic olefin monomer.  
     
     
         3 . A clear thermoplastic composition according to  claim 2 , wherein said composition according to ASTM D-1003 has a light transmission of at least about 65% and a haze value of about 32% and less, and 
 wherein said thermoplastic polyurethane is derived from a) an intermediate made from an alkylene oxide monomer having from 2 to about 6 carbon atoms or from a polyester intermediate made from a dicarboxylic acid having from 4 to about 15 carbon atoms and from a glycol having from 2 to about 12 carbon atoms, b) a polyisocyanate having the formula R(NCO) n  where n is from about 2 to about 4 and wherein R is an aliphatic, an aromatic, or combinations thereof having a total of from 2 to about 30 carbon atoms, and c) a diol having from 2 to about 10 carbon atoms.    
     
     
         4 . A clear thermoplastic composition according to  claim 3 , wherein said polycyclic olefin monomer is norbornene or tetracyclododecene, wherein said acylic 1-olefin monomer is ethylene or propylene, 
 wherein said alkylene oxide is ethylene oxide or propylene oxide,    wherein said ester intermediate is derived from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, cyclohexane acid, and combinations thereof and from a glycol including, ethylene glycol, propylene-1,2-glycol, 1,3-propanediol, butylene-1,3-glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethylpropane-1,3-diol, 2,2-diethylene-1,3-diol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and combinations thereof,    wherein said polyisocyanate is a diisocyanate comprising 4,4′-methylenebis-(phenyl isocyanate) (MDI); isophorone diisocyanate (IPDI), m-xylylene diisocyanate (XDI), toluene diisocyanate, phenylene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1,4-cyclohexyl diisocyanate (CHDI), decane-1,10-diisocyanate, diphenylmethane-3,3′-dimethoxy-4,4′-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and cyclohexyl-1,4-diisocyanate, or combinations thereof, and wherein said diol is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butane diol, 1,6-hexane diol, 1,3-butane diol, 1,5-pentane diol, 1,4-cyclohexane-dimethanol, neopentyl glycol, hydroquinone di(hydroxyethyl)ether and 2-methyl-1,3-propanediol, or combinations thereof.    
     
     
         5 . A clear thermoplastic composition according to  claim 4 , wherein said cycloolefin copolymer, and said thermoplastic polyurethane, independently, have an index of refraction of from about 1.50 to about 1.56, and wherein said thermoplastic composition according to ASTM D-1003 has a light transmission of at least about 80% and a haze value of about 27% and less.  
     
     
         6 . A clear thermoplastic composition according to  claim 5 , wherein said cycloolefin copolymer is derived from norbornene and from ethylene, wherein the amount of said ethylene is from about 60 to about 70 mole percent based upon the total number of moles of said ethylene and said norbornene, wherein said alkylene oxide is ethylene oxide, wherein said diisocyanate is MDI, and wherein said diol is butane diol.  
     
     
         7 . A clear thermoplastic composition according to  claim 6 , 
 wherein said cycloolefin copolymer, and said thermoplastic polyurethane, independently, have an index of refraction of from about 1.52 to about 1.54, and wherein said thermoplastic composition according to ASTM D-1003 has a light transmission of at least about 82% and a haze value of about 22% and less.    
     
     
         8 . A clear thermoplastic composition according to  claim 1 , including a compatibilizing agent, wherein said compatibilizing agent comprises a thermoplastic polyurethane derived from a diisocyanate, a diol, and a substantially hydrocarbon intermediate containing at least 20 carbon atoms between non-carbon atoms in the intermediate backbone, or said intermediate is derived from one or more dienes having a total of from 4 to 8 carbon atoms.  
     
     
         9 . A clear thermoplastic composition according to  claim 3 , including a compatibilizing agent, wherein said compatibilizing agent comprises a thermoplastic polyurethane derived from a diisocyanate, a diol, and a substantially hydrocarbon intermediate containing at least 20 carbon atoms between non-carbon atoms in the intermediate backbone, or said intermediate is derived from one or more dienes having a total of from 4 to 8 carbon atoms, wherein at least 80% of the initial carbon to carbon double bonds in said intermediate have been saturated, wherein said diisocyanate is ethylene diisocyanate; toluene diisocyanate; methylene bis-(4-phenylisocyanate) (MDI); isophorone diisocyanate; hexamethylene diisocyanate; naphthalene diisocyanate; cyclohexylene diisocyanate; diphenylmethane-3,3′ dimethoxy-4,4′-diisocyanate, meta-tetramethylxylene diisocyanate (m-TMXD 1), paratetramethylxylene diisocyanate (p-TMXD 1), m-xylylene diisocyanate (XDI), decane-1,10-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and combinations thereof, and wherein said diol is ethylene glycol, 1,3-propane diol, 2,3- or 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, hydroquinone bis(2-hydroxyethyl)ether, 1,4-cyclohexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, and combinations thereof.  
     
     
         10 . A clear thermoplastic composition according to  claim 7 , 
 including from about 0.25 to about 8 parts by weight of a compatibilizing agent per 100 parts by weight of said thermoplastic urethane and said cycloolefin copolymer, wherein said compatibilizing agent, wherein said compatibilizing agent comprises a thermoplastic polyurethane having a hydrocarbon intermediate derived from one or more dienes having a total of from 4 to 8 carbon atoms wherein at least 90% of the initial carbon to carbon double bonds have been saturated, wherein said diisocyanate is MDI, and wherein said diol is neopentyl glycol.    
     
     
         11 . An optical film or coating, comprising the composition of  claim 1 .  
     
     
         12 . An optical film or coating, comprising the composition of  claim 8 .  
     
     
         13 . An electrostatic dissipating thermoplastic composition, comprising: 
 a cycloolefin copolymer, an electrostatic dissipating thermoplastic composition, and a compatibilizing agent.    
     
     
         14 . An electrostatic dissipating thermoplastic composition of  claim 13  wherein said electrostatic dissipating composition contains a polymer selected from the group consisting of thermoplastic polyurethane, polyether amide, polyether ester, copolymer of ethylene oxide and propylene oxide, and copolymer of ethylene oxide and epichlorohydrin.  
     
     
         15 . An electrostatic dissipating thermoplastic composition according to  claim 13 , wherein said cycloolefin copolymer is derived from at least one polycyclic olefin monomer and at least one acyclic 1-olefin monomer, said polycyclic olefin monomer having the formula  
       
         
           
           
               
               
           
         
       
       wherein each R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , independently, are the same or different, and is a hydrogen atom or a hydrocarbon radical, and wherein said acylic 1-olefin has the formula  
       
         
           
           
               
               
           
         
       
       wherein each R 7 , R 8 , R 9 , and R 10 , independently, are the same or different, and is a hydrogen atom or a C 6 -C 10  aryl group or a C 1 -C 8  alkyl group, and wherein said electrostatic dissipating composition has a surface resistivity of from about 1×10 6  to about 1×10 12  ohm/square.  
     
     
         16 . An electrostatic dissipating thermoplastic composition according to  claim 15 , wherein said electrostatic dissipating thermoplastic composition comprises a thermoplastic polyurethane derived from one or more cyclic ether monomers, at least one diisocyanate, and at least one diol, wherein said cyclic ether monomer has the formula  
       
         
           
           
               
               
           
         
       
       wherein each R 1 , R 2 , R 3 , R 4 , and R 5 , independently, is a hydrogen atom, an unsubstituted or substituted alkyl, cycloalkyl, cycloalkenyl, aryl, aralkyl or alkaryl, and wherein said substituents which can be substituted within the foregoing are OR 6 , SR 6 , CN or a halogen, where R 6  is hydrogen, alkyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkaryl, or carboxyl, and n is 0, 1, 2, or 4, and 
 wherein said compatibilizing agent comprises a thermoplastic polyurethane derived from a diisocyanate, a diol, and a substantially hydrocarbon intermediate containing at least 20 carbon atoms between non-carbon atoms in the intermediate backbone or a hydrocarbon intermediate derived from one or more dienes having a total of from 4 to 8 carbon atoms.  
 
     
     
         17 . An electrostatic dissipating thermoplastic composition according to  claim 16 , wherein said cycloolefin copolymer is derived from norbornene or tetracyclododecene, wherein said acylic 1-olefin monomer is ethylene or propylene, 
 wherein said electrostatic dissipating thermoplastic polyurethane cyclic ether monomer is a cycloalkyl having from 3 to 8 ring carbon atoms, wherein said diisocyanate is 1,4-diisocyanatobenzene (PPDI), 4,4′-methylenebis(phenyl isocyanate) (MDI), 4,4′-methylenebis(3-methoxy phenyl isocyanate), isophorone diisocyanate (IPDI) 1,5-naphthalene diisocyanate (NDI), phenylene-1,4-diisocyanate, toluene diisocyanate (TDI), m-xylene diisocyanate (XDI), 1,4-cyclohexyl diisocyanate (CHDI), 1,10-diisocyanatonaphthylene, and 4,4′-methylenebis-(cyclohexyl isocyanate) (H 12  MDI), and wherein said glycol chain extender is ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, 1,4-cyclohexane dimethanol, neopentyl glycol, hydroquinone bis(2-hydroxyethyl) ether, or combinations thereof.    
     
     
         18 . An electrostatic dissipating thermoplastic composition according to  claim 17 , wherein said cycloolefin copolymer is derived from norbornene and ethylene, wherein the amount of said ethylene monomer is from about 45% to about 85 mole % based upon the total moles of said ethylene and said norbornene monomers, and 
 wherein said compatibilizing agent diisocyanate is ethylene diisocyanate; toluene diisocyanate; methylene bis-(4-phenylisocyanate) (MDI); isophorone diisocyanate; hexamethylene diisocyanate; naphthalene diisocyanate; cyclohexylene diisocyanate; diphenylmethane-3,3′ dimethoxy-4,4′-diisocyanate, meta-tetramethylxylene diisocyanate (m-TMXD1), paratetramethylxylene diisocyanate (p-TMXD1), m-xylylene diisocyanate (XDI), decane-1,10-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and combinations thereof, and wherein said compatibilizing agent diol is ethylene glycol, 1,3-propane diol, 2,3- or 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, hydroquinone bis(2-hydroxyethyl)ether, 1,4-cyclohexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, and combinations thereof.    
     
     
         19 . An electrostatic dissipating thermoplastic composition according to  claim 18 , wherein said electrostatic dissipating thermoplastic urethane cycloalkyl is ethylene oxide, wherein said diisocyanate is MDI and wherein said diol is butane diol, wherein said electrostatic dissipating thermoplastic polyurethane has a surface resistivity of from about 1×10 8  to about 1×10 10  ohm/square, and 
 wherein the amount of said compatibilizing agent is from about 0.25 to about 8 parts by weight per 100 parts by weight of said cycloolefin copolymer and said electrostatic dissipating thermoplastic urethane.    
     
     
         20 . An electrostatic dissipating thermoplastic composition according to  claim 19 , wherein the amount of said ethylene monomer in said cycloolefin copolymer is from about 55 to about 80 mole % based upon the total moles of said ethylene and said norbornene monomers, 
 wherein said compatibilizing agent intermediate is derived from butadiene, wherein said diisocyanate is MDI and wherein said diol is neopentyl glycol.    
     
     
         21 . An electrostatic dissipating thermoplastic composition according to  claim 20 , wherein said composition comprises co-continuous phases of said cycloolefin copolymer and said electrostatic dissipating thermoplastic urethane.  
     
     
         22 . An electronic or semi-conductor packaging material comprising the composition of  claim 13 .  
     
     
         23 . An electronic or semi-conductor packaging material comprising the composition of  claim 17 .  
     
     
         24 . An electronic or semi-conductor packaging material comprising the composition of  claim 20 .  
     
     
         25 . An electronic or semi-conductor packaging material comprising the composition of  claim 14 .  
     
     
         26 . A hard disc drive component or packaging material comprising the composition of  claim 13 .  
     
     
         27 . A hard disc drive component or packaging material comprising the composition of  claim 16 .  
     
     
         28 . A hard disc drive component or packaging material comprising the composition of  claim 20 .  
     
     
         29 . A hard disc drive component or packaging material comprising the composition of  claim 14 .  
     
     
         30 . A compatibilized polymer blend, comprising: 
 a cycloolefin copolymer, a thermoplastic polyurethane, and a compatibilizing agent.    
     
     
         31 . A compatibilized polymer blend according to  claim 30 , wherein said cycloolefin copolymer is derived from at least one polycyclic olefin monomer and from at least one acylic 1-olefin monomer and wherein the amount of said acylic 1-olefin monomer is from about 45 to about 85 mole percent based upon the total moles of said acylic 1-olefin monomer and said polycyclic olefin monomer, 
 wherein said thermoplastic polyurethane is derived from a) an intermediate made from an alkylene oxide monomer having from 2 to about 6 carbon atoms or from a polyester intermediate made from a dicarboxylic acid having from 4 to about 15 carbon atoms and from a glycol having from 2 to about 12 carbon atoms, b) a polyisocyanate having the formula R(NCO) n  where n is from about 2 to about 4 and wherein R is an aliphatic, an aromatic, or combinations thereof having a total of from 2 to about 30 carbon atoms, and c) a diol having from 2 to about 10 carbon atoms, and    wherein said compatibilizer comprises a thermoplastic polyurethane derived from a diisocyanate, a diol, and a substantially hydrocarbon intermediate containing at least 20 carbon atoms between non-carbon atoms in the intermediate backbone, or said intermediate is derived from one or more dienes having a total of from 4 to 8 carbon atoms.    
     
     
         32 . A compatibilized polymer blend according to  claim 31 , wherein said polycyclic olefin monomer is norbornene or tetracyclododecene, wherein said acylic 1-olefin monomer is ethylene or propylene; 
 wherein said alkylene oxide is ethylene oxide or propylene oxide,    wherein said ester intermediate is derived from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, cyclohexane acid, and combinations thereof and from a glycol including, ethylene glycol, propylene-1,2-glycol, 1,3-propanediol, butylene-1,3-glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethylpropane-1,3-diol, 2,2-diethylene-1,3-diol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and combinations thereof;    wherein said thermoplastic polyurethane polyisocyanate is a diisocyanate comprising 4,4′-methylenebis-(phenyl isocyanate) (MDI); isophorone diisocyanate (IPDI), m-xylylene diisocyanate (XDI), toluene diisocyanate, phenylene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1,4-cyclohexyl diisocyanate (CHDI), decane-1,10-diisocyanate, diphenylmethane-3,3′-dimethoxy-4,4′-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and cyclohexyl-1,4-diisocyanate, or combinations thereof, and wherein said thermoplastic polyurethane diol is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butane diol, 1,6-hexane diol, 1,3-butane diol, 1,5-pentane diol, 1,4-cyclohexane-dimethanol, neopentyl glycol, hydroquinone di(hydroxyethyl)ether and 2-methyl-1,3-propanediol, or combinations thereof; and    wherein said compatibilizing agent intermediate is derived from one or more dienes having a total of from 4 to 8 carbon atoms, wherein at least 80% of the initial carbon to carbon double bonds in said intermediate have been saturated, wherein said compatibilizing agent diisocyanate is ethylene diisocyanate; toluene diisocyanate; methylene bis-(4-phenylisocyanate) (MDI); isophorone diisocyanate; hexamethylene diisocyanate; naphthalene diisocyanate; cyclohexylene diisocyanate; diphenylmethane-3,3′ dimethoxy-4,4′-diisocyanate, meta-tetramethylxylene diisocyanate (m-TMXD1), paratetramethylxylene diisocyanate (p-TMXD1), m-xylylene diisocyanate (XDI), decane-1,10-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and combinations thereof, and wherein said compatibilizing agent diol is ethylene glycol, 1,3-propane diol, 2,3- or 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, hydroquinone bis(2-hydroxyethyl)ether, 1,4-cyclohexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, and combinations thereof.    
     
     
         33 . A compatibilized polymer blend according to  claim 32 , wherein said cycloolefin copolymer is derived from norbornene and from ethylene, wherein the amount of said ethylene is from about 60 to about 70 mole percent based upon the total number of moles of said ethylene and said norbornene; 
 wherein said thermoplastic polyurethane alkylene oxide is ethylene oxide, wherein said diisocyanate is MDI, and wherein said diol is butane diol; and    wherein said compatibilizing agent hydrocarbon intermediate derived from one or more dienes having a total of from 4 to 8 carbon atoms wherein at least 90% of the initial carbon to carbon double bonds have been saturated, wherein said diisocyanate is MDI, and wherein said diol is neopentyl glycol.