Aromatic Polyamide Films for Solvent Resistant Flexible Substrates

Abstract

Films with optical transmittance of >80% between 400 and 750 nm and with coefficient of thermal expansion less than 20 ppm/° C. are prepared from aromatic polyamides that are soluble in polar organic solvents yet have glass transition temperatures>300° C. The films are cross-linked in the solid state by heating at elevated temperatures for short periods of time in the presence of multifunctional epoxides. Surprisingly, the optical and thermal properties of the films do not change significantly during the curing process. The temperature required for the crosslinking process to take place can be reduced by the presence of a few free, pendant carboxyl groups along the polyamide backbones. The films are useful as flexible substrates for electronic displays and photovoltaic devices.

Having thus described the invention, it is now claimed: 
     
         1 . A transparent aromatic polyamide films comprising:
 (A) an aromatic polyamide that is capable of being thermally cross-linked, and has at least one repeat units of general formula (I):   
       
         
           
           
               
               
           
         
         wherein X represents the molar percentage of the repeat structure (I) and wherein the polyamide is soluble in polar organic solvents in the absence of inorganic salts and has a Tg higher than 300° C., and Ar 1  is selected from the group consisting of: 
       
       
         
           
           
               
               
           
         
         wherein p is 4, q is 3, and wherein R 1 , R 2 , R 3 , R 4 , R 5  are selected from the group comprising hydrogen; halogens; alkyl groups; substituted alkyl groups; cyano groups; thioalkyl groups, alkoxy groups; substituted alkoxy groups; aryl groups; substituted aryl groups; alkyl ester groups; substituted alkyl ester groups; and combinations thereof, wherein G 1  is selected from a group comprising a covalent bond; a CH 2  group; a C(CH 3 ) 2  group; a C(CF 3 ) 2  group; and a C(CM 3 ) 2  group, wherein M is selected from the group comprising a halogen; a CO group; an O atom; a S atom; a SO 2  group; a Si(CH 3 ) 2  group; a 9,9′-bisphenylenefluorene group; a substituted 9,9′-bisphenylenefluorene group; and an OZO group, wherein Z is selected from the group comprising an aryl group; a substituted aryl group; a biphenyl group; a perfluorobiphenyl group; a 9,9′-bisphenylenefluorene group; and a substituted 9,9′-bisphenylenefluorene group, and 
         wherein at least one of the Ar 1  groups in at least one of the repeat units (I) is selected from the group consisting of: 
       
       
         
           
           
               
               
           
         
         wherein Ar 2  is selected from the group consisting of: 
       
       
         
           
           
               
               
           
         
         wherein p is 4, wherein R 6 , R 7 , and R 8  are selected from the group comprising hydrogen; halogens; alkyl groups; substituted alkyl groups; cyano groups; thioalkyl groups, alkoxy groups; substituted alkoxy groups; aryl groups; substituted aryl groups; alkyl ester groups; substituted alkyl ester groups; and combinations thereof, wherein G 2  is selected from the group comprising a covalent bond; a CH 2  group; a C(CH 3 ) 2  group; a C(CF 3 ) 2  group; and a C(CM 3 ) 2  group, wherein M is selected from the group comprising a halogen; a CO group; an O atom; a S atom; a SO 2  group; a Si(CH 3 ) 2  group; a 9,9′-bisphenylenefluorene group; a substituted 9,9′-bisphenylenefluorene group; and an OZO group, wherein Z is selected from the group comprising an aryl group; substituted aryl group; a biphenyl group, a perfluorobiphenyl group, a 9,9′-bisphenylenefluorene group, and a substituted 9,9′-bisphenylenefluorene group; and 
         wherein at least one of the Ar 2  groups in at least one of the repeat units (I) is selected from the group consisting of: 
       
       
         
           
           
               
               
           
         
       
       and,
 (B) a multifunctional epoxide selected from the group comprising the general structures (II), (III), and (IV): 
 
       
         
           
           
               
               
           
         
         wherein x>1 and R 9  is selected from the group comprising 
       
       
         
           
           
               
               
           
         
         where the cyclic structure is selected from the group comprising 
       
       
         
           
           
               
               
           
         
         wherein n and n 1 >1 and R 10  is an alkyl or aromatic group. 
       
     
     
         2 . The film of  claim 1 , wherein the multifunctional epoxide is between approximately 1 and approximately 10 wt % based on the weight of the polyamide. 
     
     
         3 . The film of  claim 1 , wherein the film thickness is greater than approximately 4 μm. 
     
     
         4 . The film of  claim 3 , wherein the film thickness is greater than approximately 4 μm and less than approximately 100 μm. 
     
     
         5 . The film of  claim 3 , wherein the film is approximately 10 μm thick and has a transmittance of >80% from 400 to 750 nm. 
     
     
         6 . The film of  claim 1 , wherein the film is heated under reduced pressure or under an inert atmosphere at a temperature that results in the film becoming solvent resistant. 
     
     
         7 . The film of  claim 6 , wherein heating is conducted at less than approximately 280° C. for at least approximately 1 minute. 
     
     
         8 . The film of  claim 6 , wherein heating is conducted between approximately 250° C. and approximately 280° C. for at least approximately 1 minute and less than approximately 30 minutes. 
     
     
         9 . The film of  claim 6 , wherein the film thickness is greater than approximately 4 μm. 
     
     
         10 . The film of  claim 9 , wherein the film thickness is greater than approximately 4 μm and less than approximately 100 μm. 
     
     
         11 . The film of  claim 9 , wherein a film approximately 10 μm thick has a transmittance of >80% from 400 to 750 nm. 
     
     
         12 . The film of  claim 11 , wherein the optical transmittance is >85% at 550 nm. 
     
     
         13 . The film of  claim 9 , wherein the film is adhered to a substrate. 
     
     
         14 . The film of  claim 13 , wherein the substrate is a glass film greater than approximately 50 μm thick. 
     
     
         15 . The film of  claim 6 , wherein the average coefficient of thermal expansion is less than approximately 20 ppm/° C. between 25° C. and 250° C. 
     
     
         16 . The film of  claim 15 , wherein the average coefficient of thermal expansion is less than approximately 10 ppm/° C. between 25° C. and 250° C. 
     
     
         17 . A polymer solution capable of being made into transparent films; wherein the polymer solution comprises: (A) an aromatic polyamide that is capable of being thermally cross-linked, and has at least one repeat units of general formula (I): 
       
         
           
           
               
               
           
         
         wherein X represents the molar percentage of the repeat structure (I) and wherein the polyamide is soluble in polar organic solvents in the absence of inorganic salts and has a Tg higher than 300° C., and Ar 1  is selected from the group consisting of: 
       
       
         
           
           
               
               
           
         
         wherein p is 4, q is 3, and wherein R 1 , R 2 , R 3 , R 4 , R 5  are selected from the group comprising hydrogen; halogens; alkyl groups; substituted alkyl groups; cyano groups; thioalkyl groups, alkoxy groups; substituted alkoxy groups; aryl groups; substituted aryl groups; alkyl ester groups; substituted alkyl ester groups; and combinations thereof, wherein G 1  is selected from a group comprising a covalent bond; a CH 2  group; a C(CH 3 ) 2  group; a C(CF 3 ) 2  group; and a C(CM 3 ) 2  group, wherein M is selected from the group comprising a halogen; a CO group; an O atom; a S atom; a SO 2  group; a Si(CH 3 ) 2  group; a 9,9′-bisphenylenefluorene group; a substituted 9,9′-bisphenylenefluorene group; and an OZO group, wherein Z is selected from the group comprising an aryl group; a substituted aryl group; a biphenyl group; a perfluorobiphenyl group; a 9,9′-bisphenylenefluorene group; and a substituted 9,9′-bisphenylenefluorene group, and 
         wherein at least one of the Ar 1  groups in at least one of the repeat units (I) is selected from the group consisting of: 
       
       
         
           
           
               
               
           
         
         wherein Ar 2  is selected from the group consisting of: 
       
       
         
           
           
               
               
           
         
         wherein p is 4, wherein R 6 , R 7 , and R 8  are selected from the group comprising hydrogen; halogens; alkyl groups; substituted alkyl groups; cyano groups; thioalkyl groups, alkoxy groups; substituted alkoxy groups; aryl groups; substituted aryl groups; alkyl ester groups; substituted alkyl ester groups; and combinations thereof, wherein G 2  is selected from the group comprising a covalent bond; a CH 2  group; a C(CH 3 ) 2  group; a C(CF 3 ) 2  group; and a C(CM 3 ) 2  group, wherein M is selected from the group comprising a halogen; a CO group; an O atom; a S atom; a SO 2  group; a Si(CH 3 ) 2  group; a 9,9′-bisphenylenefluorene group; a substituted 9,9′-bisphenylenefluorene group; and an OZO group, wherein Z is selected from the group comprising an aryl group; substituted aryl group; a biphenyl group, a perfluorobiphenyl group, a 9,9′-bisphenylenefluorene group, and a substituted 9,9′-bisphenylenefluorene group; and 
         wherein at least one of the Ar 2  groups in at least one of the repeat units (I) is selected from the group consisting of: 
       
       
         
           
           
               
               
           
         
       
       and,
 (B) a multifunctional epoxide selected from the group comprising the general structures (II), (III), and (IV): 
 
       
         
           
           
               
               
           
         
         wherein x>1 and R 9  is selected from the group comprising 
       
       
         
           
           
               
               
           
         
         where the cyclic structure is selected from the group comprising 
       
       
         
           
           
               
               
           
         
         wherein n and n 1 >1 and R 10  is an alkyl or aromatic group. 
       
     
     
         18 . The polymer solution of  claim 17 , wherein the multifunctional epoxide is between approximately 1 and approximately 10 wt % based on the weight of the polyamide. 
     
     
         19 . The polymer solution of  claim 17 , wherein the polymer solution is solution cast into a film that has a film transparency of >80% between 400 nm and 750 nm. 
     
     
         20 . The polymer solution of  claim 17 , wherein the film thickness is greater than approximately 4 μm and less than approximately 100 μm. 
     
     
         21 . The polymer solution of  claim 17 , wherein the film is heated under reduced pressure or under an inert atmosphere at a temperature that results in the film becoming solvent resistant. 
     
     
         22 . The polymer solution of  claim 19 , wherein the solution cast film has an average coefficient of thermal expansion is less than approximately 20 ppm/° C. between 25° C. and 250° C. 
     
     
         23 . A polymer solution capable of being made into transparent films; wherein the polymer solution comprises:
 (A) an aromatic copolyamide that is capable of being thermally cross-linked and having at least two repeat units of general formula (I) and (V):   
       
         
           
           
               
               
           
         
         wherein X represents the molar percentage of the repeat structure (I) and Y represents the molar percentage of the repeat structure (V) and wherein the copolyamide is soluble in polar organic solvents and can be solution cast into a clear film with a Tg higher than 300° C.; and Ar 1  is selected from the group consisting of: 
       
       
         
           
           
               
               
           
         
         wherein p is 4, q is 3, and wherein R 1 , R 2 , R 3 , R 4 , R 5  are selected from the group comprising hydrogen, halogen; alkyl groups; substituted alkyl groups; cyano groups; thioalkyl groups, alkoxy groups; substituted alkoxy groups; aryl groups; substituted aryl groups; alkyl ester groups; substituted alkyl ester groups; and combinations thereof, wherein G 1  is selected from the group comprising a covalent bond; a CH 2  group; a C(CH 3 ) 2  group; a C(CF 3 ) 2  group; and a C(CM 3 ) 2  group, wherein M is selected from the group comprising a halogen; a CO group; an O atom; a S atom; a SO 2  group; a Si(CH 3 ) 2  group; a 9,9′-bisphenylenefluorene group; a substituted 9,9′-bisphenylenefluorene group; and an OZO group, wherein Z is selected from the group comprising a aryl group or substituted aryl group; a biphenyl group; a perfluorobiphenyl group; a 9,9′-bisphenylenefluorene group; and a substituted 9,9′-bisphenylenefluorene group, 
         and wherein at least one of the Ar 1  groups in at least one of the repeat units of (I) or at least one of the repeat units of (V) is selected from the group consisting of: 
       
       
         
           
           
               
               
           
         
         wherein Ar 2  is selected from the group consisting of: 
       
       
         
           
           
               
               
           
         
         wherein p is 4, wherein R 6 , R 7 , R 8  are selected from the group comprising hydrogen, halogens; alkyl groups; substituted alkyl groups; cyano groups; thioalkyl groups, alkoxy groups; substituted alkoxy groups; aryl groups; substituted aryl groups; alkyl ester groups; substituted alkyl ester groups; and combinations thereof, wherein G 2  is selected from the group comprising a covalent bond; a CH 2  group; a C(CH 3 ) 2  group; a C(CF 3 ) 2  group; and a C(CM 3 ) 2  group, wherein M is selected from the group comprising a halogen; a CO group; an O atom; a S atom; a SO 2  group; a Si(CH 3 ) 2  group; a 9,9′-bisphenylenefluorene group; a substituted 9,9′-bisphenylenefluorene group; and an OZO group, wherein Z is selected from the group comprising a aryl group or substituted aryl group; a perfluorobiphenyl group; a 9,9′-bisphenylenefluorene group; and a substituted 9,9′-bisphenylenefluorene group, and 
         wherein at least one of the Ar 2  groups in at least one of the repeat units (I) is selected from the group consisting of: 
       
       
         
           
           
               
               
           
         
       
       and 
       wherein Ar 3  is selected from the group comprising: 
       
         
           
           
               
               
           
         
         wherein t is 0 to 3, g is 0 to 4, and s is 0 to 4, wherein R 9 , R 10 , R 11  are selected from the group comprising hydrogen, halogens; alkyl groups; substituted alkyl groups; cyano groups; thioalkyl groups, alkoxy groups; substituted alkoxy groups; aryl groups; substituted aryl groups; alkyl ester groups; substituted alkyl ester groups; and combinations thereof, wherein G 3  is selected from the group comprising a covalent bond; a CH 2  group; a C(CH 3 ) 2  group; a C(CF 3 ) 2  group; and a C(CM 3 ) 2  group, wherein M is selected from the group comprising a halogen; a CO group; an O atom; a S atom; a SO 2  group; a Si(CH 3 ) 2  group; a 9,9′-bisphenylenefluorene group; a substituted 9,9′-bisphenylenefluorene group; and an OZO group, wherein Z is selected from the group comprising a aryl group; substituted aryl group; a biphenyl group; a perfluorobiphenyl group; a 9,9′-bisphenylenefluorene group; and a substituted 9,9′-bisphenylenefluorene group; and, wherein at least one Ar 3  group in at least one of the repeat units (V) is selected from: 
       
       
         
           
           
               
               
           
         
       
       and
 (B) a multifunctional epoxide selected from the group comprising the general structures (II), (III), and (IV): 
 
       
         
           
           
               
               
           
         
         wherein x>1 and R 12  is selected from the group comprising 
       
       
         
           
           
               
               
           
         
         where the cyclic structure is selected from the group comprising 
       
       
         
           
           
               
               
           
         
         wherein n and n 1 >1 and R 13  is an alkyl or aromatic group. 
       
     
     
         24 . The polymer solution of  claim 23 , wherein the copolyamide contains multiple repeat units with structures (I) and (V). 
     
     
         25 . The polymer solution of  claim 23 , wherein the copolyamide contains approximately 1 to approximately 10 mole % of the repeat unit containing at least one carboxyl group. 
     
     
         26 . The polymer solution of  claim 23 , wherein the film thickness is greater than approximately 4 μm and less than approximately 100 μm. 
     
     
         27 . The polymer solution of  claim 23 , wherein the film is approximately 10 μm thick and has a transmittance of >85% at 550 nm. 
     
     
         28 . The polymer solution of  claim 23 , wherein the film has an average coefficient of thermal expansion which is less than approximately 20 ppm/° C. between 25° C. and 250° C.