Reactive mesogen formulation with conductive additive

Abstract

The invention relates to a reactive mesogen (RM) formulation comprising a conductive additive, to a polymer film obtained thereof, and the use of the RM formulation and polymer film in optical or electrooptical components or devices, like optical retardation films for liquid crystal displays (LCDs).

1 . A formulation comprising >50% of one or more polymerisable mesogenic compounds, and one or more conductive additives. 
     
     
         2 . A formulation according to  claim 1 , characterized in that the conductive additives are selected from ionic organic compounds. 
     
     
         3 . A formulation according to  claim 2 , characterized in that the conductive additives contain an organic cation selected from the group consisting of ammonium, phosphonium, sulfonium, uronium, thiouronium, guanidinium and heterocyclic cations. 
     
     
         4 . A formulation according to  claim 3 , characterized in that the conductive additives contain an organic cation selected from the group consisting of tetraalkylammonium, tetraalkylphosphonium, N-alkylpyridinium, N,N-dialkylpyrrolidinium, 1,3-dialkylimidazolium or trialkylsulfonium cation. 
     
     
         5 . A formulation according to  claim 2 , characterized in that the conductive additives contain an anion selected from the group consisting of halide, borate, imide, phosphate, sulfonate, sulfate, succinate, naphthenate and carboxylate. 
     
     
         6 . A formulation according to  claim 5 , characterized in that the conductive additives contain an anion selected from the group consisting of chloride, bromide, iodide, tetrafluoroborate, tetracyanoborate (TCB), difluoro-dicyano borate, fluoro-tricyano borate, perfluoroalkyl-fluoro-dicyano borate, pentafluoroethyl-fluoro-dicyano borate, perfluoroalkyl-difluoro-cyano borate, pentafluoroethyl-difluoro-cyano borate, perfluoroalkyl-fluoro borate (FAB), perfluoroalkyl-alkoxy-dicyano borate, alkoxy-tricyano borate, methoxy-tricyano borate, ethoxy-tricyano borate, 2,2,2-trifluoroethoxy-tricyano borate, bis(2,2,2-trifluoroethoxy)-dicyano borate, tetraphenylborate (TPB), tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (TFPB), tetrakis(4-chlorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(2,2,2-trifluoroethoxy)borate, bis(oxalato)borate, bis(trifluoromethylsulfonyl)imide (NTF), bis(fluorosulfonyl)imide, bis[bis(pentafluoroethyl)phosphinyl]imide (FPI), tris(trifluoromethylsulfonyl)methide, (fluoroalkyl)fluorophosphates, tris(pentafluoroethyl)trifluorophosphate (FAP), bis(pentafluoroethyl)tetrafluorophosphate, (pentafluoroethyl)pentafluorophosphate, tris(nonafluorobutyl)trifluorophosphate, bis(nonafluorobutyl)tetrafluorophosphate, (nonafluorobutyl)pentafluorophosphate, hexafluorophosphate, bis(fluoroalkyl)phosphinate, bis(pentafluoroethyl)phosphinate, bis(nonafluorobutyl)phosphinate, (fluoroalkyl)phosphonate, (pentafluoroethyl)phosphonate, (nonafluorobutyl)phosphonate, nonafluorobutane sulfonate (nonaflate) (NFS), trifluoromethanesulfonate, trifluoroacetate, methanesulfonate, butanesulfonate, butylsulfate, hexylsulfate, octylsulfate, dicyanamide, tricyanomethide, thiocyanate, hydrogensulfate, trifluoroacetate, tosylate, (bis(2-2-ethyl hexyl) sulfosuccinate (AOT), naphthenates, lauryl sulphate, alkyl benzene sulfonates, alkyl naphthalene sulfonate), alkyl aryl ether phosphates, alkyl ether phosphate, alkyl carboxylates, wherein “alkyl” is C 1 -C 20 alkyl, “fluoroalkyl” is fluorinated C 1 -C 20 alkyl, “perfluoroalkyl” is C 1 -C 20  perfluoroalkyl, and “aryl” is optionally substituted C 5 -C 8 -aryl. 
     
     
         7 . A formulation according to  claim 1 , characterized in that the conductive additives are selected from ionic organic compounds comprising one or more polymerisable functional groups. 
     
     
         8 . A formulation according to  claim 1 , characterized in that the conductive additives are selected from formula 1:
   P 1 -Sp-C + A −   1
   
       wherein P 1  is a polymerisable group, Sp is a spacer group or a single bond, C +  is a cation, and A −  is an anion. 
     
     
         9 . A formulation according to  claim 8 , characterized in that the conductive additives are selected from formula 1a-1c:
   P 1 -Sp-[NR a R b R c ] + A −   1a
     P 1 -Sp-[PR a R b R c ] + A −   1b
     P 1 -Sp-[SR a R b R c ] + A −   1c
   wherein P 1 , Sp and A −  are as defined in  claim 8 , and   R a , R b , R c  independently of each other denote straight-chain, branched or cyclic alkyl with 1 to 25, preferably 1 to 10 C-atoms, wherein one or more CH 2  groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 00 —, —CO—, —CH═CH— or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and wherein one or more H atoms may also be replaced by F, Cl, Br, I or CN, or two of R a , R b  and R c  together with the N +  atom form an aliphatic or aromatic ring with 4 to 8 C atoms which is optionally substituted by one or more groups L,   L is P 1 -Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR 00 R 000 , —C(═O)X, —C(═O)OR 00 , —C(═O)R 0 , —NR 00 R 000 , —OH, —SF 5 , optionally substituted silyl, aryl or heteroaryl with 1 to 12, preferably 1 to 6 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12, preferably 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,   R 00 , R 000  independently of each other denote H or alkyl with 1 to 12 C-atoms, and   X is halogen.   
     
     
         10 . A formulation according to  claim 1 , characterized in that the conductive additives are selected from organic compounds that comprise one or more polar groups that increase the conductivity of the RM formulation and one or more polymerisable functional groups. 
     
     
         11 . A formulation according to  claim 10 , characterized in that the conductive additives are selected of formula 2
   P 1 -Sp 3 -G  2
   wherein   P 1  is a polymerisable group,   Sp 3  is an alkylene spacer with 2 to 12 C atoms, which is optionally substituted with one or more groups G, and wherein one or more CH 2  groups are optionally replaced by —O—, —S—, —CO—, NR 00 R 000 , or denotes a single bond, wherein R 00  and R 000  independently of each other denote H or alkyl with 1 to 12 C-atoms, and   G is a polar group selected from COOH, OH, NH 2 , NO 2 , SO 3 H, SH, PO 3 H 2 , and benzene that is mono- or polysubstituted with COOH, OH, NH 2 , NO 2 , SO 3 H, SH or PO 3 H 2 .   
     
     
         12 . A formulation according to  claim 1 , characterized in that it comprises one or more polymerisable mesogenic compounds having only one polymerisable functional group (monoreactive), and one or more polymerisable mesogenic compounds having two or more polymerisable functional groups (di- or multireactive). 
     
     
         13 . A formulation according to  claim 1 , characterized in that it comprises one or more RMs of formula I
   P 1 -Sp 1 -MG-Sp 2 -P 2   I
   wherein P 1  and P 2  are independently of each other a polymerisable group, Sp 1  and Sp 2  are independently of each other a spacer group or a single bond, and MG is a rod-shaped mesogenic group of formula II
   -(A 1 -Z 1 ) n -A 2 -  II
 
   wherein   A 1  and A 2  denote, in case of multiple occurrence independently of one another, an aromatic or alicyclic group, which optionally contains one or more heteroatoms selected from N, O and S, and is optionally mono- or polysubstituted by L,   L is P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR 00 R 000 , —C(═O)X, —C(═O)OR 00 , —C(═O)R 0 , —NR 00 R 000 , —OH, —SF 5 , optionally substituted silyl, aryl or heteroaryl with 1 to 12, preferably 1 to 6 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12, preferably 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,   R 00 , R 000  independently of each other denote H or alkyl with 1 to 12 C-atoms,   X is halogen, preferably F or Cl,   Z 1  denotes, in case of multiple occurrence independently of one another, —O—, —S—, —CO—, —COO—, —OCO—, —S—CO—, —CO—S—, —O—COO—, —CO—NR 00 —, —NR 00 —CO—, —NR 00 —CO—NR 000 , —NR 00 —CO—O—, —O—CO—NR 00 —, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH 2 CH 2 —, —(CH 2 ) n1 , —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 00 —, —CY 1 ═CY 2 —, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond, preferably —COO—, —OCO— or a single bond,   Y 1  and Y 2  independently of each other denote H, F, Cl or CN,   n is 1, 2, 3 or 4, preferably 1 or 2, most preferably 2,   n1 is an integer from 1 to 10, preferably 1, 2, 3 or 4.   
     
     
         14 . A formulation according to  claim 13 , characterized in that it comprises one or more RMs of formula Ia 
       
         
           
           
               
               
           
         
         wherein 
         P 0  is, in case of multiple occurrence independently of one another, a polymerisable group, preferably an acryl, methacryl, oxetane, epoxy, vinyl, vinyloxy, propenyl ether or styrene group, 
         Z 0  is —COO—, —OCO—, —CH 2 CH 2 —, —CF 2 O—, —OCF 2 —, —C≡C—, —CH═CH—, —OCO—CH═CH—, —CH═CH—COO—, or a single bond, 
         L has the meanings given in  claim 13  and is preferably, in case of multiple occurrence independently of one another, selected from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 5 C atoms, 
         r is 0, 1, 2, 3 or 4, 
         x, y are independently of each other 0 or identical or different integers from 1 to 12, 
         z is 0 or 1, with z being 0 if the adjacent x or y is 0. 
       
     
     
         15 . A formulation according to  claim 13 , characterized in that it comprises one or more RMs selected from the following formulae: 
       
         
           
           
               
               
           
         
         wherein P 0 , L, r, x, y and z are as defined in formula Ia. 
       
     
     
         16 . A formulation according to  claim 1 , characterized in that it comprises one or more RMs of formula III
   P 1 -Sp 1 -MG-R  III
   wherein P 1  is a polymerisable group, Sp 1  is a spacer group or a single bond, and MG is a rod-shaped mesogenic group of formula II
   -(A 1 -Z 1 ) n -A 2 -  II
 
   wherein   A 1  and A 2  denote, in case of multiple occurrence independently of one another, an aromatic or alicyclic group, which optionally contains one or more heteroatoms selected from N, O and S, and is optionally mono- or polysubstituted by L,   L is P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR 00 R 000 , —C(═O)X, —C(═O)OR 00 , —C(═O)R 0 , —NR 00 R 000 , —OH, —SF 5 , optionally substituted silyl, aryl or heteroaryl with 1 to 12, preferably 1 to 6 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12, preferably 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,   Z 1  denotes, in case of multiple occurrence independently of one another, —O—, —S—, —CO—, —COO—, —OCO—, —S—CO—, —CO—S—, —O—COO—, —CO—NR 00 —, —NR 00 —CO—, —NR 00 —CO—NR 000 , NR 00 —CO—O—, —O—CO—NR 00 —, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH 2 CH 2 —, —(CH 2 ) n1 , —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 00 —, —CY 1 ═CY 2 —, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond, preferably —COO—, —OCO— or a single bond.   Y 1  and Y 2  independently of each other denote H, F, Cl or CN,   n is 1, 2, 3 or 4, preferably 1 or 2, most preferably 2,   n1 is an integer from 1 to 10, preferably 1, 2, 3 or 4,   R denotes P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR 00 R 000 , —C(═O)X, —C(═O)OR 0 , —C(═O)R 00 , —NR 00 R 000 , —OH, —SF 5 , optionally substituted silyl, straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12, preferably 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,   X is halogen, preferably F or Cl, and   R 00  and R 000  are independently of each other H or alkyl with 1 to 12 C-atoms.   
     
     
         17 . A formulation according to  claim 1 , characterized in that it comprises one or more RMs selected from the following formulae: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein P 0 , L, r, x, y and z are 
         P 0  is, in case of multiple occurrence independently of one another, a polymerisable group, preferably an acryl, methacryl, oxetane, epoxy, vinyl, vinyloxy, propenyl ether or styrene group 
         L are independently of one another, selected from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 5 C atoms, 
         r is 0, 1, 2, 3 or 4, 
         x, y are independently of each other 0 or identical or different integers from 1 to 12, 
         z is 0 or 1, with z being 0 if the adjacent x or y is 0, 
         R 0  is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 or more, preferably 1 to 15 C atoms which is optionally fluorinated, or denotes Y 0  or P—(CH 2 ) y —(O) z —, 
         X 0  is —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 01 —, —NR 01 —CO—, —NR 01 —CO—NR 01 —, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 01 —, —CF═CF—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond, 
         Y 0  is F, Cl, CN, NO 2 , OCH 3 , OCN, SCN, SF 5 , optionally fluorinated alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 4 C atoms, or mono- oligo- or polyfluorinated alkyl or alkoxy with 1 to 4 C atoms, 
         A 0  is, in case of multiple occurrence independently of one another, 1,4-phenylene that is unsubstituted or substituted with 1, 2, 3 or 4 groups L, or trans-1,4-cyclohexylene, 
         R 01,02  are independently of each other H, R 0  or Y 0 , 
         u and v are independently of each other 0, 1 or 2, 
         w is 0 or 1, 
       
       and wherein the benzene and napthalene rings can additionally be substituted with one or more identical or different groups L. 
     
     
         18 . A formulation according to  claim 1 , characterized in that it further comprises one or more organic solvents. 
     
     
         19 . A formulation according to  claim 1 , characterized in that it comprises
 30 to 99.9% of polymerisable mesogenic compounds having two or more polymerisable functional groups,   0 to 90% polymerisable mesogenic compounds having only one polymerisable functional group,   0.01 to 5% of one or more conductive additives,   0 to 5% of one or more surfactants,   0 to 5% of one or more polymerisation initiators.   
     
     
         20 . A formulation according to  claim 19 , characterized in that it comprises
 50 to 80% of polymerisable mesogenic compounds having two or more polymerisable functional groups,   10 to 70% polymerisable mesogenic compounds having only one polymerisable functional group,   0.1 to 1% of one or more conductive additives,   0.1 to 1% of one or more surfactants,   0.1 to 2% of one or more polymerisation initiators.   
     
     
         21 . A polymer film obtained by polymerising an RM formulation according to  claim 1 , wherein the RMs are aligned and are polymerised at a temperature at which the RM formulation exhibits a liquid crystal phase. 
     
     
         22 . The use of an RM formulation or polymer film according to  claim 1  in an optical, electrooptical or electronic device or in a component thereof. 
     
     
         23 . An optical, electrooptical or electronic device, or a component thereof, comprising an RM formulation or polymer film according to  claim 1 . 
     
     
         24 . A component according to  claim 23 , which is selected from optical retardation films, polarizers, compensators, beam splitters, reflective films, alignment layers, colour filters, antistatic protection sheets, or electromagnetic interference protection sheets, polarization controlled lenses for autostereoscopic 3D displays, and IR reflection films for window applications. 
     
     
         25 . A device according to  claim 23 , which is selected from electrooptical displays, especially liquid crystal displays, autostereoscopic 3D displays, organic light emitting diodes (OLEDs), optical data storage devices, and window applications.