Crosslinked self-doping type electrically conducting polymer, production process thereof, product coated with the polymer and electronic device

1. A self-doping type electrically conducting polymer comprising crosslinked polymer chains, wherein the crosslinking is formed through a sulfone bond and the polymer contains an isothianaphthene skeleton having a sulfonic acid group.

2. The self-doping type electrically conducting polymer as claimed in claim 1 , wherein the sulfone bond is contained in an amount of from 1 to 90 mol % based on the repeating unit of the polymer.

3. The self-doping type electrically conducting polymer as claimed in claim 1 , wherein the polymer chains are crosslinked through a bond having a binding energy from 0.5 to 2 eV lower than the binding energy of the sulfonic acid group as measured by X-ray photoelectron spectrometry.

4. The self-doping type electrically conducting polymer as claimed in claim 1 , wherein the crosslinked structure through a sulfone bond is a isothianaphthene structure represented by formula (1)′

wherein R 1 to R 3 each independently represents a hydrogen atom, a linear or branched alkyl group having from 1 to 20 carbon atoms, a linear or branched alkoxy group having from 1 to 20 carbon atoms, a linear or branched alkenyl group having from 2 to 20 carbon atoms, a linear or branched alkenyloxy group having from 2 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a —B 1 —SO 3 − M + group, B 1 and B 2 each independently represents —(CH 2 ) p —(O) q —(CH 2 ) r —, p and r each independently represents 0 or an integer of 1 to 3, q represents 0 or 1, X represents a polymer chain selected from the group consisting of a polypyrrole structure, a polythiophene structure, a polycarbazole structure, a polyaniline structure and an arylenevinylene structure which bonds to B 2 via an aromatic ring or a heterocyclic ring contained in the polymer chain, and M + represents a hydrogen ion, an alkali metal ion or a quaternary ammonium ion.

5. The self-doping type electrically conducting polymer as claimed in claim 1 , wherein the crosslinked structure through a sulfone bond is a structure represented by formula (2):

wherein R 1 to R 6 each independently represents a hydrogen atom, a linear or branched alkyl group having from 1 to 20 carbon atoms, a linear or branched alkoxy group having from 1 to 20 carbon atoms, a linear or branched alkenyl group having from 2 to 20 carbon atoms, a linear or branched alkenyloxy group having from 2 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a —B 1 —SO 3 − M + group, B 1 represents —(CH 2 ) p —(O) q —(CH 2 ) r —, p and r each independently represents 0 or an integer of 1 to 3, q represents 0 or 1, and M + represents a hydrogen ion, an alkali metal ion or a quaternary ammonium ion.

6. The self-doping type electrically conducting polymer as claimed in claim 5 , wherein the crosslinked structure through a sulfone bond is a structure represented by formula (3)

wherein B 1 represents —(CH 2 ) p —(O) q —(CH 2 ) r —, p and r each independently represents 0 or an integer of 1 to 3, q represents 0 or 1, and M + represents a hydrogen ion, an alkali metal ion or a quaternary ammonium ion.

7. A process for producing the self-doping type electrically conducting polymer containing a crosslinked structure through a sulfone bond represented by formula (2) described in claim 5 , comprising dehydration-condensing self-doping type electrically conducting polymers having a structure represented by formula (7)

wherein R 1 to R 3 each independently represents a hydrogen atom, a linear or branched alkyl group having from 1 to 20 carbon atoms, a linear or branched alkoxy group having from 1 to 20 carbon atoms, a linear or branched alkenyl group having from 2 to 20 carbon atoms, a linear or branched alkenyloxy group having from 2 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a —B 1 —SO 3 − M + group, with the proviso that at least one of R 1 to R 3 is a hydrogen atom, B 1 represents —(CH 2 ) p —(O) q —(CH 2 ) r —, p and r each independently represents 0 or an integer of 1 to 3, q represents 0 or 1, and M + represents a hydrogen ion, an alkali metal ion or a quaternary ammonium ion.

8. A process for producing the self-doping type electrically conducting polymer containing a crosslinked structure through a sulfone bond represented by formula (2) described in claim 5 , comprising dehydration-condensing self-doping type electrically conducting polymers having a structure represented by formula (7) and/or formula (8):

wherein R 1 to R 3 and R 7 to R 10 each independently represents a hydrogen atom, a linear or branched alkyl group having from 1 to 20 carbon atoms, a linear or branched alkoxy group having from 1 to 20 carbon atoms, a linear or branched alkenyl group having from 2 to 20 carbon atoms, a linear or branched alkenyloxy group having from 2 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a —B 1 —SO 3 − M + group, with the proviso that at least one of R 7 to R 10 is a hydrogen atom, B 1 represents —(CH 2 ) p —(O) q —(CH 2 ) r —, p and r each independently represents 0 or an integer of 1 to 3, q represents 0 or 1, and M + represents a hydrogen ion, an alkali metal ion or a quaternary ammonium ion.

9. A process for producing the self-doping type electrically conducting polymer containing a crosslinked structure through a sulfone bond represented by formula (3) described in claim 6 , comprising dehydration-condensing self-doping type electrically conducting polymers obtained by (co)polymerizing a monomer represented by formula (9):

wherein B 1 represents —(CH 2 ) p —(O) q —(CH 2 ) r —, p and r each independently represents 0 or an integer of 1 to 3, q represents 0 or 1, and M + represents a hydrogen ion, an alkali metal ion or a quaternary ammonium ion.

10. The process for producing a self-doping type electrically conducting polymer as claimed in claim 7 , wherein the dehydration condensation reaction is performed by a heat treatment at a temperature range of 210 to 350° C.

11. A self-doping type electrically conducting polymer obtained by the production process described in claim 7 .

12. An electrically conducting composition comprising the self-doping type electrically conducting polymer described in claim 1 , and a solvent.

13. A method for producing an electrically conducting film, comprising coating the electrically conducting composition described in claim 12 on a substrate and heating it.

14. The method for producing an electrically conducting film as claimed in claim 13 , wherein the self-doping type electrically conducting polymer having a structure represented by formula (7) and/or formula (8) is applied onto a substrate surface and then the substrate is heated at a temperature of 210 to 350° C. for 1 to 600 seconds,

wherein R 1 to R 3 and R 7 to R 10 each independently represents a hydrogen atom, a linear or branched alkyl group having from 1 to 20 carbon atoms, a linear or branched alkoxy group having from 1 to 20 carbon atoms, a linear or branched alkenyl group having from 2 to 20 carbon atoms, a linear or branched alkenyloxy group having from 2 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a —B 1 —SO 3 − M + group, with the proviso that at least one of R 7 to R 10 is a hydrogen atom, B 1 represents —(CH 2 ) p —(O) q —(CH 2 ) r —, p and r each independently represents 0 or an integer of 1 to 3, q represents 0 or 1, and M + represents a hydrogen ion, an alkali metal ion or a quaternary ammonium ion.

15. The self-doping type electrically conducting polymer as claimed in claim 1 , wherein one of the crosslinked polymer chains contains an isothianaphthene skeleton having a sulfonic acid group and another of the crosslinked polymer chains is selected from the group consisting of a polypyrrole structure, a polythiophene structure, a polycarbazole structure, a polyaniline structure and an arylenevinylene structure.

16. An electrically conducting film produced by the method described in claim 13 .

17. The electrically conducting film as described in claim 16 , wherein the film thickness is from 1 to 1,000 nm.

18. A coated product comprising a shaped body having coated on the surface thereof the self-doping type electrically conducting polymer described in claim 1 .

19. A coated product comprising a substrate as a shaped body, wherein one surface, both surfaces or the entire surface of the substrate is coated with the self-doping type electrically conducting polymer described in claim 1 .

20. A coated product comprising a substrate as a shaped body, wherein one surface, both surfaces or the entire surface of the substrate is coated with the electrically conducting composition described in claim 12 .

21. The coated product as claimed in claim 19 , wherein the substrate is a silicon wafer.

22. The coated product as claimed in claim 19 , wherein the substrate is entirely or partially coated with indium tin oxide.

23. An electronic device comprising the self-doping type electrically conducting polymer described in claim 1 .

24. An electronic device comprising the electrically conducting composition described in claim 12 .

25. An organic light-emitting element comprising at least one light-emitting layer between a pair of anode and cathode, wherein the self-doping type electrically conducting polymer described in claim 1 is contained in the anode buffer layer.

26. The organic light-emitting element as claimed in claim 25 , wherein the self-doping type electrically conducting polymer has a sulfonic acid group.

27. The organic light-emitting element as claimed in claim 25 , wherein the self-doping type electrically conducting polymers are crosslinked through a sulfone bond.

28. An organic light-emitting element comprising the self-doping type electrically conducting polymer described in claim 1 .

29. An organic light-emitting element comprising the electrically conducting composition described in claim 12 .

30. The organic light-emitting element as claimed in claim 25 , wherein the light-emitting layer comprises a fluorescence-emitting polymer material.

31. The organic light-emitting element as claimed in 25 , wherein the light-emitting layer comprises a phosphorescence-emitting polymer material.

32. An organic EL display comprising the organic light-emitting element described in claim 25 .

33. A display device for portable terminals, comprising the organic EL display described in claim 32 .