FORMULATION CONTAINING A HIGHLY BRANCHED POLYMER, HIGHLY BRANCHED POLYMER AND ELECTRO-OPTICAL DEVICE CONTAINING THIS HIGHLY BRANCHED POLYMER

Abstract

The present invention relates to formulations comprising at least one hyperbranched polymer which contains 30 to 70 mol % of at least one hole-transporting recurring unit A, 5 to 30 mol % of least one branching recurring unit B, 5 to 30 mol % of at least one further recurring unit C and 5 to 40 mol % of least one end group E, where the recurring units A, B and C are different from one another, and at least one organic solvent, characterised in that the formulation has a viscosity of ≤25 mPas. The present invention furthermore relates to the corresponding hyperbranched polymers and to processes for the preparation thereof. The present invention additionally also relates to the use of the hyperbranched polymers according to the invention in electronic or opto-electronic devices, and to electronic or opto-electronic devices containing these polymers

Claims

1-30. (canceled)

31. Formulation comprising A) at least one highly branched polymer which contains 30 to 70 mol % of at least one hole-transporting recurring unit A, 5 to 30 mol % of at least one branching recurring unit B, 5 to 30 mol % of at least one further recurring unit C, and 5 to 40 mol % of at least one end group E, where the recurring units A, B and C are different from one another, and B) at least one organic solvent, wherein the formulation has a viscosity of ≤25 mPas.

32. Formulation according to claim 31, wherein the formulation comprises an organic solvent.

33. Formulation according to claim 31, wherein the formulation comprises a mixture of two or more organic solvents.

34. Formulation according to claim 31, wherein the at least one organic solvent has a boiling point of at least 200° C.

35. Formulation according to claim 31, wherein the concentration of the highly branched polymer in the formulation is in the range from 5 to 50 g/l.

36. Formulation according to claim 31, wherein the highly branched polymer has a molecular weight Mw in the range from 15,000 to 1,000,000 g/mol.

37. Formulation according to claim 31, wherein the hole-transporting recurring units A are selected from triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrophenazine, thianthrene, dibenzo-para-dioxin, phenoxathiyne, carbazole, azulene, thiophene, pyrrole and furan derivatives and further O-, S- or N-containing heterocycles.

38. Formulation according to claim 31, wherein the hole-transporting recurring units A are selected from triarylamine units of the following formula (A) ##STR00290## where Ar.sup.1 to Ar.sup.3 are on each occurrence, in each case identically or differently, a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which may in each case be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, C═S, C═NR.sup.1, P(═O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or an aralkyl or heteroarylaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a crosslinkable group Q, where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; R.sup.1 is on each occurrence, identically or differently, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and/or heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R.sup.1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; and the dashed lines represent bonds to adjacent structural units in the polymer.

39. Formulation according to claim 8, wherein the hole-transporting recurring units A are selected from triarylamine units of the formula (I), where Ar.sup.1, Ar.sup.2 and Ar.sup.3 can adopt the meanings indicated in claim 8, wherein Ar.sup.3 is substituted by Ar.sup.4 in at least one, of the two ortho positions, where Ar.sup.4 is a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where R can adopt the meanings indicated in claim 6.

40. Formulation according to claim 31, wherein the branching recurring units B are selected from the structural units of the formulae (B1) to (B5) ##STR00291## where Ar.sup.1 to Ar.sup.5 are on each occurrence, in each case identically or differently, a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which may in each case be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, C═S, C═NR.sup.1, P(═O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or an aralkyl or heteroarylaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a crosslinkable group Q, where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; R.sup.1 is on each occurrence, identically or differently, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and/or heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R.sup.1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; Y is C or Si, and the dashed lines represent bonds to adjacent structural units in the polymer.

41. Formulation according to claim 31, wherein the further recurring units C are selected from 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, fluorene derivatives, 9,9′-spirobifluorene derivatives, phenanthrene derivatives, 9,10-dihydrophenanthrene derivatives, 5,7-dihydrodibenzoxepine derivatives and cis- and trans-indenofluorene derivatives, but also 1,2-, 1,3- or 1,4-phenylene, 1,2-, 1,3- or 1,4-naphthylene, 2,2′-, 3,3′- or 4,4′-biphenylylene, 2,2″-, 3,3″- or 4,4″-terphenylylene, 2,2′-, 3,3′- or 4,4′-bi-1,1′-naphthylylene or 2,2′″-, 3,3′″ or 4,4′″-quaterphenylylene derivatives.

42. Formulation according to claim 31, wherein the end groups E are selected from structural units of the formulae (E1) to (E13) ##STR00292## ##STR00293## ##STR00294## where R is on each occurrence, identically or differently, HK D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which may in each case be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, C═S, C═NR.sup.1, P(═O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or an aralkyl or heteroarylaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a crosslinkable group Q, where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; R.sup.1 is on each occurrence, identically or differently, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and/or heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R.sup.1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; X is CR.sup.2, NR, SiR.sup.2, O, S, C═O or P═O, p is 0, 1, 2, 3, 4 or 5, m is 0, 1, 2, 3 or 4, n is 0, 1, 2 or 3, and the dashed line represents the bond to an adjacent structural unit in the polymer.

43. Formulation according to claim 42, wherein the end groups E contain at least one, crosslinkable group Q.

44. Formulation according to claim 31, wherein the highly branched polymer additionally contains 1 to 35 mol % of at least one crosslinkable structural unit D.

45. Formulation according to claim 44, wherein the structural units D are selected from the structural units of the formulae (D1) to (D7) ##STR00295## where Ar.sup.1 to Ar.sup.4 are on each occurrence, in each case identically or differently, a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; Q is a crosslinkable group; R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which may in each case be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, C═S, C═NR.sup.1, P(═O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or an aralkyl or heteroarylaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a crosslinkable group Q, where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; R.sup.1 is on each occurrence, identically or differently, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and/or heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R.sup.1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; X is CR.sub.2, NR, SiR.sub.2, O, S, C═O or P═O, w is 0, 1, 2, 3, 4, 5 or 6, r is 0 or 1, s and t are each 0 or 1, where the sum (s+t)=1 or 2; and the dashed lines represent bonds to adjacent structural units in the polymer.

46. Formulation according to claim 44, wherein the structural units D are selected from the structural units of the formulae (D8) to (D21) ##STR00296## ##STR00297## ##STR00298## where R and Q can adopt the meanings indicated in claim 15 in relation to the structural units of the formulae (D1) to (D7), p is 0, 1, 2, 3, 4 or 5, m is 0, 1, 2, 3 or 4, n is 0, 1, 2 or 3, y is 0, 1 or 2, and the dashed lines represent bonds to adjacent structural units in the polymer, but with the proviso that, in relation to a phenylene group, the sum (p+y) is ≤5, and with the proviso that at least one y in each structural unit is ≥1.

47. Highly branched polymer containing 30 to 70 mol % of at least one hole-transporting recurring unit A, 5 to 30 mol % of at least one branching recurring unit B, 5 to 30 mol % of at least one further recurring unit C, and 5 to 40 mol % of at least one end group E, where the recurring units A, B and C are different from one another.

48. Highly branched polymer according to claim 47, wherein the highly branched polymer has a molecular weight Mw in the range from 15,000 to 1,000,000 g/mol.

49. Highly branched polymer according to claim 47, wherein the hole-transporting recurring units A are selected from triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrophenazine, thianthrene, dibenzo-para-dioxin, phenoxathiyne, carbazole, azulene, thiophene, pyrrole and furan derivatives and further O-, S- or N-containing heterocycles.

50. Highly branched polymer according to claim 47, wherein the hole-transporting recurring units A are selected from triarylamine units of the following formula (A) ##STR00299## where Ar.sup.1 to Ar.sup.3 are on each occurrence, in each case identically or differently, a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which may in each case be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, C═S, C═NR.sup.1, P(═O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or an aralkyl or heteroarylaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a crosslinkable group Q, where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; R.sup.1 is on each occurrence, identically or differently, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and/or heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R.sup.1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; and the dashed lines represent bonds to adjacent structural units in the polymer.

51. Highly branched polymer according to claim 50, wherein the hole-transporting recurring units A are selected from triarylamine units of the formula (I), where Ar.sup.1, Ar.sup.2 and Ar.sup.3 can adopt the meanings indicated in claim 8, wherein Ar.sup.3 is substituted by Ar.sup.4 in at least one of the two ortho positions, where Ar.sup.4 is a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where R can adopt the meanings indicated in claim 6.

52. Highly branched polymer according to claim 47, wherein the branching recurring units B are selected from the structural units of the formulae (B1) to (B5) ##STR00300## where Ar.sup.1 to Ar.sup.5 are on each occurrence, in each case identically or differently, a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which may in each case be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, C═S, C═NR.sup.1, P(═O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or an aralkyl or heteroarylaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a crosslinkable group Q, where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; R.sup.1 is on each occurrence, identically or differently, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and/or heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R.sup.1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; Y is C or Si, and the dashed lines represent bonds to adjacent structural units in the polymer.

53. Highly branched polymer according to claim 47, wherein the further recurring units C are selected from 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, fluorene derivatives, 9,9′-spirobifluorene derivatives, phenanthrene derivatives, 9,10-dihydrophenanthrene derivatives, 5,7-dihydrodibenzoxepine derivatives and cis- and trans-indenofluorene derivatives, but also 1,2-, 1,3- or 1,4-phenylene, 1,2-, 1,3- or 1,4-naphthylene, 2,2′-, 3,3′- or 4,4′-biphenylylene, 2,2″-, 3,3″- or 4,4″-terphenylylene, 2,2′-, 3,3′- or 4,4′-bi-1,1′-naphthylylene or 2,2′″-, 3,3′″- or 4,4′″-quaterphenylylene derivatives.

54. Highly branched polymer according to claim 47, wherein the end groups E are selected from structural units of the formulae (E1) to (E13) ##STR00301## ##STR00302## ##STR00303## where R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which may in each case be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, C═S, C═NR.sup.1, P(═O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or an aralkyl or heteroarylaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a crosslinkable group Q, where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; R.sup.1 is on each occurrence, identically or differently, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and/or heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R.sup.1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; X is CR.sup.2, NR, SiR.sup.2, O, S, C═O or P═O, p is 0, 1, 2, 3, 4 or 5, m is 0, 1, 2, 3 or 4, n is 0, 1, 2 or 3, and the dashed line represents the bond to an adjacent structural unit in the polymer.

55. Highly branched polymer according to claim 54, wherein the end groups E contain at least one crosslinkable group Q.

56. Highly branched polymer according to claim 47, wherein the highly branched polymer additionally contains 1 to 35 mol % of at least one crosslinkable structural unit D.

57. Highly branched polymer according to claim 56, wherein the structural units D are selected from the structural units of the formulae (D1) to (D7) ##STR00304## ##STR00305## where Ar.sup.1 to Ar.sup.4 are on each occurrence, in each case identically or differently, a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; Q is a crosslinkable group; R is on each occurrence, identically or differently, H, D, F, Cl, Br, L, N(R.sup.1).sub.2, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, P(═O)(R.sup.1).sub.2, S(═O)R.sup.1, S(═O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which may in each case be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, C═S, C═NR.sup.1, P(═O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or an aralkyl or heteroarylaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a crosslinkable group Q, where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; R.sup.1 is on each occurrence, identically or differently, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and/or heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R.sup.1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; X is CR.sub.2, NR, SiR.sub.2, O, S, C═O or P═O, w is 0, 1, 2, 3, 4, 5 or 6, r is 0 or 1, s and t are each 0 or 1, where the sum (s+t)=1 or 2; and the dashed lines represent bonds to adjacent structural units in the polymer.

58. Highly branched polymer according to claim 56, wherein the structural units D are selected from the structural units of the formulae (D8) to (D21) ##STR00306## ##STR00307## ##STR00308## where R and Q can adopt the meanings indicated in claim 15 in relation to the structural units of the formulae (D1) to (D7), p is 0, 1, 2, 3, 4 or 5, m is 0, 1, 2, 3 or 4, n is 0, 1, 2 or 3, y is 0, 1 or 2, and the dashed lines represent bonds to adjacent structural units in the polymer, but with the proviso that, in relation to a phenylene group, the sum (p+y) is ≤5, and with the proviso that at least one y in each structural unit is ≥1.

59. A method comprising utilising the highly branched polymer according to claim 47 in an electronic or opto-electronic device.

60. An electronic or opto-electronic devices comprising at least one highly branched polymer according to claim 47.

Description

WORKING EXAMPLES

Part A: Synthesis of the Monomers

[0199] The monomers for the preparation of the polymers according to the invention have already been described in the prior art, are commercially available or are prepared in accordance with literature procedures and are summarised in Table 1 below:

TABLE-US-00020 TABLE 1 Synthesis in Monomer Structure accordance with Mo1-Bo [00249] WO 99/048160 A1 Mo2-Br [00250] WO 2013/156130 Mo2-Bo [00251] WO 2013/156130 Mo3-Br [00252] Borylation analogously to WO 2013/156130 Mo4-Br [00253] CAS 2043618-74-0 Mo5-Bo [00254] CAS 897404-05-6 Mo5-Br [00255] CAS 117635-21-9 Mo6-Br [00256] CAS 16400-51-4 Mo7-Br [00257] WO 2010/136111 Mo7-Bo [00258] WO 2010/136111 Mo8-Bo [00259] WO 2010/097155 A1 Mo8-Br [00260] WO 2010/097155 A1 Mo9-Br [00261] PCT/EP2017/083436 Mo9-Bo [00262] Borylation analogously to WO 2013/156130 Mo10-Br [00263] PCT/EP2017/083436 Mo10-Bo [00264] Borylation analogously to WO2013/156130 Mo11-Br [00265] PCT/EP2017/083436 Mo12-Br [00266] WO 2009 02027 Mo12-Bo [00267] WO 2009/102027 Mo12-Br [00268] CAS 198964-46-4 Mo13-Br [00269] CAS 868704-91-0 Mo14-Bo [00270] WO 03/020790 Mo15-Br [00271] Macromolecules 2000, 33, 2016-2020 Mo15-Bo [00272] CAS 628303-20-8 Mo16-Br [00273] CAS 626-39-1 M016-Bo [00274] CAS 365564-05-2 Mo17-Br [00275] CAS 4316-58-9 Mo18-Br [00276] CAS 128055-74-3 Mo19-Br [00277] CAS 92-66-0 Mo19-Bo [00278] CAS 14432-79-1 Mo20-Br [00279] CAS 3972-65-4 Mo21-Br [00280] CAS 1122-91-4

Part B: Synthesis of the Polymers

[0200] Preparation of comparative polymers V1 and V2 and polymers P1 to P22 according to the invention.

[0201] Comparative polymers V1 and V2 and polymers P1 to P22 according to the invention are prepared from the monomers disclosed in Part A by SUZUKI coupling by the process described in WO 2010/097155.

[0202] Polymers V1 and V2 as well as P1 to P22 prepared in this way contain the structural units in the percentage proportions indicated in Table 2 (percent figures=mol %) after the leaving groups have been cleaved off. In the case of the polymers prepared from monomers containing aldehyde groups, these are converted, after the polymerisation, into crosslinkable vinyl groups by WITTIG reaction by the process described in WO 2010/097155. The polymers shown correspondingly in Table 2 and employed in Part C thus contain crosslinkable vinyl groups instead of the aldehyde groups originally present.

[0203] The palladium and bromine contents of the polymers are determined by ICP-MS. The values determined are below 10 ppm.

[0204] The molecular weights M.sub.w and the polydispersities D are determined by means of gel permeation chromatography (GPC) (model: Agilent HPLC System Series 1100) (column: PL-RapidH from Polymer Laboratories: solvent: THE with 0.12 vol % of o-dichlorobenzene; detection: UV and refractive index; temperature: 40° C.). Calibrated using polystyrene standards.

TABLE-US-00021 TABLE 2 Polymer Mo A % Mo B % Mo C % Mo D % Mo E % Mw/D V1 Mo15-Br 50 Mo2-Bo 50 80K/2.3 V1a Mo15-Br 50 Mo2-Bo 50 200K/2.9  V1b Mo15-Br 50 Mo2-Bo 50 310K/23.8 V1c Mo15-Br 50 Mo2-Bo 50 175K/2.3  V2 Mo15-Br 50 Mo2-Bo 40 Mo8-Bo 10 95K P1 Mo15-Br 10.1 Mo2-Bo 47.8 Mo16-Br 15.8 Mo19-Br 26.24 26.5K/3.6  P2 Mo15-Br 20 Mo2-Bo 50 Mo16-Br 15 Mo19-Br 15 500K/27.8 P3 Mo15-Br 17.5 Mo2-Bo 50 Mo16-Br 15 Mo19-Br 20 90K/7.3 P4 Mo15-Br 17.5 Mo2-Bo 40 Mo16-Br 15 Mo19-Br 20 Mo8-Bo 10 90K/5.7 P5 Mo2-Bo 50 Mo16-Br 15 Mo5-Br 17.5 Mo19-Br 20 27K/4.6 P6 Mo15-Br 17.5 Mo2-Bo 30 Mo16-Br 15 Mo19-Br 20 Mo8-Bo 20 75K/4.3 P7 Mo15-Bo 17.5 Mo4-Br 40 Mo16-Bo 15 Mo8-Br 10 Mo19-Bo 20 95K/8.6 P8 Mo15-Br 28.3 Mo2-Bo 40 Mo16-Br 10 Mo19-Br 13.3 Mo8-Bo 10 66K/6  P9 Mo15- Br 39.2 Mo2-Bo 40 Mo16-Br 5 Mo19-Br 6.6 Mo8-Bo 10 280K/10.4 P10 Mo3-Br 17.5 Mo2-Bo 40 Mo16-Br 15 Mo19-Br 20 Mo8-Bo 10 P11 Mo15-Br 17.5 Mo2-Bo 40 Mo17-Br 15 Mo19-Br 20 Mo8-Bo 10 P12 Mo12-Br 17.5 Mo2-Bo 40 Mo16-Br 15 Mo19-Br 20 Mo8-Bo 10 85K/5.5 P13 Mo13-Br 17.5 Mo2-Bo 40 Mo16-Br 15 Mo19-Br 20 Mo8-Bo 10 100K/6.3  P14 Mo15-Br 17.5 Mo2-Bo 40 Mo16-Br 15 Mo19-Br 20 Mo10-Bo 10 95K/4.5 P15 Mo15-Br 17.5 Mo2-Bo 40 Mo16-Br 15 Mo19-Br 20 Mo9-Bo 10 80K/6.0 P16 Mo15-Br 17.5 Mo2-Bo 40 Mo16-Br 15 Mo20-Br 20 Mo9-Bo 10 105K/5.8  P17 Mo13-Br 17.5 Mo2-Bo 40 Mo16-Br 15 Mo17-Br 20 Mo12-Bo 10 P18 Mo2-Bo 40 Mo16-Br 15 Mo5-Br 17.5 Mo19-Br 20 Mo9-Bo 10 P19 Mo1-Bo 40 Mo16-Br 15 Mo7-Br 17.5 Mo19-Br 20 Mo9-Bo 10 50K/4.8 P20 Mo15-Br 10 Mo18-Br 15 Mo2-Bo 40 Mo19-Br 20 Mo8-Bo 10 P21 Mo14-Bo 17.5 Mo4-Br 40 Mo16-Bo 15 Mo19-Bo 20 Mo11-Br 10 P22 Mo15-Br 17.5 Mo2-Bo 50 Mo16-Br 15 Mo21-Br 20 75K/7.5

Part C: Characterisation of the Polymers

[0205] Part C1: Test Method for the Dissolution Behaviour of the Polymers According to the Invention

[0206] The polymer to be analysed is weighed out into a vessel, and a magnetic stirrer bar is added to the vessel. The solvent (or a mixture of a plurality of solvents produced in advance) is added to the solid. The amount of solvent is calculated so that a final solids concentration of 5 or 10 g/I is achieved in the solution. The suspension is stirred at 600 revolutions per minute at room temperature (25° C.) until the solid has completely dissolved. The end point of the dissolution is determined by visual examination. Towards the end of the dissolution operation, the solution is held in a light beam incident perpendicular to the viewing direction in order to be able to recognise still undissolved particles optimally.

[0207] The dissolution time, i.e. the time for complete dissolution of the solid material, also described as t.sub.diss, is recorded and describes the time between addition of the solvent (or solvent mixture) and the disappearance of the final undissolved solid particles. The dissolution rate is determined by division of the dissolution time by the target concentration, here 5 or 10 g/l. The polymers are described by their dissolution rate in cyclohexyl caproate.

TABLE-US-00022 TABLE 3 Target composition of the solutions for determination of the dissolution behaviour. Target concen- Solution Material Solvent tration [g/l] name P1 Cyclohexyl caproate 5 Solution A P1 Cyclohexyl caproate 10 Solution B P2 Cyclohexyl caproate 5 Solution C P2 Cyclohexyl caproate 10 Solution D P3 Cyclohexyl caproate 5 Solution E P3 Cyclonexyl caproate 10 Solution F V1 Cyclohexyl caproate 5 Solution G V1 Cyclonexyl caproate 10 Solution H V1a Cyclohexyl caproate 5 Solution I V1a Cyclohexyl caproate 10 Solution J

[0208] The materials are subsequently categorised in groups corresponding to the dissolution type in accordance with Table 4.

TABLE-US-00023 TABLE 4 Categorisation of the dissolution behaviour. Dissolution Dissolution time Dissolution rate type t.sub.DISS at 25° C. [g/(l .Math. min)] Type A 0 to 14 minutes >0.466 Type B 15 to 29 minutes 0.466-0.233 Type C 30 to 59 minutes 0.233-0.116 Type D 60 to 120 minutes 0.116-0.058 Type E More than 120 minutes <0.058 Type F Clear solution not obtained 0

[0209] The results of the dissolution test are summarised in Table 5.

TABLE-US-00024 TABLE 5 Results of the dissolution test. Solution Dissolution type Solution A Type E Solution B Type E Solution C Type E Solution D Type E Solution E Type E Solution F Type E Solution G Type D Solution H Type C Solution I Type D Solution J Type C

[0210] As is clearly evident from the results, the polymers according to the invention are very highly suitable for the preparation of printing inks. In addition to this property, these materials, even without crosslinkable groups, are suitable, in combination with correspondingly selected solvents, for conversion into solution-processed multilayer components.

[0211] Part C2: Layer Stability Test Under Ink-Jet Printing Conditions

[0212] The polymers according to the invention are investigated with respect to their layer stability to solvents. To this end, the experiment described below is carried out.

[0213] 1. Layer Preparation

[0214] A thin film of the polymer to be investigated is applied to a glass substrate measuring 30000×30000×1100 microns by spin coating from toluene. The solution has a solids content of 5 to 50 g/l. The solution is prepared by weighing out the material and addition of the solvent. The suspension is subsequently stirred for one to six hours at room temperature by means of a magnetic stirrer bar until the solid has completely dissolved. The solution is subsequently transferred into a glove box and filtered under protective gas using a PTFE filter with a pore diameter of 0.2 microns. The formulation is converted into an approximately 50 nm thick film on a flat glass substrate by spin coating. The layer thickness and homogeneity are monitored using an Alpha-step D-500 profilometer. The resultant layers typically have an average roughness (RMS) of less than one nanometre. After application of the layer, the substrates are annealed on a hotplate at a temperature of 220° C. for 60 minutes.

[0215] 2. Layer Stability Test Conditions

[0216] In order to determine the layer stability, a test solvent is introduced into a solvent-resistant disposable ink cartridge, here a ten picolitre cartridge fitting a Fujifilm Dimatix DMP-2831. The cartridge is characterised by the resultant droplet size. The printer is operated in a low-vibration environment on a flat base.

[0217] The printing parameters are adjusted for a droplet speed of 4 m/s (for a detailed description of the procedure, see documentation from the printer manufacturer Fujifilm Dimatix). The stability test is carried out with droplets from just one print head nozzle.

[0218] The prepared substrate from Step 1 is placed in the sample holder of the printer. The droplet pattern to be printed produces droplets of defined size on the substrate. To this end, 9 print droplets are arranged in a tight three by three matrix (see FIG. 1), so that they coalesce to form a droplet of greater volume (approximately ninety picolitres). The droplet volume can be varied by number and size of the droplets, but must be kept constant within an experiment. After the printing, the droplet appears on the substrate surface as sketched in FIG. 2. A droplet image of this type can be recorded using the camera built into the printer, which is installed on the print head carriage with viewing direction onto the substrate, parallel to the droplet flying direction (FIG. 3).

[0219] 3. Layer Damage Test Evaluation

[0220] Immediately after printing, a photo is taken with the printer's internal camera (FIG. 2) and the time measurement is started. A number of photos are taken over a period of five minutes, the so-called exposure time (see Table 6). The diameter of the droplet above the view camera is determined from the photo immediately after printing. The size of the droplet in the image and the actual diameter of the droplet can be calculated true to scale from the x/y coordinates. The value describes the droplet diameter on the surface and thus the interaction of the solvent with the substrate (material layer). Comparison of the images during the exposure time allows an initial estimation of the layer stability (FIG. 6). The formation of a dark ring at the contact line of the droplet indicates damage to the material layer by the solvent.

[0221] After an exposure time of five minutes, the substrate is placed in a vacuum drying chamber, and the solvent is removed in vacuo, giving a dry film again. The vacuum chamber is of such a size that a pressure of 1-10.sup.−3 mbar is achieved about 60 seconds after the vacuum pump has been switched on. The substrate remains in the vacuum chamber for at least 10 minutes. After the drying step, the substrate is removed from the vacuum chamber, and the damage to the material surface is quantified. Firstly, the substrate is placed under the camera of the inkjet printer again and a photo is taken in the dried state. The damage or layer stability is quantified by determination of the film profile and the layer thickness at the position of the original droplet (FIG. 4). The method used is profilometry by means of a fine diamond tip; other methods for the determination of surface structures, such as, for example, but not exclusively, scanning force microscopy, are likewise possible. In order to quantify the layer stability, a key performance indicator (KPI) is defined, which describes the difference between the highest and lowest points of a profile line through the centre point of the droplet location (FIG. 5). The performance indicator has the unit nanometers. The key performance indicator is converted into a layer damage indicator LDI in accordance with the criteria indicated in FIG. 7. This indicator can then be used to describe the relative stability of a combination of a material and a solvent. This procedure is repeated at least 10 times and a maximum of 50 times per material in order to ensure reproducibility of the measurement values.

TABLE-US-00025 TABLE 6 Layer damage evaluation. Exposure time [sec] 0 60 120 180 300 dry Photo? Yes Yes Yes Yes Yes Yes Determine droplet Yes No No No No No diameter

[0222] In order to determine a layer damage rate, a quantity for describing the rate of damage, the key performance indicator of the layer stability is divided by the exposure time, in this case 300 seconds. The unit for this damage rate is nanometers per second. The exposure time should be selected so that the experiment represents a realistic test scenario for the production of a solution-processed layer in an opto-electronic component. In accordance with the LDI, a damage rate of 0.066 nanometres per second is an acceptable value for use for a certain combination of a material and a solvent (see Table 7).

TABLE-US-00026 TABLE 7 Drying Damage Material temperature Test solvent experiment P5 220 1-Methyl-3-phenoxybenzene Exp 1 P5 220 Cyclohexyl caproate Exp 2 P2 220 3-Phenoxytoluene Exp 3 P2 220 Cyclohexyl hexanoate Exp 4 P3 220 1-Methyl-3-phenoxybenzene Exp 5 P3 220 Cyclonexyl caproate Exp 6 V1 180 1-Methyl-3-phenoxybenzene Ref Exp 1 V2 220 3-Methyldiphenyl ether Ref Exp 2 V1 180 Cyclohexyl hexanoate Ref Exp 3 V2 220 Cyclohexyl hexanoate Ref Exp 4

TABLE-US-00027 TABLE 8 Damage Layer damage experiment indicator LDI Exp1 o Exp2 ++ Exp3 − Exp4 + Exp5 − Exp6 + RefExp1 − RefExp2 − RefExp3 − RefExp4 +

[0223] It can clearly be seen from the examples shown (see Table 8) that the polymers according to the invention exhibit excellent solvent resistance as a layer and are highly suitable for the production of multilayered components.

[0224] Part C3: Solution Rheology

[0225] The viscosity of the formulations according to the invention (see Table 9) was determined using a Haake Mars III rotational rheometer in a plate-and-cone measurement geometry (1° cone angle). The measurement of the viscosity is carried out with temperature control at a temperature 25° C. (+/−0.2° C.) and at a shear rate of 500 s.sup.−1 (experiment index low) or 1000 s.sup.−1 (experiment index high). Each sample is measured at least three times, and the measured values are averaged. As can clearly be seen from the results (Table 9), linear, conjugated polymers in particular exhibit a certain tendency towards non-Newtonian behaviour. For use of these solutions as an ink in inkjet printing, non-Newtonian behaviour is an undesired complication in the planning of a homogeneous print image.

TABLE-US-00028 TABLE 9 Concentration Experiment Viscosity Material Solvent [% by weight] number [mPas] P3 Cyclohexyl 0.467 Visco1.sub.low 3.87 caproate P3 Cyclohexyl 0.935 Visco2.sub.low 4.36 hexanoate P3 1-Methyl-3- 0.525 Visco3.sub.low 4.91 phenoxybenzene P3 1-Methyl-3- 0.525 Visco3.sub.high 4.95 phenoxybenzene P3 3-Methyldiphenyl 1.051 Visco4.sub.low 5.65 ether P3 3-Methyldiphenyl 1.051 Visco4.sub.high 5.68 ether P3 3-Phenoxy- 3.153 Visco5.sub.low 9.98 toluene P3 3-Phenoxy- 3.153 Visco5.sub.high 10.1 toluene P1 Cyclohexyl 0.467 Visco6.sub.low 3.68 caproate P1 1-Methyl-3- 0.525 Visco7.sub.low 4.61 phenoxybenzene P1 3-Methyldiphenyl 1.051 Visco8.sub.low 4.96 ether P1 3-Phenoxy- 3.153 Visco9.sub.low 7.12 toluene P2 Cyclohexyl 0.467 Visco10.sub.low 4.12 caproate P2 1-Methyl-3- 0.525 Visco11.sub.low 5.78 phenoxybenzene P2 1-Methyl-3- 0.525 Visco11.sub.high 5.78 phenoxybenzene P2 3-Methyldiphenyl 1.051 Visco12.sub.low 7.84 ether P2 3-Methyldiphenyl 1.051 Visco12.sub.high 7.77 ether P2 3-Phenoxy- 3.153 Visco13.sub.low 20.97 toluene P2 3-Phenoxy- 3.153 Visco13.sub.high 20.2 toluene V1 Cyclohexyl 0.467 Visco14.sub.low 4.52 caproate V1 Cyclohexyl 0.467 Visco14.sub.high 4.57 caproate V1 Cyclohexyl 0.935 Visco15.sub.low 6.15 hexanoate V1 Cyclohexyl 0.935 Visco15.sub.high 6.21 hexanoate V1 Cyclohexyl 2.805 Visco16.sub.low 18.69 hexanoate V1 Cyclohexyl 2.805 Visco16.sub.high 18.8 hexanoate V1 1-Methyl-3- 0.525 Visco17.sub.low 5.81 phenoxybenzene V1 3-Methyldiphenyl 1.051 Visco18.sub.low 7.82 ether V1 3-Phenoxy- 3.153 Visco19.sub.low 21.08 toluene V1a Cyclohexyl 0.467 Visco20.sub.low 6.36 caproate V1a Cyclohexyl 0.467 Visco20.sub.high 6.4 caproate V1a Cyclohexyl 0.935 Visco21.sub.low 10.61 hexanoate V1a Cyclohexyl 0.935 Visco21.sub.high 10.7 hexanoate V1a Cyclohexyl 2.805 Visco22.sub.low 61.84 hexanoate V1a Cyclohexyl 2.805 Visco22.sub.high 61.2 hexanoate V1a 1-Methyl-3- 0.525 Visco23.sub.low 7.73 phenoxybenzene V1a 3-Methyldiphenyl 1.051 Visco24.sub.low 12.73 ether V1a 3-Phenoxy- 3.153 Visco25.sub.low 66.25 toluene V1c 1-Methyl-3- 0.525 Visco26.sub.low 9.37 phenoxybenzene V1c 1-Methyl-3- 0.525 Visco27.sub.high 9.39 phenoxybenzene V1c 3-Methyldiphenyl 1.051 Visco27.sub.low 19.74 ether V1c 3-Methyldiphenyl 1.051 Visco27.sub.high 19.1 ether V1c 3-Phenoxy- 3.153 Visco28.sub.low 130.01 toluene V1c 3-Phenoxy- 3.153 Visco28.sub.high 114 toluene V1b 1-Methyl-3- 0.525 Visco29.sub.low 8.13 phenoxybenzene V1b 1-Methyl-3- 0.525 Visco29.sub.high 8.11 phenoxybenzene V1b 3-Methyldiphenyl 1.051 Visco30.sub.low 13.19 ether V1b 3-Methyldiphenyl 1.051 Visco30.sub.high 13.1 ether V1b 3-Phenoxy- 3.153 Visco31.sub.low 72.00 toluene V1b 3-Phenoxy- 3.153 Visco31.sub.high 66.1 toluene

[0226] It can be seen from the results shown in Table 9 that the polymers according to the invention exhibit Newtonian behaviour over the entire range of possible molecular weights. This is of great advantage for control of important printing parameters, for example control of droplet size and droplet weight in ink-jet printing. The absolute values of the shear viscosity increase significantly less strongly with increasing molecular weights and increasing concentrations than in the case of the comparable linear polymers. This enables processing of more highly concentrated inks. This enables both printing of higher resolution structures and also shorter process times.

[0227] Part C4: Printability Investigation

[0228] In order to determine the printability of the polymer inks, in each case a test solution is introduced into a solvent-resistant disposable ink cartridge, here a ten picolitre cartridge fitting a Dimatix DMP-2831 ink-jet printer. The cartridge here is characterised by the resultant droplet size. The printer is operated in a low-vibration environment on a flat base.

[0229] With the aid of a camera focused on the outlet opening of the print head of the cartridge, it is possible to determine the shape and speed of the droplets on leaving the print head.

[0230] As printing parameter for control of the droplet speed, principally, but not exclusively, the voltage to be applied is adjusted (for a detailed description of the procedure, see the printer manufacturers documentation). The printability investigation is carried out over the entire parameter range to be investigated with droplets from a print head nozzle.

[0231] Table 10 below gives an overview of the experiments carried out, with details on material, solvent and concentration.

TABLE-US-00029 TABLE 10 Concentration Material Solvent [g/l] Ink P4 3-Phenoxytoluene 5 Ink 1 P2 3-Phenoxytoluene 5 Ink 2 V2 3-Phenoxytoluene 5 Ink 3 V1c 3-Phenoxyto1uene 5 Ink 4 V1b 3-Phenoxytoluene 5 Ink 5

[0232] These inks were characterised corresponding to the procedure described. Table 11 below indicates what voltage is necessary in order to achieve a target droplet speed.

TABLE-US-00030 TABLE 11 Droplet Voltage speed Ink [V] [m/s] Ink1 12.2 1 Inkl 13.5 2 Ink1 14.7 3 Ink1 15.8 4 Ink1 17.9 5 Ink1 19.5 6 Ink1 20.7 7 Ink1 21.9 8 Ink1 23.2 9 Ink1 24.7 10 Ink1 26.1 11 Ink1 27.3 12 Ink 2 13.4 1 Ink 2 14.6 2 Ink 2 15.9 3 Ink 2 17.4 4 Ink 2 19.2 5 Ink 2 20.5 6 Ink 2 21.9 7 Ink 2 23.3 8 Ink 2 24.9 9 Ink 2 26.5 10 Ink 2 28.1 11 Ink 2 29.7 12 Ink 3 12.5 1 Ink 3 13.7 2 Ink 3 14.9 3 Ink 3 16.3 4 Ink 3 17.3 5 Ink 3 19.1 6 Ink 3 20.7 7 Ink 3 21.9 8 Ink 3 23.3 9 Ink 3 24.7 10 Ink 3 26.1 11 Ink 3 27.7 12 Ink 4 13.8 1 Ink 4 15 2 Ink 4 16 3 Ink 4 17.4 4 Ink 4 19 5 Ink 4 20.4 6 Ink 4 21 7 Ink 4 22.6 8 Ink 4 24 9 Ink 4 25.2 10 Ink 4 26.8 11 Ink 4 28.2 12 Ink 5 16 1 Ink 5 16.8 2 Ink 5 18.2 3 Ink 5 19.6 4 Ink 5 20.6 5 Ink 5 22.2 6 Ink 5 23.4 7 Ink 5 24.8 8 Ink 5 26.2 9 Ink 5 27.8 10 Ink 5 29.4 11 Ink 5 30.8 12

[0233] Finally, the ligament length of a droplet is evaluated at a droplet speed on leaving the print head nozzle that is to be compared in advance. This value is a measure of the viscoelastic properties of the printing fluid. An explanatory depiction is shown in FIG. 8. This value must not exceed a critical value depending on the application, the print head/substrate separation and a target droplet speed as well as a specific resolution to be printed. Shorter ligament lengths are thus desirable, and, as is clearly evident in Table 12, the highly branched polymers according to the invention are, surprisingly, clearly advantageous here over the linear polymers.

TABLE-US-00031 TABLE 12 Material Voltage Ligament in ink [V] length [μm] P4 17.9 150 P2 19.2 180 V2 17.3 180 V1c 19 220 V1a 20.6 350

[0234] Part C5: Layer Thickness Determination

[0235] The comparative polymers and the polymers according to the invention are processed from solution.

[0236] Whether the crosslinkable variants of the polymers give a completely insoluble layer after crosslinking is tested analogously to WO 2010/097155.

[0237] Table C13 shows the remaining layer thickness of the originally 100 nm after the washing operation described in WO 2010/097155. If the layer thickness does not reduce, the polymer is insoluble and the crosslinking is thus adequate.

TABLE-US-00032 TABLE 13 Control of the residual layer thickness of originally 100 nm after washing test Residual layer thickness after washing test [in nm] Crosslinking at 220° C. for Polymer Temp 30 minutes V2 220 99 P4 220 94 P22 220 98

[0238] As can be seen in Table 13, comparative polymer V2 and polymers P4 and P22 according to the invention crosslink completely at 220° C.

[0239] Part C6: Determination of the Energy Level

[0240] Table 14 lists the energy levels measured for the polymers. The HOMOs are determined by means of a Riken AC3 measurement, whereas the energy gap is determined by means of the edge of the absorption spectrum. It can be seen that the polymers according to the invention have no deviating values of the energy levels, with the exception of polymer P5, which was specially designed to have a greater energy gap.

TABLE-US-00033 TABLE 14 Energy levels of the polymers HOMO Egap HTL [eV] [eV] V1 −5.59 2.85 V2 −5.61 2.85 P1 −5.57 2.87 P2 −5.62 2.86 P3 −5.59 2.86 P4 −5.62 2.86 P22 −5.57 2.86 P5 −5.70 3.14

Part D: Production of OLEDs

[0241] The production of solution-based OLEDs of this type has already been described many times in the literature, for example in WO 2004/037887 and WO 2010/097155. The process is adapted to the circumstances described below (layer-thickness variation, materials).

[0242] The polymers according to the invention are used in two different layer sequences:

A)

[0243] substrate, [0244] ITO (50 nm), [0245] PEDOT:PSS (20 nm), [0246] hole-transport layer (HTL) (20 nm), [0247] emission layer (EML) (60 nm), [0248] hole-blocking layer (HBL) (10 nm), [0249] electron-transport layer (ETL) (40 nm), [0250] cathode.
or

B)

[0251] substrate, [0252] ITO (50 nm), [0253] PEDOT:PSS (60 nm), [0254] hole-transport layer (HTL) (20 nm), [0255] emission layer (EML) (60 nm), [0256] hole-blocking layer (HBL) (10 nm), [0257] electron-transport layer (ETL) (40 nm), [0258] cathode.

[0259] Furthermore, the components are produced using two different processes: a) by means of spin coating or b) by means of ink-jet printing.

[0260] Processing Sequence A)

[0261] Cleaned glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm serve as substrate. These are coated with PEDOT:PSS. The spin coating is carried out from water in air. The layer is dried by heating at 180° C. for 10 minutes. PEDOT:PSS is purchased from Heraeus Precious Metals GmbH & Co. KG, Germany. The hole-transport and emission layers are applied to these coated glass plates.

[0262] The polymers according to the invention and comparative polymers, in each case dissolved in toluene, are used as hole-transport layer. The typical solids content of such solutions is about 5 g/l if, as here, the layer thicknesses of 20 nm which are typical for a device is to be achieved by means of spin coating. The layers are applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 220° C. for 30 minutes.

[0263] The emission layer is always composed of at least one matrix material (host material) and an emitting dopant (emitter). Furthermore, mixtures of a plurality of matrix materials and co-dopants may occur. An expression such as H1 30%:H2 55%:C1 15% here means that the first host material H1 is present in the emission layer in a proportion by weight of 30%, the second host material is present in the emission layer in a proportion by weight of 55% and the third co-dopant is present in the emission layer in a proportion by weight of 15%. The mixture for the emission layer is dissolved in toluene for structure A. The typical solids content of such solutions is about 17 g/l if, as here, the layer thickness of 60 nm which is typical for a device is to be achieved by means of spin coating. The layers are applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 150° C. for 10 minutes.

[0264] The materials used in the examples are shown in Table 15.

[0265] The materials for the hole-blocking layer and electron-transport layer are applied by thermal vapour deposition in a vacuum chamber and are shown in Table 16. The hole-blocking layer consists of ETM1. The electron-transport layer consists of the two materials ETM1 and ETM2, which are admixed with one another by co-evaporation in a proportion by volume of 50% each.

[0266] The cathode is formed by thermal vapour deposition of an aluminium layer with a thickness of 100 nm.

[0267] Processing Sequence B)

[0268] The substrates used are cleaned glass plates which have been coated with structured ITO (indium tin oxide) in a thickness of 50 nm and pixelated bank material.

[0269] The hole-injection layer used here is again PEDOT:PSS, which is printed onto the substrates by means of ink-jet printing. It is subsequently dried in vacuo and baked at 180° C. in air for 30 minutes. PEDOT:PSS is obtained from Heraeus Precious Metals GmbH & Co. KG, Germany.

[0270] This is followed by application of the hole-transport layer. The hole-transport layer used is the polymers according to invention and comparative polymers. The polymers are dissolved in 3-phenoxytoluene and diethylene glycol butyl methyl ether in the volume ratio 7:3. The ink is printed by means of ink-jet printing and subsequently likewise dried in vacuo and baked at 230° C. in an inert-gas atmosphere (argon) for 30 minutes.

[0271] The light-emitting layer is likewise deposited by means of ink-jet printing. The emission layer is always composed of at least one matrix material (host material) and an emitting dopant (emitter). It is also possible for mixtures of a plurality of matrix materials and co-dopants to occur. An expression such as H1 30%; H2 55%; C1 15% here means that material H1 is present in the emission layer in a proportion by weight of 30%, the second matrix material H2 is present in a proportion by weight 55% and the dopant is present in a proportion by weight of 15%.

[0272] The emission layer in structure B is printed from pure 3-phenoxytoluene. After the printing, the layers are dried in vacuo and baked at 160° C. in an inert-gas atmosphere (argon) for 10 minutes. The composition of the emitting layer is shown in Table 17, with the materials being shown in Table 15.

[0273] All ink-printing processes are carried out under yellow light and in an air atmosphere.

[0274] The hole-blocking and electron-transport layers are applied by thermal vapour deposition in a vacuum chamber and are shown in Table 16. The hole-blocking layer consists of ETM1. The electron-transport layer consists of the two materials ETM1 and ETM2, which are admixed with one another by co-evaporation in a proportion by volume of 50% each.

[0275] The cathode is formed by thermal vapour deposition of an aluminium layer with a thickness of 100 nm.

TABLE-US-00034 TABLE 15 Structural formulae of the materials used in the emission layer [00281] H1 [00282] H2 [00283] H3 [00284] C1 [00285] C2 [00286] H4 [00287] C3

TABLE-US-00035 TABLE 16 HBL and ETL materials used [00288] ETM1 [00289] ETM2

[0276] The precise composition of the OLEDs is shown in Table 17. Examples 1 to 3 are produced by means of processing A) and structure A, whereas Examples 4 to 5 are produced by means of processing B) and structure B.

TABLE-US-00036 TABLE 17 Structure of the OLEDs HTL Example polymer EML composition 1 V2 H1 30%; H2 55%; C1 15% 2 P4 H1 30%; H2 55%; C1 15% 3 P22 H1 30%; H2 55%; C1 15% 4 V1 H3 30%; H4 47%; C3 17%; C2 6% 5 P3 H3 30%; H4 47%; C3 17%; C2 6%

Part E: Characterisation of the OLEDs

[0277] The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, current/voltage/luminous density characteristic lines (IUL characteristic lines) assuming Lambert emission characteristics and the (operating) lifetime are determined. The IUL characteristic lines are used to determine characteristic numbers such as the operating voltage (in V) and the external quantum efficiency (in %) at a certain luminance.

[0278] The electroluminescence spectra are measured at a luminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. LT80 @ 1000 cd/m.sup.2 is the lifetime by which the OLED has dropped from an initial luminance of 1000 cd/m.sup.2 to 80% of the initial intensity, i.e. to 800 cd/m.sup.2. The representation of showing the lifetime at a constant current density is likewise used.

[0279] The properties of the various OLEDs are summarised in Tables 18a and 18b. Examples 1 and 4 show comparative components and Examples 2, 3 and 5 show properties of OLEDs according to the invention.

[0280] In spite of the different structure type with greatly improved process properties (cf. Part C, Characterisation of the polymers), the good properties in OLEDs are retained.

TABLE-US-00037 TABLE 18a Properties of the OLEDs with structure A Efficiency Voltage LT80 at 1000 at 1000 at 1000 cd/m.sup.2 cd/m.sup.2 cd/m.sup.2 Example % EQE [V] [h] 1 17.1 4.2 112 2 17.1 4.5 111 3 17.0 4.6 106

TABLE-US-00038 TABLE 18b Properties of the OLEDs with structure B Efficiency Voltage LT90 at 1000 at 1000 at 60 cd/m.sup.2 cd/m.sup.2 cd/m.sup.2 Example % EQE [V] [h] 4 16.3 6,6 267 5 16.2 6.9 234