Polymers containing specifically substituted triarylamine units and electroluminescent devices containing the above polymers

Abstract

The present invention relates to polymers comprising particularly substituted triarylamine repeating units, to methods for their production and to electronic devices, in particular to their use in organic electroluminescence devices called OLEDs (OLED = organic light-emitting diode). The present invention also relates to organic electroluminescence devices comprising the above polymers.

Description

Technical Field

[0001] The present invention relates to polymers comprising particularly substituted repetitive triarylamine units, methods for their preparation and their use in electronic or optoelectronic devices, in particular in organic electroluminescence devices called OLEDs (OLED = organic light emitting diode). The present invention further relates to organic electroluminescence devices comprising these polymers.

Background Art

[0002] Components of different functionality are necessary in electronic or optoelectronic devices, in particular in organic electroluminescence devices (OLEDs). In OLEDs, different functionality is usually present in different layers. In this case, a multilayer OLED system is referred to. The layers in these multilayer OLED systems comprise charge injection layers, for example electron injection and hole injection layers, charge transport layers, for example electron conducting and hole conducting layers, and layers comprising a light emitting component. These multilayer OLED systems are generally manufactured by successive layers by layer coating.

[0003] When two or more layers are applied from solution, it must be ensured that any layer that has already been applied and dried once is not destroyed by subsequent solution application for the production of the next layer. This can be achieved, for example, by crosslinking, for example by making the layer insoluble. This kind of method is disclosed, for example, in European Patent No. 0637899 and International Publication No. 96 / 20253.

[0004] Furthermore, it is also necessary to match the functionality of the individual layers with each other with respect to the materials, for example so that very good results regarding, for example, lifetime, efficiency, etc. are achieved. For example, in particular, the layer adjacent to the direct light emitting layer, in particular the hole transport layer (HTL = hole transport layer), has a considerable influence on the properties of the adjacent light emitting layer.

Summary of the Invention

[0005] Accordingly, one of the problems addressed by the present invention was to provide a compound that could be processed first from a solution and that, when used in an electronic or optoelectronic device, preferably an OLED, and more particularly in its hole transport layer, secondly improved the properties of the device, i.e., in particular those of the OLED.

[0006] Surprisingly, particularly when used in the hole transport layer of an OLED, the repeating triarylamine group in which at least one aryl group, preferably both aryl groups arranged in the main chain, is substituted has been found to result in an increase in the energy gap compared to a comparative conjugated polymer and a decrease in the energy gap compared to a comparative polymer with interrupted conjugation due to twisting as a result of the substituents. Furthermore, the polymers of the present invention, when used in an OLED, result in an improvement in efficiency compared to a comparative conjugated polymer and an improvement in lifetime compared to a comparative polymer with interrupted conjugation.

[0007] Accordingly, the present application provides the following formula (I):

Chemical formula

[0008] Preferably, Ar 1 is substituted by an R 1 radical, and / or Ar 2 is substituted by an R 2 radical.

[0009] More preferably, Ar 3is substituted at at least one, preferably one, of the two ortho positions by Ar 4 and Ar 4 is a monocyclic or polycyclic, aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms and is substituted by one or more R radicals.

[0010] Ar 4 is directly, i.e., either by a single bond or by a bridging group X, bonded to Ar 3 and may be combined.

[0011] Thus, in the first embodiment, the structural unit of formula (I) has the structure of the following formula (Ia):

Chemical formula

Brief description of the drawings

[0012]

Figure 1

[0013] In the present application, the term "polymer" is understood to mean polymer compounds, oligomer compounds and dendrimers. The polymer compounds of the present invention preferably have 10 to 10,000, more preferably 10 to 5,000, and most preferably 10 to 2,000 structural units (i.e., repeating units). The oligomer compounds of the present invention preferably have 3 to 9 structural units. The branching factor of the polymer is from 0 (linear polymer, non-branching site) to 1 (fully branched chain dendrimer).

[0014] The polymer of the present invention preferably has a molecular weight M in the range of 1,000 to 2,000,000 g / mol w more preferably in the range of 10,000 to 1,500,000 g / mol w and most preferably in the range of 50,000 to 1,000,000 g / mol w The molecular weight M w is determined by GPC (= gel permeation chromatography) with respect to an internal polystyrene standard.

[0015] The polymer of the present invention is any of a conjugated polymer, a semi-conjugated polymer or a non-conjugated polymer. Preferred are conjugated or semi-conjugated polymers.

[0016] According to the present invention, the structural units of formulas (I) and (Ia) may be incorporated into the main chain or side chain of the polymer. However, preferably, the structural units of formulas (I) and (Ia) are incorporated into the main chain of the polymer. When incorporated into the side chain of the polymer, the structural units of formulas (I) and (Ia) can be either monovalent or divalent and mean having either 1 or 2 bonds with adjacent structural units in the polymer.

[0017] In the context of the present invention, a "conjugated polymer" mainly has sp in the main chain 2A polymer containing hybrid (or optionally sp hybrid) carbon atoms, where said carbon atoms may be substituted by corresponding hybrid heteroatoms. In the simplest case, this means that double and single bonds alternate in the main chain, but the polymer has units such as meta-bonded phenylene, and should be regarded as a conjugated polymer in the context of this application. What "primarily" intends is that any natural (optional) effects that lead to disruption of conjugation do not invalidate the term "conjugated polymer". A conjugated polymer is also regarded as a polymer having a conjugated main chain and non-conjugated side chains. In addition, this application similarly represents conjugation when, for example, arylamine units, arylphosphine units, certain heterocycles (i.e., conjugation by nitrogen, oxygen or sulfur atoms) and / or organometallic complexes (i.e., conjugation by metal atoms) are present in the main chain. This applies to conjugated dendrimers. In contrast, simple alkyl crosslinks, for example, units such as (thio)ether, ester, amide or imide bonds, are clearly defined as non-conjugated segments.

[0018] In this application, a semi-conjugated polymer is understood to mean a polymer containing non-conjugated sections, intentional conjugation breakers (e.g., spacer groups) or, for example, conjugated regions separated from each other by branches where a relatively long conjugated section in the main chain is blocked by a non-conjugated section, or containing a relatively long conjugated section in the side chains of a polymer having no conjugation in the main chain. Conjugated and semi-conjugated polymers may include conjugated, semi-conjugated or non-conjugated dendrimers.

[0019] In the present application, the term "dendrimer" should be understood to mean a highly branched compound formed from a multifunctional core in which branched monomers in a regular structure are combined to obtain a dendritic structure. In this case, both the core and the monomers may be based on any desired branched structure consisting of both purely organic units and organometallic compounds or coordination compounds. The "dendrimer" should generally be understood as described, for example, by M. Fischer and F. Vogtle (Angew. Chem., Int. Ed. 1999, 38, 885) in this specification.

[0020] In the present application, the term "structural unit" is understood to mean a unit that proceeds from monomer units having at least two, preferably two respective groups each, by a bond-forming reaction, is incorporated into the polymer backbone as part of it, and thus exists bonded as a repeating unit within the prepared polymer.

[0021] The term "monocyclic or polycyclic aromatic ring system" in the present application has 6 to 60, preferably 6 to 30, more preferably 6 to 24 aromatic ring atoms, and does not necessarily contain only aromatic groups, but two or more aromatic units are separated by short non-aromatic units (<10% of atoms other than H, preferably <5% of atoms other than H), for example, sp 3 hybrid carbon atoms or oxygen or nitrogen atoms, CO groups, and other aromatic ring systems that may also be interrupted. For example, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, and 9,9-dialkylfluorene should also be regarded as aromatic ring systems.

[0022] The aromatic ring system may be monocyclic or polycyclic, which may be condensed (e.g., naphthyl) or covalently bonded (e.g., biphenyl), or may have one ring (e.g., phenyl) or two or more rings including a combination of condensed and bonded rings.

[0023] Preferred aromatic rings include, for example, phenyl, biphenyl, terphenyl, [1,1’:3’,1’’]terphenyl-2’-yl, quarterphenyl, naphthyl, anthracene, binaphthyl, phenanthrene, dihydrophenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, and spirobifluorene.

[0024] The term "monocyclic or polycyclic heteroaromatic ring system" is understood in this application to mean an aromatic ring system having 5 to 60, preferably 5 to 30, more preferably 5 to 24 aromatic ring atoms, one or more of which atoms are heteroatoms. The "monocyclic or polycyclic heteroaromatic ring system" does not necessarily contain only aromatic groups, but may be interrupted by short non-aromatic units (<10% of atoms other than H, preferably <5% of atoms other than H), for example, sp 3 hybridized carbon atoms or oxygen or nitrogen atoms, CO groups, or the like.

[0025] The heteroaromatic ring system may be monocyclic or polycyclic, and these may be fused or covalently bonded (e.g., pyridylphenyl), or may have one ring or two or more rings including a combination of fused and bonded rings. Preferred are fully conjugated heteroaryl groups.

[0026] Preferred heteroaromatic ring systems include, for example, 5-membered rings such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole; 6-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine; or groups having several rings such as carbazole, indenocarbazole, indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalineimidazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3-b]thiophene, thieno[3,2-b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, or combinations of these groups.

[0027] The monocyclic or polycyclic, aromatic or heteroaromatic ring system may be unsubstituted or substituted. In the present application, "substituted" means that the monocyclic or polycyclic, aromatic or heteroaromatic ring system has one or more R substituents.

[0028] R is preferably the same or different in each case and is H, D, F, Cl, Br, I, N(R 3 )2, CN, NO2, Si(R 3 )3, B(OR 3 )2, C(=O)R 3 , P(=O)(R 3 )2, S(=O)R 3 , S(=O)2R 3 , OSO2R 3 , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms (each of which may be substituted by one or more R 3 radicals and one or more non-adjacent CH2 groups may be replaced by R 3 C=CR 3 , C≡C, Si(R 3 )2, C=O, C=S, C=NR 3 , P(=O)(R 3 )2, SO, SO2, NR 3 , O, S or CONR 3 and may be substituted, and one or more hydrogen atoms may be substituted by D, F, Cl, Br, I or CN), or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms (in each case may be substituted by one or more R 3 radicals), or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms (may be substituted by one or more R 3 radicals), or an aralkyl or heteroaralkyl having 5 to 60 aromatic ring atoms (may be substituted by one or more R 3 radicals), or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms (one or more R 3is optionally substituted by a radical; or is a crosslinkable group Q; simultaneously, two or more R radicals may combine to form a monocyclic or polycyclic, alicyclic, aromatic and / or benzo-fused ring system.

[0029] R is more preferably the same or different in each case, and is H, D, F, Cl, Br, I, N(R 3 )2, Si(R 3 )3, B(OR 3 )2, C(=O)R 3 , P(=O)(R 3 )2, a linear alkyl or alkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms (each of these may be optionally substituted by one or more R 3 radicals, and one or more non-adjacent CH2 groups may be substituted by R 3 C=CR 3 , C≡C, Si(R 3 )2, C=O, C=NR 3 , P(=O)(R 3 ), NR 3 , O or CONR 3 and one or more hydrogen atoms may be optionally substituted by F, Cl, Br or I), or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms (either case may be optionally substituted by one or more R 3 radicals), or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms (optionally substituted by one or more R 3 radicals), or an aralkyl or heteroaralkyl group having 5 to 30 aromatic ring atoms (optionally substituted by one or more R 3 radicals), or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 20 aromatic ring atoms (one or more R 3It may be substituted by a radical), or it is a crosslinkable group Q; at the same time, two or more R radicals may combine together to form a monocyclic or polycyclic, alicyclic, aromatic and / or benzo-fused ring system.

[0030] R is most preferably the same or different in each case, H, a linear alkyl or alkoxy group having 1 to 10 carbon atoms or an alkenyl or alkynyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms (each of these may be substituted by one or more R 3 radicals, and one or more non-adjacent CH2 groups may be R 3 C=CR 3 、C≡C、C=O、C=NR 3 、NR 3 、O or CONR 3 substituted), or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms (in each case it may be substituted by one or more R 3 radicals), or an aryloxy or heteroaryloxy group having 5 to 20 aromatic ring atoms (it may be substituted by one or more R 3 radicals), or an aralkyl or heteroaralkyl group having 5 to 20 aromatic ring atoms (it may be substituted by one or more R 3 radicals), or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 20 aromatic ring atoms (it may be substituted by one or more R 3 radicals), or it is a crosslinkable group Q; at the same time, two or more R radicals may combine together to form a monocyclic or polycyclic, alicyclic, aromatic and / or benzo-fused ring system.

[0031] Preferred alkyl groups having 1 to 10 carbon atoms are shown in the following table:

Table 1

[0032] In the second embodiment of the present invention, at least one structural unit of formula (I) in the polymer of the present invention is Ar 3 is substituted by Ar at one of the two ortho positions 4 and Ar 3 is further bonded to Ar at the meta position adjacent to the substituted ortho position 4 and is characterized in that.

[0033] Therefore, in the second embodiment, the structural unit of formula (I) is the following formula (Ib):

Chemical formula

[0034] In a preferred embodiment, at least one structural unit of formula (I) is the following formulas (II), (III) and (IV):

Chemical formula

[0035] In a particularly preferred embodiment, at least one structural unit of formula (II) is of the following formula (V):

Chemical formula

[0036] Examples of preferred structural units of formula (V) are shown in the following table:

Table 2

[0037] In an even more particularly preferred embodiment, at least one structural unit of formula (III) is of the following formula (VI):

Chemical formula

[0038] Examples of preferred structural units of formula (VI) are shown in the following table:

Table 3

[0039] In an even more particularly preferred embodiment, at least one structural unit of formula (IV) is of the following formula (VII): [Chemical formula] (wherein Ar 1 , Ar 2 , R, X, m and n may be based on the definitions given above) is selected from the structural units of.

[0040] Examples of preferred structural units of formula (VII) are shown in the following table: [Table 4] (wherein Ar 1 , Ar 2 , R, m, n and p may be based on the definitions given above).

[0041] Preferably, Ar 1 and Ar 2 are the same or different in each case and are characterized by being monocyclic or polycyclic, aromatic or heteroaromatic ring systems having 5 to 30, preferably 5 to 24, aromatic ring atoms.

[0042] More preferably, Ar 1 and Ar 2 are the same or different in each case and are independently in each case a monocyclic or polycyclic aromatic ring system having 5 to 14 aromatic carbon atoms selected from phenyl, biphenyl, terphenyl, [1,1':3',1'']terphenyl-2'-yl, quaterphenyl, naphthyl, anthracene, binaphthyl, phenanthrene, dihydrophenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzpyrene, fluorene, indene, indenofluorene and spirobifluorene, preferably selected from phenyl and biphenyl, more preferably selected from phenyl.

[0043] In addition, Ar 1 and Ar 2are the same or different in each case and are independently, for the bond to the nitrogen atom of each formula, at these ortho or meta positions, R 1 and R 2 are the same or different, preferably the same in each case at the ortho or meta position, more preferably the same at the meta position, and are characterized in that they are substituted.

[0044] In a very particularly preferred embodiment, at least one structural unit of formula (V) is of the following formula (VIII):

Chemical formula

[0045] Examples of preferred structural units of formula (VIII) are shown in the following table:

Table 5

[0046] In an even more particularly preferred embodiment, at least one structural unit of formula (VI) is of the following formula (IX):

Chemical formula

[0047] Examples of preferred structural units of formula (IX) are shown in the following table:

Table 6

[0048] In an even more particularly preferred embodiment, at least one structural unit of formula (VII) is of the following formula (X): [Chemical formula] (wherein R, R 1 , R 2 , X, m, and n may be as defined above) and is selected from the structural units of.

[0049] Examples of preferred structural units of formula (X) are shown in the following table: [Table 7] (wherein R, R 1 , R 2 , m, and n may be as defined above).

[0050] Preferably, R 1 and R 2 are the same or different in each case and, independently in each case, are a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 - 40 carbon atoms or a branched-chain or cyclic alkyl, alkoxy, or thioalkoxy group having 3 - 40 carbon atoms (each of which may be substituted by one or more R 3 radicals, and one or more non-adjacent CH2 groups may be substituted by R 3 C=CR 3 , C≡C, Si(R 3 )2, C=O, C=S, C=NR 3 , P(=O)(R 3 ), SO, SO2, NR 3 , O, S, or CONR 3 and one or more hydrogen atoms may be substituted by D, F, Cl, Br, I, or CN).

[0051] More preferably, R 1 and R 2 are the same or different in each case and, independently in each case, are a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, respectively.

[0052] Preferred structural units -Ar 1 -N-Ar 2 - in formulas (I), (Ia), (Ib) and (II) to (X) are shown in the following table: [Table 8] (wherein structural units (a) to (c), (e), (i) and (j) are preferred, (a) structural units (a) and (e) are particularly preferred, and structural unit (a) is very particularly preferred).

[0053] Examples of very particularly preferred structural units of formula (II) are shown in the following table: [Table 9] JPEG2025518470000020.jpg160170(wherein structural units A1 to A11, A14, A15, A18 and A19 are preferred, structural units A1 to A10, A14, A15, A18 and A19 are particularly preferred, and structural units A6, A9 and A18 are very particularly preferred).

[0054] In Formulas (VIII), (IX) and (X), and in their preferred embodiments, Formulas (VIIIa) to (VIIIh), (IXa) to (IXg) and (Xa) to (Xc), the dotted lines represent the bonds with adjacent structural units in the polymer. These may be arranged identically, independently at the ortho, meta or para positions, preferably at the ortho, meta or para positions, more preferably at the meta or para positions, and most preferably at the para position.

[0055] The proportion of the structural units of Formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X) in the polymer ranges from 1 to 100 mol%.

[0056] In a first preferred embodiment, the polymer of the present invention contains only one structural unit of Formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X), that is, its proportion in the polymer is 100 mol%. In this case, the polymer of the present invention is a homopolymer.

[0057] In a second preferred embodiment, the proportion of the structural units of Formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X) in the polymer ranges from 50 to 95 mol%, more preferably from 60 to 95 mol%, based on 100 mol% of all polymerizable monomers present as structural units in the polymer, that is, the polymer of the present invention has not only one or more structural units of Formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X), but also additional structural units other than the structural units of Formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X).

[0058] In a third preferred embodiment, the proportion of the structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X) in the polymer is in the range of 5 to 50 mol%, more preferably in the range of 25 to 50 mol%, based on 100 mol% of all polymerizable monomers present as structural units in the polymer. That is, the polymer of the present invention has not only one or more structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X), but also additional structural units other than the structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X).

[0059] These structural units other than the structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X) include those comprehensively listed in the disclosure and WO 02 / 077060 (A1) and WO 2005 / 014689 (A2). These are regarded as forming part of the present invention by reference. The additional structural units are derived from, for example, the following classifications: Group 1: units that affect hole injection and / or the hole transporting property of the polymer; Group 2: units that affect electron injection and / or the electron transporting property of the polymer; Group 3: units having a combination of the individual units of Group 1 and Group 2; Group 4: units that modify the emission characteristics so as to obtain phosphorescence rather than fluorescence; Group 5: units that improve the transition from the singlet state to the triplet state; Group 6: units that affect the emission color of the resulting polymer; Group 7: units commonly used as the polymer backbone; Group 8: units that affect the film morphology and / or rheological properties of the resulting polymer.

[0060] Preferred polymers of the present invention are those in which at least one structural unit has charge transport properties, i.e., those containing units from Group 1 and / or 2.

[0061] Structural units from Group 1 having hole injection and / or hole transport properties are, for example, triarylamine, benzidine, tetraaryl - para - phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrophenazine, thianthrene, dibenzo - para - dioxin, phenoxathiin, carbazole, azulene, thiophene, pyrrole and furan derivatives and further O - containing, S - containing or N - containing heterocycles.

[0062] Preferred structural units from Group 1 are structural units of the following formulas (1a) - (1q): [Table 10] JPEG2025518470000022.jpg113170(wherein R, k, m and n may be subject to the definitions given above).

[0063] In formulas (1a) - (1q), the dotted lines represent possible bonds with adjacent structural units in the polymer. When two dotted lines are present in the formula, the structural unit has a bond with one or two, preferably two, adjacent structural units. When three dotted lines are present in the formula, the structural unit has a bond with one, two or three, preferably two, adjacent structural units. When four dotted lines are present in the formula, the structural unit has a bond with one, two, three or four, preferably two, adjacent structural units. These may be arranged independently, the same or different, at the ortho, meta or para positions.

[0064] Structural units from Group 2 having electron injection and / or electron transport properties are, for example, not only pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole quinoline, quinoxaline, anthracene, benzoanthracene, pyrene, perylene, benzimidazole, triazine, ketone, phosphine oxide and phenazine derivatives but also triarylbora nes and further O-containing, S-containing or N-containing heterocycles.

[0065] It may be preferred if the structure of the polymer of the present invention that increases the hole mobility and also increases the electron mobility (i.e., units from Groups 1 and 2) are directly bonded to each other or contains units from Group 3 in which there is a structure that increases both the hole mobility and the electron mobility. Some of these units function as emitters and can shift the emission color to green, yellow or red. Therefore, their use is suitable, for example, for creating other emission colors from a originally blue-emitting polymer.

[0066] The structural units of Group 4 can emit light with high efficiency even from the triplet state at room temperature, that is, exhibit electroluminescence rather than electrofluorescence that frequently results in increased energy efficiency. Suitable for this purpose are, first of all, compounds containing heavy atoms having an atomic number greater than 36. Preferred compounds are those containing a d or f transition metal that satisfies the above conditions. Particularly preferred here are the corresponding structural units containing elements of Groups 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt). Structural units useful here for the polymers of the present invention include, for example, various complexes described in International Publication No. 02 / 068435, International Publication No. 02 / 081488, European Patent Application Publication No. 1239526 and International Publication No. 2004 / 026886. The corresponding monomers are described in International Publication No. 02 / 068435 and International Publication No. 2005 / 042548.

[0067] The structural units of Group 5 improve the transition from the singlet state to the triplet state and are used in combination with the structural elements of Group 4 to improve the phosphorescence properties of these structural elements. Useful units for this purpose are, in particular, carbazole and crosslinked carbazole dimer units described, for example, in WO 2004 / 070772 and WO 2004 / 113468. Further useful units for this purpose are, for example, ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives and similar compounds described in WO 2005 / 040302.

[0068] The structural units of Group 6 include, in addition to the above, at least one further aromatic structure or another conjugated structure not within the above groups, i.e., those that are not organometallic complexes or have only a slight effect on the charge carrier mobility that has no effect on the singlet-triplet transition. This type of structural element can affect the emission color of the resulting polymer. Thus, depending on the unit, these can also be used as emitters. Preferred are aromatic structures having 6 to 40 carbon atoms or trans, stilbene or bisstyrylarylene derivatives which may each be substituted by one or more R radicals. Particularly preferred are 1,4- or 9,10-anthrylene, 1,6-, 2,7- or 4,9-pyrenylene, 3,9- or 3,10-perylenylene, 4,4'-transylene, 4,4'-stilbenylene, benzothiadiazole and corresponding oxygen derivatives, quinoxaline, phenothiazine, phenoxazine, dihydrophenazine, bis(thiophenyl)arylene, oligo(thiophenylene), phenazine, rubrene, pentacene or preferably substituted perylene derivatives, or preferably conjugated push-pull systems (systems substituted by donor and acceptor substituents) or preferably substituted squaraine or quinacridone systems and the like.

[0069] The structural units of Group 7 are units having 6 to 40 carbon atoms and containing an aromatic structure commonly used as a polymer backbone. These include, for example, 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, fluorene derivatives, 9,9-spirobifluorene derivatives, phenanthrene derivatives, 9,10-dihydrophenanthrene derivatives, 5,7-dihydrodibenzoxepin derivatives and cis- and trans-indenofluorene derivatives, as well as 1,2-, 1,3- or 1,4-phenylene, 1,2-, 1,3- or 1,4-naphthylene, 2,2’-, 3,3’- or 4,4’-biphenylene, 2,2’’-, 3,3’’- or 4,4’’-terphenylene, 2,2’-, 3,3’- or 4,4’-bi-1,1’-naphthylene or 2,2’’’-, 3,3’’’- or 4,4’’’-quarterphenylene derivatives.

[0070] Preferred structural units from Group 7 are structural units of the following formulas (7a) to (7o): [Table 11] (wherein R, k, m, n and p may be subject to the definitions given above).

[0071] In formulas (7a) to (7o), the dotted lines represent possible bonds with adjacent structural units in the polymer. When two dotted lines are present in the formula, the structural unit has a bond with one or two, preferably two, adjacent structural units. When four or more dotted lines are present in the formula (formulas (7g), (7h) and (7j)), the structural unit has a bond with one, two, three or four, preferably two, adjacent structural units. These may be arranged independently, identically or differently, at the ortho, meta or para positions.

[0072] The structural units of Group 8 are those that affect the film morphology and / or rheological properties of the polymer, such as siloxanes, alkyl chains or fluorinated groups, as well as particularly hard or flexible units, liquid crystal-forming units or crosslinkable groups.

[0073] Preferably, the polymer of the present invention not only contains the structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X) at the same time, but also further contains one or more units selected from Groups 1 to 8. Similarly, when there are two or more additional structural units from the same group present at the same time, it may be preferred.

[0074] Here, preferably, the polymer of the present invention contains not only at least one structural unit of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X), but also a unit from Group 7.

[0075] Similarly, it is preferred if the polymer of the present invention contains units that improve charge transport or charge injection, i.e., units from Group 1 and / or Group 2.

[0076] It is even more particularly preferred if the polymer of the present invention contains a structural unit from Group 7 and a unit from Group 1 and / or Group 2.

[0077] The polymer of the present invention is either a homopolymer or a copolymer of the structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X). The polymer of the present invention may be linear or branched, preferably linear. The copolymer of the present invention may contain not only one or more structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X), but also one or more additional structures from Groups 1 to 8 as detailed above.

[0078] The copolymer of the present invention can have a random, alternating or block structure, or can alternatively have two or more of these structures. More specifically, the copolymer of the present invention has a random or alternating structure. More specifically, the copolymer is a random or alternating copolymer. A copolymer having a block structure can be obtained, and a particularly preferred method for further structural elements for this purpose is described in detail, for example, in WO 2005 / 014688. This is incorporated herein by reference. Similarly, it should be emphasized once again in this regard that the polymer can also have a dendritic structure.

[0079] In a further embodiment of the present invention, the polymer of the present invention comprises not only one or more structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X), but also, if necessary, further structural units selected from the above groups 1 to 8, and further at least one, preferably one, structural unit having a crosslinkable Q group.

[0080] In the context of the present invention, a "crosslinkable Q group" means a functional group that can enter into a reaction and thus form an insoluble compound. The reaction can be a reaction with a further same Q group, a further different Q group or any other part of the same or a different polymer chain. Thus, a crosslinkable group is a reactive group. As a result of the reaction of the crosslinkable group, a correspondingly crosslinked compound is obtained. A chemical reaction can be carried out in a layer to produce an insoluble layer. Crosslinking can usually be promoted by heat or by UV irradiation, microwave irradiation, X-rays or electron beam, in the presence of an initiator if necessary. In the context of the present invention, "insoluble" preferably means that after the crosslinking reaction, i.e., after the reaction of the crosslinkable groups, the polymer of the present invention has a solubility in an organic solvent at room temperature that is lower by at least a factor of 3, preferably at least a factor of 10, than the solubility of the corresponding non-crosslinked polymer of the present invention in the same organic solvent.

[0081] In the first embodiment, the structural unit having a crosslinkable Q group may be selected from the structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X).

[0082] Preferred structural units having a crosslinkable Q group are the following formulas (XIa1) to (XIa3) derived from the structural unit of formula (Ia):

Chemical formula

[0083] Examples of preferred structural units of formula (XIa) are shown in the following table:

Table 12

[0084] In formulas (11a) to (11f), the dotted lines represent possible bonds with adjacent structural units in the polymer. When two dotted lines are present in the formula, the structural unit has a bond with one or two, preferably two, adjacent structural units.

[0085] Further preferred structural units having a crosslinkable Q group are the following formulas (XIb1) to (XI1b4) derived from the structural unit of formula (Ib):

Chemical formula

[0086] Examples of preferred structural units of formula (XIb) are shown in the following table: [Table 13] (wherein R, k, m, n, and p may be subject to the definitions given above).

[0087] In formulas (11g) to (11o), the dotted lines represent possible bonds with adjacent structural units in the polymer. When there are two dotted lines in the formula, the structural unit has one or two, preferably two, bonds with adjacent structural units.

[0088] In addition, the structural unit having a crosslinkable Q group may be selected from the structural units disclosed in Groups 1 to 8 in the second embodiment.

[0089] A preferred structural unit having a crosslinkable Q group is the following formula (XII) derived from the triarylamine unit of Group 1: [Chemical formula] (wherein Ar 1 , Ar 2 and Ar 3 may be subject to the definitions given above in relation to formula (I)) is a structural unit.

[0090] Examples of preferred structural units of formula (XII) are shown in the following table: [Table 14]

[0091] An even more preferred structural unit having a crosslinkable Q group is the following formula (XIII) derived from Group 7: [Chemical formula] (wherein Ar 1 may be as defined above in relation to the structural unit of formula (I)) is a structural unit of

[0092] . Examples of preferred structural units of formula (XIII) are shown in the following table:

[0092] Examples of preferred structural units of formula (XIII) are shown in the following table: [Table 15]

[0093] As described above, the crosslinkable Q group means a functional group that can enter into a chemical reaction and thus form an insoluble polymer compound. It is generally possible to use any Q group known to those skilled in the art. The specific functionality of this group is to bind the polymer compounds of the present invention to each other by a crosslinking reaction, optionally together with further reactive polymer compounds. This results in a crosslinked compound or, if the reaction is carried out in a layer, a crosslinked layer. A crosslinked layer in the context of the present invention is understood to mean a layer that can be obtained by carrying out a crosslinking reaction from a layer of the crosslinkable polymer compound of the present invention. The crosslinking reaction can generally be initiated by heat and / or UV irradiation, microwave irradiation, X-rays or electron beams and / or free radical generating substances, anions, cations, acids and / or photoacids. The presence of a catalyst may likewise be desirable or necessary. Preferably, the crosslinking reaction is a reaction that does not require the addition of an initiator or a catalyst.

[0094] Preferred crosslinkable Q groups according to the present invention are the following groups:

[0095] a) Terminal or cyclic alkenyl or terminal dienyl and alkynyl groups: Suitable units include terminal or cyclic double bonds, terminal dienyl groups or terminal triple bonds, especially those containing terminal or cyclic alkenyl, terminal dienyl or terminal alkynyl groups having 2 to 40 carbon atoms, preferably 2 to 10 carbon atoms, and individual CH2 groups and / or individual hydrogen atoms may be substituted by the above R groups. Further suitable are groups which can be regarded as precursors and in which double or triple bonds can be generated in situ.

[0096] b) Alkenyloxy, dienyloxy or alkynyloxy groups: Further suitable are alkenyloxy, dienyloxy or alkynyloxy groups, preferably alkenyloxy groups.

[0097] c) Acrylic acid groups: Further suitable are acrylic acid units in a broad sense, preferably acrylic acid esters, acrylamides, methacrylic acid esters and methacrylamides. Particularly preferred are acrylic acid C 1~10 alkyl and methacrylic acid C 1~10 alkyl.

[0098] a) - c) The crosslinking reaction of the above groups can be carried out by free radical, cationic or anionic mechanisms, or by addition cyclization.

[0099] It may be desirable to add a suitable initiator for the crosslinking reaction. Suitable initiators for free radical crosslinking are, for example, dibenzoyl peroxide, AIBN or TEMPO. Suitable initiators for cationic crosslinking are, for example, AlCl3, BF3, triphenylmethyl perchlorate or tropylium hexachloroantimonate. Suitable initiators for anionic crosslinking are bases, especially butyllithium.

[0100] However, in a preferred embodiment of the present invention, crosslinking is carried out without adding an initiator and is initiated solely by thermal means. The reason for preferring this is that the absence of an initiator prevents contamination of the layer which may lead to deterioration of the device characteristics.

[0101] d) Oxetanes and oxiranes: A further suitable classification of the crosslinkable group Q is the classification of oxetanes and oxiranes that are cationically crosslinked by ring opening.

[0102] It may be desirable to add a suitable initiator for the crosslinking reaction. Suitable initiators are, for example, AlCl3, BF3, triphenylmethyl perchlorate or tropylium hexachloroantimonate. Similarly, it is possible to add a photoacid as an initiator.

[0103] e) Silane: Even more suitable as a classification of the crosslinkable group is a silane group SiR3 in which at least two R groups, preferably all three R groups, are Cl or an alkoxy group having 1 to 20 carbon atoms. This group reacts in the presence of water to give an oligo- or polysiloxane.

[0104] f) Cyclobutane group When being suitable reaction conditions for the reaction of these groups, the above crosslinkable Q groups are generally known to those skilled in the art.

[0105] Preferred crosslinkable Q groups include an alkenyl group of formula Q1, a dienyl group of formula Q2, an alkynyl group of formula Q3, an alkenyloxy group of formula Q4, a dienyloxy group of formula Q5, an alkynyloxy group of formula Q6, acrylic acid groups of formula Q7 and Q8, oxetane groups of formula Q9 and Q10, an oxirane group of formula Q11 and a cyclobutane group of formula Q12:

Table 16

[0106] R in formulas Q1 to Q8 and Q11 11 、R 12 and R 13The radicals are the same or different in each case and are H or a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. More preferably, R 11 , R 12 and R 13 radicals are H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, most preferably H or methyl. The subscripts used have the following definitions: s = 0 to 8; and t = 1 to 8.

[0107] The dotted bonds in Formulas Q1 to Q11 and the dotted bond in Formula Q12 represent the bonding of a crosslinkable group to a structural unit.

[0108] The crosslinkable groups of Formulas Q1 to Q12 may be directly bonded to the structural unit or, as shown in the following Formulas Q13 to Q24, to a further monocyclic or polycyclic, aromatic or heteroaromatic ring system Ar 10 by:

Table 17

[0109] Particularly preferred crosslinkable groups Q are as follows:

Table 18

[0110] The R 11 and R 12 radicals in Formulas Q7a and Q13a to Q19a are the same or different in each case and are H or a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. More preferably, R 11 and R 12 radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, most preferably methyl.

[0111] In each case, R in formula Q7b and Q19b 13 The radical is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. More preferably, R 13 The radical is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, most preferably methyl.

[0112] The subscripts used have the following definitions: s = 0 to 8 and t = 1 to 8.

[0113] Highly particularly preferred crosslinkable groups Q are as follows: [Table 19] JPEG2025518470000036.jpg237170

[0114] For the preferred Q1 to Q24 groups, particularly preferred Q1a to Q24a groups and highly particularly preferred Q1b to Q24c groups, the dotted lines represent the bonds to the structural units. In this connection, the Q12, Q12a, Q12b and Q24 groups each have two bonds to two adjacent ring carbon atoms in the structural unit. All other crosslinkable groups have only one bond to the structural unit.

[0115] The proportion of crosslinkable structural units in the polymer is in the range of 0.01 to 50 mol%, preferably 0.1 to 30 mol%, more preferably 0.5 to 25 mol%, most preferably 1 to 20 mol% based on 100 mol% of all copolymerizable monomers present as structural units in the polymer.

[0116] The polymers of the present invention containing structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) and / or (XI) are generally prepared by polymerization of one or more monomer types, at least one of which monomers provides structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) and / or (XI) in the polymer. Suitable polymerization reactions are known to those skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions that result in C-C and C-N coupling are as follows. (A) Suzuki polymerization; (B) Yamamoto polymerization; (C) Stille polymerization; (D) Heck polymerization; (E) Negishi polymerization; (F) Sonogashira polymerization; (G) Hiyama polymerization; and (H) Hartwig-Buchwald polymerization.

[0117] How to carry out the polymerization by these methods and then how to separate and purify the polymer from the reaction medium are known to those skilled in the art and are described in detail, for example, in the literature, WO 03 / 048225, WO 2004 / 037887 and WO 2004 / 037887.

[0118] C-C coupling is preferably selected from the group of Suzuki polymerization, Yamamoto polymerization and Stille polymerization; C-N coupling is preferably coupling by Hartwig-Buchwald.

[0119] Accordingly, the present invention also provides a method for preparing the polymers of the present invention, which method is characterized in that these are prepared by Suzuki polymerization, Yamamoto polymerization, Stille polymerization or Hartwig-Buchwald polymerization.

[0120] The synthesis of the polymers of the present invention requires the corresponding monomers of formula (MI): [Chemical formula] (wherein Ar 1 , Ar 2 and Ar 3 may have the definitions given above in relation to the structural units of formula (I)). are required.

[0121] The monomers of formula (MI) that provide the structural units of formula (I) in the polymers of the present invention are compounds with the corresponding substitutions and have suitable functional groups at two positions that allow incorporation of this monomer unit into the polymer. Thus, these monomers of formula (MI) also form part of the subject matter of the present invention. The Y groups are the same or different and are leaving groups suitable for the polymerization reaction, and as a result, allow incorporation of the monomer unit into the polymer compound. Preferably, Y is the same or different chemical functional group and is selected from the group consisting of halogen, O-tosylate, O-triflate, O-sulfonate, borate ester, partially fluorinated silyl group, diazonium group, and organotin compounds.

[0122] The basic structure of the monomer compound can be functionalized by standard methods, such as Friedel-Crafts alkylation or acylation. In addition, the basic skeleton can be halogenated by standard methods of organic chemistry. The halogenated compound can be further converted, if necessary, in an additional functionalization step. For example, the halogenated compound can be used either directly or after conversion to a boronic acid derivative or an organotin derivative as a starting material for conversion to a polymer, oligomer, or dendrimer.

[0123] The above methods are merely a selection from reactions known to those skilled in the art who can use them without implementing the technology of the present invention to synthesize the compounds of the present invention.

[0124] The polymers of the present invention can be used as neat substances or as mixtures with any further polymers, oligomers, dendrimers or low molecular weight substances. In the context of the present invention, low molecular weight substances are understood to mean compounds having a molecular weight in the range from 100 to 3000 g / mol, preferably from 200 to 2000 g / mol. These further substances can, for example, improve the electronic properties or be capable of emitting light themselves. Mixtures are represented above and below as mixtures comprising at least one polymer component. In this way, it is possible to produce one or more polymer layers consisting of a mixture (formulation) of one or more polymers of the present invention having structural units of the formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X) and, if appropriate, one or more further polymers and one or more low molecular weight substances.

[0125] Accordingly, the present invention further provides a polymer formulation comprising one or more polymers of the present invention and one or more further polymers, oligomers, dendrimers and / or low molecular weight substances.

[0126] The present invention further provides solutions and formulations consisting of one or more polymers of the present invention or polymer formulations in one or more solvents. Methods for preparing such solutions are known to those skilled in the art and are described, for example, in WO 02 / 072714, WO 03 / 019694 and the documents cited therein.

[0127] Using these solutions, it is possible to produce polymer thin layers, for example, by surface coating methods (such as spin coating) or printing methods (such as inkjet printing).

[0128] Polymers containing structural units having a crosslinkable Q group are particularly suitable for producing thin films or coatings, in particular structured coatings, for example in on-site UV photopolymerization or photopatterning, for example by thermal or photoinduced on-site polymerization and on-site optimization. Here, it is possible to use these either in pure form or in formulations or mixtures of these polymers corresponding to the polymers in question. They can be used with or without the addition of solvents and / or binders. Suitable materials, methods and apparatuses for the above methods are described, for example, in WO 2005 / 083812. Possible binders are, for example, polystyrene, polycarbonate, poly(meth)acrylate, polyacrylate, polyvinyl butyral and similar optoelectronically neutral polymers.

[0129] Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fencon, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane or mixtures of these solvents.

[0130] Accordingly, the present invention further provides the use of a polymer comprising a structural unit having a crosslinkable Q group for the preparation of a crosslinked polymer. More preferably, a crosslinkable group which is a vinyl group or an alkenyl group is preferably incorporated into the polymer by a Wittig reaction or a Wittig-like reaction. When the crosslinkable group is a vinyl group or an alkenyl group, the crosslinking can be carried out by free radical or ionic polymerization which can be induced by heat or radiation. Preferred is free radical polymerization induced thermally, preferably at a temperature below 250 ° C, more preferably below 230 ° C.

[0131] If necessary, during the crosslinking process, additional styrene monomer is added to achieve a higher degree of crosslinking. Preferably, the proportion of the added styrene monomer ranges from 0.01 to 50 mol%, more preferably from 0.1 to 30 mol%, based on 100 mol% of all copolymerized monomers present as structural units in the polymer.

[0132] Therefore, the present invention provides the following steps: (a) preparing a polymer comprising structural units having one or more crosslinkable Q groups; and (b) subjecting to free radical or ionic crosslinking, preferably free radical crosslinking, which can be induced either thermally or by radiation, preferably thermally A method for preparing a crosslinked polymer comprising the above steps is also provided.

[0133] The crosslinked polymers prepared by the method of the present invention are insoluble in all standard solvents. In this way, it is possible to produce a distinct layer thickness that does not dissolve or partially redissolve upon application of subsequent layers.

[0134] Therefore, the present invention also relates to crosslinked polymers obtainable by the aforementioned method. The crosslinked polymers are preferably produced in the form of crosslinked polymer layers, as described above. Since the crosslinked polymers are insoluble in all solvents, further layers can be applied from a solvent onto the surface of such crosslinked polymer layers by the above technique.

[0135] The present invention also encompasses what is called a hybrid device capable of generating one or more layers processed from a solution and layers produced by vapor deposition of low molecular weight substances.

[0136] The polymers of the present invention can be used in or for the manufacture of electronic or optoelectronic devices.

[0137] Accordingly, the present invention further provides the use of the polymers of the present invention in electronic or optoelectronic devices, preferably organic electroluminescent devices (OLEDs), organic field effect transistors (OFETs), organic integrated circuits (O-ICs), organic thin film transistors (TFTs), organic solar cells (O-SCs), organic laser diodes (O-lasers), organic photovoltaic (OPV) elements or devices or organic photoreceptors (OPCs), more preferably organic electroluminescent devices (OLEDs).

[0138] In the case of the aforementioned hybrid devices, in combination with an organic electroluminescent device, the combined PLED / SMOLED (polymer light emitting diode / small molecule organic light emitting diode) system will be described.

[0139] Methods for manufacturing OLEDs are known to those skilled in the art and are described in detail, for example, as general methods in WO 2004 / 070772, which must be appropriately adapted in individual cases.

[0140] As described above, the polymers of the present invention are very particularly suitable as electroluminescent materials in OLEDs or as displays manufactured in this way.

[0141] In the context of the present invention, an electroluminescent material is considered to mean a material that can find use as an active layer. An "active layer" means that the layer can emit light (light emitting layer) in response to the application of an electric field and / or that the layer improves the injection and / or transport of positive and / or negative charges (charge injection or charge transport layer).

[0142] Accordingly, the present invention also preferably provides the use of the polymers of the present invention in OLEDs, particularly as electroluminescent materials.

[0143] The present invention further provides an electronic or optoelectronic component, preferably an organic electroluminescence device (OLED), an organic field effect transistor (OFET), an organic integrated circuit (O-IC), an organic thin film transistor (TFT), an organic solar cell (O-SC), an organic laser diode (O-laser), an organic photovoltaic (OPV) element or device, and an organic photoreceptor (OPC), more preferably, an electroluminescence device having one or more active layers, at least one of these active layers comprising one or more polymers of the present invention. The active layer may be, for example, a light emitting layer, a charge transport layer and / or a charge injection layer.

[0144] In the text of the present application, and in the examples that follow hereafter, the main object is the use of the polymers of the present invention in relation to OLEDs and corresponding displays. Despite such limitations of the description, without implementing further technology of the present invention, it is possible for a person skilled in the art to similarly utilize the polymers of the present invention as semiconductors for further above uses in other electronic devices.

[0145] The examples that follow hereafter are intended to illustrate without limiting the present invention. More specifically, the features, properties and advantages described therein for the defined compounds on which the examples in question are based apply to other compounds not described in detail, unless stated to the contrary elsewhere, but are also applicable to other compounds encompassed by the scope of protection of the claims.

Example

[0146] Part A: Synthesis of Monomers Unless otherwise specified, all syntheses are carried out under an argon atmosphere and in a dry solvent.

[0147] A1 Preparation of Precursors of the Monomers of the Invention A1.1 Preparation of Precursor Int-1

Chemical formula

[0148] [1,1'-Biphenyl]-2-amine (30 g, 0.18 mmol), m-bromotoluene (63.7 g, 0.37 mmol) and sodium tert-butoxide (51.1 g, 0.53 mmol) are dissolved in 600 ml of toluene. After addition of palladium acetate (1.99 g, 8.9 mmol) and tri-tert-butylphosphine (1 M toluene solution, 17.7 ml, 17.7 mmol), the reaction mixture is refluxed. After 16 hours, the reaction mixture is allowed to cool to room temperature and 300 ml of water is added. The resulting phases are separated, the aqueous phase is extracted once with toluene (200 ml), the organic phase is washed twice with water, the combined organic phases are washed with water (2 × 250 ml), dried over magnesium sulfate and then concentrated on a rotary evaporator. The residue is filtered through silica gel (eluent: heptane) and the product is obtained as crystals from ethanol. Yield: 31 g (0.09 mmol, 50% of theory)

[0149] The following precursors can be prepared in the same manner as in Example A1.1:

Table 20

[0150] A2 Preparation of the Monomers of the Invention A2.1 Preparation of Monomer Inv-Mon-Br-1

Chemical formula

[0151] 31.0 g (0.09 mmol) of Int-1 is dissolved in 350 ml of THF and cooled to 0 °C. N-Bromosuccinimide (31.4 g, 176 mmol) is added portionwise, the mixture is slowly allowed to come to room temperature and stirred for 16 hours. The reaction mixture is then concentrated, heptane is added and extraction is carried out with stirring while cooling with ice. The resulting solid is removed by suction filtration and the filtrate is concentrated. Purification is carried out by repeating crystallization from ethanol until a purity of > 99.5% (GC-MS) is obtained. Yield: 26.3 g (0.05 mol, 60%)

[0152] The following monomers can be prepared in the same manner as Inv-Mon-Br-1: [Table 21]

[0153] A3 Further Monomers Further monomers for the preparation of the polymers of the present invention and the polymers of the comparative examples are already described in the prior art, are commercially available or are prepared by the methods of the literature and are summarized in Table 1 below: [Table 22]

[0154] Part B: Synthesis of Polymers Preparation of the comparative example polymers V-HTL1 and V-HTL2 and the polymers of the present invention HTL1, HTL2, HTL3 and HTL4

[0155] The comparative example polymers V-HTL1 and V-HTL2 and the polymers of the present invention HTL1, HTL2, HTL3 and HTL4 are prepared from the corresponding monomers by Suzuki coupling by the method described in WO 2003 / 048225.

[0156] For the polymerization, the monomers are used in the percentage ratios of mol% specified in Table 2. The polymers V-HTL1, V-HTL2, HTL1, HTL2, HTL3 and HTL4 thus prepared contain structural units in the percentages reported in Table 2 (percentage = mol%) after removal of the leaving groups.

[0157] In the case of monomers having aldehyde groups, these are converted to crosslinkable vinyl groups after polymerization by the Wittig reaction by the method described in WO 2010 / 097155. Thus, the polymers listed corresponding to Table 2 and used in part C have crosslinkable vinyl groups rather than the aldehyde groups originally present.

[0158] The palladium and bromine contents of the polymer are determined by ICP-MS. The determined values are less than 10 ppm.

[0159] The molecular weight M and polydispersity D confirmed by gel permeation chromatography (GPC) (model: Agilent HPLC system series 1100) (column: PL-RapidH manufactured by Polymer Laboratories; solvent: THF containing 0.12% by volume of o-dichlorobenzene; detection: UV and refractive index; temperature: 40 °C). w Calibration is performed using polystyrene standards.

[0160] The composition of the polymer is shown in Table 2 below.

[0161]

Table 23

[0162] Part C: Manufacture of OLED There have already been many descriptions in the literature, for example, regarding the manufacture of solution-based OLEDs in WO 2004 / 037887 and WO 2010 / 097155. Match the above methods to the environments described later (layer thickness, variations in materials).

[0163] The combination of materials of the present invention is used in the following layer sequence. - Substrate, - ITO (50 nm), - Hole injection layer (HIL) (25 nm), - Hole transport layer (HTL) (20 nm), - Emission layer (EML) (60 nm), - Hole blocker layer (HBL) (10 nm), - Electron transport layer (ETL) (40 nm), - Electron injection layer (EIL) (1 nm), - Cathode (AI) (100 nm).

[0164] The substrate used is a glass plate coated with structured ITO (indium tin oxide) with a thickness of 50 nm. The hole injection layer is applied by spin coating in an inert atmosphere. For this purpose, a hole transporting crosslinkable polymer and a p-doping salt are dissolved in toluene. The corresponding materials are described, inter alia, in WO 2016 / 107668, WO 2013 / 081052 and EP 2325190. A solid content of 6 mg / ml is used for a resulting layer thickness of 25 nm. Thereafter, the layer is baked on a hot plate at 210 °C for 30 minutes in an inert gas atmosphere.

[0165] Subsequently, the hole transporting and light emitting layers are applied to these coated substrates.

[0166] The hole transporting layers used are the compounds of the invention and the compounds of the comparative examples, each dissolved in toluene. Since a layer thickness of 20 nm is to be achieved by spin coating, the solid content in these solutions is 5 mg / ml. The layers are spun in an inert gas atmosphere and baked on a hot plate at 220 °C for 30 minutes.

[0167] The materials used in this case are shown in Table 2, and the monomers used for this are shown in Table 1.

[0168] The light emitting layer consists of host material H1, host material H2 and light emitting dopant D1. The materials are present in the light emitting layer in a ratio of 45 wt% H1, 36 wt% H2 and 19 wt% D1. The mixture for the light emitting layer is dissolved in toluene. Since a layer thickness of 60 nm is to be achieved by spin coating, the solid content in this solution is 19 mg / ml. The layer is spun in an inert gas atmosphere and baked at 150 °C for 10 minutes.

[0169]

Table 24

[0170] The hole blocker and materials for electron transport and electron injection are applied by thermal evaporation in a vacuum chamber as shown in Table 4. The hole blocker layer consists of ETM1. The electron transport layer consists of two materials, ETM1 and ETM2, which are co-evaporated at a ratio of 50% by volume each. The electron injection layer consists of ETM2.

[0171]

Table 25

[0172] The cathode is formed by thermal evaporation of an aluminum layer with a thickness of 100 nm.

[0173] The OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum, Lambertian emission characteristics, and current-voltage-luminance characteristics (IUL characteristics) for estimating the (operating) lifetime are determined. The IUL characteristics are used to determine parameters such as the external quantum efficiency (%) at a specific brightness. LD80@1000cd / m 2 is the lifetime until the OLED given an initial brightness of 1000cd / m 2 decreases to 80% of the initial intensity, i.e., 800cd / m 2 until it drops.

[0174] The characteristics of various OLEDs are listed in Table 5. Examples V01 and V02 are comparative examples. Example C1 shows the characteristics of an OLED combined with the materials of the present invention and the energy gaps of the respective HTL polymers. A green-emitting OLED comprising the material of the present invention as the HTL is manufactured.

[0175] The energy gap of each polymer is determined by the absorption spectrum for its neat thin film. For this purpose, a neat thin film of the polymer is manufactured on quartz glass. For this purpose, the polymer is dissolved in toluene at a concentration of 15 mg / ml and processed into a 50 nm thick thin film by spin coating. This is baked at 220 °C for 30 minutes in an inert gas atmosphere.

[0176] Absorption measurements are performed using a Perkin Elmer Lambda850 UV-VIS spectrometer. The flank of the absorption spectrum is used for the determination of the energy gap (see Figure 1). The results are shown in Table 5 in the same way.

[0177] As shown in Table 5, the polymer of the present invention (i.e., HTL1) results in an energy gap between the blocked conjugation (i.e., V-HTL2) and the conjugated polymer (i.e., V-HTL1). In addition, it is possible to see improvements in OLEDs related to the efficiency of the conjugated polymer and improvements related to the lifetime of the polymer having blocked conjugation.

[0178]

Table 26

Claims

1. The following formula (I): 【Chemical Formula 1】 (In formula (I), Ar １ ~Ar ３ are the same or different in each case and are monocyclic or polycyclic, aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, and Ar ３ may be substituted by one or more R radicals; R is the same or different in each case and is H, D, F, Cl, Br, I, N(R ３ ) ２ , CN, NO ２ , Si(R ３ ) ３ , B(OR ３ ) ２ , C(=O)R ３ , P(=O)(R ３ ) ２ , S(=O)R ３ , S(=O) ２ R ３ , OSO ２ R ３ , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms (each of these may be substituted by one or more R ３ radicals, and one or more non-adjacent CH ２ groups may be substituted by R ３ C = CR ３ , C≡C, Si(R ３ ) ２ , C = O, C = S, C = NR ３ , P(=O)(R ３ ), SO, SO ２ , NR ３ , O, S or CONR ３ and one or more hydrogen atoms may be substituted by D, F, Cl, Br, I or CN), or a monocyclic or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms (in each case one or more R ３which may be substituted by radicals), or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms (one or more Rs ３ which may be substituted by radicals), or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms (one or more Rs ３ which may be substituted by radicals), or a diarylamino group, a diheteroarylamino group or an arylheteroarylamino group having 10 to 40 aromatic ring atoms (one or more Rs ３ which may be substituted by radicals); or a crosslinkable group Q, wherein two or more R radicals may together form a monocyclic or polycyclic, alicyclic, aromatic and / or benzo-fused ring system; R ３ is in each case the same or different and is H, D, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, an aromatic and / or heteroaromatic hydrocarbyl radical having 5 to 20 carbon atoms, wherein one or more hydrogen atoms may be substituted by F; two or more Rs ３ substituents may together form a monocyclic or polycyclic, aliphatic or aromatic ring system; The dotted line represents the bond with an adjacent structural unit in the polymer; Ar １ is substituted by R １ radicals, and / or Ar ２ is substituted by R ２ radicals, R １ and R ２ are each independently, in each case the same or different, F, Cl, Br, I, N(R ３ ), ２ CN, NO ２ Si(R ３ ), ３ B(OR ３ ), ２ C(=O)R ３ P(=O)(R ３ ), ２ S(=O)R ３, S(=O) ２ R ３ , OSO ２ R ３ , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms (in each case optionally substituted by one or more R ３ radicals, and one or more non-adjacent CH ２ groups may be R ３ C═CR ３ , C≡C, Si(R ３ ), ２ , C═O, C═S, C═NR ３ , P(═O)(R ３ ), SO, SO ２ , NR ３ , O, S or CONR ３ and may be substituted by one or more hydrogen atoms may be substituted by D, F, Cl, Br, I or CN)), a polymer having at least one structural unit of

2. Ar １ is substituted by an R １ radical, and Ar ２ is substituted by an R ２ radical, the polymer according to claim 1.

3. Ar ３ is substituted at at least one, preferably one, of the two ortho positions by Ar ４ , and Ar ４ is a monocyclic or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms (optionally substituted by one or more R radicals), the polymer according to claim 1 or 2.

4. Said at least one structural unit of formula (I) is of the following formula (Ia): 【Chemical Formula 2】 (wherein Ar １ , Ar ２ , Ar ３ , Ar ４ and R may well be based on the definitions given in claims 1 and 3, q = 0, 1, 2, 3, 4, 5 or 6, X = CR ２ , NR, SiR ２ , O, S, C=O or P=O, and r = 0 or 1) a polymer according to any one of claims 1 to 3, selected from structural units of **Claim 5** Ar ３ is substituted by Ar at one of the two ortho positions, and Ar ４ is further bonded to Ar at the meta position adjacent to the substituted ortho position, a polymer according to any one of claims 1 to 4. ３ ４ **Claim 6** Said at least one structural unit of formula (I) is of the following formula (Ib): **[Chemical Formula 3]** (wherein Ar １ , Ar ２ , Ar ３ , Ar ４ , R, and X may well be based on the definitions given in claims 1, 3 and 4, m = 0, 1, 2, 3 or 4, n = 0, 1, 2 or 3, s and t are each 0 or 1, and the sum of (s + t) = 1 or 2) a polymer according to any one of claims 1 to 5, selected from structural units of **Claim 7** Said at least one structural unit of formula (I) is of the following formulas (II), (III) and (IV): **[Chemical Formula 4]** (wherein Ar １ , Ar ２ , Ar ４ , R, m, n and X may well be based on the definitions given in claims 1, 3, 4 and 6) ​​The polymer according to any one of claims 1 to 6, selected from the structural units of **Claim 8** Said at least one structural unit of formula (II) is of the following formula (V): **Chemical Formula 5** (wherein Ar １ , Ar ２ , R and m may be as defined in claims 1 and 6, p = 0, 1, 2, 3, 4 or 5) The polymer according to claim 7, selected from the structural units of **Claim 9** Said at least one structural unit of formula (III) is of the following formula (VI): **Chemical Formula 6** (wherein Ar １ , Ar ２ , R, m and n may be as defined in claims 1 and 6) The polymer according to claim 7, selected from the structural units of **Claim 10** Said at least one structural unit of formula (IV) is of the following formula (VII): **Chemical Formula 7** (wherein Ar １ , Ar ２ , R, m, n and X may be as defined in claims 1 and 6) The polymer according to claim 7, selected from the structural units of **Claim 11** Ar １ and Ar ２ are each the same or different in each case and are monocyclic or polycyclic, aromatic or heteroaromatic ring systems having 5 to 30, preferably 5 to 24, aromatic ring atoms, the polymer according to any one of claims 1 to 10. **Claim 12** Ar １ and Ar ２is the same or different in each case and, independently in each case, is a monocyclic or polycyclic aromatic ring system having 5 to 14 aromatic carbon atoms selected from phenyl, biphenyl, terphenyl, [1,1':3',1'']terphenyl-2'-yl, quarterphenyl, naphthyl, anthracene, binaphthyl, phenanthrene, dihydrophenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene and spirobifluorene, preferably selected from phenyl and biphenyl, more preferably selected from phenyl, the polymer according to any one of claims 1 to 11.

13. Ar １ and Ar ２ is the same or different in each case and, independently, at the ortho or meta positions with respect to the bond of the nitrogen atom of formula (I), R １ and R ２ are the same or different, preferably the same in each case at the ortho or meta positions, more preferably the same at the meta positions, the polymer according to any one of claims 1 to 12.

14. R １ and R ２ is the same or different in each case and, independently in each case, is a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched-chain or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms (each of which may be substituted by one or more R ３ radicals, and one or more non-adjacent CH ２ groups are R ３ C═CR ３ , C≡C, Si(R ３ ), C═O, C═S, C═NR ２ , P(═O)(R ３ ), SO, SO ３ , NR ２ , O, S or CONR ３ ３ ​which may be substituted, and one or more hydrogen atoms may be substituted by D, F, Cl, Br, I or CN), the polymer according to any one of claims 1 to 13.

15. R １ and R ２ are the same or different in each case and, independently in each case, are a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, the polymer according to any one of claims 1 to 14.

16. The proportion of the structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI) or (VII) in the polymer is in the range of 50 to 95 mol% based on 100 mol% of all copolymerizable monomers present as structural units in the polymer, the polymer according to any one of claims 1 to 15.

17. In addition to the structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI) or (VII), the polymer has further structural units other than the structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI) or (VII), the polymer according to any one of claims 1 to 16.

18. A method for preparing the polymer according to any one of claims 1 to 17, wherein the polymer is prepared by Suzuki polymerization, Yamamoto polymerization, Stille polymerization or Hartwig-Buchwald polymerization.

19. A polymer formulation comprising one or more polymers according to any one of claims 1 to 17, wherein the polymer formulation comprises at least one structural unit of formula (I) and one or more further polymeric, oligomeric, dendrimeric and / or low molecular weight substances.

20. A solution or formulation consisting of one or more polymers according to any one of claims 1 to 17 or the polymer formulation according to claim 19 in one or more solvents.

21. Use of a polymer according to any one of claims 1 to 17 in an electronic or optoelectronic device, preferably an organic electroluminescence device (OLED), an organic light-emitting electrochemical cell (OLEC), an organic field-effect transistor (OFET), an organic integrated circuit (O-IC), an organic thin-film transistor (TFT), an organic solar cell (O-SC), an organic laser diode (O-laser), an organic photovoltaic (OPV) element or device or an organic photoreceptor (OPC), more preferably an organic electroluminescence device (OLED).

22. An electronic or optoelectronic device having one or more active layers, at least one of these active layers comprising one or more polymers according to any one of claims 1 to 17, preferably an organic electroluminescence device (OLED), an organic light-emitting electrochemical cell (OLEC), an organic field-effect transistor (OFET), an organic integrated circuit (O-IC), an organic thin-film transistor (TFT), an organic solar cell (O-SC), an organic laser diode (O-laser), an organic photovoltaic (OPV) element or device or an organic photoreceptor (OPC), more preferably an organic electroluminescence device.

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