Electroluminescent polymers comprising planar arylamine units the preparation and use thereof

Extensive basic research on the commercialization of display and lighting elements based on polymer (organic) light emitting diodes (PLEDs) has been underway for about 13 years. This development began with the basic development disclosed in WO 90/13148. The first simple but product (a small display on a Philips NV razor) has been available on the market in recent years. However, significant improvements in the materials used are still needed to make these displays a true competitor to the liquid crystal displays (LCDs) that currently dominate the market.

In order to produce all three colors, it is necessary to copolymerize certain comonomer into the corresponding polymer (see, eg, WO 00/46321, WO 03/020790, and WO 02/077060. I want to be). Starting with a blue luminescent base polymer (skeleton), it is generally possible to produce two other primary colors, red and green.

In addition, the insertion of certain arylamino groups has been reported to cause improvements in properties.

-WO 99/54385 describes polyfluorene, the efficiency and working voltage of which corresponds to triphenylamine, tetraphenyl-p-diaminobenzene, or derivatives of tetraphenyl-4,4'-diaminobiphenyl. It can be improved by copolymerizing in the main chain of the polymer.

WO 01/49769 describes a polymer containing a triarylamino group, wherein at least one aryl group is a heteroaryl group. The detailed advantages of these polymers are not described.

WO 04/037887 describes triarylamine units, which include condensed aryl substituents such as, for example, naphthyl units. These are particularly suitable for passive matrix applications.

WO 04/106409 describes tris- and tetrakistriarylamines as hole conductors and emitters in conjugate polymers.

-WO 05/017065 provides a triarylphosphine derivative instead of triarylamine as a hole conductor in a conjugated polymer.

Some polymers according to the prior art already exhibit good properties when used in PLEDs. Despite the progress already achieved, however, they still do not meet the requirements for making them high quality applications. In particular, the lifetimes of green luminescent polymers, and especially blue luminescent polymers, are still inadequate for many applications.

Surprisingly, it is found here that conjugated polymers containing certain planar bis (triarylamine) units or partially conjugated polymers have very good properties, superior to prior art. Was done. These relate, in particular, to life and current / voltage curves and polymer efficiency. Accordingly, the present invention relates to these polymers, and their use in PLEDs.

Tetraphenyl-p-diaminobenzene, whose central unit (phenylene) has a planar structure, is not suitable for this purpose because it results in a strong color shift in combination with some monomers. ..

US 6066712 describes alternating hole-injected polymers consisting of divinylarylene units and aromatic diamines that are crosslinked via polycondensed cyclic groups, such as fluorene or dihydrophenanthrene. However, these polymers are not considered suitable for high quality OLED applications, because they are only 1mA / cm.²This is because at very low current densities (and thus very low brightness), very poor lifetimes of around 200h are obtained with these in OLEDs.

The present invention is a conjugated or partially conjugated polymer of the formula (1) of at least 0.1 mol%, preferably at least 1 mol%, particularly preferably at least 5 mol%, very particularly preferably at least 7 mol% (1).<chemistry num="5"><img id="000002" he="32" wi="101" file="JP5259180B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

(The symbols and subscripts used in the formula have the following meanings: A is the same or different for each appearance, N, P or As, X is the same or different on each appearance, a divalent planar conjugated system with 6-40 C atoms (which contains at least two arylene groups, and substituent R¹May be replaced by) Ar¹, Ar², Ar³, Ar⁴, Ar⁵Are the same or different for each appearance, and are aromatic or heterocyclic aromatic rings with 2-40 C atoms (these are one or more Rs).¹It may be substituted by a group), provided that Ar¹~ Ar⁵None of the groups show a fused ring system if this group does not have a direct bond to the polymer chain. R¹Is the same or different for each appearance, H, F, Cl, Br, I, CN, NO₂, OH, N (R)¹)₂, Si (R)²)₃, B (R)²)₂, Linear, branched or cyclic alkyl group with 1-40 C atoms, alkoxy group or thioalkoxy group (where one or more non-adjacent C atoms are -CR²= CR²-, -CC-, -NR²-, -O-, -S-, -CO-O-, or -O-CO-O- may be substituted, and one or more H atoms may be replaced by fluorine), 2 Aryl, heteroaryl, aryloxy, or heteroaryloxy groups with ~ 40 C atoms (where one or more C atoms may be replaced by O, S, or N) (these are , 1 or more non-aromatic groups R¹It may be substituted by a group) and has two or more Rs¹The groups may form an aliphatic or aromatic monocyclic or polycyclic ring system with each other. R²Is an aliphatic or aromatic hydrocarbon group having H, or 1 to 20 C atoms, which is the same or different on each appearance. n is the same or different for each appearance and contains units of 0, 1 or 2), and the binding of the unit of formula (1) to the polymer is the unit Ar.¹~ Ar⁵Concerning conjugated or partially conjugated polymers that are made through one or two of (provided that equation (2)).<chemistry num="6"><img id="000003" he="26" wi="159" file="JP5259180B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

(During the ceremony, Ar₂₁, Ar₂₂, Ar₂₄Is an arylene group which may have a substituent, respectively, and Ar₂₅Is an arylene group or a divalent polycondensation ring group which may have a substituent and Ar.₂₃And Ar₂₆Are alkyl, aralkyl or aryl groups, respectively, which may have a substituent, m.₁Is 0, 1, 2 or 3 and n₁Is a natural number) excluding polymers).

The polymers according to the invention are preferably conjugated.

The unit of formula (1) may be bound in the main chain or side chain of the polymer, preferably in the main chain. If the unit of formula (1) is bound in the main chain of the polymer, Ar¹~ Ar⁵Two of the groups are divalent groups attached to the polymer chain and the other are monovalent groups. If the unit of formula (1) is bound in the side chain of the polymer, Ar¹~ Ar⁵One of the groups is a divalent group attached to the polymer chain and the other is a monovalent group.

As is clear from the description, the structural units of equation (1) may be asymmetrically substituted, i.e., in a single unit, different atoms A, different groups X and / or different groups Ar.¹~ Ar⁵, Or a different substituent R¹And R²It should be explicitly pointed out that may be present, or they may be combined at different positions.

For the purposes of the present invention, the "divalent planar conjugated system" described by the symbol X is conjugated to each other and to atom A, and its dihedral angle is less than 35 °, preferably less than 30 °, in particular. It is intended to be construed to mean a divalent conjugated system containing at least two arylene groups, preferably less than 25 °. The measured or calculated dihedral angle always depends on the measuring method, and the dihedral angle needs to be determined by quantum chemistry calculation for the purposes of the present invention. To this end, the shape is placed in internal coordinates using the semi-empirical method AM1 (eg, MJS Dewar et al., J. Am. Chem. Soc. 1985, 107, 3902), "Berny. ) Determined by optimization (HB Schlegel et al., J. Comp. Chem. 1996, 17, 49). Next, the energy and orbit are converted into the hybrid function B3PW91 (JP Perdew, Phys. Rev. B 1996, 54, 16533), and "split valence" basis set 6-31 G (d) (JA Pople et al., J. Phys. Chem. 1971, 54, 724). All calculations are performed using the Gaussian 98 program package (JA Pople, Gaussian, Pittsburgh PA, 2001). The planar conjugated system does not necessarily have to contain only conjugated groups and may include, for example, an aliphatic bridge that crosslinks an arylene group and thus results in the planarity of the system. The system may be substituted as well, where the substituents themselves may form one or more ring systems. A rigid planar conjugated system that does not deviate from flatness due to rotation around a single bond is preferred.

Examples of planar conjugate systems are fluorene (dihedral angle 0.1 ° in diamine), trans-indenofluorene (dihedral angle 0.5 ° in diamine), dihydrophenanthrene (dihedral angle 20.2 ° in diamine), and trans (dihedral angle 20.2 °). Dihedral angle 0.7 °), where Tran is not a solid system. In contrast, the dihedral angle of biphenyls used according to the prior art is 42 °, so biphenyls are not planar.

For the purposes herein, the arylene group shall mean a simple or condensed divalent aromatic group or heterocyclic aromatic group, such as, for example, phenylene, naphthylene, etc. In contrast, for example, biphenyl or fluorene systems are not construed to mean simple arylene groups, because the two phenylene units are bonded by a single bond (in fluorene, by a further non-conjugated crosslink). This is because it has been done. Here, the aromatic group contains at least 6 C atoms, and the heterocyclic aromatic group contains at least 2 C atoms.

For the purposes of the present invention, an aromatic ring system or a heterocyclic aromatic ring system is not necessarily a system containing only an aromatic group or a heterocyclic aromatic group, but a plurality of aromatic groups or heterocyclic groups. For aromatic groups, for example, sp³Interpreted to mean a system that may be mediated by short non-aromatic units such as hybrids C, O, N, etc. (&lt;10% atoms other than H, preferably &lt;5% atoms other than H). It is intended to be done. That is, systems such as, for example, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, etc. are also construed to mean an aromatic ring system for the purposes of the present invention. Is intended. Here, the aromatic ring system contains at least 6 C atoms, and the heterocyclic aromatic ring system contains at least 2 C atoms.

For the purposes of the present invention, C₁~ C₄₀-Alkyl groups (where individual H atoms or CH₂The group may be substituted with the above-mentioned group), particularly preferably methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl. Group, t-butyl group, 2-methylbutyl group, n-pentyl group, s-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, n-octyl group, cyclooctyl group , 2-Ethylhexyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, ethenyl group, propenyl group, butyl group, pentenyl group, cyclopentenyl group, hexenyl group, cyclohexenyl group, It is interpreted to mean a heptenyl group, a cycloheptenyl group, an octenyl group, a cyclooctenyl group, an ethynyl group, a propynyl group, a butyl group, a pentynyl group, a hexynyl group, or an octynyl group. C₁~ C₄₀-Alkoxy groups are particularly preferably interpreted to mean methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, or 2-methylbutoxy. To. Aromatic or heterocyclic aromatic ring systems with 2 to 40 C atoms (in each case, these may be substituted with the R groups described above, and these are aromatic ring systems. Or may be attached at the desired position on the heterocyclic aromatic ring system), in particular benzene, naphthalene, anthracene, phenanthrene, pyrene, chrysene, perylene, fluorantene, naphthalene, pentacene, benzopyrene, biphenyl, biphenylene, Telphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene , Pyrol, indole, isoindole, oxazole, pyridine, quinoline, isoquinolin, aclysine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine , Pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridiimidazole, pyrazine imidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthrooxazole, isooxazole , 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxalin, 1,5-diazaanthracene, 2,7-diazapylene, 2,3-diazapylene, 1, 6-Diazapyrene, 1,8-Diazapyrene, 4,5-Diazapyrene, 4,5,9,

For the purposes of the present invention, conjugate polymers are predominantly sp in the main chain.²A polymer containing a hybrid (or optionally sp hybrid) carbon atom, which may be replaced by a corresponding heteroatom. In the simplest case, this means the alternating presence of double and single bonds in the backbone. It mainly means that the naturally occurring (rather than irregular) defects that result in the disruption of conjugates do not diminish the value of the term "conjugated polymer". In addition, the term conjugate refers to, for example, arylamines, arylphosphine or arylarsin units, such as the unit of formula (1), and / or certain heterocyclic groups (ie, N, O, P or S atoms). It is also used herein that an organic metal complex (ie, conjugated via a metal atom) is located in the main chain. In contrast, units such as simple alkyl crosslinks, (thio) ethers, esters, amides or imide bonds are clearly defined as non-conjugated sites. A partially conjugated polymer is a polymer in which a relatively long conjugate portion in the main chain is interrupted by a non-conjugated moiety, or a polymer containing a relatively long conjugate moiety in the side chain of a polymer that is unconjugated in the main chain. Is intended to be interpreted as meaning.

Incorporation of the unit of formula (1) into the conjugate polymer, aromatic unit Ar¹~ Ar⁵It can be carried out at any desired position. Incorporation into the side chain, preferably Ar¹Incorporation into the main chain by Ar¹And Ar³To do. The bond is such that an even C atom (or the corresponding heteroatom, ie N, O and / or S) intervenes between the bond to the polymer and to the nitrogen or phosphorus or arsenic atom A. It is preferably done. The number of C atoms (or corresponding heteroatoms) is particularly preferably a multiple of 4.

In addition to the units of formula (1), the polymers according to the invention preferably contain additional structural elements and may therefore be referred to as copolymers. In particular, a relatively extensive list of WO 02/077060, WO 05/014689 and the literature listed above can be referenced. These other structural units can be derived, for example, from the classes described below.

Group 1: Unit indicating the polymer skeleton Units in this group include aromatic, carbocyclic structures with 6-40 C atoms, which may or may not be substituted. Fluorene derivatives (eg EP 0842208, WO 99/54385, WO 00/22027, WO 00/22026, WO 00/46321) are suitable here. In addition, spirobifluorene derivatives (eg EP 0707020, EP 0894107, WO 03/020790) are also feasible. A polymer containing the combination of the two previously mentioned monomer units (WO 02/077060) has also been proposed. WO 05/014689 describes dihydrophenanthrene derivatives. In addition, cis-or trans-indenofluorene derivatives (eg, GB 0226010.7, WO 04/113412) are also suitable, and also, for example, dihydropyrene, or tetrahydropyrene derivatives, and additional aromatics not explicitly mentioned. The structure is also suitable.

Group 2: Units that modify morphology or emission color Structural units that can affect the morphology and the emission color of the resulting polymer are also expected. Substituted or unsubstituted aromatic structures with 6-40 C atoms, or, for example, 1,4-phenylene, 1,4-naphthylene, 1,4- or 9,10-anthrylene, 1,6- or 2 , 7- or 4,9-pyrenylene, 3,9- or 3,10-perylene, 2,7- or 3,6-phenanthrenylene, 4,4'-biphenylylene, 4,4''-terphenylylene, Tran, stilbene, bisstyrylarylene derivatives such as 4,4'-bi-1,1'-naphthylylene, 4,4'-stillbenylene, or 4,4''-bisstyrylarylene derivatives are preferred.

Group 3: Units that enhance the hole injectability and / or hole transportability of the polymer These are generally, for example, substituted or unsubstituted triarylamines, benzidines, N, N, N', N'-tetraaryl-para-phenylenediamines, triarylphosphines, phenothiazines, phenothiazines, dihydrophenazines, thiantolenes. , Dibenzo-p-dioxin, phenothiazine, carbazole, azulene, thiophene, pyrrole, furan, and additional O-, S-, or N-containing heterocycles with high HOMO (HOMO) It is an aromatic amine or an electron-rich heterocycle. However, since the unit of formula (1) already has hole conductivity, the polymer according to the invention has appropriate hole conductivity without the additional use of hole transport units. be able to.

Group 4: Units that enhance the electron injectability and / or electron transportability of polymers These generally include, for example, substituted or unsubstituted pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline, benzothiadiazole, or phenazine, as well as triarylborane and low LUMO (LUMO = lowest empty orbit). It is an electron-deficient aromatic or heterocycle such as a compound such as a heterocycle containing additional O-, S- or N-.

Group 5: Units with individual unit combinations from groups 3 and 4 It is also preferred that the units in which the structures that increase hole mobility and electron mobility are directly bonded to each other are present in the polymer according to the invention. Some of these units shift the emission color to green, yellow or red. Thus, these uses are suitable, for example, for the generation of other emission colors from polymers that would otherwise emit blue light.

Group 6: A unit that emits light from the triplet state or enhances the transition from the singlet state to the triplet state. Structural units from group 6 are capable of emitting light from the triplet state with high efficiency, even at room temperature, i.e. exhibiting electrophosphorescence instead of electrofluorescence. First, compounds containing heavy atoms with atomic numbers greater than 36 are suitable for this purpose. Particularly suitable compounds include d-transition metals or f-transition metals that satisfy this condition. Structural units containing elements from groups 8-10 (Ru, Os, Rh, Ir, Pd, Pt), especially containing iridium and / or platinum, are highly preferred. These metal complexes can be attached in the main and / or side chains of the polymer.

For the use of such structural elements, it is preferred to use in a manner that supports additional structural elements that enhance the transition from the singlet state to the triplet state and thus enhance the electric field phosphorescence. For example, the carbazole units described in WO 04/070772 and WO 04/113468, preferably crosslinked carbazole dimer units, and, for example, the keto units described in unpublished patent application DE 10349033.7 are suitable for this purpose. ing.

In addition to the units of formula (1), polymers according to the invention further comprising one or more units selected from groups 1-6 are preferred. It is also advantageous that more than one structural unit from one of groups 1-6 is present at the same time.

Very particularly preferably, polymers containing at least 50 mol% of these units, including units from Group 1, in addition to the units of formula (1), are particularly preferred. Units from group 1 are preferably selected from spirobifluorene, fluorene, dihydrophenanthrene, cis-indenofluorene and / or trans-indenofluorene, which may or may not be substituted. Will be done.

The ratio of the unit of the formula (1) of 1 to 50 mol% is preferable. The ratio of the unit of the formula (1) of 5 to 30 mol% is preferable, and the ratio of 7 to 15 mol% is very particularly preferable. This proportion was found to be particularly suitable for electroluminescent polymers, among others. For other applications, such as charge transport polymers in various applications, a much higher percentage of units of formula (1), eg, up to 100 mol% of units of formula (1), would be suitable. Let's go.

Polymers according to the invention are preferred, where A, which is the same or different at each appearance, represents N or P, particularly preferably N.

Further, the polymer according to the present invention is preferable in which X, which is the same or different for each appearance, represents the unit of the formula (3).<chemistry num="7"><img id="000004" he="48" wi="114" file="JP5259180B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

(In the formula, the following applies to the symbols and subscripts used, i.e. Y is the same or different for each appearance, -C (R¹)₂-, -C (R)¹)₂-C (R)¹)₂-, -N (R)¹)-, -O-, -S-, -P (R)¹)-, -P (= O) (R¹)-, -OC (R¹)₂-Or -OC (= O)-, preferably -C (R)¹)₂-Or -C (R)¹)₂-C (R)¹)₂-And m is the same or different for each occurrence and is 0 or 1, preferably 0, where the Y group is excluded and does not correspond to a chemical bond when the subscript m = 0. o and p are the same or different for each occurrence and are 0 or 1, however, o and p cannot be 0 at the same time, where the subscript o or p = 0 The Y group is excluded, and does not correspond to a chemical bond, q is the same or different for each occurrence, 0, 1 or 2, preferably 0 or 1. The dashed line in equation (3) indicates the bond from this equation to the A atom in the structural unit of equation (1)).

In addition, the same or different symbol Ar for each appearance¹~ Ar⁵But R¹An aromatic or heterocyclic aromatic ring system having 4 to 30 C atoms, which may be substituted with, is preferably R.¹The polymer according to the present invention, which represents an aromatic ring system or a heterocyclic aromatic ring system having 6 to 25 C atoms, which may be substituted with, is preferable.

The subscript n more preferably represents 0 or 1, and particularly preferably 0.

Further, the symmetrical unit of the equation (1) is preferable. This preference is due to the easier synthetic reachability of the monomers. That is, all A's in the unit of equation (1) are the same, and the unit is Ar.¹~ Ar⁵It is preferable to have a symmetrical structure with respect to. If there are multiple units X, they should preferably be chosen to be the same.

An example of the unit of the formula (1) is a structure according to the following examples (1) to (30), where the dashed line bond means a bond into the polymer. For the sake of clarity, possible substituents are not generally indicated, but it is understandable that they are preferred for synthetic reasons, solubility, efficiency, or system stability.<chemistry num="8"><img id="000005" he="145" wi="159" file="JP5259180B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry><chemistry num="9"><img id="000006" he="232" wi="159" file="JP5259180B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry><chemistry num="10"><img id="000007" he="75" wi="159" file="JP5259180B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

The polymer according to the invention is either a homopolymer containing the unit of formula (1) or a copolymer. In addition to one or more structures of formula (1), the copolymer according to the invention can optionally have one or more additional structures from groups 1-6 above. The copolymers according to the invention may have random, alternating, or block-like structures, or may have a plurality of these structures in alternating arrangements. A method for obtaining a copolymer having a block-like structure is described in detail in, for example, WO 05/014688. This is incorporated herein by reference as part of the present invention. It should be emphasized here that the polymer must not have a linear structure and instead can have a branched or dendritic structure.

The polymers according to the invention preferably have 10 to 10,000 repeating units, particularly preferably 20 to 5000, and very particularly preferably 50 to 2000 repeating units.

Polymers according to the invention are generally prepared by polymerization of one or more types of monomers, of which at least one monomer provides a unit of formula (1) in the polymer. In principle, there are many corresponding polymerization reactions. However, some types that result in CC or CN bonds are illuminated here to be particularly successful. That is, (A) Suzuki Polymerization, (B) Yamamoto Polymerization, (C) STILLE polymerization, (D) HARTWIG-BUCHWALD polymerization Is.

Methods in which the polymerization can be carried out by these methods and methods of separating and purifying the polymer from the reaction medium are described in detail in, for example, WO 03/048225 or WO 04/022626.

Corresponding monomers are required for the synthesis of polymers. For the synthesis of units from groups 1-6, see WO 05/014689 and the literature listed therein.

The monomer that provides the structural unit of formula (1) in the polymer according to the invention is the corresponding triarylamine derivative (or the corresponding phosphorus and arsenic derivatives), which is appropriately substituted at the appropriate position and It has the appropriate functional groups that allow this monomer to be incorporated into the polymer.

These monomers are novel and are therefore also the subject of the present invention.

The present invention further relates to bifunctional monomer compounds of formulas (4) and (5).<chemistry num="11"><img id="000008" he="50" wi="153" file="JP5259180B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

(In the formula, A, X, Ar¹, Ar², Ar³, Ar⁴, Ar⁵, R¹, R²And n have the same meaning as described in equation (1), and further Z is a functional group that is the same or different on each appearance and copolymerizes under the conditions of a CC bond reaction or a CN bond reaction, preferably Cl, Br, I, O-tosylate, O-triflate, O. -SO₂R¹, B (OR¹)₂, Or Sn (R)¹)₃And particularly preferably Br, I, B (OR)¹)₂, Or Sn (R)¹)₃And r is 0 or 1).

The CC binding reaction is preferably selected from the group of Suzuki couplings, Yamamoto couplings, and STILLE couplings, and the CN binding reaction is preferably a HARTWIG-BUCHWALD coupling.

For the functional monomer compounds of formulas (4) and (5), the same preferences as described above for the structural units of formula (1) also apply here.

Furthermore, it is also preferred that the polymers according to the invention are not used as pure substances, but instead be used as mixtures (compounds) with any additional polymer, oligomer, dendritic or low molecular weight material of any desired type. They can, for example, improve their electronic properties or emit light themselves. However, electronically inert ingredients may also be suitable, for example, to control the viscosity of the solution or the morphology of the film formed. Therefore, this type of formulation is also part of the present invention.

The invention further relates to solutions or formulations of one or more polymers or formulations according to the invention in one or more solvents. Methods by which polymer solutions can be prepared are described, for example, in WO 02/072714, WO 03/019694 and in the literature listed therein. These solutions can be used, for example, by an area coating method (eg, spin coating) or by a printing method (eg, inkjet printing) to produce a thin polymer layer.

Polymers and formulations according to the invention can be used in PLEDs. The methods by which PLEDs can be manufactured are described in detail in WO 04/037887 as a general method, which needs to be adapted to accommodate individual cases. As mentioned above, the polymers according to the invention are very particularly suitable as electroluminescent materials in PLEDs or displays manufactured in this way.

For the purposes of the present invention, electroluminescence material is construed to mean a material that can be used as an active layer in PLED. Active layers are layers that can radiate light when an electric field is applied (light emitting layer) and / or layers that improve the injection and / or transport of positive and / or negative charges (charge injection layer or charge transport). Layer) means. It can also be used as a "buffer layer" between the light emitting layer and the hole injection layer.

Accordingly, the present invention relates to the use of polymers or formulations according to the invention in PLEDs, especially as luminescent materials.

The present invention further relates to PLEDs having one or more active layers, wherein at least one of these active layers comprises one or more polymers or formulations according to the present invention. The active layer may be, for example, a light emitting layer and / or a transport layer, and / or a charge injection layer.

The polymers according to the invention are polyspirobifluorene described in WO 03/020790, polyfluorene described in WO 02/077060, and polydihydrophenanthrene described in WO 05/014689 (these are formula (1)). It does not include the unit of, and has the following surprising advantages over (here, listed as the most recent prior art).

(1) Lifespan is a comparative polymer, which does not contain the unit of formula (1), instead the aromatic unit at its center contains a bis (triarylamine) derivative that does not have a planar structure, the others Longer than (having the same composition). Improvements in lifespan are very important for use, because inadequate lifespan has been the greatest obstacle to use, especially in the case of blue and green luminescent polymers.

(2) Polymers according to the invention, which otherwise have the same composition, have comparable or higher luminous efficiency in the application. This is very important as the same brightness is achieved with lower energy consumption, which is especially important for mobile applications that rely on rechargeable or other batteries (cell phones, pagers, PDAs, etc.). It is very important in the display). Conversely, higher brightness is obtained for the same energy consumption, which is interesting, for example, for lighting applications.

(3) The current / voltage curve is steeper when using triarylamine units with planar (and preferably rigid) cross-linking units. Therefore, the triarylamine unit according to the present invention is a better hole conductor than the triarylamine unit according to the prior art.

The present specification and the following examples relate to the use of polymers according to the invention with respect to PLEDs and corresponding displays. Notwithstanding this limitation described, those skilled in the art can use other electronic devices, such as organic field effect transistors (O-FETs), organic integrated circuits (to name a few examples), without the need for further invention. Further in O-ICs, Organic Thin Film Transistors (O-TFTs), Organic Solar Cells (O-SCs), Organic Field-quench devices (O-FQDs), or Organic Laser Diodes (O-lasers) Also for use, the polymers according to the invention can be used as semiconductors (or, in the case of proper doping, conductors). The invention also relates to the use of polymers according to the invention in corresponding devices. Therefore, the present invention also comprises an organic field effect transistor (O-FET), an organic integrated circuit (O-IC), an organic thin film transistor (O-TFT), and an organic solar cell (O-FET) containing at least one polymer according to the present invention. O-SC), organic field-quench Devices) (O-FQD), and organic laser diodes (O-laser).

Moreover, it will be readily apparent to those skilled in the art to apply the above description for conjugated or partially conjugated polymers to conjugated or partially conjugated dendrimers or oligomers without the need for further inventions. Therefore, the present invention also relates to this type of dendrimer and oligomer.

Example Example 1: N, N'-bis (4-bromophenyl) -N, N'-bis (4-tert-butylphenyl) -9,9-dioctylfluorene-2,7-diamine (monomer EM1 according to the invention) Synthesis of<chemistry num="12"><img id="000009" he="51" wi="81" file="JP5259180B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

a) N, N'-diphenyl-N, N'-bis (4-tert-butylphenyl) -9,9-dioctylfluorene-2,7-diamine As described in 26 g (47.4 mmol) of 2,7-dibromo-9,9-dioctylfluorene (M. Ranger, M. Leclerc, Chem. Commun. 1997, 1597) in 150 ml of toluene. Synthesized in), and 20.2 g (91 mmol) of a degassed solution of 4-tert-butylphenylphenylamine (synthesized as described in J. Org. Chem. 2003, 68, 452), N.₂Saturated for 1 hour. Then, first, 174 mg (0.86 mmol) of P (^tBu)₃, Followed by 96 mg (0.42 mmol) of Pd (OAc)₂In addition to this solution, 5.4 g (56 mmol) of NaO in solid state^tBu was added subsequently. The reaction mixture was refluxed for 5 hours. After cooling to room temperature, 0.8 g NaCN and 40 ml water were carefully added. Organic phase, 4 x 50 ml H₂Wash with O and DDL₄And the solvent was removed under reduced pressure. Chromatographic purification on silica gel gave a yellow oil. The yield was 33 g (85% of theory) with a purity of 99.3% according to HPLC.

¹H-NMR (CDCl₃, 500MHz): 0.65 (m, 4H), 0.83 (t, J = 7.03Hz, 6H), 0.99-1.28 (m, 20H), 1.31 (s, 18H), 1,71-1.79 (m, 4H), 6.90-7.11 (m, 12H), 7.21-7.31 (m, 10H), 7.40-7.51 (m, 2H).

b) N, N'-bis (4-bromophenyl) -N, N'-bis (4-tert-butylphenyl) -9,9-dioctylfluorene-2,7-diamine (EM1) 36.6 g (43.7 mmol) of N, N'-diphenyl-N, N'-bis (4-tert-butylphenyl) -9,9-dioctylfluorene-2,7-diamine was introduced into 500 ml of THF. .. Subsequently, a solution of 15.15 g (84.4 mmol) of NBS dissolved in 300 ml of THF was added dropwise at 0 ° C., excluding light, and the mixture was warmed to room temperature for an additional 4 Stirred for hours. Add 500 ml of water to this mixture, then CH₂Cl₂Was extracted using. EDTA organic phase₄The solvent was removed under reduced pressure. The product was washed by stirring with hot hexanes and filtered through aspiration to give a white solid of 35 g (68% of theory), which was 99.9% after repeated recrystallization from ethyl acetate. It had the HPLC purity of.

¹H-NMR (CDCl₃, 500MHz): 0.66 (m, 4H), 0.85 (t, J = 7.03Hz, 6H), 0,99-1.28 (m, 20H), 1.33 (s, 18H), 1,73-1.79 (m, 4H) ), 6,85-7.10 (m, 12H), 7,21-7.35 (m, 8H), 7,40-7.51 (m, 2H).

Example 2: N, N'-bis (4-bromophenyl) -N, N'-bis (4-tert-butylphenyl) -9,10-dibutyl-9,10-dimethoxy-9,10-dihydrophenanthrene- Synthesis of 2,7-diamine (monomer EM2 according to the present invention)<chemistry num="13"><img id="000010" he="55" wi="84" file="JP5259180B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

a) N, N'-diphenyl-N, N'-bis (4-tert-butylphenyl) -9,10-dibutyl-9,10-dimethoxy-9,10-dihydrophenanthrene-2,7-diamine Using 24.2 g (47.4 mmol) of 2,7-dibromo-9,10-dibutyl-9,10-dimethoxy-9,10-dihydrophenanthrene (synthesized as described in WO 05/014689) as a starting material. , Example 1a) was synthesized. Chromatographic purification on silica gel gave a yellow oil. The yield was 30 g (81% of theory) with a purity of 99.0% according to HPLC.

¹H-NMR (CDCl₃, 500MHz): 0.53 (m, 2H), 0.81 (t, J = 7.03Hz, 6H), 0.94-1.19 (m, 6H), 1.25 (s, 18H), 1.62 (m, 2H), 2.05 (t, J = 7.03Hz, 2H), 3.31 (s, 6H), 6.61-7.5 (m, 24H).

b) N, N'-bis (4-bromophenyl) -N, N'-bis (4-tert-butylphenyl) -9,10-dibutyl-9,10-dimethoxy-9,10-dihydrophenanthrene-2 , 7-Diamine (EM2) 34.9 g (43.7 mmol) N, N'-diphenyl-N, N'-bis (4-tert-butylphenyl) -9,10-dibutyl-9,10-dimethoxy-9,10-dihydrophenanthrene-2, Using 7-diamine as a starting material, synthesis was carried out in the same manner as in Example 1b). After repeated recrystallization from ethyl acetate, 24 g (70% of theory) white solid with 99.9% HPLC purity was obtained.

¹H-NMR (CDCl₃, 500MHz): 0.53 (m, 2H), 0.81 (t, J = 7.03Hz, 6H), 0.94-1.19 (m, 6H), 1.25 (s, 18H), 1.62 (m, 2H), 2.05 (t, J = 7.03Hz, 2H), 3.31 (s, 6H), 6.85-7.05 (m, 10H), 7.11-7.20 (m, 2H), 7.25-7.33 (m, 8H), 7.42-7.48 (m, 2H) ..

Example 3: N, N'-bis (4-bromophenyl) -N, N'-bis (4-tert-butylphenyl) -2', 7'-bis (tert-butyl) -9,9'-spiro Synthesis of bifluorene-2,7-diamine (monomer EM3 according to the present invention)<chemistry num="14"><img id="000011" he="55" wi="81" file="JP5259180B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

a) N, N'-diphenyl-N, N'-bis (4-tert-butylphenyl) -2', 7'-bis (tert-butyl) -9,9'-spirobifluorene-2,7- Diamine Synthesis was carried out in the same manner as in Example 1a) using 31.0 g (54 mmol) of 2,7-dibromo-2', 7'-bis (tert-butyl) -9,9'-spirobifluorene as a starting material. .. Chromatographic purification on silica gel gave a yellow oil. The yield was 50 g (99% of theory) with a purity of 99.2% according to HPLC.

¹H-NMR (Acetone-d₆, 500MHz): 1.28 (s, 36H), 6.39 (s, 2H), 6.81-6.89 (m, 12H), 6.98 (dd, J = 2Hz, J = 8.3Hz, 2H), 7.05-7.20 (m, 12H) ), 7.34 (dd, J = 1.7Hz, J = 8.0Hz, 2H), 7.06 (d, J = 8.0Hz, 2H), 7.79 (d, J = 8.3Hz, 2H).

b) N, N'-bis (4-bromophenyl) -N, N'-bis (4-tert-butylphenyl) -2', 7'-bis (tert-butyl) -9,9'-spirobi Fluorene-2,7-diamine (EM3) 52g (60.8 mmol) N, N'-diphenyl-N, N'-bis (4-tert-butylphenyl) -2', 7'-bis (tert-butyl) -9,9'-spirobifluorene- Using 2,7-diamine as a starting material, synthesis was carried out in the same manner as in Example 1b). After repeated recrystallization from ethyl acetate, 68 g (97.5% of theory) white solid with 99.8% HPLC purity was obtained.

¹H-NMR (CDCl₃, 500MHz): 1.25 (s, 36H), 6.49 (s, 2H), 6.65-7.15 (m, 20H), 7.32 (dd, J = 1.6Hz, J = 8.0Hz, 2H), 7.56 (d, J = 8.0Hz, 2H), 7.66 (s, J = 8.0Hz, 2H).

Example 4: Synthesis of other comonomer The structures of the polymers according to the invention and other monomers (M) for comparative polymers are shown below. The synthesis of the monomers M1 to M6 is described in WO 03/020790, WO 05/014689, and in the literature listed therein.<chemistry num="15"><img id="000012" he="233" wi="158" file="JP5259180B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

Example 5: Polymer synthesis The polymer was synthesized by the Suzuki coupling described in WO 03/048225. The compositions of the synthesized polymers P1 to P5 are shown in Table 1. In addition, comparative polymers C1 to C5 containing the monomer M4 were synthesized in place of the monomers EM1 and EM2 according to the present invention. The composition of the comparative polymer is also shown in Table 1.

Example 6: Manufacture of PLED The polymer was investigated in detail for use in PLED. The PLED was a two-layer system in each case, i.e. substrate // ITO // PEDOT // polymer // cathode. PEDOT is a polythiophene derivative (HC Stark, Baytron P from Goslar). The cathode used in all cases was Ba / Ag (Aldrich). The methods by which PLEDs can be manufactured are described in detail in WO 04/037887 and the literature cited therein.

Example 7 ~ 11: Device example The results obtained using the polymers P1 to P5 in PLED are shown in Table 1. The electroluminescence results obtained using the comparative polymers C1 to C5 are also shown. Since the emission colors of the polymers according to the invention and the comparative polymers are not always the same, 400 cd / m²The correction values for the initial brightness and the y-color coordinates of 0.2 are shown for the lifetime of the blue luminescent polymer for better comparison.

Quite clearly, the polymer according to the invention containing the planar triarylamine unit of formula (1) according to the invention is significantly better than the polymer containing the triarylamine unit according to the prior art, especially in terms of lifetime. It had electroluminescence. Therefore, improvements up to more than 6-fold (polymer P2 or C2) were observed over lifetime. This effect is less pronounced for all polymers, but a significant prolongation of life is observed for all polymers according to the invention.<tables num="1"><img id="000013" he="239" wi="122" file="JP5259180B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

Table 1: Device results using polymers and comparative polymers according to the invention^aCIE coordinates: Commission Internationale de l'Eclairage 1931 color coordinates^bLifespan: The time it takes for the brightness to drop to 50% of the initial brightness. Corrected life is 6.6W / m²Energy density, ie 400 cd / m²With respect to brightness and 0.2 yCIE color coordinates. The modified lifetime can be calculated from the actually measured lifetime, from the initial brightness, and from the color coordinates.

Example 12: Comparison of current / voltage curves The current density / voltage curves for polymer P2 and comparative polymer C2 are shown in FIG. As is clear, the curve for the polymer P2 containing the triarylamine unit according to the present invention is considerably steeper than for the comparative polymer C2 containing the triarylamine unit according to the prior art. Therefore, it is clear that the triarylamine unit according to the present invention is a better hole conductor.

<figref num="1">Current density / voltage curves for polymer P2 and comparative polymer C2 according to the present invention.</figref>