WO2004077888A1 - Material for organic el device and organic el device therefrom - Google Patents

Abstract

A material for organic EL device characterized by comprising at least a compound of the formula: (W)k-X-(Y)l (I) wherein X represents a core moiety; each of Y and W independently represents a phenylazomethine dendron subunit or a carbazole dendron subunit; l is an integer indicating the number of Ys bonded to X; and k is an integer indicating the number of Ws bonded to X.

Description

 Description Material for organic EL device and organic EL device using it

 The invention of this application relates to a material for an organic EL device and an organic EL device using the same. More specifically, the invention of this application comprises a phenylazomethine-based compound or a phenylazomethine mono-rubazole-based compound useful as a material for a hole transport layer and Z or a light-emitting layer in an organic EL device. It is about materials. Background art

 In recent years, with the spread of mobile phones and personal digital assistants (PDAs), further miniaturization and weight reduction have been demanded, and as a means of doing so, a new flat panel display technology has been developed. Expectations for organic EL (electroluminescence) element technology are increasing.

 In general, an organic EL device has a structure in which a hole transport layer, a light emitting layer, an electron transport layer, and the like are stacked between a transparent anode such as IT0 and a cathode made of a metal having a low work function. Then, by passing a direct current between the electrodes, holes are injected from the anode to the hole transport layer, and the electrons and holes injected from the cathode recombine in the light emitting layer to generate excitons. Is done. When this exciton is deactivated, light energy (fluorescence or phosphorescence) is released, and light emission occurs.

OLEDs are self-luminous and do not require a backlight, thus reducing power consumption, response speed, viewing angle, and contrast. 2004/002383 The characteristics such as the ratio are much better than the conventional TFT liquid crystal display device. However, there are still issues such as improvement of luminous efficiency, high brightness, and long life for practical use.

 So far, materials for the hole transport layer, the light emitting layer, and the electron transport layer have been studied as a method for improving the luminous efficiency of the organic EL device. For example, as an organic EL element material, an aromatic amine derivative having a low ionization potential and a high hole transporting property, or a polymer material having an aromatic amine in a side chain is used. Furthermore, in order to increase the efficiency and stability of organic EL devices, dimethylbenzene derivatives with a triphenylamine group and a vinyl group and derivatives with an oxadiazole group known as an electron transport material are used. Has been. In addition, rare-earth metal complex-based materials that exhibit strong fluorescent properties, π-conjugated polyphenylenevinylene (PPV), and non-conjugated polyvinyl carbazole (PVK) derivatives are also used as materials for the light-emitting layer and hole transport layer. (SA VanSlyke, CH Chen, C.. Tang, Appl. Phys. Lett. 1996, 69, 2160; Y. Shirota, Y. Kuwabara, H. Inada, T. Wakimoto, H. Nakada, Y. Yonemoto, S. Kawami, K. Imai, Appl. Phys. Lett. 1994, 65, 807 .; SA Carter, M. Angelopoulos, S. Karg, PJ Brock, and JC Scott, Appl. Phys. Lett. 1997, 70, 2067).

 On the other hand, in order to extend the life of the organic EL device, the film formation state of each layer, that is, the morphological stability of the thin film is extremely important. Furthermore, a reduction in drive voltage is desired to reduce the power consumption of the device.

However, none of the materials for organic EL devices reported so far has low morphological stability in a thin film state and sufficient durability has not been obtained. In particular, for hole transport materials, the length of organic EL elements In order to enhance the initial stability, polymer materials such as polyphenylenevinylene and polyvinylcarbazole are used as amorphous materials with a high glass transition point (Tg), and a buffer layer is provided between each layer. required lifetime and S dynamic voltage not been realized force, one / this _α

 Therefore, the invention of this application has been made in view of the circumstances described above, and has as its object to solve the problems of the prior art and to provide an organic EL device having excellent luminous efficiency and high durability. I have. Disclosure of the invention

 The invention of the present application solves the above-mentioned problems. First, at least the following formula (I)

(W) _k —— X— (Y), (I)

 (However, X is a carbon atom, a nitrogen atom, an amine derivative, benzene and its derivatives, heterocycle and its derivatives, porphyrin and its derivatives, fluorinine and its derivatives, cyclam and its derivatives, and vinyl polymer and its derivatives. A core site selected from the group consisting of derivatives, wherein Y and W are the same or different;

(Where N is a nitrogen atom, and R ¹ is selected from the group consisting of an alkylene group, a phenylene group and a heterocyclic group which may have a substituent. R ² is a phenyl group which may have one or more substituents, and m is an integer of 1 to 6) Phenylazomethine dendron subunit or the following formula (III)

(Where N is a nitrogen atom, and n is an integer of 1 to 6), and 1 is an integer representing the number of Y bonded to X And k is an integer representing the number of W bonded to X.) A material for an organic EL device is provided. '

 Second, the invention of this application is represented by the following formula (IV)

(However, X is carbon atom, nitrogen atom, amine derivative, benzene and , A heterocyclic ring and its derivative, porphyrin and its derivative, furocyanine and its derivative, and a cyclam and its derivative, a core site selected from the group consisting of: N is a nitrogen atom; R ¹ is substituted A substituent selected from the group consisting of an alkylene group which may have a group, a phenylene group and a heterocyclic group, or may be absent; and R ² has one or more substituents. And m is an integer of 1 to 6, and 1 is an integer of 1 to 6 representing the number of dendron subunits bonded to X). Provide a material for an organic EL device, which is characterized by comprising a methine dendrimer.

Thirdly, the invention of the present application has the following formula (V)

 (Where N is a nitrogen atom, n is an integer from 1 to 6, and k is an integer representing the number of dendron subunits bonded to X) Provide a material for an organic EL device characterized by the following.

Fourth, the invention of this application is expressed by the following formula (VI)

(However, N is a nitrogen atom, X is a carbon atom, a nitrogen atom, an amine derivative, a benzene and its derivative, a heterocycle and its derivative, a porphyrin and its derivative, a phthalocyanine and its derivative, and a cycle and its derivative. R ¹ is a substituent selected from the group consisting of an optionally substituted alkylene group, a phenylene group and a heterocyclic group, or is present. R ² is a phenyl group which may have one or more substituents; m is an integer of 1 to 6, n is an integer of 1 to 6; k and 1 are Which is an integer satisfying the condition 1 ≤ k + 1 ≤ 6, which represents the number of dendron subunits, each of which is bonded to X). Yes To provide for the EL element material.

Fifth, the invention of this application is based on the following formula (VI I)

 (However, N is a nitrogen atom, S is a sulfur atom, O is an oxygen atom, and Ar is benzene, thiophene, pyrrole, or 1,3,4-oxazidazole). The present invention provides a material for an organic EL device having a structure selected from the group consisting of (a) to (m).

(νπΐ)

(Where p and q are integers of 1 or more representing the degree of polymerization). Seventh, the invention of the application of the present application has the following formula (IX)

(However, N is a nitrogen atom, and R ¹ is a substituent selected from an alkylene group, a phenylene group and a heterocyclic group which may have a substituent, or may be absent. R ² is a phenyl group which may have one or more substituents, m is an integer of 1 to 6, n is an integer of 1 to 6, p and Q are one or more integers representing the degree of polymerization. The present invention provides a material for an organic EL device, comprising a phenylazomethine-potassium rubazole copolymer represented by the following formula:

 Eighth, the invention of this application is expressed by the following formula (X)

(However, N is a nitrogen atom, and R ¹ is a substituent selected from the group consisting of an alkylene group, a phenylene group and a heterocyclic group which may have a substituent, or absent. R ² is a phenyl group which may have one or more substituents, m is an integer of 1 to 6), and a compound represented by the following formula (XI )

 (Where N is a nitrogen atom and n is an integer of 1 to 6). A method for producing a material for an organic EL device, characterized by reacting a vinylcarbazole monomer represented by the following formula: .

 A ninth aspect of the invention of this application is an organic EL comprising at least an anode, a hole transport layer formed on the anode, a light emitting layer in contact with the hole transport layer, and a cathode in contact with the light emitting layer. In the device, the hole transporting layer or the light emitting layer is formed of a thin film containing any of the above-mentioned materials for an organic EL device. The organic EL device is characterized in that the light-emitting layer is formed of a thin film containing a metal salt together with any one of the materials for an organic EL device described above, and, first, the hole transport layer or the light-emitting layer An organic EL device comprising a thin film obtained by photocrosslinking any of the above materials for an organic EL device.

 Further, the invention of the present application also provides, 12thly, a light-emitting or display device characterized by including any one of the above-mentioned organic EL devices. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic diagram illustrating the organic EL device of the present invention. (However, 1: organic EL element, 21: transparent substrate, 22: anode, 3: hole transport layer, 4: light emitting layer, 5: cathode, 6: conducting wire)

 FIG. 2 is a diagram showing characteristics (voltage-luminance curve) of the organic EL device constructed in the example of the invention of this application. (However, the hole transport layer is a: phenylazomethine dendrimer (4th generation), b: phenylazomethine dendrimer (4th generation), high temperature measurement, c: phenylazomethine dendrimer (4th generation) ' Tin chloride, d: diaminomethyl-substituted phenylazomethine dendrimer (3rd generation)

 FIG. 3 is a diagram showing the characteristics (voltage-luminance curve) of the organic EL device constructed in the example of the invention of this application. (However, the hole transport layer is a: phenylazomethine dendrimer (4th generation) · tin chloride / polyvinylcarbazole, b: polyvinylcarbazole)

 FIG. 4 is a diagram showing characteristics (voltage-luminance curve) of the organic EL device constructed in the example of the present invention. (However, the light-emitting layer is a: phenylazomethine dendrimer (4th generation) · tin chloride Z polyphenylenevinylene, b: polyphenylenevinylene)

 FIG. 5 is a diagram showing characteristics (voltage-luminance curve) of the organic EL device constructed in the example of the invention of this application. (However, the hole transport layer is a: 4- (diphenylazomethine) styrene-vinyl carbazole copolymer, b: 4- (diphenyl azomethine) styrene-vinyl carbazole copolymer · tin chloride , C: Polyvinyl carpazole)

FIG. 6 is a diagram showing characteristics (voltage-luminance curve) of the organic EL device constructed in the example of the present invention. (However, the hole transport layer is composed of a: phenylazomethine one-pot rubazolyl asymmetric dendrimer, b: phenyl azomethine one-pot lupusole asymmetric dendrimer Eu (0T f) ₃ ) FIG. 7 is a diagram showing characteristics (voltage-luminance curve) of the organic EL device constructed in the example of the present invention. (However, for the hole transport layer, a: Carpazolide dendrimer (3rd generation) photocrosslinking, b: force Lubazolide dendrimer, uncrosslinking)

 FIG. 8 is a diagram showing the lifetime (time-luminance curve) of the organic EL device constructed in the example of the invention of this application. (However, the hole transport layer is a: Carpazole dendrimer (3rd generation) Photocrosslinking b: Force uncrosslinked rubazole dendrimer) Best mode for carrying out the invention

 The material for an organic EL device of the present invention has a phenyl azomethine dendron subunit having a metal accumulating ability and / or a carbazole dend subunit having an excellent hole transporting property, and is easily prepared by a solution casting method. It can form a thin film. In addition, the morphological characteristics of the interface of the obtained thin film are significantly improved as compared with conventional materials for organic EL devices.

 The material for an organic EL device of the invention of this application is represented by the following formula (I)

(W) _k ~~ X—— (Y), (I)

It consists of a compound represented by these.

Here, X is a group consisting of a carbon atom, a nitrogen atom, an amine derivative, benzene and its derivatives, a heterocycle and its derivatives, porphyrin and its derivatives, phthalocyanine and its derivatives, cyclam and its derivatives, and a vinyl polymer and its derivatives. And Y and W are the same or different, and are represented by the following formula (II): 383

(However, N is a nitrogen atom, and R ¹ is a substituent selected from the group consisting of an alkylene group which may have a substituent, a phenylene group and a heterocyclic group, R ² is a phenyl group optionally having one or more substituents, and m is an integer of 1 to 6), or a phenylazomethine dendron subunit; or And the following equation (III)

 (Where N is a nitrogen atom and n is an integer of 1 to 6).

 At this time, m and n in equations (11) and (III) are integers of 1 to 6 representing the number of generations in each dendro subunit, and 1 and k in equation (I) are Represents the number of connected dendrosubunits, ie, Y and W.

The material for an organic EL device of the invention of the present application is characterized in that at least phenylazomethine or sorbazole dend It is a combination of ronsubunits.

 Such compounds include dendrimers having X as a core and only Y, only W, or both Y and W as dendron subunits.

 Specifically, the following equation (IV)

(However, N, X, R ¹ , R ² , m and 1 are as defined above), or a phenylazomethine dendrimer represented by the following formula (V)

 (Where N, n and k are as described above).

A carbazole dendrimer represented by the following formula (VI)

^{(N, X, R!,} R 2, m and n in which one of the) phenylalanine § zone methine Ichiriki carbazole asymmetric dendrimer represented by the Ru is illustrated.

 In the dendrimers of the formulas (IV) to (VI), X represents a carbon atom, a nitrogen atom, an amine derivative, benzene and its derivatives, a heterocycle and its derivatives, porphyrin and its derivatives, phthalocyanine and its derivatives, and cyclam And its derivatives, but for X, the phenylazomethine dendron subunit (Y) and the rubazodyl dendron subunit (W) are 1 to 6 in total. Can be combined. The number of such Y and W can be appropriately selected according to the number of possible positions of X.For example, when X is benzene, Y and W can be combined up to a total of six. When X is a carbon atom, Y and W can bond up to a total of four. Of course, X that can combine more than 6 Y and W is considered, but in that case, attention must be paid to the steric hindrance of the dendrimer.

Specifically, at least core structure X has the following formula (VI I)

(DAB: a), 3,6-dimethyl-benzene (DMDABz: b), triphenylamine (TATPA: c), tetraphenyl-21H, 23H-porphyrin (TAPo: d), naphtha Len (DANPh: e), pyrene (DAPy: f), 1,4,8,11 tetraaza-cyclotetradecane (g), cyclic phenylazomethine trimer (CPA: h), 2,5-bis ( Phenyl)-1,3,4-oxaziazol (DAPOX: i), 2,5- (diphenyl) -thiophene (DAPTh: j), perylene (k), 1,2,3-triphenyl- Having 1,3,4-tetrazole (1) and triphenylamine derivative (m) Are preferably exemplified. In addition, Ar in the above (m) represents an aromatic ring such as benzene, thiophene, pyrrole or 1,3,4-oxaziazol.

 In these core sites X, if the point of attachment of Y or W is indicated as (D), then:

That is, benzene (DAB: a) (Y + W = 2 (1, 4-)) benzene (TABz: a-2) (Y + W = 3 (1, 3, 5-)), 3, 6-dimethyl-benzene (DMDABz: b) (Y + W = 2 (1, 4-)), Trif Enilamine (TATPA: c) (Y + W = 3 (4, 4 ', 4''-)), Tetraphenyl-21H, 23Η-Bolphyrin (TAPo: d) (Y + W = 4 ( 5, 10, 15, 20-)), naphtha (DA Ph: e) (Y + W = 2 (1, 5-)), pyrene (DAPy: ί) (Y + W =

2 (1, 6-)), 1,4,8,11 Tetraaza-cyclotetradecane (g) (Y + W = 4 (1,4,8,11-)), cyclic phenylazomethine trimer (CPA: h)

(γ + W = 4 (4, 4 ', 4 ",-)), 2,5-bis (phenyl) -1,3,4-oxoxadiazole (DAPOX: i) (Y + W = 2 ( 4—))), 2,5- (diphenyl) -thiophene (DAPTh: j) (Y + W = 2 (4,4 ′)), perylene (k), 1,2,3-triene Phenyl-1,3,4-tetrazole (1) (Y + W = 3 (4, 4 ', 4' '-)) and triphenylamine derivative (m) (Y + W =

3 (4, 4 ', 4 "-)), etc. (where Υ + W represents the total number of Υ and W that do not bind to each X 、, and follows Y + W (Figures in parentheses indicate the position of (D), that is, the position where Υ and / or W combine.)

The method for synthesizing such phenylazomethine dendrimer, carbazole dendrimer, and phenylazomethine monofunctional rubazole asymmetric dendrimer is not particularly limited, and the Divergent method for synthesizing from the center of the dendrimer outward. A known method such as the Convergent method for synthesizing from outside the dendrimer toward the center can be applied. For example, dendrons Y and W of each generation are synthesized respectively, and a core compound X having a reactive group (for example, I, Br, NH _2, etc.) is subjected to a dehydration condensation reaction in the presence of a catalyst by a convergent method. A phenylazomethine dendrimer and / or a phenylazomethine asymmetric rubazole asymmetric dendrimer can be synthesized (for example, Japanese Patent Application No. 2000-02). 0 1 0; Japanese Patent Application 2 0 0 2 — 0 6 6 1 9 1; Masayoshi Higuchi, Satoshi Shiki, and Kimihisa Yaiamoto, Org. Lett. 2000, Vol. 2, No. 20, 3079-3082; Masayoshi Higuchi, Satoshi Shiki, Katsuhiko Ariga, and Kiiihisa Yaiamoto, J. Am. Chew. Soc. 2001, 123, 4414-4420).

 In the material for an organic EL device of the invention of the present application, X is the following formula (VIII)

CH-H-CH ₅ (Vni)

 P q

 (However, p and (1 is an integer of 1 or more representing the degree of polymerization)) may be used.

 In such an organic EL element material, the dendant subunits of Y and W exist as side chains of the vinyl polymer. Specifically, the following equation (IX)

(Wherein N, R ¹ , R ² , m, n, p and q are as described above).

Such a phenylazomethine one-pot rubazole copolymer has the following formula (X)

 (Wherein R ', R K and m are as described above), and the following formula (XI)

 (Where n is the same as described above), which is obtained by reacting a vinyl carbazole monomer represented by the following formula: It proceeds by heating to 80. Preferably, it is obtained by reacting in the presence of a radical initiator such as tert-butyl hydroperoxide, benzoyl peroxide, and azobisisoptirononitrile (AIBN).

At this time, P and Q in the phenylazomethine-carpazole copolymer of the formula (VIII) represent the phenylazomethine dendrite subunit and the carbazole dendron subunit, respectively. Is an integer of 1 or more indicating the degree of polymerization of the site having the following, but this does not mean that the phenylazomethine-potassium copolymer is limited to a block copolymer. Phenyl of formula (VIII) The azomethine-potassium rubazole copolymer may be a random copolymer or a copolymer in which phenyl azomethine dendron subunits and carbazole monodentate subunits are alternately and regularly arranged. Is also good. Although the ratio of p to q is not particularly limited, the purpose is that phenylazomethine dendron subunit has high metal accumulation ability, and carbazole dend subunit has high hole transport ability. It can be appropriately changed according to the characteristics of the material for the organic EL element to be used.

In the material for an organic EL device of the invention of the present application, R ¹ in phenylazomethine dendron subunit (Y) is a substituent selected from alkylene, phenylene, a heterocyclic group and a derivative thereof, Specific examples include heterocycles such as methylene, ethylene, propylene, phenylene, pyrrole, thiophene, and oxadiazole. R ² in Y is a phenyl group which may have one or more substituents, and these substituents may further have a substituent. As such R ² , a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, an amino group, a cyano group, a dimethylamino group, or the like may be any one of the o-, m-, and p-positions. Or a substituted phenyl group bonded to two or more sites. Since the electron density of phenylazomethine dendron subunit changes depending on the nature of R ² (electron donating property, Z electron withdrawing property, etc.), R ² can be appropriately selected according to the purpose and used for organic EL devices. It is possible to adjust the properties of the whole material (or the luminous efficiency of the whole organic EL device).

Further, in the material for an organic EL device of the invention of the present application, fenilazomethine dendrosubunit (Y) and By selecting the number of generations of the knit (W), that is, the values of m and n, the hole transport property and the light emission property can be adjusted.

 The inventors of the present application have previously reported that phenylazomethine dendrimer has an electron gradient due to the electron density difference (basicity) of the next-generation imine site in the molecule, so that various metals must be added. Has been reported to produce a stepwise complexation with the imine site in the molecule (for example, Masayos i Higuc i, Satoshi Siki, and Kimihisa Yamamoto, Org. Lett. 2000, Vol. 2, No. 20, 3079-3082; Masayoshi Higuchi, Satoshi Shiki, Katsuhiko Ariga, and Kimihisa Yamamoto, J. Am. Chem. Soc. 2001, 123, 4414-4420; Kimihisa Yamamoto, Masayoshi Higuchi, Satoshi Shiki, Masanori Tsuruta and Hiroshi Chiba, Nature, Vol. 415, No. 6871, 509-511, 31 Jan 2002).

 Similarly, in the material for an organic EL device of the invention of the present application, phenylazomethine dendrimer, phenylazomethine-potassium asymmetric dendrimer or phenylazomethine-carbazolyl copolymer Metals can be complexed with the combined phenylazomethine dendron subunits.

 As described above, the material for an organic EL device of the invention of this application can form a dense and high-strength thin film. Since such a thin film is electrochemically stable and exhibits high heat resistance, by using it as a hole transport layer or a light emitting layer, it is possible to realize excellent luminous efficiency and high durability. . Therefore, the invention of this application also provides an organic EL device having a hole transport layer or a light emitting layer formed of a thin film containing the material for an organic EL device as described above.

FIG. 1 shows an outline of the organic EL device of the present invention. That is, this The organic EL element (1) of the invention of the application comprises at least an anode (22), a hole transport layer (3) formed on the anode (22), and a light emitting layer (3) in contact with the hole transport layer (3). 4) and a cathode (5) in contact with the light emitting layer (4), wherein at least one of the hole transport layer (3) and the light emitting layer (4) is at least one of the organic EL devices described above. What is necessary is just to be comprised by the thin film containing the material for use.

 In the organic EL device (1) according to the present invention, the hole transport layer (3) is in contact with the anode (22) and transports holes injected from the anode (22) to the light emitting layer (4). Any material may be used as long as it contains the material for an organic EL device as described above.

 The material for an organic EL device of the invention of this application has, for example, an electron gradient due to the electron density difference (basicity) of the next-generation imine site of phenylazomethine dendrimer. Therefore, in the organic EL device (1) of the invention of this application, by using such a material for an organic EL device for the hole transport layer (3), the energy of the anode (22) and the hole transport layer (3) can be improved. (1) The gap is reduced, and the hole injection into the hole transport layer (3) and the hole transport from the hole transport layer (3) to the light emitting layer (4) can be performed efficiently. Therefore, the luminous efficiency of the organic EL device (1) can be improved, the open discharge pressure can be reduced, and the drive voltage can be reduced.

The light emitting layer (4) in the organic EL device (1) of the invention of the present application is a place where recombination of injected holes and electrons takes place. Any material can be used as long as it reacts to emit light. Various materials generally used for organic EL devices, specifically, tris (8-quinolinolato) aluminum complex (A1Q3), bis (benzoquinolinolato) ) Beryllium complex (BeBd2), bis (8-quinolato) zinc complex (ZnoJ Metal complexes such as palladium complex (Eu (TTA) ₃ (phen)) and low molecular weight fluorescent dyes such as perylene, quinacridone, and coumarin thinned by vapor deposition, poly (p-phenylenevinylene) (PPV) or polyfluorene

A polymer obtained by dissolving a π-conjugated polymer such as (PF) or a polymer containing a fluorescent dye in a side chain such as polypinylcarbazole in a solvent and forming a thin film by a wet coating method can be suitably used. Preferably, the light emitting layer

(4) shall consist of a thin film containing any of the above-mentioned materials for an organic EL device together with a material which emits light in response to energy released by recombination of holes and electrons. When the light emitting layer (4) contains the above-mentioned material for an organic EL device, the light emitting characteristics of the device are improved, which is preferable.

 As described above, the material for an organic EL device of the invention of this application is capable of complexing a metal to phenylazomethine dendron subunit. An electron gradient is generated based on the electron density difference (basicity). Therefore, in the organic EL device (1) of the invention of this application, the hole transport layer (3) or the light emitting layer (4) is formed of a thin film containing a metal salt together with the organic EL device material. It may be.

The metal integrated in the phenylazomethine dendron subunit of the material for an organic EL device of the invention of this application may be any metal as long as it can form a complex with the imine group of phenylazomethine as a ligand. There is no particular limitation. For example, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag ゝ Au, Zn, Cd, Mo, W, Mn, Sn, Eu, Tb, Nd and the like can be mentioned. Preferably, transition metal chlorides such as tin (Sn) chloride (SnCl ₂ ), copper (Cu), iron (Fe), and gold (Au) (eg, CuCl ₂ , FeCl ₃ , AuCl _3, etc.) , Europium (Eu), terbium (Tb) and other rare earth metal chlorides (eg EuCl ₃ , TbCl ₃ ), copper trifluoromethanesulfonic acid (Cu (0Ti) ₃ ), dimethyl trifluoromethanesulfonic acid (Eu (0Ti) ₃ ), terpium trifluoromethanesulfonic acid (Tb (0Ti ) ₃ ), and neodymium trifluoromethanesulfone (Nd (OTf) ₃ ).

 Such a complex is formed by a metal which can form a complex with the solution of the material for the organic EL device using the imine group in the phenylazomethine structure as a ligand.

(Ion or compound) can be mixed. Then, after confirming the formation of the complex, if this solution is cast, a complex thin film of the material for the organic EL device is obtained. At this time, if the metal compound is added in an equimolar amount to the imine site to be complexed in the phenylazomethine dendron subunit, the metal equivalent of the phenylazomethine dendron of each generation with respect to the imine is controlled. be able to. Then, after confirming the complex formation by -Vis spectrum, the solvent is concentrated and a thin film of the material for organic EL devices is obtained. At this time, the solvent is not particularly limited, and for example, chloroform-formacetonitrile can be used.

The organic EL device (1) according to the invention of the present application is further characterized in that a thin film obtained by photocrosslinking the organic EL device material is used as a hole transport layer (3) or a light emitting layer (4). May be. For example, a solution of the organic EL element material is cast to form a thin film, and then the cast film is irradiated with light to crosslink the formed dendrimer. At this time, the light to be irradiated may be at least light that includes an absorption wavelength region of phenylazomethine and / or carbazole in the material for an organic EL device, and various light sources are used. . Preferably, the wavelength range of the irradiated light is an ultraviolet light range of 500 nm or less. As described above, a thin film obtained by photocrosslinking a material for an organic EL device is a film in which a carbazole group-phenyl ring is crosslinked intra- or intermolecularly by a photocrosslinking reaction. Specifically, in a material for an organic EL device having a carbazole dendron subunit, a cross-linking reaction occurs at either the 3-position or the 6-position in the carbazole dendron subunit by light irradiation, and the cross-linking occurs. It becomes a film. In the case of a compound having a phenylazomethine dendron subunit, for example, a cross-linking reaction occurs between the adjacent 2-positions of a phenyl group, and a cross-linked film is formed. Such a crosslinked film has low solubility in organic solvents and is almost insoluble in general organic solvents. Therefore, if the photocrosslinked thin film is used as the hole transport layer (3), the hole transport layer (3) can be formed even if the light emitting layer (4) is further formed by casting an organic solvent solution. Does not dissolve.

 In the organic EL device (1) of the present invention, the anode (22) is preferably made of a material having a high hole injection ability (in other words, a material having a large work function). For example, indium Z tin oxide (IT0) ), Tin oxide, gold or the like. Above all, # 0 is suitable because it has high visible light transmittance and can take out light emitted from the organic EL device (1). Further, the anode (22) may be formed on a transparent substrate (21) such as glass or plastic, and the film thickness and the like are not limited. Of course, a commercially available conductive glass may be used as the anode (22).

Further, the material and thickness of the cathode (5) are not particularly limited as long as the cathode (5) has conductivity and can achieve the purpose of injecting electrons (へ) into the light emitting layer (4). Preferably, a group III metal such as an alkali metal, an alkaline earth metal, aluminum, gallium, and indium having a low work function is used. Among them, alloys of magnesium and silver or copper, which are chemically stable and inexpensive, and aluminum alloys which are inexpensive and easy to form films Pum is preferred. These materials may be formed on a transparent substrate such as glass or plastic.

 As described above, the organic EL device (1) of the invention of this application can be used as a flat panel display of various devices such as a mobile phone, a notebook computer, and a PDA by being combined with a conductor, a power cable, a filter, and the like. Things.

 Hereinafter, embodiments will be described in more detail with reference to examples. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in details. Example

Example 1>

 [Preparation]

 (a) Anode: A 3 mm wide anode was prepared by etching the IT0 surface of an IT0 glass electrode (20 mm X 20; Oji Tobi) with hydrochloric acid. .

(b) Hole transport layer: Org. Lett. 2000, Vol. 2, No. 20, 3079-3082 The following formula (IV-a) synthesized by the method described in

Phenylazomethine dendrimer (4th generation) represented by the formula below is dissolved in 1 ml of 1 ml dendrimer with 1 ml of black-mouthed form, and spin-cast method (2,500 rpm, 2 times at 1 minute intervals) A 500 A thick hole transport layer was formed by casting.

(c) Light-emitting layer: A3 (Tokyo Kasei Co., Ltd.) was applied to the obtained hole-transporting layer using a vacuum evaporation apparatus (Ulvac VPC-410A) under a reduced pressure of 50 × 10 " ⁶ Torr to 2-3 A. Vacuum deposition was performed at a deposition rate of / sec to form a light emitting layer (electron transporting property) with a thickness of 500A.

 (d) Cathode: Using A1 wire (diameter 1 nun) for the obtained light emitting layer,

A1 was vacuum deposited at a deposition rate of 2 to 5 A / sec under the same conditions as in (c) to form a cathode having a thickness of 1000 A.

 [Evaluation of organic EL device]

The obtained organic EL device with an area of 0.1 cm ² was 2383 Voltage-current and voltage-luminance measurements were performed.

 The characteristics of the organic EL device are shown in FIG. 2a.

When a voltage of 5 V or more was applied using the IT0 electrode as the anode, green light emission derived from A1Q3 was observed. At 15 V, a maximum luminance of 1600 cd / m ² was confirmed. The turn-on voltage reaching 0.1 cd / iD ² was 5.6 V, and the luminous efficiency at a luminance of 300 cd / i ² was 1.2 lm / W.

Furthermore, high temperature measurement (at 100, in air) of the organic EL device was performed. As shown in Fig. 2b, the emission intensity is equal to the initial value (turn-on voltage: 5.5 V, maximum brightness: 1560 cd / m ² at 15 V, emission efficiency of 330 cd / m ² : 1. 16 lm / W). This confirmed the stability of this EL device. Example 2>

 In the step (b) of forming the hole transport layer in Example 1, 1 equivalent of tin chloride was used together with the phenylazomethine dendrimer of the formula (IV-a) (based on the number of imines in the phenylazomethine dendrimer). Was mixed in acetonitrile, complexed, concentrated, and spin-cast under the same conditions as in Example 1 to form a 500 A thick hole transport layer.

 Further, an organic EL device was constructed and evaluated in the same manner as in Example 1.

From FIG. 2, it was confirmed that the maximum luminance was 18000 cd / m ² at 12 V, and the luminous efficiency at a luminance of 300 cd / m ² was as high as 2.6 lm / W. In addition, when the turn-on voltage was about 4 V and the dendrimer alone was used as the hole transport layer, the voltage was reduced by 1.5 V or more compared to the case where the hole transport layer was used (Example 1).

As described above, the use of phenylazomethine dendrimer-metal complex as a hole transport material significantly reduced the power consumption of organic EL devices. It was confirmed that it can be reduced.

 This is considered to be because the energy gap between the hole injection electrode (anode) and the hole transport layer becomes smaller, and the efficiency of hole injection into the hole transport layer increases.

<Example 3>

 Formula (IV-b)

 Dimethylamine-substituted phenylazomethine dendrimer represented by

(Third generation) was used as a hole transport material to construct and evaluate an organic EL device.

As shown in FIG. 2d, the maximum luminance was 4500 cd / m ² at 14 V, and the luminous efficiency at a luminance of 300 cd / m ² was 1.8 lm / W. It also has a turn-on voltage of about -5.0 V, and unsubstituted phenylazomethine dendrites It was confirmed that the device exhibited higher device characteristics than the case where the mask was used as the hole transport layer (Example 1). This is probably because the introduction of an electron-donating dimethylamine group into the dendrimer terminal increased the electron density inside the dendrimer.

<Comparative Example 1>

 A mouth form solution of polyvinyl carpazole was prepared, and this mouth form solution was spin-cast under the same conditions as in Example 1 to form a hole transport layer having a thickness of 500 persons.

 Further, an organic EL device was constructed and evaluated in the same manner as in Example 1.

In the obtained organic EL device, green luminescence derived from Al Q was confirmed by applying a voltage of 4 V or more. Further, as shown in FIG. 3 b, the highest luminance 600 cd / m ² at 1 1 V, reaches ^{0. 1 cd / m 2 rn -} on voltage 4. 5 V, luminance 300 cd / m ² The luminous efficiency at was 2.0 lm / W.

<Example 4>

 An oral form solution of polyvinyl carbazole was prepared, and the phenylazomethine dendrite of formula (IV-a) used in Example 1 (4th generation) was added to the polyvinyl carbazole. And 1 equivalent of tin chloride (based on the number of imines in the phenylazomethine dendrimer). This black-hole form solution was spin-cast under the same conditions as in Example 1 to form a hole transport layer having a thickness of 500 A.

In addition, an organic EL Hatako was constructed in the same manner as in Example 1 and evaluated. 4002383 valued.

As shown in FIG. 3 a, the obtained organic EL device showed a maximum brightness 1500 cd / m ² at 10 V, the luminous efficiency at luminance 300 cd / m ² showed a 3.5 li / W and high emission efficiency Was. Furthermore, the turn-on voltage reaching 0.1 cd / m ² was about 3 V, and the polypinylcarbazole of Comparative Example 1 was used as the hole transport layer (without phenylazomethine dendrimer). V or more dropped. Therefore, low power consumption of the device was confirmed.

 As can be seen from Examples 2 and 4, a high luminous efficiency and low turn-on voltage characteristics of the device are realized by using a thin film containing dendrimer in which metal is integrated (complexed) as the hole transport layer. Was confirmed. In addition, the energy gap between the hole injection electrode IT0 and the hole transport layer became smaller, suggesting that the efficiency of hole injection into the hole transport layer was increased.

<Comparative Example 2>

 [Preparation]

 (a) Anode: The IT0 surface of the IT0 glass electrode (20 thighs x 20 baskets; Oji Tobi) was etched with hydrochloric acid to prepare a 3 mm wide anode and used.

 (b) Hole transport layer: An aqueous solution of poly (3,4-ethylenedioxythiophene) -polystyrenesulfonic acid (PED0T: PSS) was spin-cast under the same conditions as in Example 1 to obtain a 300-A thick layer. A hole transport layer was formed.

 (c) Light-emitting layer: A benzene solution of a polyphenylenevinylene derivative (MEH-PPV) was prepared and spin-cast to form a light-emitting layer having a thickness of 500A.

(d) Cathode: 2 to 5 A / sec of the obtained light emitting layer under the same conditions as in Example 1 Ca was vacuum-deposited at a deposition rate to form a cathode having a thickness of 1000A.

 [Evaluation of organic EL device]

Room temperature of the organic EL device having an area of 0.1 cm ² obtained by the above (a) to (d). Voltage-current and voltage-brightness measurements were performed in the atmosphere.

 Fig. 4b shows the characteristics of the organic EL device.

By applying a voltage of 5 V or more with the IT0 electrode as the positive electrode, green light emission derived from MEH-PPV was confirmed. Further, sea urchin by shown in FIG. 4 b, 12 V maximum brightness 350 cd / a shown in, 0.1 cd / turn-on voltage reaching i ² is 5.6 V, the luminance 300 cd / luminous efficiency in m ² is 1.2 lm / W.

<Example 5>

 A hole transport layer was formed in the same manner as in Comparative Example 2, and a phenylenevinylene derivative (MEH-PPV) was added thereto with 1% by weight of a phenylazomethine dendrimer of the formula (IV-a) (MEH-PPH). A chlorobenzene solution containing 1 equivalent of tin chloride (based on the number of imines in the phenylazomethine dendrimer) and 1 equivalent of tin chloride (based on the number of imines in the phenylazomethine dendrimer) was spin-cast to form a light emitting layer having a thickness of 500A.

In the same manner as in Comparative Example 2, a cathode was formed on the light-emitting layer, and the characteristics of the obtained organic EL device having an area of 0.1 cm ² are shown in FIG. 4A.

This organic EL device exhibited a maximum luminance of 850 cd / i ² at 11 V and a high luminous efficiency of 2.1 lm / at a luminance of 300 cd / m ² . In addition, the turn-on voltage reaching 0.1 cd / m ² was 4.5 V, which was 1 V higher than that of the organic EL device in which only the MEH-PPV of Comparative Example 2 was used as the light emitting layer (does not include the ferazomethine dendrimer). It fell above. Therefore, low power consumption of the device Power consumption was confirmed.

<Example 6>

 [Preparation] Synthesis of 4- (diphenylazomethine) styrene monomer (a)

 According to the following reaction formula (A), 4- (diphenylazomethine) styrene monomer was synthesized as a first-generation dendron.

4-Aminostyrene (0.35 il, 1 eq), benzophenone (0.65 g, 1.2 eq) and 1,4-diazabicyclo [2,2,2] octane (DABC0) are dissolved in 15 ml of benzene (PhCl). Then, titanium tetrachloride (TiCl ₄ ) (0.25 ml, 0.75 equivalent) was added to 100 ml of Niloflaco with stirring under a nitrogen atmosphere, and dehydration reaction was performed for 12 hours. Compound a was obtained in a yield of 56%. The obtained compound a was identified by TOF-Mass, elemental analysis, and 1H-NMR.

 TOF-Mass 283.21 found (283.37 calcd.)

 Elemental analysis C: 88.95 found (89.01 calcd.),

 Η: 6.01 (6.05),

 Ν: 4.91 (4.94)

 [Experiment] Synthesis of 4- (diphenylazomethine) styrene-vinyl carbazole copolymer (b) (ρ / α = 1/1)

According to the following reaction formula (II), 4- (diphenylazomethine) styrene-vinylcarbazole copolymer was synthesized.

 The obtained 4- (diphenylazomethine) styrene monomer a (0.35 1 equivalent), vinylcarbazole (1.89 g, 8 equivalents), and azobisisobutyronitrile (AIBN, 22 ig) were dissolved in 20 ml of toluene. And refluxed at 80 in a 300 ml two-necked flask. Compound b was obtained in 25% yield.

 The obtained compound was identified by GPC, 1H-NM, and UV.

 Mn: 5640 Mw: 6430 <Example 7>

Compound b (2 mg) obtained in Example 1 was dissolved in black hole form, and a thin film having a thickness of 500 A was formed on an IT0 glass electrode by a spin casting method to form a hole transport layer. Aid was vacuum-deposited thereon to form a thin film having a thickness of 500 A, which was used as a light emitting layer and an electron transport layer. Further, A1 was formed as a cathode to a thickness of 1000 A, and an organic EL element having an area of 0.1 cm ² was produced.

 With respect to the obtained organic EL device, voltage-current and voltage-brightness were measured at room temperature in the atmosphere, and the results are shown in FIG. 5a.

By applying a voltage of 5 V or more with the IT0 electrode as the positive electrode, green light emission from A was confirmed, and a maximum luminance of 800 cd / m ² was confirmed at 20 V.

The turn-on (drive) voltage reaching 0.1 cd / m ² was 6.2 V, and the luminous efficiency at a luminance of 300 cd / m ² was 0.8 lm / W. <Comparative Example 3>

 Polyvinyl carbazole (PVK, Kanto Kagaku Cat. No. 32777-31) 2 nig was dissolved in black hole form, and a thin film of 500A thickness was formed on IT0 glass electrode by spin casting, and the hole transport layer was formed. It was. Next, an organic EL device was produced in the same manner as in Example 5.

 For this organic EL device, voltage-current, voltage-brightness were measured at room temperature in the atmosphere, and the results are shown in FIG. 5c.

When a voltage of 5 V or more was applied with the IT0 electrode as the positive electrode, green light emission derived from Aid was confirmed, and a maximum luminance of 1100 cd / ffl ² was confirmed at 16 V. The turn-on (drive) voltage reaching 0.1 cd / m ² was 5.2 V, and the luminous efficiency at a luminance of 300 cd / m ² was 0.9 lm / W. Example 8>

 An acetonitrile solution of the compound b used in Example 7 and an acetonitrile solution of tin chloride U equivalent (based on the imine number of the dendron of the copolymer) was mixed, and the solvent was concentrated. A thin film was formed in the same manner as in Example 7, and used as a hole transport layer. An organic EL device was manufactured in the same manner as in Example 7.

 With respect to the obtained organic EL device, voltage-current and voltage-brightness were measured at room temperature in the atmosphere, and the results are shown in FIG. 5b.

This organic EL device exhibited a maximum luminance of 9000 cd / m ² at 10 V and a high luminous efficiency of 1.7 lm / W at a luminance of 300 cd / m ² .

Furthermore, the turn-on (drive) voltage is about 4.1 V, which is 2.0 V or more, and that PVK is used as the hole transport layer when a hole transport layer not complexed with a metal is used (Example 5). 1.0V or more lower than the case (Comparative Example 3) It was confirmed that the power consumption of the device could be reduced. The use of a copolymer in which metals are integrated (complexed) as a hole transport layer increased the luminous efficiency of the organic EL device and further reduced the turn-on (drive) voltage at the hole injection electrode. This is probably because the energy gap between a certain IT0 and the hole transport layer became smaller, and the efficiency of hole injection into the hole transport layer increased. Example 9>

 Next formula (VI-a)

 2000, Vol. 2, No. 20, 3079-3082, J. Am. Chem. Soc. 2001, 123, 4414-4420, and Nature Vol. Synthesized according to the method described in 415, No. 6871, 509-511. Table 1 shows the identification results of the obtained phenylazomethine monocyclic rubazole asymmetric dendrimers.

Using compound c as the hole transport material, IT0 / An organic EL device consisting of dendrimer / A1Q / CSF / A1 was constructed. The voltage-current and voltage-brightness measurements of the organic EL device at room temperature in the atmosphere were performed, and the results are shown in FIG. 6a.

 Gl dendnmer

Έ Nffi (400MHz, CDC1 _3> TS standard, 3 (TC, ppi): δ 8.11 (d, 7.2Hz, 2H), 7.82 (d, J = 7. Hz, 2H), 7.53-7.20 (i, 16H) , 6.93 (d, J = 8.8Hz, 2H)

_{^{13 C Nffi (100MHz, CDC1 3}} , TMS standard, 30 ° C, ppi): δ 169.03, 150.59, 140.98, 139.29, 135.97, 132.51, 130.92, 129.52, 129.36, 128.82, 128.22, 127.97, 127.32, 125.71, 123.08, 122.27, 120.14, 119.59, 109.63

MALDI-TOF- S: 420.6 ([M] ⁺ calcd for C ₃₁ H ₂₂ N ₂ : 422.2).

 G2 dendrimer

^J H NMR (400 MHz, CDC13 _> TMS standard, 30. C, ppm): δ 8.27 (s, 2H), 8.16 (d, J = 7.6 Hz, 4H), 7.77 (d, J = 7.2 Hz, 2H) , 7.70 (d, J = 7.2Hz, 21H), 7.63-6.94 (m, 40H), 6.78 (d, J = 8.4Hz, 2H), 6.68 (d, J = 8.4Hz, 2H),

¹³ C NMR (100 MHz, CDCI3, MS standard, 31 5 168.93, 168.68, 168.45 153.85, 151.99, 151.58, 141.67, 139.20, 1 135.75, 134.23, 131.41, 130.95, 130.49, 130.35, 130.12, 130.04, 1 129.25, 128.82, 128.67, 128.18, 128.02, 127.69, 127.36, 126.07, 1 123.63, 123.04, 122.88, 120.55, 120.34, 120.19, 119.57, 111.30, 1

MALDI-TOF-MS: 1109.0 ([M] + calcd for C ₈₁ H ₅₄ N ₆ : 1110.4).

 G3 dendrimer

_{Ή NMR (400MHz, CDC1 3,} TMS standard, 30 ° C, ppm): δ 8.51 (s, 2H), 8.30 (s, 4H), 8.15 (d, J = 7.2Hz, 8H), 7.80-6.55 (m , 104H).

MALDI-TOF-MS: 2486.3 (M + calcd for C ₁₈₁ H „ ₈ N ₁₄ : 2487.0).

<Example 10>

Further, a solution of the c-form of compound c and an acetonitrile solution of Eu (0Ti) ₃ (1 equivalent: based on the number of imines of phenylazomethine dendron) were mixed and complexed, and the same as in Example 7 was performed. The organic EL device was constructed in the following manner.

The obtained EL device was tested for voltage-current, Voltage-brightness measurements were performed and the results are shown in Figure 6b. <Example 11>

 (a) Anode: IT0 glass electrode (20 mm x 20 bandages; Oji Tobi) The IT0 surface was etched with hydrochloric acid to prepare a 3 nun-wide anode and used.

 (b) Hole transport layer: The following formula (Va)

The carbazole dendrimer (3rd generation) represented by is dissolved in a black hole form and a hole transport layer having a thickness of 500 A was formed by spin casting.

 Next, light irradiation was performed for 1 hour using a xenon lamp (150 W) to perform an optical bridge reaction.

 (c) Emission layer: Thickness is determined by casting using a toluene solution of PPV.

3S A 50 OA PPV cast film was formed.

 (d) Cathode: A1 was formed to a thickness of 1000 A by vacuum evaporation. An element having an area of 5 millimeters was produced.

 The voltage-current and voltage-brightness of the obtained organic EL device were measured at room temperature in the atmosphere, and the results are shown in FIG. 7A.

Orange color light emission was confirmed by applying a voltage of 3 V or more with the IT0 electrode as the positive electrode. The maximum luminance at 11 V was 8000 cd / m ² , and the light emission efficiency at the time of light emission at 300 cd / m ² was 1.51 mW.

In addition, as shown in FIG. 8A, the half-life at a luminance of 100 cd / i ² under vacuum conditions was 1000 hours or more, confirming excellent durability.

<Comparative Example 4>

 A carbazole dendrimer having the same thickness is cast, dried without forming photocrosslinking to form a hole transport layer, and then spin-cast using a toluene solution of PPV as a light emitting layer. The measurement results of the EL element formed and the back electrode were prepared are shown in FIGS. 7b and 8b. In devices that have not been photocrosslinked, the hole transport layer may be solubilized when the light emitting layer is cast. Either create the light emitting layer by vacuum evaporation or use a solution caster that uses a solvent that does not erode the hole transport layer. It was suggested that it is desirable to use a cross-linking method or to prepare a cross-linking method. Industrial applicability

As described above in detail, according to the present invention, a phenylazomethine dendron subunit having a metal accumulating ability and / or a carbazole dendron subunit having an excellent hole transporting property are provided. Provided is a material for an organic EL device, having a thin film easily formed by a solution casting method.

 By using such a material for an organic EL device, a dense and high-strength film having improved morphological characteristics at the interface can be formed. Such a thin film is electrochemically stable and exhibits high heat resistance. In addition, by using such a material for an organic EL device for the hole transport layer or the light emitting layer, it is expected that the luminous efficiency of the organic EL device is improved, the open-circuit voltage is reduced, and the drive voltage is further reduced. High usefulness.

Claims

The scope of the claims

1 · At least the following equation (I)

(W) _k —— X—— (Υ) ι (I)

 (Where X is carbon atom, nitrogen atom, amine derivative, benzene and its derivative, heterocycle and its derivative, porphyrin and its derivative, fluorinine and its derivative, cyclam and its derivative, and vinyl polymer and A core site selected from the group consisting of derivatives thereof, wherein Y and W are the same or different, and are represented by the following formula (II):

(However, N is a nitrogen atom, and R ¹ is a substituent selected from the group consisting of an alkylene group, a phenylene group and a heterocyclic group which may have a substituent, or absent. R ² is a phenyl group optionally having one or more substituents, and m is an integer of 1 to 6.

Phenylazomethine dendrite subunit represented by the following formula or (III)

(However, N is a nitrogen atom and n is an integer of 1 to 6)

, Where 1 is an integer representing the number of Y bound to X, and k is an integer representing the number of W bound to X)

A material for an organic EL device, comprising a compound represented by the formula:

2. The following equation (IV)

(However, X is selected from the group consisting of a carbon atom, a nitrogen atom, an amine derivative, benzene and its derivatives, a heterocycle and its derivatives, porphyrin and its derivatives, furocyanine and its derivatives, and cyclam and its derivatives. N is a nitrogen atom; R ¹ Is a substituent selected from the group consisting of an alkylene group which may have a substituent, a phenylene group and a heterocyclic group, or may be absent; and R ² is one or more substituents. And m is an integer of 1 to 6, and 1 is an integer of 1 to 6 representing the number of dendron sap units bonded to X.

2. The material for an organic EL device according to claim 1, comprising a phenylazomethine dendrimer represented by the following formula:

3. The following equation (V)

 (Where N is a nitrogen atom, n is an integer from 1 to 6, and k is an integer representing the number of dendron subunits bonded to X) The material for an organic EL device according to claim 1, which is characterized in that:

4. Next equation (VI)

(However, N is a nitrogen atom, X is a carbon atom, a nitrogen atom, an amine derivative, a benzene and its derivative, a heterocycle and its derivative, a porphyrin and its derivative, a phthalocyanine and its derivative, and a cycle and its derivative. R ¹ is a substituent selected from the group consisting of an optionally substituted alkylene group, a phenylene group and a heterocyclic group, or is present. R ² is a phenyl group which may have one or more substituents; m is an integer of 1 to 6, n is an integer of 1 to 6; k and 1 are Is an integer that satisfies the condition 1 ≤ k + 1 ≤ 6, which represents the number of dendron subunits each connected to X)

2. The material for an organic EL device according to claim 1, comprising a phenylazomethine-asymmetric dendrimer represented by the following formula: 5 X is at least the following equation (VI I)

 (However, N is a nitrogen atom, S is a sulfur atom, O is an oxygen atom, and Ar is benzene, thiophene, pyrrole, or 1,3,4-oxadiazole.)

5. The material for an organic EL device according to claim 1, having a structure selected from the group consisting of compounds (a) to (m) represented by:

X is the following formula (VIII)

-rl ゥ —H i GH2 rl-(νπΐ) (Where p and ci are integers of 1 or more representing the degree of polymerization).

7 · Next equation (IX)

(However, N is a nitrogen atom, and R ¹ is a substituent selected from an alkylene group, a phenylene group and a heterocyclic group which may have a substituent, or may be absent. R ² is a phenyl group optionally having one or more substituents, m is an integer of 1 to 6, n is an integer of 1 to 6, p and q are one or more of degrees of polymerization. Is an integer)

2. The material for an organic EL device according to claim 1, comprising a phenylazomethine-carpazole copolymer represented by the following formula:

8. The following equation (X)

(However, N is a nitrogen atom, and R ¹ has a substituent. R ² is a substituent selected from the group consisting of an alkylene group, a phenylene group and a heterocyclic group or may be absent, and R ² is a phenyl group optionally having one or more substituents. And m is an integer from 1 to 6)

And a vinylazomethine monomer represented by the following formula (XI)

 (Where N is a nitrogen atom and n is an integer of 1 to 6). The method for producing a material for an organic EL device according to claim 7, wherein the vinyl carbazole monomer is reacted.

9. An organic EL device comprising at least an anode, a hole transport layer formed on the anode, a light-emitting layer in contact with the hole transport layer, and a cathode in contact with the light-emitting layer, wherein a hole transport layer or light emission is provided. An organic EL device comprising a layer comprising a thin film containing the material for an organic EL device according to claim 1.

10. The organic EL device according to claim 9, wherein the hole transport layer or the light emitting layer comprises a thin film containing a metal salt together with the material for an organic EL device according to any one of claims 1 to 7.

11. The organic EL device according to claim 8, wherein the hole transport layer or the light emitting layer is formed of a thin film obtained by photocrosslinking the material for an organic EL device according to any one of claims 1 to 7. 12. A light-emitting or display device comprising the organic EL device according to any one of claims 9 to 11.