JPH10312073A - El device, photoconductive image forming member, and manufacture of star burst aromatic amine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance heat stability and movement stability by incorporating the star burst aromatic amine compound in a positive hole introducing and transferring zone. SOLUTION: The EL device comprises a substrate, a cathode, a positive hole introducing and transferring zone or layer, and an anode laminated in this order. This zone contains the star burst aromatic amine compound represented by formula I in which N is a nitrogen atom; each of A<1> -A<3> is a 6-24 C biaryl, such as biphenyl or bitolyl group; each of Ra -Rc is one of functional groups represented by formulae II-IV in which N is same as before; each of Ar<1> and Ar<2> is a 6-24C aryl group having a halogen and C atoms and an alkoxy group; and each of R1 -R8 is an H or halogen atom, or a 1-10C hydrocarbon or 1-6C alkoxy group; and X is a 2-20C alkylene group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates generally to electroluminescent (EL) devices, photoconductive imaging members and methods for producing starburst aromatic amines.
More specifically, the present invention relates to an organic EL device having improved thermal stability and operation stability, and thus improved durability.
This device uses a novel hole transporting composition containing a starburst aromatic amine capable of forming an amorphous film having excellent thermal stability. Also disclosed is a method for producing a starburst aromatic amine.

The amine can be selected for photoconductive imaging members, especially layered imaging members, such as the photoconductive imaging member shown in US Pat. No. 4,265,990. Starburst amines function primarily as charge transport components or molecules in the component.

[0003]

BACKGROUND OF THE INVENTION Hole transport materials containing certain aromatic tertiary amines facilitate hole injection and hole transport processes,
Therefore, although it is generally known to improve the device performance of organic EL devices, these materials are thermally and morphologically unstable as hole injection and transport thin film layers, so that organic EL devices are practically used. The operating life of the device was short and the durability was poor.

To overcome the above-mentioned complications and difficulties associated with organic EL devices, the present invention provides a class of novel hole transports that can form amorphous thin films with enhanced thermal and morphological stability. Provided are a material and an organic EL device manufactured from the material. This device has excellent hole injection characteristics, high EL efficiency, and excellent operation stability and improved device durability.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic EL device having improved thermal stability and operation stability.

Another object of the invention is to provide, for example, about 5 to about 1
An object of the present invention is to provide an improved EL device that exhibits high electroluminescence efficiency at relatively low operating voltages, such as 9.5V and less than about 20V.

It is yet another object of the present invention to provide an improved EL device comprising an anode, a cathode, and an organic electroluminescent intermediate between the anode and the cathode, wherein the organic EL device comprises an organic EL device. The luminescent intermediate has at least one layer containing a starburst aromatic amine hole transport component.

It is another object of the present invention to provide certain starburst aromatic amine compounds for EL devices and a method for producing the same. It has a high glass transition temperature which exceeds

It is a further object of the present invention to have excellent hole injecting and transporting ability and excellent thermal stability, and can be easily vacuum deposited as a thin film and used as a hole injecting and / or transporting component in EL devices. To provide an EL device having a starburst aromatic amine.

It is a further object of the present invention to provide a method for producing a starburst amine and a photoconductive imaging member thereof.

It is another object of the present invention to provide certain starburst aromatic amine compounds for photoconductive members and a method for producing the same. It has a high glass transition temperature exceeding ℃.

[0012]

SUMMARY OF THE INVENTION In an embodiment, the present invention provides a hole injection and hole transport zone or anode containing a starburst aromatic amine between an anode, a cathode, and the anode and cathode. The invention relates to a layered organic EL device comprising a layer, and an organic luminescent intermediate consisting of an electron injection and transport zone or layer, said device having improved thermal stability, long device lifetime, high electroluminescence efficiency, excellent positive luminescence. It has a number of advantages, such as hole injection and electron transport properties, and the device can be easily manufactured using vacuum deposition techniques. The EL devices of the present invention have improved thermal and operational stability and exhibit excellent device durability at about 50 ° C or higher, for example, about 50 to about 100 ° C. Further, the present invention relates to an EL device in which a support substrate, an anode, a hole injection and transport zone or layer, an electron injection and transport zone or layer, and a cathode are stacked in this order, and the hole injection and transport zone has the following structural formula ( It contains a starburst aromatic amine represented by I).

[0013]

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In the formula (I), N is nitrogen; and A ^{1 to} A ³ are, for example, 12 to about 6
Biaryl having 0 carbon atoms; R _a , R _b and R
_c is one of the functional groups of the structural formulas (A) to (C) shown below.

[0015]

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In the formulas (A) to (C), N is nitrogen; Ar ¹ and Ar ² are, for example, phenyl, tolyl, halo such as chlorophenyl, alkoxy such as methoxyphenyl, biphenyl or naphthyl. 6 to about 2
An aryl group having 4 carbon atoms; R ₁ -R ₈ are
X represents an oxygen atom, a sulfur or a substituent selected from the group consisting of, for example, a hydrocarbon group having 1 to 10 carbon atoms and an alkoxy group having, for example, 1 to 6 carbon atoms; Represents an atom or alkylene having about 2 to about 20 carbon atoms, such as a methylene group.

[0017]

More particularly, FIG. 1 shows an EL device comprising a support substrate 2, for example glass, an anode 3, a vacuum-deposited hole containing a starburst aromatic amine. The organic light emitting diode includes a low work function metal of the injection and hole transport layer 4, the electron injection and electron transport layer 5, and the cathode 6 in contact therewith. In an EL device, a luminescent zone in which electron-hole recombination occurs and emits light surrounds the hole transport layer and / or the electron transport layer. If desired, a fluorescent material capable of emitting light after electron-hole recombination can be added to the luminescent zone where the charge transport component functions as a host material.

In an embodiment, the hole injection layer can function to perform hole injection, hole transport, or a combination thereof, and the electron injection layer can also perform electron injection, electron injection. Transport or a combination thereof can be performed. In the embodiment, the zones 4 and 5 can be replaced with another layer. That is, instead of the zones 4 and 5, the hole injection layer 4a is arranged so as to be in contact with the anode, and the starburst hole transport layer 4b can be arranged thereon. And place
The electron injection layer 5b can be arranged thereon.

Examples of the supporting substrate include a polymer component, glass, polyester such as MYLAR (registered trademark), polycarbonate, polyacrylate, polymethacrylate, polysulfone, quartz and the like. For example, other substrates may be selected provided that they have essentially no function and can support other layers. The thickness of the substrate can be, for example, about 25 to about 1,000 μm or more, especially about 50 to about 6,000 μm, depending on the structural requirements of the device, for example.

Examples of anodes adjacent to the substrate include positive charge injection electrodes such as indium tin oxide, tin oxide, gold, platinum; those having a work function equal to or greater than about 4 eV, eg, about 4 to about 8 eV. And π-conjugated polymers such as polyaniline and polypyrrole. The thickness of the anode can be in the range of about 10-5,000 °, but the preferred range is determined by the optical constants of the anode material. One suitable thickness range is from about 20 to about 1,000.
0 °.

The hole transport layer 4 including the transport layer for the photoconductive imaging member is as shown in the text and has the following structural formula
It contains a starburst aromatic amine represented by (I).

[0022]

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In the formula (I), the substituents are as shown in the text. For example, A ^{1 to} A ³ each represent a biaryl having, for example, 12 to about 60, preferably 12 to about 40 carbon atoms, which biaryl can be substituted, more particularly a biphenyl group or a vitrile Group. R _a , R _b and R _c have the following structural formulas (A) to (C)
Represents one of the following functional groups.

[0024]

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In the formulas (A) to (C), N is nitrogen; other substituents are as shown in the text, for example, Ar ¹ and A
r ² is a phenyl group, a tolyl group, chlorophenyl group, a methoxyphenyl group, such as biphenyl or naphthyl group, 6 to about 30, preferably an aryl group having from 6 to about 24 carbon atoms; R _{1 to} R ₈ are each a substituent selected from the group consisting of hydrogen, halogen or a hydrocarbon containing 1 to about 10 carbon atoms and an alkoxy containing 1 to 6 carbon atoms; Represents an alkylene having 2 to about 20 carbon atoms such as an oxygen atom, a sulfur atom or a methylene group. This new class of starburst aromatic amines offers many advantages as described herein, these compounds being vacuum depositable and capable of forming thin films, which generally have high glass transition temperatures. Furthermore, these starburst amines can be selected as the hole transport component in layered photoconductive imaging members, and these members are selected for xerographic (electrophotographic) imaging methods, including digital methods. be able to.

Starburst aromatic amines are prepared by converting primary aryl amines (II) with aryl iodides (III) and (IV) in the presence of a copper ligand catalyst as shown in Scheme 1 below. U.S. Pat. Nos. 609,259, 608,858 and 60, all of which are hereby incorporated by reference and are hereby incorporated by reference in their entirety, as well as direct Ullmann condensation.
No. 7,953. Substituents such as Ra in Scheme 1 are as set forth in the text.

[0027]

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More specifically, a method for producing a starburst amine of the structural formula (I) comprises the steps of converting a primary arylamine (II) to an aromatic iodide compound of the structural formula (III) Reacting with an iodide compound, the reaction being accomplished in the presence of a coordinated copper catalyst, wherein the ligand is a monodentate tertiary tertiary compound.
It is selected from the group consisting of amines and bidentate tertiary amines.
This reaction generally involves a coordinated copper catalyst, such as 1,10-
Phenanthroato copper (1) (monovalent) chloride, dipyridino copper (1) chloride, 1,10-phenanthrolate copper (1) bromide, dipyridino copper (1) bromide,
1,10-phenanthrolate copper (1) chloride, 1,
About 100 to about 1 in the presence of 10-phenanthroato copper (1) bromide or dipyridino copper (1) bromide
This is achieved in an inert solvent such as toluene, xylene, mesitylene, dodecane at a temperature of 90 ° C, preferably about 120 to about 160 ° C. The catalyst selected is important, and in embodiments comprises copper containing an organic ligand, the ligand being a monodentate tertiary amine and a bidentate tertiary tertiary as shown herein.
It is selected from the group consisting of amines. More specifically, the ligand is a copper catalyst or compound, such as (1,10-phenanthorato) Cu (X) and bis (pyridinato) Cu (X), where X is a halide such as chloride. is there.
The coordination of the copper salt greatly increases the efficiency of the catalyst and can result in very rapid reactions, generally at low temperatures, for about several hours.

The important catalysts selected for the process of the present invention are as indicated in the text, and in embodiments, chloride,
Consisting of coordinated copper salts, including copper (1), including halide salts such as bromide, iodide and fluoride, wherein the ligand is a monodentate tertiary amine or bidentate such as 1,10-phenanthroline or pyridine It is a tertiary amine. The amount of catalyst selected will vary, and generally the catalyst will be, for example, from about 1 to about 20 mole% of the reactants, preferably from about 5 to about
It is used in an effective amount, such as about 12 mole%. Examples of hypothetical structures of copper catalysts are as follows, where X represents a halide such as chloride or bromide.

[0030]

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The catalyst is prepared by adding a copper salt such as cuprous chloride to 1,1
It can be prepared by reacting with a suitable ligand such as 0-phenanthroline, which reaction is achieved by heating, for example, at about 70 to about 125 ° C. It is believed that the resulting reaction mixture can be cooled and the product catalyst isolated, for example, by filtration.
The catalyst is preferably prepared in a system.

Specific examples of the starburst aromatic amines of the present invention include, as shown in the following structural formula, (1) tris [4 ′-(phenyl-m-tolylamino) -1,1′-
Biphenyl-4-yl] amine, (2) N, N-bis (4′-di-m-tolylamino-1,1′-biphenyl-4-yl] -N ′, N′-diphenylbenzidine,
(3) tris [4 ′-(m-methoxydiphenylamino) -1,1′-biphenyl-4-yl] amine,
(4) Tris [4 '-(diphenylamino) -1,1'
-Biphenyl-4-yl] amine, (5) tris [4 '
-(Carbazol-9-yl) -1,1'-biphenyl-4-yl] amine, (6) tris [4 '-(1-naphthylphenylamino) -1,1'-biphenyl-4-yl] amine , (7) N, N-bis [4 '-(phenyl-
m-tolylamino) -1,1'-biphenyl-4-yl] -N'-phenyl-N'-m-tolyl-3,3'-
Dimethylbenzidine, (8) N, N-bis (4'-diphenylamino-1,1'-biphenyl-4-yl)-
N'-phenyl-N'-m-tolyl-3,3'-dimethylbenzidine, (9) N, N-bis (diphenylamino-1,1'-biphenyl-4-yl) -N'-phenyl-N '-M-tolylbenzidine, (10) N, N-bis [4'-(di-m-tolylamino) -1,1'-biphenyl-4-yl] -N'-phenyl-N'-p-tolyl Benzidine, (11) tris [4 '-(8H-10H-
(Acridin-10-yl) -1,1′-biphenyl-4
-Yl] amine, (12) tris [4 '-(9,9-dimethyl-9H-10H-acridin-10-yl)-
1,1′-biphenyl-4-yl] amine, (13) tris [4′-phenoxazin-10-yl-1,1′-
Biphenyl-4-yl] amine, (14) tris [4 ′
-Phenothiaxazin-10-yl-1,1'-biphenyl-4-yl] amine, (15) N, N-bis [4 '
-(Phenyl-m-tolylamino) -1,1'-biphenyl-4-yl] -4 '-(carbazol-9-yl)
-1,1'-biphenyl-4-amine, (16) N, N
-Bis [4 '-(carbazol-9-yl) -1,1'
-Biphenyl-4-yl] -N'-phenyl-N'-m
-Tolylbenzidine, (17) N, N-bis [4'-
(1-Naphthylphenylamino) -1,1′-biphenyl-4-yl] -4 ′-(carbazol-9-yl)-
1,1'-biphenyl-4-amine, (18) N, N-
Bis [4 '-(9H-10H-acridin-10-yl) -1,1'-biphenyl-4-yl] -4'-(9
H-10H-acridin-10-yl) -3,3'-dimethyl-1,1'-biphenyl-4-amine and the like.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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In accordance with the present invention, the entire hole injection and hole transport zone can be formed from a single layer containing the aforementioned starburst aromatic amine. Further, it may be beneficial for the hole injection and transport zone to contain a starburst aromatic amine in combination with a porphyrin compound or tetraarylamine compound. For example, about 75 to about 95
When an effective amount of a starburst aromatic amine, which is% by weight, is used in combination with the porphyrin compound, the porphyrin compound may be a compound positioned as a layer disposed between the anode and the starburst aromatic amine layer. it can. Examples of porphyrin compounds include porphyrin,
1,10,15,20-tetraphenyl-21H, 23
H-porphyrin copper (II), copper phthalocyanine, copper tetramethyl phthalocyanine, zinc phthalocyanine, titanium oxide phthalocyanine, magnesium phthalocyanine and the like.

In forming the hole injection and transport zone,
When a starburst aromatic amine compound is selected in combination with a triarylamine, tetraarylamine, or the like, the amine is disposed, for example, as a layer having a thickness of about 200 mm, and the amine is disposed between the starburst aromatic amine layer and the electron injection and transport zone. Be placed. Examples of aromatic tertiary amines are as set forth in the related application filed herewith, together with the application cited herein, and include the following structural formula:

[0044]

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In the formula, Ar ^{1 to} Ar ⁴ are, for example, 6 to about 3
An aryl group having 0 carbon atoms, for example, each selected from phenyl, tolyl, xylyl, naphthyl, 4-biphenylyl and the like; P is an arylene such as a phenylene group; n is an integer of 1-4. A specific example is
N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine, N, N'-diphenyl-N, N'-bis (4- Methylphenyl) -1,1′-biphenyl-4,4′-diamine, N, N, N ′, N′-tetra-p-tolyl-1,
1'-biphenyl-4,4'-diamine, N, N'-di-1-naphthyl-N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine, N, N'-di -2-naphthyl-N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine, N, N'-di-1-naphthyl-
N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine, N, N'-di-1-naphthyl-N, N'-bis (4-methylphenyl) -1,
1'-biphenyl-4,4'-diamine, N, N'-di-4-biphenylyl-N, N'-diphenyl-1,1 '
-Biphenyl-4,4'-diamine, N, N'-di-4
-Biphenylyl-N, N'-bis (4-methylphenyl) -1,1'-biphenyl-4,4'-diamine and the like.

The electron injection and transport zone in the EL device of the present invention can contain any conventional electron injection and transport compounds. Examples of useful electron transporting compounds are fused ring luminescent materials such as anthracene, phenanthracene, pyrene, perylene and the like as shown in US Pat. No. 3,172,862; 1,4-diphenylbutadiene and tetraphenylbutadiene; Butadiene, and U.S. Patent Nos. 4,356,429 and 5,516,
577, etc .; and optical brightness materials as disclosed in U.S. Pat. No. 4,539,507.

Particularly preferred electron transporting materials are the metal chelates of 8-hydroxyquinoline disclosed in US Pat. Nos. 4,539,507, 5,151,629 and 5,150,006. Examples of metal chelate compounds include tris (8-hydroxyquinolinate) aluminum (AlQ3), tris (8-hydroxyquinolinate) gallium, bis (8-hydroxyquinolinate) magnesium, bis (8-hydroxyquinolinate) ) Zinc, tris (5-methyl-8-hydroxyquinolinato) aluminum, tris (7-propyl-8-quinolinolato) aluminum, bis [benzo {f} -8-quinolinate] zinc, bis (10-hydroxybenzo) [H] Quinolinate) beryllium, bis (2-methylquinolinolato) aluminum (III) -μ-oxo-bis (2-methyl-8-quinolinolato) aluminum (II)
I), bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) (para-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (2- Naphthalate) including aluminum.

Another type of suitable electron injecting and transporting compound is a metal thioxinoid compound. Examples of the metal thioxinoid compounds include bis (8-quinolinethiolate) cadmium, bis (8-quinolinethiolate) cadmium, tris (8-quinolinethiolate) gallium, and tris (8-quinolinethiolate) gallium.
Quinolinethiolato) indium, bis (5-methylquinolinethiolato) zinc, tris (5-methylquinolinethiolato) gallium, tris (5-methylquinolinethiolato) indium, bis (5-methylquinoline) Aurato) cadmium, bis (3-methylquinolinethiolate) cadmium, bis (5-methylquinolinethiolate) zinc, bis [benzo {f} -8-quinolinethiolate] zinc, bis [3-methylbenzo {F} -8-quinolinethiolato] zinc, bis [3,7-dimethylbenzo {f} -8-quinolinethiolato] zinc and the like.

In an embodiment of the present invention, the overall thickness of the organic luminescent intermediate, including the hole injection and transport zone 4 and the electron injection and transport zone 5, is under a relatively low voltage applied across the electrodes. For example, less than about 1 [mu] m, such as about 0.05 to about 1 [mu] m, is preferred so that a current density adapted to effective light emission at the substrate can be maintained. Suitable thicknesses for the hole injection and transport layers range from about 50 to about 2,000, preferably about 400 to 1,000. Similarly, the thickness of the electron injection and transport layer can range from about 50 to about 2,000, preferably about 400 to 1,000.

The cathode 6 can contain any metal, including high or low work function metals. For example, about 4 eV
A low work function metal that is less than about 2 eV to about 4 eV;
Cathodes obtained from the combination with at least one second metal further provide advantages such as improved device performance and stability. Suitable ratios of low work function metal to second metal range from about 0.1 to about 99.9% by weight, and in embodiments can range from about 1 to about 90% by weight. Examples of low work function metals include alkaline metals,
It includes Group 2A or Group III metals including alkaline earth metals, rare earth metals and actinide metals. Lithium, magnesium and calcium are particularly preferred.

The thickness of the cathode 6 is, for example, about 10 to about 5,0.
00, more particularly from about 50 to about 250. The Mg: Ag cathode of U.S. Pat.
One preferred cathode structure. Another suitable cathode structure is described in U.S. Pat. No. 5,429,884, in which the cathode is formed from a lithium alloy with other high work function metals such as aluminum and indium. The disclosure of each patent is incorporated herein by reference in its entirety.

Both the cathode 6 and anode 3 of the organic EL device of the present invention can take any convenient form. A thin conductive cathode layer of, for example, 200 ° can be coated on a light transmissive substrate, for example a transparent or almost transparent glass plate or a plastic film. The EL device can include a light-transmissive anode 3 formed of tin oxide or indium tin oxide coated on a glass plate. Also, for example, less than 200 °, for example, about 50 to about 200 °,
A very thin, light-transmissive metal anode, such as gold or palladium, can also be selected. Further, a transparent or translucent thin conjugate polymer, for example, 200 °, such as polyaniline or polypyrrole, can be selected. For example, any light transmissive polymer film having a thickness of about 50 to about 200 ° can be selected as the substrate. Further, the anode 3 and the cathode 6
Is shown in U.S. Pat. No. 4,885,211.

The photoconductive imaging member comprises a support substrate, such as MYLAR, a polymer, and a metal such as aluminum, and a resin binder, such as phthalocyanine, selenium, hydroxygallium phthalocyanine, titanyl phthalocyanine, perylene, on the substrate. A photogenerating layer containing a known photogenerating pigment that can be dispersed in
The layer in contact with and overlying the photogenerating layer is a charge transport layer containing a starburst amine, as shown herein and dispersible in a resin binder. Resin binder,
The thickness of each layer, the amount of components selected for each layer, and other layers present, etc., are described in U.S. Pat. Nos. 4,265,990, 4,585,884, 4,584,253, 563,408, 4,587,189, 4,555,463, 5,153,313, 5,614,493, and 5,189,155. Shown in US patents. For example, MYLA
The R support substrate is coated with a photogenerating layer containing 100% or 95% by weight of a photogenerating pigment and 5% by weight of a resin binder, and a charge transport layer containing a starburst amine shown in the text. Is coated on this.

[0054]

EXAMPLES Example I Tris [4 '-(phenyl-m-tolylamino) -1,1
Synthesis of 1'-biphenyl-4-yl] amine-Compound
(1) 25 with mechanical stirrer, reflux condenser and argon inlet
A 0 ml 3-neck round bottom flask was purged with argon and then N-phenyl-Nm-tolylbenzidine (8.0
g, 0.023 mol), 4'-iodo-N-phenyl-
Nm-tolyl-4-aminobiphenyl (17.5 g,
0.038 mol), xylene (15 ml), 1,10-
Phenanthroline (0.34 g, 1.9 mmol), cuprous chloride (0.188 g, 1.9 mmol) and potassium hydroxide flakes (17.06 g, 0.3 mol) were charged. The reaction mixture was heated under an argon atmosphere and refluxed using an oil bath and the reaction was allowed to proceed at this temperature, after which time chromatographic analysis indicated that the reaction was complete after about 6 hours. The oil bath was removed and then 100 ml of toluene and 25 ml of water were added and stirred efficiently. The resulting biphasic mixture was transferred to a separatory funnel and the layers were separated. The organic phase was washed with water and treated with 25 g of alumina under argon. After separation of the alumina by filtration, the organic phase was evaporated to remove most of the toluene. The above product, compound (1), was obtained by recrystallizing the residue from cyclohexane. Yield 1
2.3 g, melting point 234.28 ° C, Tg 134 ° C.

Example II N, N-bis (4'-di-m-tolylamino-1,1 '
-Biphenyl-4-yl) -N ', N'-diphenylbe
Synthesis of Ndidine-Compound (2) 25 with mechanical stirrer, reflux condenser and argon inlet
A 0 ml 3-neck round bottom flask was purged with argon and then N, N-diphenylbenzidine (6.056 g,
0.009 mol), 4'-iodo-N-phenyl-N-
m-tolyl-4-aminobiphenyl (6.734 g,
0.015 mol), xylene (10 ml), 1,10-
Phenanthroline (0.135 g, 0.75 mmol), cuprous chloride (0.074 g, 0.75 mmol)
And potassium hydroxide flakes (6.73 g, 0.12 mol). The reaction mixture was heated under an argon atmosphere and refluxed using an oil bath and the reaction was allowed to proceed at this temperature, after which time chromatographic analysis indicated that the reaction was complete after about 6 hours. The oil bath was removed and then 100 ml of toluene and 10 ml of water were added and stirred efficiently. The resulting biphasic mixture was transferred to a separatory funnel and the layers were separated. The organic phase was washed with water and treated with 20 g of alumina under argon. After separation of the alumina by filtration, the organic phase was evaporated to remove most of the toluene. The above product was obtained by recrystallizing the residue from cyclohexane. Yield 8.75 g,
The melting point was 254.5 ° C and the Tg was 128 ° C.

Example III Tris [4 '-(m-methoxydiphenylamino)-
Synthesis of 1,1′-biphenyl-4-yl] amine
Product (3) 25 with mechanical stirrer, reflux condenser and argon inlet
A 0 ml 3-neck round bottom flask was purged with argon, then Nm-methoxyphenyl-N-phenylbenzidine (6.2 g, 0.017 mol), 4'-iodo-N-.
m-methoxyphenyl-N-phenyl-4-aminobiphenyl (13.49 g, 0.028 mol), xylene (15 ml), 1,10-phenanthroline (0.25
2 g, 1.4 mmol), cuprous chloride (0.139 g,
1.4 mmol) and potassium hydroxide flakes (12.
57 g, 0.224 mol). The reaction mixture was heated under an argon atmosphere and refluxed using an oil bath and the reaction was allowed to proceed at this temperature, after which time chromatographic analysis indicated that the reaction was complete after about 8 hours. The oil bath was removed and then 100 ml of toluene and 25 ml of water were added and stirred efficiently. The resulting biphasic mixture was transferred to a separatory funnel and the layers were separated. The organic phase was washed with water and treated with 20 g of alumina under argon. After separation of the alumina by filtration, the organic phase was evaporated to remove most of the toluene. The crude product was further chromatographed on silica gel using hexane-toluene 10: 1 as eluent to give pure tris [4- (3-methoxydiphenylamino) -1,1 ′.
-Biphenylyl] amine was obtained as an amorphous powder. The yield was 10.1 g.

Example IV Tris [4 '-(diphenylamino) -1,1'-biph
Synthesis of phenyl-4-yl] amine-compound (4) 25 equipped with mechanical stirrer, reflux condenser and argon inlet
A 0 ml 3-neck round bottom flask was purged with argon and then N, N-diphenylbenzidine (4.95 g, 0.9 g).
0147 mol), 4'-iodo-N, N-diphenyl-
4-aminobiphenyl (11.0 g, 0.0246 mol), xylene (15 ml), 1,10-phenanthroline (0.22 g, 1.22 mmol), cuprous chloride (0.122 g, 1.22 mmol) And potassium hydroxide flakes (11.04 g, 0.197 mol). The reaction mixture was heated under an argon atmosphere and refluxed using an oil bath to allow the reaction to proceed at this temperature.
Chromatographic analysis indicated that the reaction was complete after about 6 hours. The oil bath was removed and then 100 ml of toluene and 20 ml of water were added and stirred efficiently. The resulting biphasic mixture was transferred to a separatory funnel and the layers were separated. The organic phase was washed with water and treated with 25 g of alumina under argon. After separation of the alumina by filtration, the organic phase was evaporated to remove most of the toluene. The above product was obtained by recrystallizing the residue from cyclohexane. Yield 6.9 g, mp 283.
97 ° C and Tg 141 ° C.

Example V Tris [4 '-(carbazol-9-yl) -1,1'
Synthesis of -biphenyl-4-yl] amine-compound (5) 25 equipped with mechanical stirrer, reflux condenser and argon inlet
A 0 ml 3-neck round bottom flask was purged with argon, then 4 '-(9-carbazolyl) -4-aminobiphenyl (5.1 g, 0.0153 mol), 4- (9-carbazolyl) -4. '-Iodo-1,1'-biphenyl (1
1.394 g, 0.0255 mol), 1,3,5-trimethylbenzene (15 ml), 1,10-phenanthroline (0.23 g, 1.28 mmol), cuprous chloride (0.126 g, 1.28 mol) Mmol) and potassium hydroxide flakes (11.45 g, 0.204 mol). The reaction mixture was heated under an argon atmosphere and refluxed using an oil bath to allow the reaction to proceed at this temperature.
Chromatographic analysis indicated that the reaction was complete after about 12 hours. The oil bath was removed, then 150 ml of toluene and 15 ml of water were added and stirred efficiently. The resulting biphasic mixture was transferred to a separatory funnel and the layers were separated. The organic phase was washed with water and treated with 20 g of alumina under argon. After separation of the alumina by filtration, the organic phase was evaporated to remove most of the toluene. The residue was chromatographed on silica gel using cyclohexane-dichloromethane 10: 1 as eluent to give 2.1 g of the product compound. Melting point 28
3.13 ° C.

EXAMPLE VI An organic EL was prepared as shown in a related application filed herewith with the present application incorporated herein by reference and for example by the following method. 1. Approximately 1 mm thick glass coated with 500 ° thick indium tin oxide (ITO) was washed with a commercial detergent, rinsed with deionized water, and dried in a vacuum oven at 60 ° C. for 1 hour. Immediately before use, the glass was treated with UV ozone for 0.5 hour. 2. The ITO substrate manufactured as described above was placed in a vacuum evaporation chamber. The deposition rate and layer thickness were controlled by an Inficon model IC / 5 controller. About 5
Example I at a pressure slightly below × 10 ^-6 Torr
Evaporate the starburst amine such as ~ IV from the electrically heated tantalum boat and leave 80
A hole transport layer of nm (800 °) was deposited. The deposition rate of the amine compound was controlled at 0.6 nm / sec. 3. Tris (8-hydroxyquinolinate) aluminum was deposited on the transport layer 2 at a deposition rate of 0.6 nm / sec to form an 80 nm electron injection and transport layer. 4. Individually controlled, containing Mg and Ag respectively
By simultaneously evaporating from two tantalum boats, a 100 nm alloy of magnesium and silver
Per second at an overall deposition rate of 3 μm / sec. A typical composition had a 9: 1 atomic ratio of Mg to Ag. Finally, a 200 nm layer of silver is deposited on the M layer mainly to protect the reactive Mg from ambient moisture.
g: Coated on Ag cathode.

The device manufactured as described above was stored in a drying chamber continuously purged with nitrogen gas. The performance of the device was evaluated by measuring the current-voltage characteristics and the light output in the direct current measurement. Keithley (Ke
ithley) Model 238 High Current Source Measurement System (High Current
The current-voltage characteristics were determined using a Source Measure Unit). The ITO electrode was always connected to the positive terminal of the power supply.
At the same time, the light output from the device was monitored by a silicon photodiode.

At a constant current density of 33 mA / cm ² ,
The performance characteristics of these devices were evaluated. Due to the sustained operation time when the light intensity is reduced to half the level of the initial intensity,
The operating life was measured. The initial light intensity and operating lifetime of devices using starburst amine compounds (1)-(5) are summarized in the table below.

[0062]

[Table 1]

These results show that a high level of light output can be sustained in an organic EL device containing a starburst aromatic amine hole transport component. Furthermore, the current-light intensity characteristics of the organic EL device using the starburst aromatic amine compound (2) as the hole transport layer did not change even after being exposed to a temperature of 60 ° C. for 72 hours.

As indicated herein, a photoconductive layered device can be manufactured, more particularly as shown in the related US patents incorporated herein by reference, in which the starburst amine comprises a charge transport component. Can function as

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing one embodiment of an EL device of the present invention.

[Explanation of symbols]

 2 support substrate 3 anode 4 hole injection and hole transport layer 5 electron injection and electron transport layer 6 cathode

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 279/26 C07D 279/26 C09K 11/06 645 C09K 11/06 645 655 655 H05B 33/14 H05B 33/14 B 33/22 33/22 D // C07D 209/86 C07D 209/86 (72) Inventor Shoan Cie L5 El 5K8 Canada Mississauga Colonial Drive, Ontario 3220 (72) Inventor Ben S. On Canada El 5 El 4 Buoys 9 Ontario Mississauga Harvey Crescent 2947 (72) Inventor Zorandy. Popovic El 5 El 2 Zet 8 Canada Mississauga Sawmill Valley Drive, Ontario 3349 (72) Inventor Army Ho Canada El 5 El 5 B 1 Ontario Mississauga Marcaster Road 3407 (72) Inventor Pin Liu Canada El 5 El 1 Jay 7 Ontario Mississauga Mississauga Road North Number 12-3349

Claims (9)

[Claims] 1. An electroluminescent (EL) device containing a starburst aromatic amine represented by the following structural formula (I), wherein N is nitrogen, and A ¹ to A ³ represents a biaryl, respectively,
_a , R _b and R _c represent one of the functional groups of the following structural formulas (A) to (C), respectively, and have the formulas (A) to (C)
Wherein N is nitrogen, Ar ¹ and Ar ² are each aryl, and R _{1 to} R ₈ are hydrogen, halogen, hydrocarbon,
And EL is a substituent individually selected from the group consisting of: and alkoxy, wherein X is oxygen, sulfur or alkylene. Embedded image Embedded image 2. The method of claim 1, wherein the starburst aromatic amine is on an anode, an electron injection and electron transport layer is on the amine, and a cathode is on the injection layer. 3. The EL device according to claim 1. 3. The method according to claim 1, wherein the starburst amine is tris [4 ′-(phenyl-m-tolylamino) -1,1′-
Biphenyl-4-yl] amine, N, N-bis (4'-
Di-m-tolylamino-1,1′-biphenyl-4-yl] -N ′, N′-diphenylbenzidine, tris [4 ′-(m-methoxydiphenylamino) -1,1 ′
-Biphenyl-4-yl] amine, tris [4 '-(diphenylamino) -1,1'-biphenyl-4-yl]
Amine, tris [4 '-(carbazol-9-yl)-
1,1′-biphenyl-4-yl] amine, tris [4 ′-(1-naphthylphenylamino) -1,1′-
Biphenyl-4-yl] amine, N, N-bis [4'-
(Phenyl-m-tolylamino) -1,1′-biphenyl-4-yl] -N′-phenyl-N′-m-tolyl-
3,3′-dimethylbenzidine, N, N-bis (4′-
Diphenylamino-1,1′-biphenyl-4-yl)
-N'-phenyl-N'-m-tolyl-3,3'-dimethylbenzidine, N, N-bis (diphenylamino-
1,1′-biphenyl-4-yl) -N′-phenyl-
N'-m-tolylbenzidine, N, N-bis [4'-
(Di-m-tolylamino) -1,1′-biphenyl-4
-Yl] -N'-phenyl-N'-p-tolylbenzidine, tris [4 '-(8H-10H-acridine-10
-Yl) -1,1′-biphenyl-4-yl] amine,
Tris [4 ′-(9,9-dimethyl-9H-10H-acridin-10-yl) -1,1′-biphenyl-4-
Yl] amine, tris [4′-phenoxazine-10-
Yl-1,1′-biphenyl-4-yl] amine, tris [4′-phenothiaxazin-10-yl-1,1 ′
-Biphenyl-4-yl] amine, N, N-bis [4 '
-(Phenyl-m-tolylamino) -1,1'-biphenyl-4-yl] -4 '-(carbazol-9-yl)
-1,1'-biphenyl-4-amine, N, N-bis [4 '-(carbazol-9-yl) -1,1'-biphenyl-4-yl] -N'-phenyl-N'-m -Tolylbenzidine, N, N-bis [4 '-(1-naphthylphenylamino) -1,1'-biphenyl-4-yl]-
4 ′-(carbazol-9-yl) -1,1′-biphenyl-4-amine and N, N-bis [4 ′-(9H-
10H-acridin-10-yl) -1,1′-biphenyl-4-yl] -4 ′-(9H-10H-acridin-10-yl) -3,3′-dimethyl-1,1′-biphenyl- The device of claim 1, wherein the device is selected from the group consisting of a 4-amine. 4. A photoconductive imaging member comprising a starburst aromatic amine compound of structural formula (I):
In (I), N is nitrogen, A ^{1 to} A ³ each represent a biaryl, and R _a , R _b, and R _c are functional groups of the following structural formulas (A) to (C): And N is nitrogen, Ar ¹ and Ar ² are each aryl, and R _{1 to} R ₈ are hydrogen, halogen, hydrocarbon, and alkoxy in formulas (A) to (C). A photoconductive imaging member wherein X is oxygen, sulfur or alkylene, each substituent being individually selected from the group consisting of: Embedded image Embedded image 5. The method according to claim 5, wherein the aromatic amine is tris [4′-
(Phenyl-m-tolylamino) -1,1′-biphenyl-4-yl] amine, N, N-bis (4′-di-m-
Tolylamino-1,1′-biphenyl-4-yl]-
N ', N'-diphenylbenzidine, tris [4'-
(M-methoxydiphenylamino) -1,1′-biphenyl-4-yl] amine, tris [4 ′-(diphenylamino) -1,1′-biphenyl-4-yl] amine,
Tris [4 ′-(carbazol-9-yl) -1,1 ′
-Biphenyl-4-yl] amine, tris [4 '-(1
-Naphthylphenylamino) -1,1'-biphenyl-
4-yl] amine, N, N-bis [4 ′-(phenyl-
m-tolylamino) -1,1'-biphenyl-4-yl] -N'-phenyl-N'-m-tolyl-3,3'-
Dimethylbenzidine, N, N-bis (4′-diphenylamino-1,1′-biphenyl-4-yl) -N′-phenyl-N′-m-tolyl-3,3′-dimethylbenzidine, N, N -Bis (diphenylamino-1,1'-biphenyl-4-yl) -N'-phenyl-N'-m-tolylbenzidine, N, N-bis [4 '-(di-m-tolylamino) -1, 1'-biphenyl-4-yl] -N '
-Phenyl-N'-p-tolylbenzidine, tris [4 '-(8H-10H-acridin-10-yl)-
1,1′-biphenyl-4-yl] amine, tris [4 ′-(9,9-dimethyl-9H-10H-acridin-10-yl) -1,1′-biphenyl-4-yl]
Amine, tris [4'-phenoxazin-10-yl-
1,1′-biphenyl-4-yl] amine, tris [4′-phenothiaxazin-10-yl-1,1′-
Biphenyl-4-yl] amine, N, N-bis [4'-
(Phenyl-m-tolylamino) -1,1′-biphenyl-4-yl] -4 ′-(carbazol-9-yl)-
1,1'-biphenyl-4-amine, N, N-bis [4 '-(carbazol-9-yl) -1,1'-biphenyl-4-yl] -N'-phenyl-N'-m- Tolylbenzidine, N, N-bis [4 '-(1-naphthylphenylamino) -1,1'-biphenyl-4-yl]-
4 ′-(carbazol-9-yl) -1,1′-biphenyl-4-amine and N, N-bis [4 ′-(9H-
10H-acridin-10-yl) -1,1′-biphenyl-4-yl] -4 ′-(9H-10H-acridin-10-yl) -3,3′-dimethyl-1,1′-biphenyl- The member of claim 4, wherein the member is selected from the group consisting of a 4-amine. 6. The member according to claim 4, comprising a photogenerating layer containing a photogenerating pigment of perylene, titanyl phthalocyanine, hydroxygallium phthalocyanine or vanadyl phthalocyanine. 7. A method for producing a starburst aromatic amine compound represented by the following structural formula (I), wherein N is nitrogen, and A ^{1 to} A ³ each represent a biaryl. , R _a , R _b, and R _c represent one of the functional groups of structural formulas (A)-(C) below, respectively,
In (C), N is nitrogen, Ar ¹ and Ar ² are aryl, and R _{1 to} R ₈ are substituents individually selected from the group consisting of hydrogen, halogen, hydrocarbon, and alkoxy; X is oxygen, sulfur or alkylene, and in the presence of a copper ligand catalyst, a primary amine (II) (ie, _Ra- A
—NH ₂ ), iodide aryl (III) (ie, R _b —A ²
-I) and aryl (IV) iodide (ie, R _c -A ^3-
I) wherein R _a , R _b and R _c and A ¹ -A ³ are aryl and the ligand is a monodentate tertiary amine and a bidentate tertiary amine. A method for producing a starburst aromatic amine compound selected from the group consisting of three amines. Embedded image Embedded image 8. The catalyst according to claim 1, wherein the catalyst is 1,10-phenanthrolat copper (1) (monovalent) chloride, dipyridino copper (1) chloride, 1,10-phenanthrolato copper (1) bromide, dipyridino copper (1) bromide, and The method according to claim 7, wherein the method is selected from the group consisting of 1,10-phenanthroato copper (1) chloride. 9. The method according to claim 7, wherein the catalyst is represented by any one of the following structural formulas. Embedded image