JP2869378B2 - Amine compound and organic electroluminescent device using the compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel amine compound useful as a charge transporting agent for use in an organic electroluminescent device and an electrophotographic photoreceptor, and an organic electroluminescent device using the compound.

[0002]

2. Description of the Related Art Electroluminescent devices comprising an organic compound as a component have been conventionally studied, but have not been able to obtain sufficient light-emitting characteristics. However, in recent years, by adopting a structure in which several kinds of organic materials are laminated, the characteristics are remarkably improved,
Since then, studies on electroluminescent devices using organic substances have been actively conducted. The electroluminescent device having such a laminated structure is manufactured by Kodak Corporation. W. First reported by Tang et al. (Appl. Phys. Lett. 51 (1987)).
913), among which 1000 cd at a voltage of 10 V or less.
/ M ² or more was obtained, and it was shown that the inorganic electroluminescent element which has been practically used conventionally has much higher characteristics than the case where a high voltage of 200 V or more is required.

[0003] These laminated electroluminescent elements have a structure in which an organic phosphor, a charge transporting organic substance (charge transporting agent) and electrodes are laminated, and the charges (holes and electrons) injected from each electrode are stacked. ) Move through the charge transport agent and emit light when they recombine. Organic dyes that emit fluorescence, such as 8-quinolinol aluminum complex and coumarin, are used as the organic phosphor. Further, as a charge transport agent, various compounds well-known as an organic material for an electrophotographic photosensitive member have been studied,
For example, diamines such as N, N'-di (3-tolyl) -N, N'-diphenyl-4,4'-diaminodiphenyl and 1,1-bis [N, N-di (4-tolyl) aminophenyl] cyclohexane And hydrazone compounds such as 4-diphenylaminobenzaldehyde N, N-diphenylhydrazone. Further, porphyrin compounds such as copper phthalocyanine have been used.

[0004] Although organic electroluminescent devices have high light-emitting characteristics, they are not sufficient in terms of stability during light emission and storage stability, and have not been put to practical use. As one of the problems in the stability during light emission and storage stability of the device,
The stability of the charge transport agent has been pointed out. The layer formed of an organic material of the electroluminescent device is very thin, 50 to several hundred nanometers, and the electric field intensity applied per unit thickness is very high. In addition, heat is generated by light emission and energization. Therefore, the charge transporting agent is required to have electrical, thermal or chemical stability. Further, the charge transport layer in the device is generally in an amorphous state, but with the lapse of time due to light emission or storage, crystallization occurs, thereby observing a phenomenon that light emission is inhibited or device breakdown occurs. Have been. For this reason, the charge transporting agent is required to easily form an amorphous state, that is, a glassy state, and to have a performance of stably maintaining the state.

[0005] Regarding the stability of the light emitting device caused by such a charge transporting agent, for example, a tetraphenyldiamine compound and a porphyrin compound are electrically and thermally stable and have relatively high emission characteristics. However, degradation of the element due to crystallization has not been solved. In addition, hydrazone compounds are not preferable materials because of insufficient electrical and thermal stability.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel amine useful as a charge transporting agent capable of realizing an organic electroluminescent device which is excellent not only in light emission characteristics but also in stability during light emission and storage stability. An object of the present invention is to provide a compound and an organic electroluminescent device using the compound.

[0007]

The present invention provides a compound represented by the following general formula [1]:

[0008]

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[In the formula, Ar ₁ represents an aryl group which may have a substituent, Ar ₂ represents a phenylene group, a naphthylene group, a biphenylene group or an anthrylene group which may have a substituent; ₁ represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, X represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and Y has a substituent. An aryl group or a compound represented by the following general formula [2]

[0010]

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(Wherein, R ₁ has the same meaning as described above.)
Represents a monovalent group represented by And an amine compound represented by the formula:

The amine compound represented by the general formula [1] of the present invention is a novel compound, and these compounds are obtained by subjecting the corresponding amino compound to an N-arylation reaction (condensation reaction) generally by U11mann reaction or the like. The synthesized triarylamine compound is formylated and synthesized by a modified Wittig reaction with the corresponding phosphonate. Formylation is generally performed by a Vilsmeier reaction. For example, the following general formula [3]

[0013]

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Wherein Ar ₂ and Y have the same meaning as in the above formula [1]. And a diarylamine compound represented by the following general formula [4]:

[0015]

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[In the formula, R ₁ has the same meaning as in the general formula [1], and A represents a chlorine atom, a bromine atom or an iodine atom. The following general formula [5] obtained by a condensation reaction with a halogenated tetralin compound represented by the following formula:

[0017]

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[In the formula, Ar ₂ , R ₁ and Y have the same meaning as in the general formula [1]. Is subjected to formylation with N, N-dimethylformaldehyde and phosphorus oxychloride to form a triarylamine compound represented by the following general formula [6]:

[0019]

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[In the formula, Ar ₂ , R ₁ and Y have the same meaning as in the general formula [1]. To obtain an aldehyde compound represented by the formula: Next, this aldehyde compound is represented by the following general formula [7]

[0021]

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[Wherein, Ar ₁ and X have the same meanings as in the general formula [1], and R ₄ represents a lower alkyl group. To give the amine compound of the present invention represented by the general formula [1].

The following general formula [8] was used to synthesize the amine compound of the present invention.

[0024]

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[Wherein, Ar ₂ and R ₁ represent the above-mentioned general formula [1]
Has the same meaning as Or an aminoaminotetralin compound represented by the following general formula [9]:

[0026]

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[Wherein R ₁ and Y have the same meaning as in the above formula [1]. Using the tetralin compound represented by the general formula [1] as a starting material, the condensation reaction, the formylation reaction, and the modified Wittig reaction are also performed to obtain the amine compound of the present invention represented by the general formula [1]. be able to. The amine compound of the present invention thus obtained is also characterized by having good solubility.

The above-mentioned condensation reaction of a diarylamine compound with a halogenated tetralin compound is a reaction known as a U11 mann reaction, and is carried out without a solvent or in the presence of a solvent. As the solvent, a high boiling point solvent such as nitrobenzene, dichlorobenzene, or dimethyl sulfoxide is used. Potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide and the like are used as deoxidizing agents. The reaction is usually performed using a catalyst such as copper powder or copper halide. The reaction temperature is usually from 160 to 230 ° C.

The condensation reaction between the aldehyde compound and the phosphonic acid ester is a reaction known as a modified Wittig reaction, and is preferably carried out in the presence of a basic catalyst. In this case, as the basic catalyst, potassium hydroxide, sodium amide, sodium methylate, potassium tert-butoxide and the like are used. As the solvent, methyl alcohol, ethyl alcohol, ter
t-Butyl alcohol, toluene, tetrahydrofuran, dioxane, dimethylsulfoxide, N, N-dimethylformamide and the like are used. The reaction temperature is usually from room temperature to 100 ° C.

The phosphonic acid ester represented by the above general formula [7] used as a raw material in the present invention can be obtained by directly converting a corresponding halogen compound and a trialkyl phosphite or using toluene, xylene, N, N-dimethylformamide or the like. It is easily synthesized by performing a heat reaction in an organic solvent.

In the present invention, when Ar ₁ is an aryl group having a substituent, the amine compound represented by the general formula [1] is a lower alkyl group having 1 to 4 carbon atoms, A lower alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a benzyl group, a phenyl group, a halogen atom, or the like, and further when the substituent is a lower alkyl group or a lower alkoxy group; May be further substituted with a lower alkoxy group having 1 to 4 carbon atoms or a halogen atom, and when the substituent is a benzyl group or a phenyl group, a lower alkyl group having 1 to 4 carbon atoms and 1 carbon atom And may be further substituted with a lower alkoxy group or a halogen atom.

The aryl group of Ar ₁ includes a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a pyrenyl group and the like.

When Ar ₂ is a substituted phenylene group, naphthylene group, biphenylene group or anthrylene group, the substituent may be a lower alkyl group having 1 to 4 carbon atoms or a lower alkyl group having 1 to 4 carbon atoms. Examples thereof include a lower alkoxy group and a halogen atom. When the substituent is a lower alkyl group or a lower alkoxy group, it may be further substituted with a lower alkoxy group having 1 to 4 carbon atoms or a halogen atom.

When X, Y or Z is an aryl group having a substituent, examples of the substituent include the same substituents as those described above that can be possessed by Ar ₁ . When X is an alkyl group having a substituent, the substituent is a lower alkoxy group having 1 to 4 carbon atoms, and 5 to 6 carbon atoms.
And a halogen atom and the like.

The aryl group of X, Y or Z includes a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a pyrenyl group and the like.

When R ₁ or R ₂ is a lower alkyl group or a lower alkoxy group, examples of the lower alkyl group include straight-chain or branched alkyl groups having 1 to 4 carbon atoms. Is a linear or branched alkoxy group having 1 to 4. When R ₃ is a lower alkyl group, examples of the lower alkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms.

Specific examples of the amine compound represented by the general formula [1] of the present invention include the following.

Compound No (1)

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Compound No (2)

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Compound No (3)

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Compound No (4)

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Compound No (5)

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Compound No (6)

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Compound No (7)

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Compound No. (8)

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Compound No (9)

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Compound No (10)

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Compound No (11)

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Compound No (12)

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Compound No (13)

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Compound No (14)

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Compound No (15)

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Compound No (16)

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Compound No (17)

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Compound No (18)

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Compound No (19)

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Compound No (20)

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Compound No (21)

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Compound No (22)

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Compound No (23)

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Compound No (24)

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Compound No (25)

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Compound No (26)

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Compound No (27)

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Compound No (28)

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Compound No (29)

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Compound No (30)

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Compound No (31)

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Compound No (32)

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Compound No (33)

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Compound No (34)

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Compound No (35)

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Compound No (36)

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Compound No (37)

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Compound No (38)

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Compound No (39)

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Compound No (40)

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Compound No (41)

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Compound No (42)

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Compound No (43)

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Compound No (44)

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Compound No (45)

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Compound No (46)

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Compound No (47)

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Compound No (48)

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Compound No (49)

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Compound No (50)

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Compound No (51)

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Compound No (52)

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Compound No (53)

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Compound No (54)

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Compound No (55)

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Compound No (56)

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Compound No (57)

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Compound No (58)

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Compound No (59)

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Compound No (60)

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Compound No (61)

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Compound No (62)

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Further, in the present invention, the amine compound represented by the above-mentioned general formula [1] is used as the hole transport layer in an organic electroluminescent device comprising at least an electrode, a hole transport layer, a light emitting layer and an electrode. An organic electroluminescent device.

The organic electroluminescent device has a two-layer structure and a three-layer structure. These layer structures are provided on a transparent electrode serving as a substrate, and a counter electrode is provided thereon to form an organic electroluminescent device. I do. In the case of a two-layer structure, it consists of a combination of a hole transport layer and an electron-transporting light-emitting layer or a combination of an electron transport layer and a hole-transport light-emitting layer. A structure in which the light emitting layers are sandwiched. The configuration according to the present invention has a two-layer structure of a hole transport layer and an electron transporting luminescent agent, or a three-layer structure in which an electron transport layer is further laminated thereon. FIG. 1 shows an organic electroluminescent device having a two-layer structure.

[0102]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples of the electron-transporting luminescent agent include chelating oxinoid compounds such as tris (8-quinolinol) aluminum, bis (8-quinolinol) magnesium, and tris (5-chloro-8-quinolinol) gallium. And coumarin derivatives, perylene pigments, chelated 2,2'-bipyridine compounds, and chelate compounds of salicylidene-O-aminophenol derivatives.

Examples of the electron transporting agent include, for example, 2-
(4-tert-butylphenyl) -5- (4-biphenylyl) -1,3,5-oxadiazole, 2,4,7
-Trinitro-9-fluorenone, 4-butoxycarbonyl-9-dicyanomethylidenefluorene, 3,3'-
Bis (tert-butyl) -5,5′-dimethyl-4,
4'-diphenoquinone, 3,5'-bis (tert-butyl) -5,3'-dimethyl-4,4'-diphenoquinone, 3,5, -bis (tert-butyl) -3 ', 5'
-Dimethyl-4,4'-diphenoquinone and the like can be used.

The support of the organic electroluminescent element is made of glass, plastic, quartz or the like. On this substrate, a metal such as gold, aluminum, indium, silver, magnesium or indium-tin-oxide (ITO) is formed. ,
An electrode of a thin film made of tin oxide, zinc oxide, or the like is formed by a vapor deposition method or the like, so as to be a translucent or transparent electrode. A charge transport layer and a light emitting layer are laminated thereon, and further, an electrode similar to that described above is formed thereon to form an organic electroluminescent element. Light is emitted by applying a DC voltage thereto.

[0105]

The present invention will be described below in detail with reference to examples.

Example 1 (Synthesis of Compound No. 1) [Synthesis of Iodotetralin] 132.2 g (1.00 mol) of tetralin was dissolved in 600 ml of 80% acetic acid, and 101.5 g (0.40 mol) of iodine was dissolved. ), Periodate dihydrate 45.5 g (0.20 mol)
And 15 ml of concentrated sulfuric acid, and the mixture was heated to 70 ° C. while stirring. The mixture was stirred at the same temperature for 3 hours, and the reaction was terminated when it was confirmed that tetralin had disappeared. The reaction mixture was added to 1000 ml of water, and the separated oil was added to 100 ml of toluene.
Extracted with 0 ml. The toluene layer was washed with water, concentrated and distilled under reduced pressure (bp: 120 ° C./3 mmHg). 215.3 g (yield; 83.4%) was obtained as a main fraction. This product was a mixture of 5-iodotetralin and 6-iodotetralin, and the mixing ratio was 1: 2.

[Synthesis of N- (1,2,3,4-tetrahydronaphth-5-yl) aniline] 233.0 g of the iodotetralin mixture synthesized above.
(0.90 mol) of acetanilide in 81.0 g (0.6
0 mol), 3.8 g (0.06 mol) of copper powder, and 103.5 g (0.75 mol) of anhydrous potassium carbonate.
Stirred at C for 8 hours. When the disappearance of acetanilide was confirmed, the reaction was terminated. 120 ml of isoamyl alcohol and 84 g of 85% potassium hydroxide (1.27
Mol) dissolved in 160 ml of water,
The hydrolysis reaction was performed at １４０140 ° C. for 10 hours. After confirming the completion of the hydrolysis reaction, 600 ml of water was added, and isoamyl alcohol was distilled off by azeotropic distillation. 1000 ml of toluene was added to the residue to dissolve the product, and the toluene layer was separated. The toluene layer was washed with 500 ml of water and concentrated, and the obtained oil was subjected to column chromatography (carrier;
The mixture was separated and purified with silica gel, eluent; toluene / hexane = 1/1). N- (1,2,3,4-
The fraction of tetrahydronaphth-5-yl) aniline was concentrated to obtain 30.9 g of N- (1,2,3,4-tetrahydronaphth-5-yl) aniline (yield: 23.1).
%). At the same time, a fraction of N- (1,2,3,4-tetrahydronaphth-6-yl) aniline is also fractionated, concentrated and concentrated similarly. Il) aniline 65.1 g (yield;
48.7%).

[Synthesis of N- (1,2,3,4-tetrahydronaphth-5-yl) diphenylamine] N- (1,2,3,4-tetrahydronaphth-5-yl) aniline 22 synthesized above. 0.3 g (0.10 mol)
12.3 g (0.15 mol) of iodobenzene, 0.65 g (0.01 mol) of copper powder, and anhydrous potassium carbonate
8 g (0.10 mol) and 15 ml of nitrobenzene were mixed and stirred at 200 ° C. for 18 hours. N- (1,2,3,4
The reaction was terminated upon confirming that -tetrahydronaphth-5-yl) aniline had disappeared. 300 ml of toluene
Was added to dissolve the product, followed by filtration and concentration. The concentrate is subjected to column chromatography (carrier; silica gel, eluent;
Purification by toluene / hexane = 1/5)
23.6 g of (1,2,3,4-tetrahydronaphth-5-yl) diphenylamine (yield; 78.8%, melting point;
89.5-90.5 ° C).

[Synthesis of N- (1,2,3,4-tetrahydronaphth-5-yl) -4-formyldiphenylamine] The N- (1,2,3,4-tetrahydronaphth-5-synthesized above) was synthesized. Yl) diphenylamine 18.0 g (0.0
6 mol) was dissolved in 170 ml of N, N-dimethylformamide, and 13.1 g (0.085 g) of phosphorus oxychloride was dissolved at room temperature.
Mol) was added dropwise over 15 minutes. The temperature was raised to 50 ° C., and the mixture was stirred for 10 hours. The reaction was terminated when it was confirmed that N- (1,2,3,4-tetrahydronaphth-5-yl) diphenylamine had disappeared. The reaction product was poured into an aqueous solution in which 25 g (0.58 mol) of 93% sodium hydroxide was dissolved in 500 ml of water. The crystals precipitated by cooling are filtered, washed with water,
After drying, N- (1,2,3,4-tetrahydronaphtho-
18.1 g of 5-yl) -4-formyldiphenylamine
(Yield; 92.1%) was obtained.

[Synthesis of N- (1,2,3,4-tetrahydronaphth-5-yl) -4- (2,2-diphenylvinyl) diphenylamine (Compound No. 1)] N- ( 7. 1,2,3,4-tetrahydronaphth-5-yl) -4-formyldiphenylamine
2 g (0.025 mol) and 11.4 g (0.038 mol) of diethyl diphenylmethylphosphonate were dissolved in 90 ml of tetrahydrofuran, and potassium-tert-
Butoxide 5.3 g (0.047 mol) was added over 30 minutes. After the addition, the mixture was heated to 50 ° C. and stirred for 2 hours.
When the disappearance of the formyl compound was confirmed, the reaction was terminated. The reaction product was poured into 450 ml of methanol at 5 ° C. or lower, and the precipitated crystals were filtered, washed with methanol and washed with water, and dried. The crystals were subjected to column chromatography (carrier; silica gel, eluent; toluene / hexane = 1).
/ 4) and purified by N- (1,2,3,4-tetrahydronaphth-5-yl) -4- (2,2-diphenylvinyl) diphenylamine (Compound No. 1) 10.2 g
(Yield; 85.3%, melting point: 139.0-140.5)
° C). The elementary analysis value was as shown below as C ₃₆ H ₃₁ N. Carbon: 90.39% (90.53
%), Hydrogen: 6.75% (6.54%), nitrogen: 2.7
1% (2.93%) (Calculated values are shown in parentheses.) Characteristic base number (cm) of infrared absorption spectrum (KBr tablet method)
^-1 ) was 2922, 1587, 1490, 1307 and the like.

Example 2 (Synthesis of Compound No. 14) 4.91 g of N- (1,2,3,4-tetrahydronaphth-5-yl) -4-formyldiphenylamine synthesized in Example 1 .015 mol) and 5.45 g (0.023 mol) of diethyl methylbenzylphosphonate were dissolved in 40 ml of tetrahydrofuran, and potassium-ter was added at room temperature.
3.36 g (0.03 mol) of t-butoxide were added over 30 minutes. After the addition, the mixture was heated to 50 ° C. and stirred for 2 hours. When the disappearance of the formyl compound was confirmed, the reaction was terminated. The reaction product was poured into 300 ml of methanol at 5 ° C. or lower, and the precipitated crystals were filtered, washed with methanol and washed with water, and dried. The crystals were purified by column chromatography (carrier; silica gel, eluent; toluene / hexane = 1/4) to give N- (1,2,3,4-tetrahydronaphth-5-yl) -4- (4- Methylstyryl) diphenylamine (Compound No. 14) 4.09
g (yield; 73.6%, melting point; 113.5-114.5)
° C). Elemental analysis was as follows, as C ₃₁ H ₂₉ N. Carbon: 89.74% (89.60
%), Hydrogen: 7.19% (7.03%), nitrogen: 3.4
1% (3.37%) (Calculated values are shown in parentheses.) Characteristic base wave number (cm) of infrared absorption spectrum (KBr tablet method)
^-1 ) was 2,922, 1585, 1486, 1269, and the like.

Example 3 (Synthesis of Compound No. 2) In the reaction of N- (1,2,3,4-tetrahydronaphth-5-yl) aniline with iodobenzene in Example 1, iodobenzene was used. N-Synthesized in the same manner as in Example 1 except that 4-iodotoluene was used instead of N-toluene.
(1,2,3,4-tetrahydronaphth-5-yl)-
4-formyl-4'-methyldiphenylamine 5.12
g (0.015 mol) and 5.47 g (0.018 mol) of diethyl diphenylmethylphosphonate are dissolved in 50 ml of tetrahydrofuran, and 2.52 g (0.023 mol) of potassium tert-butoxide is added at room temperature over 30 minutes. did. After the addition, the mixture was heated to 50 ° C. and stirred for 2 hours.
When the disappearance of the formyl compound was confirmed, the reaction was terminated. The reaction product was poured into 600 ml of methanol at 5 ° C. or lower, and the precipitated crystals were filtered, washed with methanol and washed with water, and dried. The crystals were subjected to column chromatography (carrier: silica gel, eluent: toluene / hexane =
精製) and purified by N- (1,2,3,4-tetrahydronaphth-5-yl) -4- (2,2-diphenylvinyl) -4′-methyldiphenylamine (compound N
o. 2) 5.17 g (yield; 77.7%, this compound did not show a clear melting point and the melting onset temperature was 78 ° C). Elemental analysis were as shown below as _C 3 _{7H 33} N. Carbon: 90.49% (90.38
%), Hydrogen: 6.65% (6.77%), nitrogen: 2.7
1% (2.85%) (Calculated values are shown in parentheses.) Characteristic base wave number of infrared absorption spectrum (KBr tablet method) (cm
^-1 ) was 2924, 1592, 1499, 1314 and the like.

Example 4 (Synthesis of Compound No. 15) N- (1,2,3,4-tetrahydronaphth-5-yl) -4-formyl-4′-methyldiphenylamine synthesized in Example 3 5.12 g (0.015 mol) and 4.36 g (0.018 mol) of diethyl methylbenzylphosphonate were dissolved in 50 ml of tetrahydrofuran, and 2.52 g (0.023 mol) of potassium tert-butoxide was added at room temperature.
Mol) was added over 30 minutes. After the addition, the mixture was heated to 50 ° C. and stirred for 2 hours. When the disappearance of the formyl compound was confirmed, the reaction was terminated. The reaction product was poured into 400 ml of methanol at 5 ° C. or lower, and the precipitated crystals were filtered, washed with methanol and washed with water and dried. The crystals were purified by column chromatography (carrier; silica gel, eluent; toluene / hexane = 1/4) to give N-
(1,2,3,4-tetrahydronaphth-5-yl)-
4.58 g of 4- (4-methylstyryl) -4′-methyldiphenylamine (Compound No. 15) (yield; 78.
9%, melting point: 126.0-127.0 ° C). Elemental analysis was as follows, as C ₃₂ H ₃₁ N.
Carbon: 89.64% (89.46%), hydrogen: 7.35
% (7.27%), nitrogen: 3.03% (3.26%)
(Calculated values are shown in parentheses.) Infrared absorption spectrum (K
The characteristic base wave number (cm ⁻¹ ) of the Br tablet method) is 2920,
594, 1501, 1313 and the like.

Examples 5 to 8 (Compound Nos. 30, 43, 31, 4
Synthesis of 4) Instead of using N- (1,2,3,4-tetrahydronaphth-5-yl) aniline in Examples 1 and 3,
When N- (1,2,3,4-tetrahydronaphth-5-yl) aniline synthesized in Example 1 was obtained by separation and purification, N- (1,2,3) was obtained as another product. , 4-
N- (1,2,2) synthesized by N-phenylation or N-4-tolylation and formylation in the same manner as in Example 1 or Example 3 except for using tetrahydronaphth-6-yl) aniline. Using 3,4-tetrahydronaphth-6-yl) -4-formyldiphenylamine or N- (1,2,3,4-tetrahydronaphth-6-yl) -4-formyl-4′-methyldiphenylamine, respectively The Wittig reaction and purification were performed in the same manner as in Examples 1 and 2 or Examples 3 and 4, and N- (1,2,3,3) was obtained.
4-tetrahydronaphth-6-yl) -4- (2,2-
Diphenylvinyl) diphenylamine (Compound No. 3)
0), N- (1,2,3,4-tetrahydronaphth-6
-Yl) -4- (4-methylstyryl) diphenylamine (Compound No. 43), N- (1,2,3,4-tetrahydronaphth-6-yl) -4- (2,2-diphenylvinyl)- 4'-methyldiphenylamine (compound N
o. 31) and N- (1,2,3,4-tetrahydronaphth-6-yl) -4- (4-methylstyryl)-
4′-Methyldiphenylamine (Compound No. 44) was obtained. The results are shown in [Table 1] and [Table 2].

[0115]

[Table 1]

[0116]

[Table 2]

Example 9 An ITO glass electrode (a transparent conductive film standard type, manufactured by Matsuzaki Vacuum Co., Ltd.) was coated with a vapor deposition apparatus (manufactured by Vacuum Instruments Co., Ltd., LC-6).
F-type) fixed on a substrate holder, and compound N
o. 1 (N- (1,2,3,4-tetrahydronaphtho-
(5-yl) -4- (2,2-diphenylvinyl) diphenylamine) and reduced to 1 × 10 ⁻⁶ Torr. The heating boat was heated to perform deposition at a deposition rate of 12 nm / min. One hole transport layer was formed on the ITO glass electrode. Next, Tris (8-
(Quinolinol) aluminum was placed in a heating boat, heated and deposited at a deposition rate of 20 nm / min.
m light emitting layers were formed on the hole transport layer. Further, a 150-nm-thick magnesium vapor-deposited film was formed thereon at a vapor deposition rate of 40 nm / min to serve as a counter electrode, thereby producing an organic electroluminescent device. When a direct current of 12 Volt was applied using an ITO electrode as a positive electrode and a magnesium electrode as a negative electrode, a bright green light was emitted and a luminance meter (LS-1 manufactured by Minolta Camera Co., Ltd.)
10) was used to measure the luminance.
showed m ^2. When a continuous lighting test was performed at a luminance of 300 cd / m ² , the half life of the luminance was 250 hr.

Example 10 In Example 9, Compound No. Instead of using 1, compound N
o. An organic electroluminescent device was produced in the same manner as in Example 9 except that 14 (N- (1,2,3,4-tetrahydronaphth-5-yl) -4- (4-methylstyryl) diphenylamine) was used. . When a DC voltage of 13 Volt was applied, bright green light was emitted at a luminance of 1040 cd / m ² . When a continuous lighting test was performed at a luminance of 300 cd / m ² , the half life of the luminance was 220 Hr.

Example 11 In Example 9, Compound No. Instead of using 1, compound N
o. 31 (N- (1,2,3,4-tetrahydronaphth-6-yl) -4- (2,2-diphenylvinyl)-
An organic electroluminescent device was produced in the same manner as in Example 9 except that 4′-methyldiphenylamine) was used. DC 12
When Volt was applied, a bright green light was emitted at a luminance of 1400 cd / m ² . When a continuous lighting test was performed at a luminance of 300 cd / m ² , the half-life of the luminance was 240
Hr.

Example 12 In Example 9, Compound No. Instead of using 1, compound N
o. 44 (N- (1,2,3,4-tetrahydronaphth-6-yl) -4- (4-methylstyryl) -4′-methyldiphenylamine) in the same manner as in Example 9 except that 44 (N- (1,2,3,4-tetrahydronaphth-6-yl) -4- (4-methylstyryl) -4′-methyldiphenylamine) was used. A light-emitting element was manufactured. DC 13 Volt
When light was applied, a bright green light was emitted at a luminance of 1200 cd / m ² . When a continuous lighting test was performed at a luminance of 300 cd / m ² , the half life of the luminance was 200 Hr.

Examples 13 to 23 In Example 9, the compound No. An organic electroluminescent device was produced in the same manner as in Example 9 except that the amine compound shown in [Table 3] was used instead of using the amine compound of No. 1. The emission luminance when 13 Volt DC was applied is shown in [Table 3].

[0122]

[Table 3]

[0123]

The novel amine compound of the present invention has excellent hole transporting ability and can be widely used as a hole transporting material. In addition, the organic electroluminescent device of the present invention, which forms a thermally stable and good thin film and is produced using these compounds as a hole transporting agent, shows excellent light emitting characteristics and can be widely used as a display device. Has the advantage that

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an organic electroluminescent device.

[Explanation of symbols]

 Reference Signs List 1 glass substrate 2 ITO electrode 3 hole transport layer 4 light emitting layer 5 magnesium electrode

Continued on the front page (58) Fields surveyed (Int.Cl. ⁶ , DB name) C07C 211/57-211/61 C07C 217/92 C09K 11/06 CA (STN) REGISTRY (STN) WPI / L (QUESTEL)

Claims (2)

(57) [Claims] [Claim 1] The following general formula [1] [In the formula, Ar ₁ represents an aryl group which may have a substituent, Ar ₂ represents a phenylene group, a naphthylene group, a biphenylene group or an anthrylene group which may have a substituent, and R ₁ is hydrogen. An atom, a lower alkyl group or a lower alkoxy group, X represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and Y may have a substituent. A good aryl group or the following general formula [2] (Wherein, R ₁ represents the same meaning as described above)
Represents a valence group. ] The amine compound represented by these. 2. An organic electroluminescent device comprising at least an electrode, a hole transporting layer, a light emitting layer and an electrode, wherein a charge transporting agent used in the hole transporting layer has the following general formula [1]: [In the formula, Ar ₁ represents an aryl group which may have a substituent, Ar ₂ represents a phenylene group, a naphthylene group, a biphenylene group or an anthrylene group which may have a substituent, and R ₁ is hydrogen. An atom, a lower alkyl group or a lower alkoxy group, X represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and Y may have a substituent. A good aryl group or the following general formula [2] (Wherein, R ₁ represents the same meaning as described above)
Represents a valence group. ] An organic electroluminescent device characterized by using at least one amine compound represented by the following formula: