JP3508984B2 - Organic compound and light emitting device using the organic compound - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel organic compound and a light emitting device using the organic compound.

[0002]

2. Description of the Related Art The electroluminescence phenomenon of organic materials was observed in 1963 by an anthracene single crystal by Pope et al. (J. Chem. Phys. 38 (1963) 2
042), followed by Helflich (He) in 1965.
lfinch) and Schneider
Has succeeded in observing a relatively strong injection type EL by using a solution electrode system with high injection efficiency (Phys.
v. Lett. 14 (1965) 229).

Since then, US Pat. No. 3,172,862
U.S. Pat. No. 3,173,050, U.S. Pat. No. 3,71
0,167, J. Chem. Phys. 44 (196
6) 2902, J. Chem. Phys. 50 (196
9) 14364, J. Chem. Phys. 58 (19
73) 1542, or Chem. Phys. Let
t. 36 (1975) 345, etc.,
Studies have been conducted on the formation of organic luminescent materials with conjugated organic host materials and conjugated organic activators with fused benzene rings. Naphthalene, anthracene, phenanthrene, tetracene, pyrene, benzopyrene, chrysene, picene, carbazole, fluorene, biphenyl, terphenyl,
Triphenylene oxide, dihalobiphenyl, trans-stilbene, 1,4-diphenylbutadiene and the like are shown as examples of organic host materials, and anthracene, tetracene, pentacene and the like are given as examples of activators. However, these organic light-emitting substances are all 1 μm
It existed as a single layer having a thickness exceeding the above, and required a high electric field for light emission. For this reason, research on thin film devices by the vacuum deposition method has been advanced (for example, Thin Solid
Films 94 (1982) 171, Polyme
r 24 (1983) 748, Jpn. J. Appl.
Phys. 25 (1986) L773). However, although thinning was effective in reducing the driving voltage, it was not possible to obtain a practically high brightness device.

However, in recent years, Tang et al. (App
l. Phys. Lett. 51 (1987) 913 or US Pat. No. 4,356,429), devising an EL device in which two extremely thin layers (a charge transport layer and a light emitting layer) are laminated by vacuum vapor deposition between an anode and a cathode, and a low driving High brightness is realized by voltage. This type of laminated organic EL device has been actively researched since then, and is disclosed in, for example, JP-A-59-194393.
U.S. Pat. No. 4,539,507, JP-A-59-
194393, U.S. Pat. No. 4,720,432,
JP-A-63-264692, Appl. Phy
s. Lett. 55 (1989) 1467, JP-A-3-
163188 and the like.

Furthermore, Jpn. J. Appl. Phy
s. 27 (1988) L269. In L713, an EL device having a three-layer structure in which the functions of carrier transport and light emission are separated has been reported. The constraint on carrier transport performance is relaxed when selecting the dye of the light emitting layer that determines the emission color, and the degree of freedom in selection is increased. It is also suggested that holes and electrons (or excitons) can be effectively confined in the central light emitting layer to improve the light emission.

A vacuum evaporation method is generally used to form a laminated organic EL element, but it has been reported that an element having a considerable brightness can be obtained also by the casting method (for example, the 50th reaction product). Proceedings of academic conference
006 (1989) and Proceedings of the 51st Annual Meeting of the Society of Biological Society of Japan 1041 (1990)).

Further, even a mixed single-layer type EL device formed by a dip coating method from a solution in which polyvinylcarbazole as a hole transport compound, oxadiazole derivative as an electron transport compound and coumarin 6 as a light emitter are mixed, has a considerably high luminous efficiency. It is reported that you can get it (for example,
Proceedings 1086 (19)
91)). As mentioned above, recent advances in organic EL devices have marked a wide range of potential applications.

However, the history of these studies is still shallow, and the studies for materials and devices have not been sufficiently conducted. At present, there is still a problem in terms of durability such as light output with higher brightness, deterioration with time due to long-term use, and deterioration due to atmospheric gas containing oxygen or moisture. Furthermore, blue, green, when considering application to full-color displays,
Problems such as diversification of emission wavelengths for precisely selecting the red emission hue have not yet been sufficiently solved.

Under these circumstances, the organic compound represented by the following general formula (A) was used as a hole-transporting agent in JP-A-5-25473 as an organic compound capable of low voltage driving, high emission intensity and high durability. A light emitting device is disclosed.

[0010]

[Chemical 3] (In the formula, R ¹¹ represents an alkyl group or an aralkyl group, R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are hydrogen atoms,
An alkyl group, an alkoxy group or a halogen atom is shown. )

However, according to a study made by the present inventors, a light emitting element is used to drive an LED (Light E
When a light emitting device or a display is configured to emit light or display, heat is inevitably generated, and the heat generation causes the durability of the light emitting element to be shortened. Since the compounds shown have relatively low melting points and glass transition points, it has become clear that the expected high durability cannot actually be obtained.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel organic compound material that contributes to high-luminance light output and high durability. Another object of the present invention is to provide a light emitting device which has various emission wavelengths, exhibits various emission hues, and is extremely durable. Still another object of the present invention is to provide a light emitting device capable of outputting light with high brightness.

[0013]

Means for Solving the Problems That is, the present invention provides the following general formula (1):

[0014]

[Chemical 4]

(In the formula, X represents a substituted or unsubstituted arylene group or heterocyclic group, and Ar ¹ , Ar ² , Ar
³ , Ar ⁴ represents a substituted or unsubstituted aryl group.
However, at least one of Ar ¹ or Ar ³ and Ar ²
Alternatively , at least one of Ar ⁴ is a halogen atom,
Alkyl group, alkoxy group, aralkyl group, nitro group,
Selected from an ano group, amino group, aryl group, heterocyclic group
Substituted with a substituted group or unsubstituted
Represents a fluorenyl group. ) Is an organic compound represented by.

Further, the present invention is a light emitting device constructed by disposing an organic compound layer between a pair of electrodes, wherein the organic compound layer is represented by the following general formula (1).

[0017]

[Chemical 5]

(In the formula, X represents a substituted or unsubstituted arylene group or heterocyclic group, and Ar ¹ , Ar ² , Ar
³ , Ar ⁴ represents a substituted or unsubstituted aryl group.
However, at least one of Ar ¹ or Ar ³ and Ar ²
Alternatively , at least one of Ar ⁴ is a halogen atom,
Alkyl group, alkoxy group, aralkyl group, nitro group,
Selected from an ano group, amino group, aryl group, heterocyclic group
Substituted with a substituted group or unsubstituted
Represents a fluorenyl group. ) Is a light-emitting device characterized by being configured using an organic compound represented by

According to the light emitting device of the present invention, light emitting devices exhibiting various emission hues can be easily constructed, and the light emitting device is
It is extremely durable. Further, according to the light emitting device of the present invention, it is possible to output light with high brightness.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The organic compound of the present invention is represented by the following general formula (1).

[0021]

[Chemical 6]

In the general formula (1), X represents a substituted or unsubstituted arylene group or heterocyclic group, and Ar
¹ , Ar ² , Ar ³ and Ar ⁴ represent a substituted or unsubstituted aryl group. However, at least Ar ¹ or Ar ³
One and at least one of Ar ² or Ar ⁴ is halo.
Gen atom, alkyl group, alkoxy group, aralkyl group,
Nitro group, cyano group, amino group, aryl group, heterocycle
Is substituted by a substituent selected from the group
Represents an unsubstituted fluorenyl group.

Regarding Ar ¹ , Ar ² , Ar ³ and Ar ⁴ ,
All four can be substituted or unsubstituted fluorenyl groups, but it is necessary that at least two are substituted or unsubstituted fluorenyl groups. When all four are not fluorenyl groups, the rest are composed of substituted or unsubstituted aryl groups.

The construction method when ^{two of} Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are substituted or unsubstituted fluorenyl groups is as follows. That is, (1) one of Ar ¹ or Ar ³ and Ar ² or Ar ⁴
Is one of.

Further, when ^{three of} Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are constituted by a substituted or unsubstituted fluorenyl group, there are the following two ways of constitution. That is one Ar ^1, Ar ³ of one of Ar ¹ or ^{Ar 3 Ar 2, Ar 4 Ar} 2 or Ar ^4.

Next, specific examples of the organic compound of the present invention are shown in general formula (4). The example represented by the general formula (4) is configured by arranging a substituted or unsubstituted fluorenyl group for Ar ³ and Ar ⁴ in the general formula (1).

[0027]

[Chemical 7]

In the general formula (4), X represents a substituted or unsubstituted arylene group or heterocyclic group. Ar ¹ and Ar ² represent a substituted or unsubstituted aryl group, and R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, an aryl group. Represents any of the following. R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, an alkoxy group, an aryl group, an amino group or a carbonyl group.

Examples of the substituted or unsubstituted arylene group which can form X include phenylene, biphenylene,
Examples include terphenylene, naphthylene, fluorenylene, pyrenylene and stilbene. Examples of the unsubstituted heterocyclic group include divalent groups such as carbazole, dibenzofuran, dibenzotifufen, fluorenone, oxazole, oxadiazole and thiadiazole.

The substituted arylene group or substituted heterocyclic group is a group in which an unsubstituted arylene group or heterocyclic group is substituted with a substituent. Specific examples of the substituent include a fluorine atom, Chlorine atom, bromine atom, halogen atom such as iodine atom, methyl, ethyl, n-propyl, is
Alkyl groups such as o-propyl, alkoxy groups such as methoxy, ethoxy and phenoxy, aralkyl groups such as benzyl, phenethyl and propylphenyl, nitro groups, cyano groups, substituted amino such as dimethylamino, dibenzylamino, diphenylamino and morpholino. Groups, phenyl, toluyl, biphenyl, naphthyl, anthryl, pyrenyl and other aryl groups, pyridyl, thienyl, furyl, quinolyl,
Heterocycles such as carbazolyl and the like can be mentioned.

In the general formula (4), Ar ¹ and Ar ² represent a substituted or unsubstituted aryl group. Specific examples thereof include a phenyl group, a polycyclic aromatic group, an aromatic heterocyclic group, biphenyl, terphenyl, naphthyl,
Anthryl, pyrenyl and the like can be mentioned. Specific examples of the substituent include the same substituents as the above X.

R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an aryl group.
Specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl and iso-propyl, alkoxy groups such as methoxy, ethoxy and phenoxy, aryl groups such as phenyl, biphenyl and naphthyl. Specific examples of the substituent include the same substituents as the above X.

R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, an alkoxy group, an aryl group, an amino group,
Represents any of the carbonyl groups. Specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl and iso-propyl, alkoxy groups such as methoxy, ethoxy and phenoxy, aryl groups such as phenyl, biphenyl and naphthyl, and amino such as dimethylamino and diphenylamino. And a carbonyl group such as methylcarbonyl, phenylcarbonyl, cyclohexylcarbonyl and the like. Specific examples of the substituent include the same substituents as the above X.

The example represented by the general formula (4) is ^{two of} Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represented by the general formula (1).
This corresponds to (1) (described above) of the method of constructing one with a substituted or unsubstituted fluorenyl group .

Next, another specific example of the organic compound of the present invention is shown by the general formula (5).

[0036]

[Chemical 8]

The example represented by the general formula (5) is constituted by arranging a substituted or unsubstituted fluorenyl group on all of Ar ¹ , Ar ² , Ar ³ and Ar ^{4 in} the general formula (1).

In the general formula (5), X represents a substituted or unsubstituted arylene group or a heterocyclic group, like other general formulas. Specific examples thereof include the same substituents as X in the above general formula (4).

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R
¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an aryl group. As a concrete example,
The same substituents as R ¹ , R ² , R ³ and R ^{4 in the} above general formula (4) can be mentioned.

R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group,
It represents any of a substituted or unsubstituted alkyl group, alkoxy group, aryl group, amino group and carbonyl group. Specific examples thereof include R in the above general formula (4).
⁵ include the same substituents as R ^6.

Using the general formulas (4) and (5),
Ar ¹ , Ar ² , Ar ^{3 represented} by the general formula (1),
An example is shown in which two or ^four of Ar ⁴ are composed of a substituted or unsubstituted fluorenyl group. Similarly to this,
The above-mentioned example in which three of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are substituted or unsubstituted fluorenyl groups can also be constituted.

The organic compound represented by the general formula (1) of the present invention can be obtained, for example, by reacting a corresponding iodine compound with an amine compound. The reaction is preferably carried out in the presence of a catalyst, and examples of the catalyst include metal catalysts such as copper catalysts.

The specific manufacturing method is as follows.
That is, the following general formula (2)

[0044]

[Chemical 9] (Wherein, X represents a substituted or unsubstituted arylene group or heterocyclic group), and a compound represented by the following general formula (3)

[0045]

[Chemical 10] (Wherein Ar and Ar ′ each represent a substituted or unsubstituted fluorenyl group or a substituted or unsubstituted aryl group), and the compound represented by the following general formula (1)

[0046]

[Chemical 11] (Wherein at least two of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent a substituted or unsubstituted fluorenyl group and the remaining represent a substituted or unsubstituted aryl group). It is also.

Specific examples of the organic compound represented by the general formula (1) are shown below, but the organic compound of the present invention is not limited to these. However, the following exemplified compound N
o. 71 to 86 are organic compounds represented by the general formula (1).
It is a compound that is not included in things.

[0048]

[Chemical 12]

[0049]

[Chemical 13]

[0050]

[Chemical 14]

[0051]

[Chemical 15]

[0052]

[Chemical 16]

[0053]

[Chemical 17]

[0054]

[Chemical 18]

[0055]

[Chemical 19]

[0056]

[Chemical 20]

[0057]

[Chemical 21]

[0058]

[Chemical formula 22]

[0059]

[Chemical formula 23]

[0060]

[Chemical formula 24]

[0061]

[Chemical 25]

[0062]

[Chemical formula 26]

[0063]

[Chemical 27]

[0064]

[Chemical 28]

[0065]

[Chemical 29]

[0066]

[Chemical 30]

[0067]

[Chemical 31]

[0068]

[Chemical 32]

[0069]

[Chemical 33]

[0070]

[Chemical 34]

[0071]

[Chemical 35]

[0072]

[Chemical 36]

[0073]

[Chemical 37]

The present invention includes a light emitting device. The light emitting device of the present invention is configured by disposing an organic compound layer composed of the compound represented by the general formula (1) between a pair of electrodes.

In the light emitting device of the present invention, the compound represented by the above general formula (1) is formed between the anode and the cathode by a vacuum vapor deposition method, a solution coating method or the like. The thickness of the organic layer is thinner than 2 μm, preferably 0.5 μm or less, and more preferably 1 nm to 500 nm.

The light emitting device of the present invention can also be constructed by disposing a plurality of layers between a pair of electrodes. Of the plurality of layers,
At least one layer may be composed of the compound represented by the general formula (1). In the light emitting device of the present invention,
By appropriately selecting the compound represented by the general formula (1), a light emitting device exhibiting a desired emission color can be formed.

Hereinafter, the light emitting device of the present invention will be described in more detail with reference to the drawings. FIG. 1 is a sectional view showing an example of the light emitting device of the present invention. FIG. 1 shows a structure in which an anode 2, a light emitting layer 3 and a cathode 4 are sequentially provided on a substrate 1. The light emitting device used here is useful when it has a single hole transporting ability, an electron transporting ability and a light emitting ability by itself, or when a compound having each characteristic is mixed and used.

FIG. 2 is a sectional view showing another example of the light emitting device of the present invention. In FIG. 2, an anode 2, a hole transport layer 5, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. In this case, the light-emitting substance uses a material having a hole-transporting property, an electron-transporting property, or both for each layer, and is used in combination with a simple hole-transporting substance or electron-transporting substance having no light-emitting property. Useful in cases. In this case, the light emitting layer 3 is composed of the hole transport layer 5 and the electron transport layer 6.

FIG. 3 is a sectional view showing still another example of the light emitting device of the present invention. FIG. 3 shows a structure in which an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. This separates the functions of carrier transport and light emission, and is used in combination with compounds that have hole transporting, electron transporting, and light emitting properties in a timely manner to greatly increase the degree of freedom in material selection and to increase light emission. Since various compounds having different wavelengths can be used, the emission hue can be diversified. Further, it becomes possible to effectively confine holes and electrons (or excitons) in the central light emitting layer to improve the light emitting efficiency. FIG. 4 shows an example in which the hole injecting and transporting layer 7, the hole transporting layer 5, and the electron transporting layer 6 are arranged between the anode and the cathode.

The compounds represented by the above-mentioned general formula (1) used in the present invention are all compounds having extremely excellent light emission characteristics as compared with the conventional compounds, and, if necessary, any of the compounds shown in FIGS. It is also possible to use an electroluminescent device having a form.

The compound represented by the general formula (1) used in the present invention has a hole transporting property, an electron transporting property, or both depending on the structure.
In either case of FIG. 4, only the compound represented by the general formula (1) may be used alone or in combination of two or more kinds,
Further, a layer of the compound of the general formula (1) and a layer of a compound different from this may be used in combination.

In the present invention, the compound represented by the general formula (1) is used as a constituent component of the light emitting layer or a constituent component of the charge transport layer. If necessary, it is studied in the field of electrophotographic photoreceptors. Hole-transporting compounds, known hole-transporting luminescent compounds (for example, compounds shown in Tables 1 to 5) or electron-transporting compounds, and known electron-transporting luminescent compounds (for example, compounds shown in Tables 1 to 5). The compounds listed in Tables 6 to 9) can also be used together.

Further, Table 10 shows examples of the dopant dyes, which are capable of significantly improving the light emission efficiency and changing the light emission color by doping a small amount in the light emitting layer. Used as.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

[Table 5]

[0089]

[Table 6]

[0090]

[Table 7]

[0091]

[Table 8]

[0092]

[Table 9]

[0093]

[Table 10]

In the electroluminescent device of the present invention, the layer containing the compound represented by the general formula (1) and the layer containing other organic compounds are generally formed into a thin film by vacuum vapor deposition or in combination with an appropriate binder resin. Form.

The binder can be selected from a wide range of binder resins, for example, polyvinylcarbazole resin, polycarbonate resin, polyester resin, polyarylate resin, butyral resin, polystyrene resin, polyvinyl acetal resin, diallyl phthalate resin, acrylic resin. , Methacrylic resin, phenolic resin, epoxy resin,
Examples thereof include silicone resin, polysulfone resin, and urea resin, but are not limited thereto. You may use these individually or in mixture of 2 or more types as a homopolymer or a copolymer polymer.

As the anode material, one having a work function as large as possible is preferable, and examples thereof include nickel, gold, platinum, palladium, selenium, rhenium, iridium and alloys thereof, tin oxide, indium tin oxide (ITO), and copper iodide. Is preferred. Further, a conductive polymer such as poly (3-methylthiophene), polyphenylene sulfide or polypyrrole can also be used.

On the other hand, as the cathode material, silver, lead, tin, magnesium, aluminum, calcium, manganese, indium, chromium or an alloy thereof having a small work function is used.

At least one of the materials used for the anode and the cathode is 50 in the emission wavelength region of the device.
%, It is preferable to transmit more light. Further, as the transparent substrate used in the present invention, glass, plastic film or the like is used.

[0099]

The present invention will be described below with reference to specific examples.
It is not limited to these examples.

Example 1 Synthesis of N, N, N ', N' tetra- [2- (9,9'-dimethylfluorenyl)]-2,7-diamino-9,9-dimethylfluorene (exemplified compound No. 48) 2,7-diamino-9,9-in a 100 ml eggplant flask.
Dimethylfluorene 2.24 g, 2-iodo-9,9-
Dimethylfluorene 19.2 lg, potassium carbonate 7.5
g, 6.0 g of copper powder, and 50 ml of orthodichlorobenzene were charged, a cooling pipe was attached, and reflux stirring was continued for 32 hours. The reaction solution was cooled and then filtered, and orthodichlorobenzene was concentrated and removed under reduced pressure, and then toluene was added to precipitate a crude crystal, which was collected by filtration.

The crude crystals thus obtained were purified with a toluene / hexane mixed solvent using a silica gel column to give N, N, N ', N' tetra-represented by the following structural formula.
[2- (9,9'-Dimethylfluorenyl)]-2,7
5.4 lg (yield 54.6%) of pale yellow fine crystals of -diamino-9,9-dimethylfluorene were obtained.

[0102]

[Chemical 38]

A differential scanning calorimeter (Differential Scanning Ca) manufactured by Perkin-Elmer Co., Ltd.
The melting point (Tm) and the glass transition point (Tg) of the obtained compound were measured using a lorimeter). As a result, Tm: 309.0 to 310.5 ° C, Tg: 186 ° C
Met.

Further, IR measurement was performed using an FT-IR measuring device manufactured by JASCO Corporation. The obtained IR chart is shown in FIG.

Example 2 N, N'-di (4-biphenyl) -N, N'-di [2-
(9,9-Dimethylfluorenyl)]-4,4′-diaminobiphenyl Synthesis (Exemplified Compound No. 7) 4.88 g of N, N′-diphenylbenzidine and 2-iodo-9,9 in a 100 ml round-bottomed flask. -Dimethylfluorene 6.40 g, potassium carbonate 4.00 g, copper powder 3.0
g and 30 ml of ortho-dichlorobenzene were charged, a cooling tube was attached, and reflux stirring was continued for 20 hours. After cooling the reaction solution, it was filtered, and orthodichlorobenzene was concentrated and removed under reduced pressure, and then methanol was added to precipitate a crude crystal, which was collected by filtration.

The obtained crude crystals were purified with a toluene / hexane mixed solvent using a silica gel column to give N, N'-di (4-biphenyl) -N, N'-di [represented by the following structural formula. 5.50 g (yield 63.0%) of pale yellow fine crystals of 2- (9,9-dimethylfluorenyl)]-4,4'-diaminobiphenyl were obtained.

[0107]

[Chemical Formula 39]

When the melting point (Tm) and the glass transition point (Tg) were measured in the same manner as in Example 1, Tm: 267.0
It was 268.5 ° C and Tg: 120.5 ° C. Further, IR measurement was performed in the same manner as in Example 1. Figure 6 shows the IR chart
Shown in.

Example 3 Here, a light emitting device was actually manufactured and the luminance was measured. Tin oxide-indium (ITO) on glass substrate
Was used to form a film having a thickness of 100 nm by a sputtering method as a transparent supporting substrate. After cleaning this transparent support substrate,
The exemplified compound No. 13 is formed to a film thickness of 65 nm,
After forming an aluminum quinolinol film on it with a film thickness of 65 nm, a metal electrode having an atomic ratio of Mg: Ag of 10: 1 was further formed by vacuum vapor deposition to form an organic EL device. The degree of vacuum during vapor deposition was 3 to 4 × 10 ⁻⁶ torr, and the film formation rate was 0.2 to 0.3 nm / se for the organic layer.
c and the metal electrode was set to 2.0 nm / sec.

When a direct current was applied to the element thus obtained with the ITO electrode as an anode and the Mg / Ag electrode as a cathode, a current flowed through the element at a current density of 37 mA / cm ² at an applied voltage of 11 V, Green light emission was observed at a luminance of 2,130 cd / m ² . When a current density was maintained at 4.7 mA / cm ² in a nitrogen atmosphere and a voltage was applied for 100 hours, the initial luminance was changed from 180 cd / m ² to 155 cd / m ² after 100 hours, and the deterioration of luminance was very small.

Examples 4 to 8 Exemplified compound No. used in Example 3 above. 13 in place of the exemplified compound No. A device was prepared in the same manner as in Example 3 except that 8, 38, 48, 51 and 52 were used.

The results of measuring the performance of the device are shown in Table 11 below.

[0113]

[Table 11]

It is understood from Table 11 that all the light emitting elements have high brightness and the deterioration of the brightness is very small.

Comparative Example 1 Exemplified compound No. used in Example 3 above. A device was prepared in the same manner as in Example 3 except that the compound of the following structural formula was used instead of 13.

[0116]

[Chemical 40]

When a direct current was applied to the element thus obtained with the ITO electrode as an anode and the Mg / Ag electrode as a cathode, a current flowed through the element at a current density of 15 mA / cm ² at an applied voltage of 15 V, Green light emission was observed at a brightness of 35 cd / m ² . When the current density was kept at 27 mA / cm ² under a nitrogen atmosphere and a voltage was applied for 100 hours, the initial luminance was 100 cd / m ² to 8 c after 100 hours.
It became d / m ² .

As is clear from Examples 3 to 8 and Comparative Example 1, the light emitting device using the organic compound of the present invention is extremely excellent in brightness and life as compared with the light emitting device using the comparative compound. Recognize.

Example 9 A light emitting device having the structure shown in FIG. 4 was prepared. A transparent support substrate was prepared by depositing tin oxide-indium (ITO) (anode 2) on the glass substrate 1 by sputtering to have a film thickness of 100 nm. After washing this transparent support substrate, the exemplified compound No. 53 is formed into a film with a thickness of 20 nm (hole injecting and transporting layer 7), and a hole transporting compound (TPD) shown below is formed into a film with a thickness of 50 nm on the hole transporting layer 5.
And Next, the electron transport compound (Alq
₃ ) is formed into a film having a thickness of 65 nm to form an electron transport layer 6, and then a metal electrode made of aluminum (cathode 4) is formed thereon.
Was formed with a film thickness of 150 nm to prepare an element.

[0120]

[Chemical 41]

When a direct current was applied to the device thus obtained with the ITO electrode as an anode and the Al electrode as a cathode, a current flowed through the device at a current density of 230 mA / cm ² at an applied voltage of 15 V. Green light emission was observed at a luminance of 000 cd / m ² . When a current density was kept at 4.3 mA / cm ² and a voltage was applied for 100 hours under a nitrogen atmosphere, the initial luminance was changed from 200 cd / m ² to 185 cd / m ² after 100 hours, and the deterioration of luminance was very small.

Example 10 A transparent support substrate was prepared by depositing tin oxide-indium (ITO) on a glass substrate by sputtering to have a film thickness of 100 nm. After washing this transparent support substrate, the exemplified compound No. 46 with a film thickness of 60 nm, and a fluorescent dye (DCM) represented by the following structural formula 1
After forming a film with a film thickness of 0 nm, an electron transport compound (A
1q3) was formed into a film having a thickness of 65 nm. Then, a metal electrode made of aluminum was formed thereon with a film thickness of 150 nm, to fabricate an element having the structure shown in FIG.

[0123]

[Chemical 42]

When a direct current was applied to the element thus obtained with the ITO electrode as the anode and the Al electrode as the cathode, a current flowed through the element at a current density of 150 mA / cm ² at an applied voltage of 17 V, Orange emission was observed at a luminance of 170 cd / m ² .

The current density was 5.1 m in a nitrogen atmosphere.
When a voltage was applied for 100 hours keeping the A / cm ^2, the initial luminance 100 cd / m ² to 100 more hours after 85cd / m ²
The deterioration of the brightness was very small.

Example 11 A transparent support substrate was prepared by depositing tin oxide-indium (ITO) on a glass substrate by sputtering to have a film thickness of 100 nm. After washing this transparent support substrate, the exemplified compound No. 17, 0.10 g, oxadiazole compound (OXD-7) of the following structural formula 0.10 g, polycarbonate resin (weight average molecular weight 35,000) 0.30
A coating liquid prepared by dissolving g of the above in 25 ml of tetrahydrofuran was prepared, and this coating liquid was applied onto a substrate by a dip coating method to form a film having a thickness of 120 nm. Mg / I on it
A metal electrode made of n was formed with a film thickness of 150 nm to prepare an element having the structure shown in FIG.

When a direct current was applied to the element thus obtained using the ITO electrode as an anode and the Mg / In electrode as a cathode, a current flowed through the element at a current density of 25 mA / cm ² at an applied voltage of 12 V, Blue-green light emission was observed at a luminance of 250 cd / m ² .

In addition, the current density was 10 mA in a room atmosphere.
When a voltage was applied for 100 hours while maintaining at / cm ² , the initial luminance was changed from 130 cd / m ² to 95 cd / m ² after 100 hours, and the deterioration of luminance was very small.

[0129]

[Chemical 43]

Comparative Example 2 Exemplified compound No. 1 used in Example 3 above. A device was prepared in the same manner as in Example 3 except that the compound of the following structural formula was used instead of 13.

[0131]

[Chemical 44]

When a direct current was applied to the element thus obtained using the ITO electrode as an anode and the Mg / Ag electrode as a cathode, a current flowed through the element at a current density of 20 mA / cm ² at an applied voltage of 15 V, Green light emission was observed at a brightness of 41 cd / m ² . When the current density was kept at 15 mA / cm ² and a voltage was applied for 100 hours in a nitrogen atmosphere, the initial luminance was 30 cd / m ² to 1 cd after 100 hours.
/ M ² .

[0133]

As described above, according to the present invention, it is possible to obtain a novel organic compound material that contributes to high-luminance light output and high durability. Further, according to the present invention, it is possible to obtain a light emitting device having various emission wavelengths, exhibiting various emission hues and extremely durable. Further, according to the light emitting element of the present invention, it is possible to output light with high brightness.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a light emitting device of the present invention.

FIG. 2 is a cross-sectional view showing an example of a light emitting device of the present invention.

FIG. 3 is a sectional view showing an example of a light emitting device of the present invention.

FIG. 4 is a sectional view showing an example of a light emitting device of the present invention.

5 is an exemplary compound No. 1 synthesized in Example 1. FIG. 48 I
It is an R chart figure.

6 is an exemplary compound No. 1 synthesized in Example 2. FIG. IR of 7
It is a chart figure.

[Explanation of symbols]

1 substrate 2 anode 3 light emitting layer 4 cathode 5 hole transport layer 6 Electron transport layer 7 hole injection transport layer

Continuation of the front page (72) Inventor Seiji Mashita 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-5-25473 (JP, A) JP-A-4-78859 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) CA (STN) REGISTRY (STN)

Claims (18)

(57) [Claims] 1. The following general formula (1): (Wherein, X represents a substituted or unsubstituted arylene group or a heterocyclic ^{group, Ar 1, Ar 2, Ar} 3, Ar 4 represents a substituted or unsubstituted aryl group. However, Ar ¹
Alternatively , at least one of Ar ³ and Ar ² or Ar
^At least one of ⁴ is a halogen atom, an alkyl group, or
Lucoxy group, aralkyl group, nitro group, cyano group, amine
Group, an aryl group, or a heterocyclic group
More substituted or unsubstituted fluorenyl
Represents a group. ) An organic compound represented by. 2. The organic compound according to claim 1, wherein the arylene group is selected from phenylene, biphenylene, terphenylene, naphthylene, fluorenylene, pyrenylene and stilbene. 3. The organic compound according to claim 1, wherein the heterocyclic group is selected from the divalent groups of carbazole, dibenzofuran, dibenzotifufen, fluorenone, oxazole, oxadiazole and thiadiazole. 4. The aryl group is selected from a phenyl group, a polycyclic aromatic group, and an aromatic heterocyclic group.
The organic compound according to. 5. ^{One of} said Ar ¹ or Ar ³ and Ar
The organic compound according to claim 1, wherein one of ^{2 and} Ar ⁴ is composed of a substituted or unsubstituted fluorenyl group. 6. One of Ar ¹ or Ar ³ and Ar
^2. The organic compound according to claim 1, wherein Ar and Ar ⁴ are substituted or unsubstituted fluorenyl groups. 7. One of Ar ² or Ar ⁴ and Ar
The organic compound according to claim ¹ , wherein ¹ and Ar ³ are each a substituted or unsubstituted fluorenyl group. 8. The organic compound according to claim ¹ , wherein all of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are constituted by a substituted or unsubstituted fluorenyl group. 9. A compound represented by the general formula (1)
However, the following No. 7 or No. Compound represented by 48
The organic compound according to claim 1, which is [Chemical formula 45] 10. A light emitting device comprising an organic compound layer disposed between a pair of electrodes, wherein the organic compound layer is represented by the following general formula (1): (Wherein, X represents a substituted or unsubstituted arylene group or a heterocyclic ^{group, Ar 1, Ar 2, Ar} 3, Ar 4 represents a substituted or unsubstituted aryl group. However, Ar ¹
Alternatively , at least one of Ar ³ and Ar ² or Ar
^At least one of ⁴ is a halogen atom, an alkyl group, or
Lucoxy group, aralkyl group, nitro group, cyano group, amine
Group, an aryl group, or a heterocyclic group
More substituted or unsubstituted fluorenyl
Represents a group. ) A light-emitting device comprising an organic compound represented by the formula (1). Wherein said arylene group is phenylene, biphenylene, terphenylene, naphthylene, fluorenylene, pyrenylene, claim 1 selected from stilbenes
The light emitting device according to 0 . 12. The light emitting device according to claim 10 , wherein the heterocyclic group is selected from a divalent group of carbazole, dibenzofuran, dibenzotifufen, fluorenone, oxazole, oxadiazole and thiadiazole. Wherein said aryl group is a phenyl group or a polycyclic aromatic group, claims selected from aromatic heterocyclic groups
10. The light emitting device according to 10 . 14. One of said Ar ¹ or Ar ³ and A
The light emitting device according to claim 10 , wherein one of r ^{2 and} Ar ⁴ is composed of a substituted or unsubstituted fluorenyl group. 15. ^{One of} said Ar ¹ or Ar ³ and A
The light emitting device according to claim 10 , wherein r ² and Ar ⁴ are each composed of a substituted or unsubstituted fluorenyl group. 16. One of said Ar ² or Ar ⁴ and A
The light emitting device according to claim 10 , wherein r ¹ and Ar ³ are each composed of a substituted or unsubstituted fluorenyl group. 17. All of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are composed of a substituted or unsubstituted fluorenyl group.
The light emitting device according to claim 10 . 18. A compound represented by the general formula (1)
However, the following No. 7 or No. Compound represented by 48
The light emitting device according to claim 10, wherein [Chemical formula 46]