JPH0812600A - Phenylanthracene derivative and organic el element - Google Patents

Abstract

PURPOSE:To provide the subject new phenylanthracene derivative having a specified structure, exhibiting a low crystallinity, capable of forming a thin film having a stable amorphous state and useful for, e.g. a light-emitting layer of an organic EL device capable of stably emitting high-brightness blue light. CONSTITUTION:This is a new phenylanthracene derivative having a structure of the formula, A1LA2 (A1 and A2 are each monophenylanthryl or diphenylanthryl; L is a single bond or a divalent bonding group), represented by formula I (R1 and R2 are each an alkyl, a cyclo-alkyl, an aryl, an alkenyl, an alkoxy, an aryloxy, amino or a heterocyclic group; r1 and r2 are each 0 or 1 to 5; L1 is single bond, an arylene, etc.) or formula II (R3 and R4 are each same as R1; r3 and r4 are each 0 or 1 to 5; L2 is same as L1) and useful for, e.g. a light-emitting layer for emitting blue light in an organic EL device. This compound is synthesized by coupling 2-chloro-9,10-diphenylanthracene, etc., in the presence of bis(1,5-cyclooctadiene)nickel, 2,2'-bipyridyl, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an organic EL (electroluminescence).
More specifically, the present invention relates to an element that emits light by applying an electric field to a laminated thin film made of an organic compound.

[0002]

2. Description of the Related Art An organic EL device has a structure in which a thin film containing a fluorescent organic compound is sandwiched between a cathode and an anode, and electrons and holes are injected into the thin film to recombine to generate excitons ( An element that emits light by utilizing the emission of light (fluorescence/phosphorescence) when the exciton is deactivated.

The characteristic of the organic EL element is that it is capable of surface emission with high luminance of about 100 to 10000 cd/m ² at a low voltage of about 10 V, and it emits light from blue to red by selecting the type of fluorescent substance. Is possible.

On the other hand, the problems of the organic EL device are that the emission life is short, the storage durability and the reliability are low, and the cause of this is that the physical change of the organic compound (such as the growth of crystal domains causes the interface This causes non-uniformity, which causes deterioration of the charge injection capability of the device, short circuit, and dielectric breakdown.In particular, when a low molecular weight compound having a molecular weight of 500 or less is used, the appearance and growth of crystal grains occur, and the film property is significantly deteriorated.
Further, even if the interface of ITO or the like is rough, the appearance and growth of crystal grains occur remarkably, the luminous efficiency is lowered, the current leaks, and no light is emitted. It also causes a dark spot, which is a partially non-luminous portion. )

Oxidation/peeling of cathode (Na, Mg, Al, etc. have been used as a metal having a small work function in order to facilitate injection of electrons. These metals react with moisture and oxygen in the atmosphere. , Peeling of the organic layer from the cathode occurs and charge injection becomes impossible.In particular, when a film is formed by spin coating using a polymer compound or the like,
Residual solvent and decomposition products during film formation accelerate the oxidation reaction of the electrode,
The peeling of the electrode occurs and a partial non-light emitting portion is generated. )

Low luminous efficiency and high calorific value (Because a current is passed through the organic compound, the organic compound must be placed under a high electric field strength and cannot escape from heat generation.
Due to the heat, deterioration and destruction of the element occur due to melting, crystallization, thermal decomposition of the organic compound. )

Examples include photochemical changes and electrochemical changes of the organic compound layer.

In particular, regarding blue light emitting devices, there are few blue light emitting materials that provide highly reliable and stable devices. Generally, blue light emitting materials have high crystallinity. For example, although diphenylanthracene has a high fluorescence quantum yield,
Due to its high crystallinity, it was not possible to provide a device with high brightness, high efficiency and high reliability even if a device was manufactured using this compound as a light emitting material [C.Adachi, et al., Appli.Phys.Lett ,.56,
799 (1990) ].

[0009]

The object of the present invention is to provide a novel phenylanthracene derivative as an optoelectronic functional material which is less susceptible to physical changes, photochemical changes and electrochemical changes. Used,
It is to realize an organic EL element having various emission colors with high reliability and emission efficiency, particularly an emission color of blue. In particular, using an organic thin film formed by vapor deposition of a compound with a large molecular weight, high reliability that suppresses the rise and decrease in driving voltage when driving the device, current leakage, and the appearance/growth of partial non-light emitting parts. It is to realize a high brightness light emitting device.

[0010]

[In the formula (I), A ₁ and A ₂ each represent a monophenylanthryl group or a diphenylanthryl group, and these may be the same or different. L represents a single bond or a divalent linking group. ]

(2) The phenylanthracene derivative of the above (1) represented by the following chemical formula 3 or chemical formula 4.

[0011]

[Chemical 3]

[0012]

[Chemical 4]

[In Chemical Formula 3, R ₁ and R ₂ each represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group, which may be the same or different. May be r1 and r2 each represent 0 or an integer of 1 to 5. When each of r1 and r2 is an integer of 2 or more, R _{1 s} and R _{2 s} may be the same or different, and R _{1 s} or R _{2 s} are bonded to each other to form a ring. Good. L ₁ represents a single bond or an arylene group, and the arylene group is an alkylene group, —O—, or —S.
-Or-NR- (wherein R represents an alkyl group or an aryl group) may be present. Conversion 4
In the formula, R ₃ and R ₄ each represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group,
These may be the same or different. r3 and r4 each represent 0 or an integer of 1 to 5. When r3 and r4 are each an integer of 2 or more, R _{3 s} and R _{4 s} may be the same or different, and R _{3 s} or R _{4 s} are bonded to each other to form a ring. Good. L ₂ represents a single bond or an arylene group, and the arylene group is an alkylene group, —O—, —S— or —NR—.
(Here, R represents an alkyl group or an aryl group.)
May intervene. (3) An organic EL device having at least one organic compound layer containing the phenylanthracene derivative of (1) or (2) above. (4) The organic EL device according to (3), wherein the organic compound layer containing the phenylanthracene derivative is a light emitting layer. (5) The organic EL device according to (4), further including at least one hole injection layer, at least one hole transport layer, and at least one electron injection transport layer. (6) The above (4), further having at least one hole injection layer, at least one hole transport layer, at least one electron transport layer, and at least one electron injection layer.
Organic EL device. (7) The organic EL device according to (3), wherein the organic compound layer containing the phenylanthracene derivative is an electron injecting and transporting layer, and further has a light emitting layer. (8) At least one light emitting layer is provided, and the light emitting layer is a mixed layer of an electron injecting and transporting compound and a hole injecting and transporting compound, and the mixed layer contains the phenylanthracene derivative. 3) Organic EL device.

[0014]

In the organic EL device of the present invention, the compound represented by the above formula (I), preferably the chemical formulas 3 and 4 is used for the light emitting layer, and therefore, a high brightness of about 10,000 cdm ^-2 or more is stable. can get. It also has high heat resistance and durability,
Stable driving is possible even when the device current density is about 1000 mAcm ^-2 .

Since the vapor-deposited film of the above compound is in a stable amorphous state, the physical properties of the thin film are good and uniform light emission is possible without unevenness. Also, it is stable for more than a year in the atmosphere and does not cause crystallization.

Further, it is possible to form a stable amorphous thin film by spin coating with a chloroform solution.

Further, the organic EL device of the present invention efficiently emits light at a low driving voltage.

The maximum emission wavelength of the organic EL device of the present invention is about 400 to 700 nm.

[0019]

[Specific Structure] The specific structure of the present invention will be described in detail below.

The phenylanthracene derivative of the present invention is represented by the formula (I). Explaining the formula (I), A ₁ and A ₂ each represent a monophenylanthryl group or a diphenylanthryl group, and these may be the same or different.

The monophenylanthryl group or diphenylanthryl group represented by A ₁ or A ₂ may be unsubstituted or may have a substituent. When the substituent is present, the substituent is alkyl. A group, an aryl group, an alkoxy group, an aryloxy group, an amino group and the like can be mentioned, and these substituents may be further substituted. These substituents will be described later. Further, the substitution position of such a substituent is not particularly limited, but not an anthracene ring,
It is preferably a phenyl group bonded to the anthracene ring.

Further, the bonding position of the phenyl group in the anthracene ring is preferably 9-position and 10-position in the anthracene ring.

In the formula (I), L represents a single bond or a divalent group, and the divalent group represented by L is preferably an arylene group in which an alkylene group or the like may be present. Such an arylene group will be described later.

Among the phenylanthracene derivatives represented by the formula (I), those represented by Chemical formulas 3 and 4 are preferable. Explaining Chemical formula 3, in Chemical formula 3, R ₁ and R ₂ each represent an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group.

The alkyl group represented by R ₁ and R ₂ may be linear or branched, and is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. Is preferred. In particular, an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and specifically, a methyl group, an ethyl group,
(N-,i-)propyl group, (n-,i-,s-,t
-) Butyl group and the like can be mentioned.

Examples of the cycloalkyl group represented by R ₁ and R ₂ include a cyclohexyl group and a cyclopentyl group.

The aryl group represented by R ₁ and R ₂ preferably has 6 to 20 carbon atoms and may have a substituent such as a phenyl group and a tolyl group. Specific examples thereof include a phenyl group, (o-, m-, p-)tolyl group, pyrenyl group, naphthyl group, anthryl group, biphenyl group, phenylanthryl group and tolylanthryl group.

The alkenyl group represented by R ₁ and R ₂ preferably has 6 to 50 carbon atoms in total, and may be unsubstituted or may have a substituent.
It is preferable to have a substituent. At this time, the substituent is preferably an aryl group such as a phenyl group. Specific examples include a triphenyl vinyl group, a tritolyl vinyl group, a tribiphenyl vinyl group and the like.

The alkoxy group represented by R ₁ and R ₂ preferably has an alkyl group moiety having 1 to 6 carbon atoms, and specific examples thereof include a methoxy group and an ethoxy group. The alkoxy group may be further substituted.

Examples of the aryloxy group represented by R ₁ and R ₂ include a phenoxy group.

The amino group represented by R ₁ and R ₂ may be unsubstituted or may have a substituent, but preferably has a substituent. In this case, the substituent is an alkyl group (methyl group). Group, ethyl group, etc.), aryl group (phenyl group, etc.) and the like. Specific examples thereof include a diethylamino group, a diphenylamino group and a di(m-tolyl)amino group.

The heterocyclic group represented by R ₁ and R ₂ is
Examples thereof include a bipyridyl group, a pyrimidyl group, a quinolyl group, a pyridyl group, a thienyl group, a furyl group and an oxadiazoyl group. These may have a substituent such as a methyl group and a phenyl group.

In the chemical formula 3, r1 and r2 are respectively
It represents 0 or an integer of 1 to 5, and 0 or 1 is particularly preferable. When r1 and r2 are each an integer of 1 to 5, particularly 1 or 2, R ₁ and R ₂ are each an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an amino group. Is preferred.

In Chemical Formula 3, R ₁ and R ₂ may be the same or different, and when a plurality of R ₁ and R ₂ are present, R ₁ and R ₂ are the same or different. may also be, R ₁ or between R ₂ together may form a ring of benzene ring, attached, preferably even when they form a ring.

In the chemical formula 3, L ₁ represents a single bond or an arylene group. As the arylene group represented by L ₁ ,
It is preferably unsubstituted, and specific examples thereof include ordinary arylene groups such as a phenylene group, a biphenylene group, and an anthrylene group, as well as those in which two or more arylene groups are directly linked. L ₁ is a single bond, p
-Phenylene group, 4,4'-biphenylene group and the like are preferable.

The arylene group represented by L ₁ is 2
One or more arylene groups are alkylene groups, -O
It may be linked via -, -S- or -NR-. Here, R represents an alkyl group or an aryl group. Examples of the alkyl group include a methyl group and an ethyl group, and examples of the aryl group include a phenyl group. Among them, the aryl group is preferred, other phenyl group of the above, A _1, may be A _2, further it may be those A ₁ or A ₂ is substituted in the phenyl group.

As the alkylene group, a methylene group,
Ethylene groups and the like are preferred. Specific examples of such an arylene group are shown below.

[0038]

[Chemical 5]

Next, the chemical formula 4 will be explained. In the chemical formula 4, R ₃ and R ₄ are the same as the R ₁ and R ₂ in the chemical formula 3.
And also r3 and r4 are r1 and r2 in Chemical formula 3.
Further, L ₂ has the same meaning as L ₁ in Chemical formula 3, and preferred ones are also the same.

The reduction in the 4 may be one that is different even in the same R ₃ and R _4, when R ₃ and R ₄ there are a plurality each, R ₃ together, R ₄ together are different in each identical R _{3 s} or R _{4 s} may be bonded to each other to form a ring such as a benzene ring, and the case of forming a ring is also preferable.

The compounds represented by Chemical formulas 3 and 4 are exemplified below, but the present invention is not limited thereto. It should be noted that in Chemical formula 6, Chemical formula 8, Chemical formula 10, Chemical formula 12, Chemical formula 14, Chemical formula 16, and Chemical formula 18, general formulas are shown, and Chemical formula 7, Chemical formula 9, Chemical formula 11, Chemical formula 13,
Specific examples corresponding to Chemical formula 15, Chemical formula 17, Chemical formula 19, and Chemical formula 20 are R _{11 to} R ₁₅ , R _{21 to} R _25, or R _{31 to} R ₃₅ , R _41.
It is shown as a combination of R ₄₅ .

[0042]

[Chemical 6]

[0043]

[Chemical 7]

[0044]

[Chemical 8]

[0045]

[Chemical 9]

[0046]

[Chemical 10]

[0047]

[Chemical 11]

[0048]

[Chemical formula 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]

The phenylanthracene derivative of the present invention (hereinafter, also referred to as "the compound of the present invention") is prepared by converting (1) a halogenated diphenylanthracene compound into Ni(cod)
₂ [cod: 1,5-cyclooctadiene], or a dihalogenated aryl is Grignard to form NiCl ₂ (dppe) [dppe: diphenylphosphinoethane], NiCl ₂ (dpppp) [dpp
p: diphenylphosphinopropane], etc., and a method of cross-coupling using a Ni complex or the like, It can be obtained by a method such as cross coupling.

The compound thus obtained can be identified by elemental analysis, mass spectrometry, infrared absorption spectrum, ¹ H or ¹³ C nuclear magnetic resonance absorption (NMR) spectrum and the like.

The phenylanthracene derivative of the present invention is
It has a molecular weight of about 400 to 2000, further about 400 to 1000, a high melting point of 200 to 500° C., and 8
It exhibits a glass transition temperature (Tg) of 0-250°C, even 100-250°C, even more 130-250°C, especially 150-250°C. Therefore, a smooth and good film in an amorphous state, which is transparent and stable even at room temperature or more, is formed by ordinary vacuum vapor deposition and the good film state is maintained for a long period of time.

The organic EL device of the present invention (hereinafter, also referred to as “EL device”) has at least one organic compound layer, and at least one organic compound layer contains the compound of the present invention. An example of the structure of the organic EL device of the present invention is shown in FIG. The organic EL device 1 shown in the figure has an anode 3, a hole injecting and transporting layer 4, a light emitting layer 5, an electron injecting and transporting layer 6, and a cathode 7 in this order on a substrate 2.

The light emitting layer has a function of injecting holes and electrons, a function of transporting them, and a function of generating excitons by recombination of holes and electrons. The hole injecting and transporting layer has a function of facilitating injection of holes from the anode, a function of transporting holes and a function of hindering electron transport, and the electron injecting and transporting layer is
These layers have the function of facilitating the injection of electrons from the cathode, the function of transporting electrons, and the function of hindering the transport of holes. These layers increase and confine holes and electrons injected into the light emitting layer. To optimize the recombination region and improve the luminous efficiency. The electron injecting and transporting layer and the hole injecting and transporting layer are
It is provided as necessary in consideration of the electron injection, electron transport, hole injection, and hole transport functions of the compound used for the light emitting layer. For example, when the compound used for the light emitting layer has a high hole injecting/transporting function or an electron injecting/transporting function, the light emitting layer is not provided with the hole injecting/transporting layer or the electron injecting/transporting layer. It can be configured to also serve as a transport layer. In some cases, neither the hole injecting/transporting layer nor the electron injecting/transporting layer may be provided. Also,
The hole injecting and transporting layer and the electron injecting and transporting layer may each be provided with a layer having an injection function and a layer having a transport function separately.

Since the compound of the present invention is a relatively neutral compound, it is preferably used for the light emitting layer, but it is also applicable to the hole injecting and transporting layer and the electron injecting and transporting layer.

Further, recombination is achieved by controlling the film thickness while considering the carrier mobility and carrier density (determined by the ionization potential and electron affinity) of the light emitting layer, electron injecting and transporting layer and hole injecting and transporting layer to be combined. It is possible to freely design the region and the light emitting region, and it is possible to design the emission color, control the emission brightness and emission spectrum by the interference effect of both electrodes, and control the spatial distribution of emission.

The case where the compound of the present invention is used in the light emitting layer will be described. In addition to the compound of the present invention, other fluorescent substances may be used in the light emitting layer. As other fluorescent substances,
For example, compounds such as those disclosed in JP-A-63-264692, such as quinacridone, rubrene,
At least one selected from compounds such as styryl dyes
Seed. The content of such a fluorescent substance is preferably 10 mol% or less of the compound of the present invention.
By appropriately selecting and adding such a compound,
The emitted light can be shifted to the long wavelength side.

The light emitting layer may contain a singlet oxygen quencher. Examples of such a quencher include nickel complex, rubrene, diphenylisobenzofuran, and tertiary amine. The content of such a quencher is preferably 10 mol% or less of the compound of the present invention.

When the compound of the present invention is used in the light emitting layer, the hole injecting and transporting layer and the electron injecting and transporting layer may be formed in the usual organic E
Various organic compounds used in the L element, for example, JP-A-63-295695 and JP-A-2-191694.
Various organic compounds described in, for example, Japanese Patent Laid-Open No. 3-792 can be used. For example, an aromatic tertiary amine, a hydrazone derivative, a carbazole derivative, a triazole derivative, an imidazole derivative or the like can be used for the hole injecting/transporting layer, and an organic metal complex such as aluminum quinolinol is used for the electron injecting/transporting layer. A derivative, an oxadiazole derivative, a pyridine derivative, a pyrimidine derivative, a quinoline derivative, a quinoxaline derivative, a diphenylquinone derivative, a perylene derivative, a fluorene derivative, or the like can be used.

When the hole injecting and transporting layer is separately formed into the hole injecting layer and the hole transporting layer, preferred combinations can be selected and used from the compounds for the hole injecting and transporting layer. At this time, it is preferable to stack layers of a compound having a small ionization potential in this order from the anode (ITO or the like) side. Further, it is preferable to use a compound having a good thin film property on the surface of the anode. This stacking order is the same when two or more hole injecting and transporting layers are provided. By adopting such a stacking order, the driving voltage is lowered, and it is possible to prevent the occurrence of current leakage and the generation/growth of dark spots. In addition, since vapor deposition is used for device formation, a thin film of about 1 to 10 nm can be made uniform and pinhole-free, so that the hole injection layer has a small ionization potential and absorption in the visible region. Even if such a compound is used, it is possible to prevent a decrease in efficiency due to a change in the color tone of the emission color or reabsorption.

When the electron injecting and transporting layer is separately formed into the electron injecting layer and the electron transporting layer, preferred combinations can be selected and used from the compounds for the electron injecting and transporting layer. At this time, it is preferable to stack the layers of the compound having a large electron affinity value in this order from the cathode side. This stacking order is the same when two or more electron injecting and transporting layers are provided.

In the present invention, it is also preferable that the light emitting layer is a mixed layer of an electron injecting/transporting compound and a hole injecting/transporting compound. Then, the compound of the present invention is contained in such a mixed layer. Since the compound of the present invention is usually contained as a fluorescent substance, more specifically, when the compound of the present invention is an electron injecting and transporting compound, another hole injecting and transporting compound may be further added. Is preferable, and when the compound of the present invention is a hole injecting/transporting compound, it is preferable to add another electron injecting/transporting compound. The mixing ratio of the electron injecting and transporting compound and the hole injecting and transporting compound in the above mixed layer is 60:40 to 40:60 in terms of weight ratio of electron injecting and transporting compound:hole injecting and transporting compound.
Is preferable, and particularly about 50:50 is preferable.

The electron injecting and transporting compound used for this mixing is selected from the above compounds for the electron injecting and transporting layer, and the hole injecting and transporting compound is selected from the above compounds for the hole injecting and transporting layer. Can be used. Moreover, you may select and use from the compound of this invention depending on the case. Furthermore, in the mixed layer, an electron injecting and transporting compound,
The hole injecting and transporting compounds may be used alone or in combination of two or more. The mixed layer may be doped with the compound of the present invention or another fluorescent substance in order to increase the emission intensity.

Further, a mixed layer of another electron injecting/transporting compound and another hole injecting/transporting compound may be formed, and such a mixed layer may be doped with the compound of the present invention.

By applying such a mixed layer to an EL device, the stability of the device is improved.

The compound of the present invention is also preferably used in the electron injecting and transporting layer. In this case, as the fluorescent substance used in the light emitting layer, it is preferable to use a substance having fluorescence having a wavelength longer than or about the same as the wavelength of the compound of the present invention. For example, it can be selected and used from the above-mentioned fluorescent substances that can be used in combination with the compound of the present invention in the light emitting layer. Also,
In such a constitution, the compound of the present invention can be further used in the light emitting layer. The compound of the present invention can also be used in a light emitting layer which also serves as an electron injecting and transporting layer.

The compound of the present invention can be used in the hole injecting and transporting layer.

When the compound of the present invention is used in the hole injecting and transporting layer, the fluorescent substance used in the light emitting layer may be selected from those having fluorescence of a longer wavelength than that of the compound of the present invention. It may be appropriately selected from one or more fluorescent substances used in combination with the compound of the present invention in the layer. In such a case, the compound of the present invention can be used in the light emitting layer.

In the above, when another fluorescent substance is mainly used in the light emitting layer, the compound of the present invention may be added as a fluorescent substance in an amount of 10 mol% or less and used in combination.

The thickness of the light emitting layer, the thickness of the hole injecting and transporting layer, and the thickness of the electron injecting and transporting layer are not particularly limited, and are usually about 5 to 1000 nm, especially 8 depending on the forming method.
It is preferable that the thickness is ˜200 nm.

The thickness of the hole injecting/transporting layer and the thickness of the electron injecting/transporting layer may be the same as the thickness of the light emitting layer or about 1/10 to 10 times, although it depends on the design of the recombination/light emitting region. .. When the electron injection layer and the electron injection layer are separated from the transport layer, it is preferable that the injection layer has a thickness of 1 nm or more and the transport layer has a thickness of 20 nm or more. At this time, the upper limit of the thickness of the injection layer and the transport layer is usually about 100 nm in the injection layer and 100 in the transport layer.
It is about 0 nm.

For the cathode, it is preferable to use a material having a low work function, for example, Li, Na, Mg, Al, Ag, In or an alloy containing at least one of these. The cathode preferably has fine crystal grains, and particularly preferably is in an amorphous state. The thickness of the cathode is 10
It is preferably about 1000 nm.

At least one of the electrodes must be transparent or semi-transparent in order to allow the EL element to emit surface light.
Since the material of the cathode is limited as described above, it is preferable to determine the material and thickness of the anode so that the transmittance of emitted light is 80% or more. In particular,
For example, ITO, SnO ₂ , Ni, Au, Pt, Pd,
It is preferable to use polypyrrole doped with a dopant for the anode. The thickness of the anode is 10-500nm
It is preferable to set it to a degree. Further, it is necessary that the driving voltage is low in order to improve the reliability of the element, but as a preferable example, ITO having about 10 to 30Ω/□ or less and 10Ω/□ or less (usually 5 to 10Ω/□) can be mentioned. ..

The substrate material is not particularly limited, but in the illustrated example, a transparent or semitransparent material such as glass or resin is used in order to take out emitted light from the substrate side. In addition, the emission color may be controlled by using a color filter film or a dielectric reflection film on the substrate.

When an opaque material is used for the substrate, the stacking order shown in FIG. 1 may be reversed.

Next, a method for manufacturing the organic EL device of the present invention will be described.

The cathode and the anode are preferably formed by vapor phase growth methods such as vapor deposition and sputtering.

For forming the hole injecting/transporting layer, the light emitting layer and the electron injecting/transporting layer, it is preferable to use the vacuum deposition method because a uniform thin film can be formed. When the vacuum deposition method is used, a homogeneous thin film having an amorphous state or a crystal grain size of 0.1 μm or less (usually 0.01 μm or more) can be obtained. If the crystal grain size exceeds 0.1 μm, non-uniform light emission occurs, the drive voltage of the device must be increased, and the charge injection efficiency is significantly reduced.

The conditions of vacuum vapor deposition are not particularly limited, but 1
The degree of vacuum is 0 ^-5 Torr or less, and the deposition rate is 0.1 to 1 nm/
It is preferably about sec. Moreover, it is preferable to form each layer continuously in a vacuum. If they are continuously formed in vacuum, impurities can be prevented from adsorbing to the interface of each layer, so that high characteristics can be obtained. Further, the driving voltage of the element can be lowered.

When a vacuum vapor deposition method is used to form each of these layers, when a plurality of compounds are contained in one layer, the temperature of each boat containing the compounds is individually controlled while monitoring with a quartz oscillator film thickness meter. Co-deposition is preferred.

The EL device of the present invention is usually used as a DC drive type EL device, but it can also be AC drive or pulse drive. The applied voltage is usually about 2 to 20V.

[0093]

EXAMPLES Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention together with comparative examples.

Example 1 Synthesis of Compound I-1 Bis(1,5-cyclooctadiene)nickel (Ni
(Cod) ₂ ) 0.37 g (1.35 mmol), 2,2'
-0.20 g (1.28 mmol) of bipyridine and 1,5-
Cyclooctadiene (0.20 ml) was mixed with N,N-dimethylformamide (20 ml) in a nitrogen atmosphere, followed by addition of 2-
Chloro-9,10-diphenylanthracene 1.00 g
(2.74 mmol) was added, and the mixture was stirred at 60° C. for 24 hours.
The reaction solution was poured into a 1N aqueous hydrochloric acid solution, extracted with toluene and chloroform, washed with water, and dried over magnesium sulfate. The obtained product was reprecipitated with acetone, recrystallized three times from chloroform, and purified with silica column using toluene as an extraction solvent to obtain 0.53 g of a yellowish white solid. 0.5 g of the obtained yellow-white solid was purified by sublimation to obtain 0.23 g of a yellow-white solid having blue fluorescence.

Elemental analysis: C H calculated value/% 94.80 5.20 Measured value/% 94.96 4.90 Mass spectrometry: m/e 658 (M ⁺ ) Infrared absorption spectrum: FIG. 2 NMR spectrum: FIG. 3 Differential scanning calorimetry (DSC): melting point 450°C, glass transition temperature 181°C

Example 2 Synthesis of Compound II-1 Bis(1,5-cyclooctadiene)nickel (Ni
(Cod) ₂ ) 0.37 g (1.35 mmol), 2,2'
-0.20 g (1.28 mmol) of bipyridine and 1,5-
Cyclooctadiene (0.20 ml) was mixed with 20 ml of N,N-dimethylformamide in a nitrogen atmosphere, and 1-
Chloro-9,10-diphenylanthracene 1.00 g
(2.74 mmol) was added, and the mixture was stirred at 60° C. for 24 hours.
The reaction solution was poured into a 1N aqueous hydrochloric acid solution, extracted with toluene and chloroform, washed with water, and dried over magnesium sulfate. The obtained product was reprecipitated with acetone, recrystallized from chloroform three times, and purified with silica column using toluene as an extraction solvent to obtain 0.20 g of a yellowish white solid.

Elemental analysis: C H calculated value/% 94.80 5.20 Measured value/% 94.60 4.97 Mass spectrometry: m/e 658 (M ⁺ ) Infrared absorption spectrum: FIG. 4 NMR spectrum: FIG. 5

Example 3 Synthesis of compound III-1 0.267 g (10 mmol) of magnesium activated under argon in a Schlenk flask and 2.22 g (5.46 mmol) of 4,4'-di-iodobiphenyl. 50 ml of a tetrahydrofuran (THF) solution was added dropwise to form a Grignard. 0.4 g of NiCl ₂ (dppe) was added to this reaction solution.
And 2-chloro-9,10-diphenylanthracene 4.
00 g (10 mmol) was added, and the mixture was refluxed at 60° C. for 4 hours.
The reaction solution was poured into a 1N aqueous hydrochloric acid solution, extracted with toluene and chloroform, washed with water, and dried over magnesium sulfate. After the solvent was distilled off, the residue was recrystallized from acetone/dichloromethane and further purified by silica column using toluene and hexane as extraction solvents to obtain 2.0 g of a yellowish white solid exhibiting blue-green fluorescence. 1.0 g of this yellowish white solid was purified by sublimation,
0.6 g of a pure yellowish white solid was obtained.

Elemental analysis: C H calculated value/% 94.54 5.45 Measured value/% 94.50 5.40 Mass spectrometry: m/e 586 (M ⁺ ) Differential scanning calorimetry (DSC): Melting point 350° C. , Glass transition temperature 120℃, ionization potential: 5.95eV

The above compound was identified also from the results of infrared absorption spectrum and NMR spectrum.

Example 4 Synthesis of compound V-1 0.267 g (10 mmol) of magnesium activated under argon in a Schlenk flask and 2.02 g (4.97 mmol) of 4,4'-di-iodobiphenyl. 50 ml of THF solution was added dropwise to form Grignard. This reaction solution was added dropwise to a THF solution containing 1.04 g (5 mmol) of anthraquinone and stirred for 1 hour. Thereafter, a THF solution of phenylmagnesium iodide was added dropwise, and the mixture was refluxed at 60°C for 2 hours. The reaction solution was poured into a 1N aqueous hydrochloric acid solution, extracted with toluene and chloroform, washed with water, and dried over magnesium sulfate. Next, this product was dissolved in 100 ml of acetic acid, an aqueous hydrogen iodide solution was added dropwise, and the mixture was stirred for 4 hours. A solution of tin dichloride (SnCl ₂ ) in hydrochloric acid was added to this solution until free iodine disappeared. It was extracted with chloroform and toluene and dried over magnesium sulfate. After the solvent was distilled off, the residue was purified with a silica column using toluene as an elution solvent and then recrystallized from acetone/toluene. Elemental analysis: C H calculated value/% 94.80 5.20 Measured value/% 94.58 5.10 Mass spectrometry: m/e 658 (M ⁺ ) In addition, from the results of infrared absorption spectrum and NMR spectrum, The compound was identified as the above compound.

Example 5 Synthesis of Compound VII-2 A Schlenk flask was charged with Biantron 1.
0 g (2.6 mmol) was dissolved in 50 ml of THF, an ether solution of 4-methylphenylmagnesium bromide (6.0 mmol) was added dropwise to this solution, and the mixture was refluxed for 4 hours.
The reaction solution was poured into an aqueous solution of ammonium chloride, extracted with toluene and chloroform, washed with water, and dried over magnesium sulfate. Next, this product was dissolved in 100 ml of acetic acid, an aqueous solution of hydrogen iodide was added dropwise, the mixture was stirred for 4 hours, a hydrochloric acid solution of tin dichloride (SnCl ₂ ) was added dropwise, and the temperature was further increased to 100°C.
It was stirred for 1 hour. After this, water was added, extracted with chloroform and toluene, and dried over magnesium sulfate. After the solvent was distilled off, the residue was washed with acetone and methanol, purified by a silica column using toluene and hexane (1:4) as an elution solvent, and recrystallized from toluene to obtain 0.8 g of a white solid. Mass spectrum: m/e 535 (M+1) ⁺ infrared absorption spectrum: FIG. 6 NMR spectrum: FIG. 7 Differential scanning calorimetry (DSC): melting point 365° C., glass transition temperature 162° C.

The calculated and measured values in elemental analysis were in good agreement.

Example 6 Synthesis of Compound VII-1 Synthesized according to Example 5. Mass spectrum: m/e 506 (M ⁺ ) Infrared absorption spectrum: FIG. 8 NMR spectrum: FIG. 9 Differential scanning calorimetry (DSC): melting point 350° C., glass transition temperature 130° C.

The calculated and measured values in elemental analysis were in good agreement.

<Example 7> Compound VII-3 was synthesized according to Example 5. Mass spectrum: m/e 619 (M+1) ⁺ infrared absorption spectrum: FIG. 10 NMR spectrum: FIG. 11 Differential scanning calorimetry (DSC): melting point 411° C.

The calculated and measured values in elemental analysis were in good agreement.

Example 8 Synthesis of Compound VII-4 Synthesized according to Example 5. Mass spectrum: m/e 566 (M+1) ⁺ infrared absorption spectrum: FIG. 12 NMR spectrum: FIG.

The calculated and measured values in elemental analysis were in good agreement.

Example 9 Synthesis of compound VII-8 was synthesized according to Example 5. Mass spectrum: m/e 658 (M ⁺ ) Infrared absorption spectrum: FIG. 14 NMR spectrum: FIG. 15 Differential scanning calorimetry (DSC): melting point 345° C., glass transition temperature 188° C.

The calculated and measured values in elemental analysis were in good agreement.

Example 10 Synthesis of Compound VII-12 Synthesized according to Example 5. Mass spectrum: m/e 535 (M+1) ⁺ infrared absorption spectrum: FIG. 16 NMR spectrum: FIG. 17 Differential scanning calorimetry (DSC): melting point 391° C., glass transition temperature 166° C.

The calculated and measured values in elemental analysis were in good agreement.

Example 11 Synthesis of Compound VII-14 Synthesized according to Example 5. Mass spectrum: m/e 647 (M+1) ⁺ infrared absorption spectrum: FIG. 18 NMR spectrum: FIG. 19 Differential scanning calorimetry (DSC): Sublimation at melting point 414° C.

The calculated and measured values in elemental analysis were in good agreement.

Example 12 Synthesis of compound VII-15 Synthesized according to Example 5. Mass spectrum: m/e 659 (M+1) ⁺ infrared absorption spectrum: FIG. 20 NMR spectrum: FIG. 21 Differential scanning calorimetry (DSC): melting point 323° C., glass transition temperature 165° C.

The calculated and measured values in elemental analysis were in good agreement.

<Example 13> Synthesis of compound VII-16 was carried out according to Example 5. Mass spectrum: m/e 659 (M+1) ⁺ infrared absorption spectrum: FIG. 22 NMR spectrum: FIG. 23 Differential scanning calorimetry (DSC): melting point 295° C., glass transition temperature 141° C.

The calculated and measured values in elemental analysis were in good agreement.

<Example 14> Synthesis of compound VII-24 was synthesized according to Example 5. Mass spectrum: m/e 618 (M ⁺ ) Infrared absorption spectrum: FIG. 24 NMR spectrum: FIG. 25 Differential scanning calorimetry (DSC): melting point 273° C., glass transition temperature 105° C.

The calculated and measured values in elemental analysis were in good agreement.

<Example 15> Synthesis of compound VII-25 was synthesized according to Example 5. Mass spectrum: m/e 567 (M+1) ⁺ infrared absorption spectrum: FIG. 26 NMR spectrum: FIG. 27

The calculated and measured values in elemental analysis were in good agreement.

<Example 16> Synthesis of compound VII-26 was synthesized according to Example 5. Mass spectrum: m/e 606 (M ⁺ ) Infrared absorption spectrum: FIG. 28 NMR spectrum: FIG. 29 Differential scanning calorimetry (DSC): melting point 453° C., glass transition temperature 235° C.

The calculated and measured values in elemental analysis were in good agreement.

Example 17 Synthesis of compound I-20 Synthesis was carried out according to Example 1. Mass spectrum: m/e 883 (M+1) ⁺ infrared absorption spectrum: FIG. 30 NMR spectrum: FIG. 31 Differential scanning calorimetry (DSC): melting point 342.6° C., glass transition temperature 103° C.

The calculated and measured values in elemental analysis were in good agreement.

<Example 18> Synthesis of compound VII-27 was synthesized according to Example 5. Mass spectrum: m/e 896 (M ⁺ ) Infrared absorption spectrum: FIG. 32 NMR spectrum: FIG. 33 Differential scanning calorimetry (DSC): Melting point 361.5° C., glass transition temperature 164° C.

The calculated and measured values in elemental analysis were in good agreement.

<Example 19> Synthesis of compound VII-23 was synthesized according to Example 5. Infrared absorption spectrum: FIG. 34 NMR spectrum: FIG. 35 Differential scanning calorimetry (DSC): melting point 423° C., glass transition temperature 190° C.

The calculated and measured values in elemental analysis were in good agreement.

<Example 20> Synthesis of compound I-17 was synthesized according to Example 1. Infrared absorption spectrum: FIG. 36 NMR spectrum: FIG. 37 Differential scanning calorimetry (DSC): Glass transition temperature 177° C.

The calculated and measured values in elemental analysis were in good agreement.

Other exemplified compounds represented by Chemical formulas 6 to 24 were also synthesized according to Examples 1 to 20. These compounds are
It was identified from the results of elemental analysis, infrared absorption spectrum, NMR spectrum, mass spectrometry and the like.

Example 21 A glass substrate having an ITO transparent electrode (anode) having a thickness of 100 nm is ultrasonically washed with a neutral detergent, acetone, and ethanol, and then pulled out from boiling ethanol and dried to deposit the vapor deposition apparatus. After fixing to the substrate holder of No. 1, the pressure was reduced to 1×10 ⁻⁶ Torr.

Then, N,N'-diphenyl-N,N'
-M-Tolyl-4,4'-diamino-1,1'-biphenyl (TPD-1) was vapor-deposited at a vapor deposition rate of 0.2 nm/sec to a thickness of 50 nm to form a hole injecting and transporting layer.

Then, the compound I-1 of Example 1 was vapor-deposited at a vapor deposition rate of 0.2 nm/sec to a thickness of 50 nm to form a light-emitting layer.

Then, while maintaining the reduced pressure, tris(8-quinolinolato)aluminum was vapor-deposited at a vapor deposition rate of 0.2 nm/sec to a thickness of 10 nm as an electron injecting and transporting layer.

Further, while maintaining the reduced pressure state, MgAg
(Weight ratio 10:1) 200nm at deposition rate 0.2nm/sec
Was evaporated to a cathode to obtain an organic EL device.

[0140] When a current flows by applying a voltage to the organic EL element, 15V, 217mA / cm ² at 4500 cd / m ²
Of blue (maximum emission wavelength λ max =485 nm) was confirmed, and this emission was stable for 500 hours or more in a dry nitrogen atmosphere. There was no appearance or growth of partial non-emissive areas. Brightness half-life is 10 mA/cm ² at constant current drive of 10
It was 0 hours.

Example 22 A glass substrate having an ITO transparent electrode (anode) having a thickness of 100 nm is ultrasonically washed with a neutral detergent, acetone, and ethanol, and is pulled out from boiling ethanol and dried to obtain a vapor deposition apparatus. After fixing to the substrate holder of No. 1, the pressure was reduced to 1×10 ⁻⁶ Torr.

Then, poly(thiophene-2,5-diyl) was vapor-deposited to a thickness of 10 nm to form a hole injection layer.

Then, N,N'-diphenyl-N,N'
-M-Tolyl-4,4'-diamino-1,1'-biphenyl (TPD-1) was vapor-deposited at a vapor deposition rate of 0.2 nm/sec to a thickness of 50 nm to form a hole-transporting layer.

Then, the compound I-1 of Example 1 was added at 50 nm.
Was evaporated to a light emitting layer.

Then, while keeping the reduced pressure, tris(8-quinolinolato)aluminum was vapor-deposited at a vapor deposition rate of 0.2 nm/sec to a thickness of 10 nm as an electron injecting and transporting layer.

Further, with the reduced pressure maintained, MgAg
(Weight ratio 10:1) 200nm at deposition rate 0.2nm/sec
Was evaporated to a cathode to obtain an organic EL device.

When a voltage was applied to this organic EL element to pass a current, it was 10,000 cd/m ² at 12 V and 625 mA/cm ^2.
The emission of blue color ² (maximum emission wavelength λmax =485 nm) was confirmed, and this emission was stable in a dry nitrogen atmosphere for 1000 hours or more. There was no appearance or growth of partial non-emissive areas. The luminance half-life was 400 hours when driven at a constant current of 10 mA/cm ² .

<Example 23> An organic EL device was obtained in the same manner as in Example 22 except that the electron injecting and transporting layer was not provided.

[0149] When a current flows by applying a voltage to the organic EL element, 12V, 825mA / cm ² at 2260cd / m ²
Of blue (maximum emission wavelength λ max =485 nm) was confirmed, and this emission was stable for 500 hours or more in a dry nitrogen atmosphere. There was no appearance or growth of partial non-emissive areas. Brightness half-life is 10 mA/cm ² at constant current drive of 10
It was 0 hours.

Example 24 An element was manufactured in the same manner as in Example 22. However, instead of the hole transport material TPD-1, N,N,N′,N′-tetrakis(3-biphenyl)-4,4′-diamino-1,1′-biphenyl(T
PD-2) was used.

[0151] When a current flows by applying a voltage to the organic EL element, 12V, 675mA / cm ² at 5500cd / m ²
Of blue (maximum emission wavelength λ max =485 nm) was confirmed, and this emission was stable for 1000 hours or more in a dry nitrogen atmosphere. There was no appearance or growth of partial non-emissive areas. Brightness half-life is 6 with constant current drive of 10 mA/cm ^2.
It was 00 hours.

Example 25 A hole transport layer was formed in the same manner as in Example 24, and then TPD-2 and the compound I-1 of Example 1 were used as a light emitting layer in a ratio of 1:1 (weight ratio). ) Was vapor-deposited at a deposition rate of 0.2 nm/sec to a thickness of 20 nm.

Then, while maintaining the reduced pressure, Compound I-1 was vapor-deposited to a thickness of 50 nm as an electron transport layer.

Then, while keeping the reduced pressure, tris(8-quinolinonato)aluminum was vapor-deposited as an electron injection layer at a vapor deposition rate of 0.2 nm/sec to a thickness of 10 nm.

Further, with the reduced pressure maintained, MgAg
(Weight ratio 10:1) 200nm at deposition rate 0.2nm/sec
Was evaporated to a cathode to obtain an organic EL device.

When a voltage was applied to this device and a current was passed through it, blue light emission (maximum emission wavelength λmax =480 nm) of 12000 cd/m ² was confirmed at 12 V and 540 mA/cm ² . This luminescence was stable for more than 5000 hours in a dry nitrogen atmosphere. There was no appearance, growth, or current leakage of the partial non-emission area. The luminance half-life was 1500 hours when driven at a constant current of 10 mA/cm ² .

Example 26 A glass substrate having an ITO transparent electrode (anode) having a thickness of 100 nm is ultrasonically cleaned with a neutral detergent, acetone, and ethanol, and is pulled up from boiling ethanol and dried to deposit the vapor deposition apparatus. After fixing to the substrate holder of No. 1, the pressure was reduced to 1×10 ⁻⁶ Torr.

Next, poly(thiophene-2,5-diyl) was evaporated to a thickness of 10 nm to form a hole injection layer.

Then, N,N'-diphenyl-N,N'
-M-Tolyl-4,4'-diamino-1,1'-biphenyl (TPD-1) was vapor-deposited at a vapor deposition rate of 0.2 nm/sec to a thickness of 50 nm to form a hole-transporting layer.

Then, the compound II-1 of Example 2 was added to 50 nm.
Was evaporated to a light emitting layer.

Then, while maintaining the reduced pressure, tris(8-quinolinolato)aluminum was vapor-deposited to a thickness of 10 nm as an electron injecting and transporting layer at a vapor deposition rate of 0.2 nm/sec.

Further, with the reduced pressure maintained, MgAg
(Weight ratio 10:1) 200nm at deposition rate 0.2nm/sec
Was evaporated to a cathode to obtain an organic EL device.

When a voltage was applied to this organic EL element to pass a current, it was 12000 cd/m ² at 12 V and 625 mA/cm ^2.
The emission of bluish green (maximum emission wavelength λ max =495 nm) of 2 was confirmed, and this emission was stable for 1000 hours or more in a dry nitrogen atmosphere. There was no appearance or growth of partial non-emissive areas. The half-life of luminance was 100 hours when driven with a constant current of 10 mA/cm ² .

<Example 27> An organic EL device was obtained by using the compound VII-2 of Example 5 in place of the compound I-1 in Example 21.

When a voltage was applied to this element and a current was applied, blue light emission of 1921 cdm ^-2 (emission maximum wavelength λ max =460 nm) was confirmed at 14 V and 450 mA/cm ² , and this light emission was performed in a dry nitrogen atmosphere. It was stable for more than 1000 hours. There was no appearance or growth of partial non-emissive areas. Luminance half-life is 30 with constant current drive of 10 mA/cm ^2.
It was 0 hours.

Example 28 In Example 22, after forming the light emitting layer, tris(8-quinolinato)aluminum was vapor-deposited at a vapor deposition rate of 0.2 nm/sec to a thickness of 20 nm to form an electron transport layer. Next, tetrabutyldiphenoquinone was vapor-deposited to a thickness of 10 nm to form an electron injection layer. afterwards,
An organic EL device was obtained in the same manner as in Example 22.

When a voltage was applied to this organic EL device under the same conditions as in Example 22, it was 1 at 12 V and 625 mA/cm ² .
Blue at 0000 cd/m ² (Maximum emission wavelength λmax =485n
Light emission of m) was confirmed, and this light emission was stable for 1000 hours or more in a dry nitrogen atmosphere. There was no appearance or growth of partial non-emissive areas. Luminance half-life is 10mA/cm ²
It was a constant current drive for 80 hours.

Example 29 A glass substrate having an ITO transparent electrode (anode) having a thickness of 100 nm is ultrasonically cleaned with a neutral detergent, acetone, and ethanol, and is pulled up from boiling ethanol and dried to obtain a vapor deposition apparatus. After fixing to the substrate holder of No. 1, the pressure was reduced to 1×10 ⁻⁶ Torr.

Next, poly(thiophene-2,5-diyl) was evaporated to a thickness of 10 nm to form a hole injection layer.

Then, N,N'-diphenyl-N,N'
-M-Tolyl-4,4'-diamino-1,1'-biphenyl (TPD-1) was vapor-deposited at a vapor deposition rate of 0.2 nm/sec to a thickness of 50 nm to form a hole-transporting layer.

Next, tetraphenylcyclopentadiene was evaporated to a thickness of 50 nm to form a light emitting layer.

Then, with the vacuum kept, the compound I-1 of Example 1 was deposited as an electron injecting and transporting layer at a deposition rate of 0.
It was vapor-deposited at a thickness of 10 nm at 2 nm/sec.

Further, while keeping the reduced pressure, MgAg
(Weight ratio 10:1) 200nm at deposition rate 0.2nm/sec
Was evaporated to a cathode to obtain an organic EL device.

When a voltage was applied to this organic EL element to pass a current, blue emission of 800 cd/m ² (maximum emission wavelength λ max =460 nm) was confirmed at 12 V and 100 mA/cm ² , and this emission was dried. It was stable in a nitrogen atmosphere for 100 hours or more. There was no appearance or growth of partial non-emissive areas. The half-life of brightness was 10 hours when driven with a constant current of 10 mA/cm ² .

In Examples 21 to 29, chemical formulas 6 to 24 were used.
One or two or more of the compounds of the present invention listed in 1 above are appropriately used and used in a light emitting layer or an electron injecting and transporting layer in a combination other than the above examples, depending on the layer structure of the organic EL device. The same results as in the above example were obtained.

Comparative Example 1 A glass substrate having a 100 nm thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone, and ethanol, and was pulled up from boiling ethanol and dried to obtain a vapor deposition apparatus. After fixing to the substrate holder of No. 1, the pressure was reduced to 1×10 ⁻⁶ Torr.

Then, N,N'bis(m-methylphenyl)-N,N'-diphenyl-1,1'-biphenyl-
4,4'-diamine (TPD-1) was evaporated to a thickness of 50 nm to form a hole injecting and transporting layer.

Then, while maintaining the reduced pressure state, 1,3-
Bis(5-(4-t-butylphenyl)-1,3,4-
Oxadiazo-2-yl)benzene (OXD-7) was vapor-deposited at a vapor deposition rate of 0.2 nm/sec to a thickness of 50 nm to form a light emitting layer.

Next, while maintaining the reduced pressure, tris(8-quinolinonato)aluminum was vapor-deposited as an electron injecting/transporting layer at a vapor deposition rate of 0.2 nm/sec to a thickness of 10 nm.

Further, while maintaining the reduced pressure, MgAg
(Weight ratio 10:1) 200nm at deposition rate 0.2nm/sec
The EL element was obtained by evaporating to a thickness of 4 to form a cathode.

When a voltage was applied to this EL element and a current was passed through it, blue light emission (maximum emission wavelength λ max =480 nm) of 550 cd/m ² at 14 V and 127 mA/cm ² was confirmed.
In this light emission, the appearance and growth of a partial non-light emitting portion were observed in a dry nitrogen atmosphere for 10 hours, and dielectric breakdown occurred in 20 hours. The half-life of luminance was 20 minutes when driven with a constant current of 10 mA/cm ² .

Comparative Example 2 C. Adachi et al., Appli. Ph
An organic EL device having the same structure as this document was assembled by using 9,10-diphenylanthracene described in ys. Lett., 56 , 799 (1990) for the light emitting layer. That is, in Comparative Example 1, 9,10-diphenylanthracene was similarly evaporated to a thickness of 50 nm without providing an electron injecting and transporting layer,
The light emitting layer also serves as an electron injecting and transporting layer.

In this EL device, the organic compound layer was crystallized, and when a voltage was applied in a state where it was electrically short-circuited, blue emission was observed, but dielectric breakdown occurred.

[0184]

INDUSTRIAL APPLICABILITY The phenylanthracene derivative of the present invention has low crystallinity and can form a film in a good amorphous state. Therefore, it is used as a compound for organic EL devices, particularly as a blue light emitting material or an electron injecting/transporting material. You can In fact, the organic EL device of the present invention using the phenylanthracene derivative of the present invention has no current leakage, no generation/growth of non-light emitting portions (dark spots), and crystallization in the film is suppressed. It becomes a highly reliable element. In particular, when it is used for the light emitting layer, blue light emission with high brightness of 10,000 cd/m ² or more is possible.

[Brief description of drawings]

FIG. 1 is a side view showing a configuration example of an EL element of the present invention.

FIG. 2 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 3 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 4 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 5 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 6 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 7 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 8 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 9 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 10 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 11 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 12 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 13 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 14 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 15 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 16 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 17 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 18 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 19 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 20 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 21 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 22 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 23 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 24 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 25 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 26 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 27 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 28 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 29 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 30 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 31 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 32 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 33 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 34 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 35 is a graph showing an NMR spectrum of the compound of the present invention.

FIG. 36 is a graph showing an infrared absorption spectrum of the compound of the present invention.

FIG. 37 is a graph showing an NMR spectrum of the compound of the present invention.

[Explanation of symbols]

1 Organic EL Element 2 Substrate 3 Anode 4 Hole Injecting and Transporting Layer 5 Light Emitting Layer 6 Electron Injecting and Transporting Layer 7 Cathode

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 211/54 211/61 217/78 7457-4H 217/94 7457-4H 321/30 7419-4H C07D 271/10 333/08 C09K 11/06 Z 9280-4H

Claims (8)

[Claims] 1. A phenylanthracene derivative represented by the following formula (I): Formula (I) A ₁ -LA ₂ [In Formula (I), A ₁ and A ₂ each represent a monophenylanthryl group or a diphenylanthryl group, and these may be the same or different. .. L represents a single bond or a divalent linking group. ] 2. The method according to claim 1 or 2 below.
Phenylanthracene derivative of. [Chemical 1] [Chemical 2] [In Chemical Formula 1, R ₁ and R ₂ are each an alkyl group,
It represents a cycloalkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group, which may be the same or different. r1
And r2 each represent 0 or an integer of 1 to 5. r
When 1 and r2 are each an integer of 2 or more, R ₁
R ₁ and R ₂ may be the same or different, and R ₁ or R ₂ may be bonded to each other to form a ring. L ₁ represents a single bond or an arylene group, and the arylene group is an alkylene group, —O—, —S— or —N.
R- (wherein R represents an alkyl group or an aryl group) may be present. In chemical formula 2,
R ₃ and R ₄ each represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group, and these may be the same or different. r3 and r4 are
Each represents 0 or an integer of 1 to 5. r3 and r4
Each is an integer of 2 or more, R _{3 s} and R _{3
The four} groups may be the same or different, and R ₃
R _{4 and} R ₄ may combine with each other to form a ring. L
₂ represents a single bond or an arylene group, and the arylene group may be an alkylene group, -O-, -S- or -NR- (wherein R represents an alkyl group or an aryl group). Good. ] 3. An organic EL device having at least one organic compound layer containing the phenylanthracene derivative according to claim 1. 4. The organic EL device according to claim 3, wherein the organic compound layer containing the phenylanthracene derivative is a light emitting layer. 5. The organic EL device according to claim 4, further comprising at least one hole injection layer, at least one hole transport layer, and at least one electron injection transport layer. 6. The method according to claim 4, further comprising at least one hole injection layer, at least one hole transport layer, at least one electron transport layer, and at least one electron injection layer. Organic EL device. 7. The organic EL device according to claim 3, wherein the organic compound layer containing the phenylanthracene derivative is an electron injecting and transporting layer, and further has a light emitting layer. 8. At least one light emitting layer is provided, and the light emitting layer is a mixed layer of an electron injecting and transporting compound and a hole injecting and transporting compound, and the mixed layer contains the phenylanthracene derivative. The organic EL device according to claim 3.