KR100701143B1 - Organic Electroluminescence Element - Google Patents

Abstract

The present invention relates to an organic electroluminescent device having an organic light emitting layer between a positive electrode and a negative electrode, wherein the organic light emitting layer contains a 1,3,6,8-4 substituted pyrene compound having a specific structure as an organic light emitting layer forming material. When used alone or as a guest, it exhibits blue light emission with high color purity, high luminous efficiency, stable organic light emitting layer formation for long-term driving, high luminous efficiency, long organic EL element, and luminous efficiency. It is possible to provide a high performance organic EL display having a high and long driving life.

1,3,6,8-4 substituted pyrene, organic electroluminescent (EL) element, organic light emitting layer, organic EL display

Description

Organic Electroluminescence Element

The present invention relates to an organic light emitting layer forming material, an organic EL element and an organic EL display in an organic electroluminescent (hereinafter also referred to as "organic EL") element.

The organic EL device is a report of a stacked device in which each organic thin film of hole transporting and electron transporting is laminated (see, for example, CW Tang and SA VanSlyke, Applied Physics Letters, 1987, 51, p.913]), which is expected to be applied to flat panel displays as a display device having characteristics such as self-luminous and high-speed response, and is particularly interesting as a large area light emitting device that emits light at a low voltage of 10 V or less. Are gathering.

The stacked organic EL device basically has a configuration of a positive electrode / hole transport layer / organic light emitting layer / electron transport layer / negative electrode. Among these, the organic light emitting layer may have a configuration in which the hole transporting layer or the electron transporting layer has the same function as in the case of the two-layered device of the hot and half-sleeve described above.

In order to obtain an organic EL device of high light emission efficiency, the organic light emitting layer needs to have high light emission efficiency. As the structure of the organic light emitting layer, in addition to a single film formed of one kind of material, a dye doped film is formed in which a small amount of a doped fluorescent substance is used as a guest in a host material which is a main component as a guest. CW Tang), SA VanSlyke and CH Chen, Journal of Applied Physics, 1989, Vol. 65, p. 3610].

However, it was a reality that the organic light emitting layer forming material used for such an application has a high luminous efficiency and does not sufficiently satisfy the need for a material that is stable for long time driving.

As an organic light emitting layer forming material, having a polycyclic aromatic ring in a luminescent molecular skeleton (for example, Unexamined-Japanese-Patent No. 2002-124385 (patent claim)), 1,3,6,8- tetraphenylpyrene derivative (For example, Japanese Patent Laid-Open No. 2001-118682 (claims)) is known.

SUMMARY OF THE INVENTION The present invention solves the above problems, and provides an organic EL device having a high luminous efficiency and a long driving life, a high-performance organic EL display using the same, and blue light emission having high color purity when used alone or as a guest. It is intended to provide an organic light emitting layer forming material which exhibits high luminous efficiency and is stable against long time driving. Still other objects and advantages of the present invention will become apparent from the following description.

According to one aspect of the present invention, a 1,3,6,8-4 substituted pyrene compound represented by the following formula (1) is provided.

Wherein R has the structure of formula (2) independently of one another.

{Wherein, R ¹ to R ⁵ independently represent hydrogen or a substituent, provided that at least one of R ¹ to R ⁵ is any one of groups represented by the following Chemical Formulas 3 to 6}

{Wherein R ⁶ to R ¹² independently represent hydrogen or a substituent}

R ⁶ and R ^{7 in} Formula 3 are both aromatic groups which may independently have a substituent, R ¹² in Formula 6 is an aromatic group which may have substituents, and the compound is an organic light emitting layer forming material in an organic EL device What is used as a thing, specifically what is used as an organic light emitting layer formation material as a host or a guest in an organic electroluminescent element, etc. are a preferable aspect.

When used alone or as a guest according to the present invention, an organic light emitting layer forming material exhibiting blue light emission with high color purity, high luminous efficiency, and stable for long time driving is provided.

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising the above-described 1,3,6,8-4 substituted pyrene compound as an organic light emitting layer forming material.

When the 1,3,6,8-4 substituted pyrene compound represented by the formula (1) is an organic light emitting layer forming material as a host or a guest, or the 1,3,6,8-4 substituted pyrene compound represented by the formula (1) It may be preferable to consist of a single layer of.

The organic light emitting layer comprises one or more aromatic amine compounds represented by the following formula (7),

{In Formula, Ar <^1> represents the divalent, tri or tetravalent aromatic group which may have a substituent, R <^17> and R <^18> respectively independently represents the monovalent aromatic group which may have a substituent, n represents the integer of 2-4. Indicates}

In particular, the aromatic amine compound represented by the formula (7) is N, N'-dinaphthyl-N, N'-diphenyl- [1,1'-biphenyl] -4,4'-diamine represented by the following formula (8) that,

The organic light emitting layer comprises one or more carbazole compounds represented by the following formula (9),

{Wherein Ar ² represents a di, tri or tetravalent aromatic group which may have a substituent, and R ¹³ and R ^{13 ′} each independently represent a hydrogen atom, a halogen atom, or an alkyl group, an aralkyl group or an alkenyl group which may be substituted; , Aromatic group, cyano group, amino group, acyl group, alkoxycarbonyl group, carboxyl group, alkoxy group, alkylsulfonyl group, hydroxyl group, amide group or aromatic oxy group; n represents an integer of 2 to 4}

In particular, the carbazole compound represented by the formula (9) is 4,4'-bis (9-carbazolyl) -biphenyl represented by the following formula (10),

CBP

CBP

An organic light emitting layer comprising one or more hydroxyquinoline-oxyaryl complexes represented by the following formula (11),

{In formula, R <^14> is hydrogen or the alkyl group which may have a substituent, R <^15> represents the aromatic group which may have a substituent, M represents a trivalent metal, n represents 1 or 2.}

It is particularly preferable that the hydroxyquinoline-oxyaryl complex represented by the formula (11) is an aluminum hydroxyquinoline-oxybiphenyl complex represented by the following formula (12).

According to the aspect of this invention, the organic electroluminescent element which has high luminous efficiency and long drive life is provided.

According to still another aspect of the present invention, there is provided an organic electroluminescent display using the organic electroluminescent element described above.

According to the aspect of this invention, the high performance organic electroluminescent display using the organic electroluminescent element with high luminous efficiency and long drive life is provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a typical perspective view which shows the case where the organic electroluminescent element of this invention is used for a passive matrix display.

2 is a schematic perspective view showing a case where the organic EL device of the present invention is used for an active matrix display.

3 is a schematic cross-sectional view showing an organic EL device.

4 is an IR spectrum of 1,3,6,8-tetrakis [3- (3-methyldiphenylamino) phenyl] pyrene obtained in Example 3. FIG.

Best Mode for Carrying Out the Invention

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described using drawings, chemical formulas, examples, and the like. In addition, these figures, chemical formulas, examples and the like are illustrative of the present invention and do not limit the scope of the present invention. Other embodiments may fall within the scope of the present invention, so long as they are consistent with the spirit of the present invention. In addition, the same code | symbol is attached | subjected about the same element in drawing.

As a result of examining the above problem, an organic EL device manufactured by using a specific 1,3,6,8-4 substituted pyrene compound as an organic light emitting layer forming material emits light with high luminous efficiency, has a long driving life, and is stable in driving. I found this possible. These 1,3,6,8-4 substituted pyrene compounds can be obtained by a relatively easy synthetic method.

As one of the means for applying an organic EL element to a full color display, the method of preparing organic electroluminescent element of each color of red, green, and blue, and using these three combinations as one pixel is widely performed. The organic EL element used for such a full color display is required to have good color purity of each color. The organic EL device of the present invention exhibits blue light emission with high color purity when the organic light emitting layer forming material of the present invention is used alone or as a guest.

The chemical structure of the specific 1,3,6,8-4 substituted pyrene compound, which is the organic light emitting layer forming material of the present invention, may be represented by the general formula (1).

In Formula 1, R has the structure of Formula 2 independently of each other. In formula (2), R ¹ to R ⁵ independently represent hydrogen or a substituent. Provided that at least one of R ¹ to R ⁵ is one of the groups represented by Formulas 3 to 6.

In Formulas 3 to 6, R ⁶ to R ¹² independently represent hydrogen or a substituent.

As a specific example of R <^6> -R <^12> , hydrogen, the linear or branched aliphatic group which may have a substituent, the aromatic group which may have a substituent, and the alicyclic group which may have a substituent are mentioned. In either case, elements other than carbon and hydrogen may be included in the structure, such as oxygen, sulfur, nitrogen, and the like. In addition, when referring to an aromatic group in the present invention, including an aryl group, a bibenzenoid aromatic group and a heterocyclic aromatic group are included unless otherwise specified.

Among the above, as an alicyclic group which may have a linear or branched aliphatic group or a substituent, a C1-C10 linear, branched, or cyclic hydrocarbon group is mentioned preferably, Specifically, methyl , Ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, isononyl, decyl, isodedecyl, cyclobutyl, Cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc. are mentioned preferably.

As an aromatic group which may have a substituent, For example, a monocyclic aromatic ring group, the group which the aromatic ring couple | bonds with four rings or less, has 5 ring or less condensed aromatic ring, and the sum total of the atomic number of carbon, oxygen, nitrogen, and sulfur is 50 or less Group etc. are mentioned preferably.

The group of the monocyclic aromatic ring is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include phenyl, tolyl, xylyl, cumenyl, styryl, mesityl, cinnamil, phenethyl, benzhydryl, and the like. And they may be substituted with a substituent.

It does not specifically limit as group which aromatic ring couple | bonds with four or less rings, According to the objective, it can select suitably, For example, naphthyl, anthryl, phenanthryl, indenyl, azlenyl, benzanthracenyl, etc. are mentioned. And these may be substituted with a substituent.

The group having a condensed aromatic ring of 5 rings or less and having a total number of atoms of carbon, oxygen, nitrogen and sulfur of 50 or less is not particularly limited and can be appropriately selected according to the purpose. For example, pyrrolinyl, furyl, thier Nilyl, pyridyl, quinolyl, isoquinolyl, imidazolyl, pyridinyl, pyrrolopyridinyl, thiazoyl, pyrimidinyl, thiophenyl, indolyl, quinolinyl, pyridyl, adenyl and the like. And these may be substituted with a substituent.

It is preferable that both R ⁶ and R ⁷ in the general formula (3) are aromatic groups which may independently have a substituent. Moreover, it is preferable that it is also an aromatic group which may have a substituent also about R <^12> of general formula (6). This is because when used alone or as a guest, it exhibits blue light emission with high color purity, high luminous efficiency, and becomes an organic light emitting layer forming material that is stable to driving for a long time.

These 1,3,6,8-4 substituted pyrene compounds, depending on the characteristics of each compound, when used to emit light by itself, when used as a guest that emits light with the help of a host, and to help light emission of other guests Applicable when used as a host. In the present invention, unless specifically mentioned, the term "organic light emitting layer forming material" means a material having at least one of these three functions or similar functions, for example, a function of enhancing the function of a host or a guest.

The organic EL device of the present invention has an organic light emitting layer between the positive electrode and the negative electrode, and the organic light emitting layer contains the aforementioned 1,3,6,8-4 substituted pyrene compound as the organic light emitting layer forming material. The organic EL device is characterized by high luminous efficiency and long driving life.

As described above, when the 1,3,6,8-4 substituted pyrene compound of the present invention is used as an organic light emitting layer forming material of an organic EL device, the single layer of the 1,3,6,8-4 substituted pyrene compound of the present invention As an example, the organic light emitting layer may be formed and the 1,3,6,8-4 substituted pyrene compound of the present invention may be dispersed and used as a guest in the host material in the organic light emitting layer.

When the organic light emitting layer is formed as a single layer of the 1,3,6,8-4 substituted pyrene compound of the present invention, the 1,3,6,8-4 substituted pyrene compound of the present invention may have a thickness difference due to crystallization or the like. It is rare to form a layer, and it can be easily formed as a uniform amorphous layer in many cases, and it is possible to make use of the characteristic that an organic light emitting layer can be easily formed with high luminous efficiency and stable for long time driving, and with other materials. It is advantageous in that co-deposition is not necessary and the manufacturing process can be simplified. However, in this case, the emission efficiency decreases due to concentration quenching may occur when light emitting molecules approach each other.

On the other hand, in the organic light emitting layer by host-guest dispersion, a host material having an excitation energy greater than that of the 1,3,6,8-4 substituted pyrene compound, which is a luminescent dye (ie, 1,3,6,8-4 substituted pyrene compound By using the light absorbing means as a mixture with a material having a short wavelength, a uniform film-like layer can be more easily formed while preventing light emission efficiency deterioration due to concentration quenching and maintaining light emission characteristics by molecules alone.

At this time, if the fluorescence emission spectrum of the host material overlaps the absorption spectrum of the 1,3,6,8-4 substituted pyrene compound as the guest material and the wavelength region, an effective transfer of the excitation energy from the host to the guest becomes possible. Light emission from the guest material can be efficiently generated without hardly any light emission of the host material, and high purity light emission color can be obtained.

As a host material in the case where the 1,3,6,8-4 substituted pyrene compound of the present invention is used as a guest material, 4,4'-bis (2,2'-diphenylvinyl) -1 represented by the following general formula (13) , 1'-biphenyl (DPVBi), p-sexyphenyl represented by the following formula (14), 1,3,8,10-tetraphenylpyrene represented by formula (15) or derivatives thereof, aromatic amine compound, or carbazole compound And hydroxyquinoline complexes. These compounds may be used alone or in combination of two or more thereof.

Among these, as the aromatic amine compound, an aromatic amine compound represented by the formula (7) or a derivative thereof is preferable. In formula (7), Ar ¹ represents a divalent, trivalent or tetravalent aromatic group which may have a substituent. R ¹⁷ and R ¹⁸ each independently represent a monovalent aromatic group which may have a substituent. n represents the integer of 2-4.

As the carbazole compound, a carbazole compound represented by the formula (9) or a derivative thereof is preferable. In formula (9), Ar ² represents a di, tri or tetravalent aromatic group which may have a substituent. R ¹³ and R ^{13 '} are each independently a hydrogen atom, a halogen atom, or an alkyl group, aralkyl group, alkenyl group, aromatic group, cyano group, amino group, acyl group, alkoxycarbonyl group, carboxyl group, alkoxy group, alkylsulfo which may be substituted A silyl group, a hydroxyl group, an amide group, or an aromatic oxy group is shown. n represents the integer of 2-4.

Examples of Ar ¹ and Ar ² in the formulas (7) and (9) include the following groups.

With respect to the group described above, the hydrogen atom may be substituted with another group. In addition, the following example is mentioned as a bivalent coupling group X.

The aromatic amine compound and carbazole compound represented by these chemical formulas, when mixed with the 1,3,6,8-4 substituted pyrene compound of the present invention, interact with the 1,3,6,8-4 substituted pyrene compound Since it is small, the influence on the intrinsic luminescence property of a 1,3,6,8-4 substituted pyrene compound is small, and it is especially effective as a host material.

Examples of the aromatic amine compound represented by the formula (7) and the carbazole compound represented by the formula (9) include N, N'-dinaphthyl-N, N'-diphenyl- [1,1'- represented by the formula (8), respectively. Biphenyl] -4,4'-diamine (NPD), and 4,4'-bis (9-carbazolyl) -biphenyl (CBP) represented by General formula (10) is mentioned.

Moreover, as a hydroxyquinoline complex, the hydroxyquinoline-oxyaryl complex represented by General formula (11) and its derivative (s) are preferable. In Formula 11, R ¹⁴ represents hydrogen or an alkyl group which may have a substituent, and R ¹⁵ represents an aromatic group which may have a substituent. M represents a trivalent metal. n represents 1 or 2.

As an example of the hydroxyquinoline-oxyaryl complex represented by General formula (11), the aluminum hydroxyquinoline-oxybiphenyl complex (BAlq) represented by General formula (12) is mentioned more specifically.

In the case of using the host material as described above, the organic light emitting layer may serve as a hole transporting layer or an electron transporting layer, and may be a hole transporting layer, an organic light emitting layer, or an organic light emitting layer and an electron transporting layer. The aromatic amine compound can provide the function of the hole transport layer, and the carbazole compound or the electron hydroxyquinoline-oxyaryl complex can provide the function of the electron transport layer.

The 1,3,6,8-4 substituted pyrene compound of the present invention may be used as a host material of the organic light emitting layer of the organic EL device, not as a guest. As a guest material of the organic light-emitting layer to mix at this time, the material which shows light emission of longer wavelength than the 1,3,6,8-4 substituted pyrene compound of this invention is used. The following materials are mentioned as an example.

1,3,6,8-tetrakis (diphenylamino) pyran (green)

Quinacridone (Green Luminous)

DCJTB

4-dicyanomethylene-6-cp-zoloridinostyryl-2-tert-butyl-4H-pyran (red luminescence)

The method for producing the 1,3,6,8-4 substituted pyrene compound of the present invention is not particularly limited and may be appropriately selected from known methods according to the purpose. For example, the method shown below is preferably used. .

1,3,6,8-tetrahalogenated pyrene is synthesized by reaction of 1 equivalent of pyrene with 4 equivalents of halogen. Tetrahalogenation is likely to occur at the 1,3,6 and 8 positions due to the reactivity of pyrenes. As a method of halogenation reaction, the method similar to the halogenation method of a typical aromatic hydrocarbon, ie, the method of adding halogen single substance to the pyrene dissolved in the solvent, is mentioned preferably. As halogen, chlorine, bromine and iodine are advantageous in carrying out the reaction of the next step, but chlorine and bromine are particularly preferred from the ease of the halogenation reaction.

Subsequently, 1,3,6,8-tetrahalogenated pyrene and a boronic acid derivative corresponding to the desired compound are heated in the presence of a catalyst and a base, and the reaction of 1,3, Obtain a 6,8-4 substituted pyrene compound. The route of the reaction is shown in the following scheme.

In the formula, R has the same meaning as R in formula (1). In the above formula, the intermediate or the final product may be used in a mixture state.

As a catalyst, palladium compounds, such as tetrakis (triphenylphosphine) palladium (0), can be used. As a base, sodium alkoxides, such as sodium carbonate, potassium carbonate, sodium hydroxide, sodium t-butoxide, etc. can be used.

Examples of the boric acid derivative [RB (OH) ₂ ] usable in the above reaction include the followings. Mixtures can also be used. In addition, in the following reaction formula, the line in which the chemical group is not described in the terminal means a methyl group.

In addition, 1,3,6,8-tetrakis (phenyl chloride) pyrene is synthesized by Suzuki coupling of 1,3,6,8-tetrahalogenated pyrene and chlorinated phenylboronic acid, where the presence of a catalyst and a base is present. In some cases, an amination reaction may be performed to obtain a 1,3,6,8-4 substituted pyrene compound of the present invention. As halogen of the starting material 1,3,6,8-tetrahalogenated pyrene, bromine or iodine is preferable from the viewpoint of reactivity. The route of the reaction is shown in the following scheme.

In the formula, R ⁶ and R ⁷ have the same meaning as R ⁶ and R ⁷ of formula (3). In addition, in said formula, n is an integer of 1-5 independently from each other, and represents the number of substitution of chlorine and an amino group. In the above formula, the intermediate or the final product may be used in a mixture state.

Palladium compounds, such as a palladium- tributylphosphine complex, copper powder, etc. can be used as a catalyst of an amination reaction, As a base, sodium alkoxides, such as sodium carbonate, potassium carbonate, sodium hydroxide, sodium t-butoxide, etc. are mentioned. Can be used.

Examples of the chlorinated phenylboronic acid that can be used in the reaction include those represented by the following chemical formulas.

Moreover, what is represented by the following formula is mentioned as an example of the amine which can be used by the said reaction.

The organic EL device has a configuration in which a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, an electron injection layer, and the like are sandwiched between the positive electrode and the negative electrode. Among these, a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer may not exist. It may also comprise other layers. It may have a plurality of functions in one layer. Usually, the said laminated body is comprised on the transparent substrate containing glass etc. The organic EL element of the present invention may also contain the transparent substrate.

When the example of a structure of a layer is shown, the following are mentioned.

ㆍ positive electrode / hole injection layer / hole transport layer / organic light emitting layer / electron transport layer / electron injection layer / negative electrode

ㆍ positive electrode / hole injection layer / hole transport layer / organic light emitting layer / electron transport layer / negative electrode

ㆍ positive electrode / hole transporting layer / organic light emitting layer / electron transporting layer / electron injection layer / negative electrode

ㆍ positive electrode / hole transport layer / organic light emitting layer / electron transport layer / negative electrode

ㆍ positive electrode / hole injection layer / hole transport layer / organic light emitting layer and electron transport layer / electron injection layer / negative electrode

ㆍ positive electrode / hole injection layer / hole transport layer / organic light emitting layer and electron transport layer / negative electrode

ㆍ positive electrode / hole transporting layer / organic light emitting layer and electron transporting layer / electron injection layer / negative electrode

ㆍ positive electrode / hole transporting layer / organic light emitting layer and electron transporting layer / negative electrode

ㆍ positive electrode / hole injection layer / hole transport layer and organic light emitting layer / electron transport layer / electron injection layer / negative electrode

ㆍ positive electrode / hole injection layer / hole transport layer and organic light emitting layer / electron transport layer / negative electrode

ㆍ positive electrode / hole transporting layer and organic light emitting layer / electron transporting layer / electron injection layer / negative electrode

ㆍ positive electrode / hole transporting layer and organic light emitting layer / electron transporting layer / negative electrode

ㆍ positive electrode / hole transporting layer, electron transporting layer, organic light emitting layer / negative electrode

Moreover, if the material used for each layer, the film thickness of each layer, and a manufacturing method are illustrated, it is as follows.

ㆍ positive

The material of the positive electrode is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include metals, alloys, metal oxides, electrically conductive compounds, mixtures thereof, and the like, and materials having a work function of 4 eV or more among them. Is preferred.

Specific examples of the positive electrode material include conductive metal oxides such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), metals such as gold, silver, chromium and nickel, mixtures or laminates of these metals and conductive metal oxides, and iodide Inorganic conductive materials such as copper and copper sulfide, organic conductive materials such as polyaniline, polythiophene, polypyrrole, laminates of these and ITO, and the like. These may be used independently and may use 2 or more types together. Among these, a conductive metal oxide is preferable, and ITO is especially preferable from a viewpoint of productivity, high conductivity, transparency, etc.

Although it does not restrict | limit especially as a thickness of a positive electrode, Although it can select suitably according to a material etc., 1-5000 nm is preferable and 20-200 nm is more preferable.

A positive electrode is normally formed on substrates, such as glass, such as a soda-lime glass and an alkali free glass, and a transparent resin. When using glass as a board | substrate, the alkali free glass, the silica, and the soda-lime glass which gave the barrier coating from a viewpoint of reducing the elution ion from glass are preferable.

The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength. However, when glass is used as the substrate, the thickness is usually 0.2 mm or more, and 0.7 mm or more is preferable.

The positive electrode is, for example, a vapor deposition method, a wet film production method, an electron beam method, a sputtering method, a reactive sputtering method, a molecular beam epitaxial (MBE) method, a cluster ion beam method, an ion plating method, a plasma polymerization method (high frequency excitation ion plating method), a molecule It can form preferably by the lamination method, the printing method, the transfer method, the chemical reaction method (sol-gel method, etc.) by the method of apply | coating dispersion, such as ITO.

The positive electrode can also reduce the drive voltage of the organic EL element or improve the luminous efficiency by performing cleaning and other processing. As another process, when the raw material of the said positive electrode is ITO, UV-ozone process, a plasma process, etc. are mentioned preferably, for example.

ㆍ hole injection layer

Although it does not restrict | limit especially as a material of a hole injection layer, According to the objective, it can select suitably, For example, the starburst amine (4,4 ', 4 "-tris [3-methylphenyl (phenyl) amino] represented by a following formula. Triphenylamine, m-MTDATA), copper phthalocyanine, polyaniline, etc. are mentioned preferably.

The thickness of the hole injection layer is not particularly limited and may be appropriately selected according to the purpose. For example, about 1 to 100 nm is preferable, and 5 to 50 nm is more preferable.

The hole injection layer may be, for example, a vapor deposition method, a wet film production method, an electron beam method, a sputtering method, a reactive sputtering method, an MBE method, a cluster ion beam method, an ion plating method, a plasma polymerization method (high frequency excitation ion plating method), a molecular lamination method, It can form suitably by LB method, the printing method, the transfer method, etc.

ㆍ hole transport layer

The material of the hole transporting layer is not particularly limited and may be appropriately selected according to the purpose. For example, an aromatic amine compound, carbazole, imidazole, triazole, oxazole, oxadiazole, polyarylalkane, pyrazoline, pyra Zolon, phenylenediamine, arylamine, amino substituted chalcone, styryl anthracene, fluorenone, hydrazone, stilbene, silazane, styrylamine, aromatic dimethylidene compound, porphyrin compound, polysilane compound, poly (N -Vinylcarbazole), aniline copolymers, thiophene oligomers and polymers, conductive polymer oligomers and polymers such as polythiophene, and carbon films. In addition, when the material of these hole transport layers is mixed with the material of the light emitting layer to form a film, a hole transporting layer and a light emitting layer can be formed.

These may be used independently and may use 2 or more types together, and among these, an aromatic amine compound is preferable. Specifically, N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD), NPD, etc. represented by a following formula More preferred is an aromatic amine.

The thickness of the hole transport layer is not particularly limited and may be appropriately selected according to the purpose, but is usually 1 to 500 nm, preferably 10 to 100 nm.

In the formation of the hole transport layer, the same method as in the case of the hole injection layer can be appropriately used by changing the raw materials and conditions.

ㆍ electron transport layer

The material of the electron transporting layer is not particularly limited and may be appropriately selected according to the purpose. For example, hydroxyquinoline complexes such as tris (8-quinolinolate) aluminum (Alq), BAlq, etc. Hydroxyquinoline-oxyaryl complex, oxadiazole compound, triazole compound, phenanthroline compound, perylene compound, pyridine compound, pyrimidine compound, quinoxaline compound, diphenylquinone compound, nitro substituted fluorene compound, etc. Can be. In addition, the light emitting layer and the electron transporting layer may be formed by mixing the material of the electron transporting layer with the material of the light emitting layer to form the light emitting layer and the electron transporting layer. In addition, the hole transporting layer, the light emitting layer and the electron transporting layer may be formed by mixing the material of the hole transporting layer. have.

It does not specifically limit as thickness of an electron carrying layer, According to the objective, it can select suitably, For example, it is about 1-500 nm normally, and 10-50 nm is preferable.

The electron transport layer may have a configuration of two or more layers. In this case, as the electron transporting layer material adjacent to the organic light emitting layer, when a material having a shorter wavelength of light absorbing means than the 1,3,6,8-4 substituted pyrene compound of the present invention is used, the light emitting region in the element can be limited to the organic light emitting layer. It is preferable because it can prevent and useless light emission from an electron carrying layer.

Hydroxyquinoline-oxyaryl complex, phenanthroline compound, oxadiazole compound, triazole compound, 8-quine as a material having a shorter wavelength of light absorption means than the 1,3,6,8-4 substituted pyrene compound of the present invention A nolinol compound, the organometallic complex which makes the compound a ligand, etc. are mentioned. Particularly preferred are compounds represented by BAlq and the following formula.

2,9-diphenyl-4,7-diphenyl-1,10-phenanthroline

2- (4-tert-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole

3-phenyl-4- (1-naphthyl) -5-phenyl-1,2,4-triazole

3- (4-tert-butylphenyl) -4-phenyl-5- (4'-biphenylyl) -1,2,4-triazole

In addition, three branches in which the chemical group is not described in the front end in the said formula mean a tert- butyl group.

In formation of an electron carrying layer, the method similar to the case of a hole injection layer can be used suitably, changing a raw material and conditions.

ㆍ electron injection layer

The material of the electron injection layer is not particularly limited and can be appropriately selected according to the purpose. For example, alkali metal fluorides such as lithium fluoride, alkaline earth metal fluorides such as strontium fluoride and the like can be preferably used. The thickness of the electron injection layer is not particularly limited and can be appropriately selected according to the purpose, for example, usually about 0.1 to 10 nm, and preferably 0.5 to 2 nm.

The electron injection layer can be preferably formed by, for example, a vapor deposition method, an electron beam method, a sputtering method, or the like.

ㆍ Negative

The material of the negative electrode is not particularly limited, and may be appropriately selected according to the adhesion between the negative electrode such as the electron transport layer, the light emitting layer, and the molecule, the ionization potential, the stability, and the like. For example, a metal, an alloy, a metal oxide, an electric Conductive compounds, mixtures thereof, and the like.

Specific examples of the negative electrode material include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys or the like Mixed metals, lithium-aluminum alloys or mixed metals thereof, magnesium-silver alloys or mixed metals thereof, rare earth metals such as indium and ytterbium, and alloys thereof. These may be used independently and may use 2 or more types together. Among these, materials having a work function of 4 eV or less are preferable, and aluminum, lithium-aluminum alloy or mixed metals thereof, magnesium-silver alloy or mixed metals thereof and the like are more preferable.

Although it does not restrict | limit especially as thickness of a negative electrode, Although it can select suitably according to the material of a negative electrode, etc., 1-10000 nm is preferable and 20-200 nm is more preferable.

The negative electrode is, for example, a vapor deposition method, a wet film production method, an electron beam method, a sputtering method, a reactive sputtering method, an MBE method, a cluster ion beam method, an ion plating method, a plasma polymerization method (high frequency excitation ion plating method), a printing method, a transfer method, or the like. It can form preferably.

When using 2 or more types together as a material of a negative electrode, an alloy electrode etc. may be formed by depositing 2 or more types of materials simultaneously, and an alloy electrode etc. may be formed by depositing the alloy manufactured previously.

ㆍ Other layer

The organic EL element of this invention may have another layer suitably selected according to the objective. As another layer, a hole blocking layer, a protective layer, etc. are mentioned preferably, for example.

The hole blocking layer is disposed between the light emitting layer and the electron transport layer. When the organic EL element has a hole blocking layer, holes transported from the positive electrode side are blocked by the hole blocking layer, and electrons transported from the negative electrode pass through the hole blocking layer to reach the light emitting layer, whereby Recombination of holes occurs. Therefore, recombination of holes and electrons in the organic thin film layers other than the light emitting layer can be prevented, and light emission of the target light emitting dye can be efficiently obtained, which is advantageous in terms of color purity and the like. The material of the hole blocking layer is not particularly limited and may be appropriately selected from the same materials as the material of the electron transporting layer, depending on the purpose.

The thickness of the hole blocking layer is not particularly limited, and may be appropriately selected depending on the purpose, for example, usually about 1 to 500 nm, preferably 10 to 50 nm. The hole blocking layer may have a single layer structure or a laminated structure.

The hole blocking layer may be, for example, a vapor deposition method, a wet film production method, an electron beam method, a sputtering method, a reactive sputtering method, an MBE method, a cluster ion beam method, an ion plating method, a plasma polymerization method (high frequency excitation ion plating method), a molecular lamination method, It can form suitably by LB method, the printing method, the transfer method, etc.

The protective layer is a layer which protects the organic EL element from the influence of the external field, and is formed to surround the laminate including each of the above-described layers. The material of the protective layer is not particularly limited and can be appropriately selected according to the purpose. However, for example, it is possible to suppress the invasion of molecules or substances in the organic EL device that promote deterioration of the organic EL device such as water or oxygen. It is desirable to have.

Examples of the material for the protective layer include metals such as In, Sn, Cu, Al, Ti, Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, Fe ₂ O ₃ , Y ₂ O _3, TiO _2, such as a metal oxide, SiN, SiN _x O _y, such as a nitride, MgF _2, LiF, AlF _3, CaF ₂ metal fluoride, polyethylene, polypropylene, methylmethacrylate, such as methacrylate, polyimide, Polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymers of chlorotrifluoroethylene and dichlorodifluoroethylene, including tetrafluoroethylene and one or more comonomers The copolymer obtained by copolymerizing the monomer mixture mentioned above, the fluorine-containing copolymer which has a cyclic structure in a copolymer main chain, the water absorbency of 1 weight% or more in water absorption, the moisture proof material of 0.1 weight% or less in water absorption, etc. are mentioned.

The protective layer is preferably, for example, by a vapor deposition method, a wet film production method, a sputtering method, a reactive sputtering method, an MBE method, a cluster ion beam method, an ion plating method, a plasma polymerization method (high frequency excitation ion plating method), a printing method, a transfer method, or the like. Can be formed.

Here, the manufacturing method of the organic light emitting layer can be formed according to a known method, for example, vapor deposition such as vacuum deposition, wet film production method, MBE method, cluster ion beam method, molecular lamination method, LB method, printing It can form preferably by the method, the transcription method, etc. Among these, the vapor deposition method is preferable in that the organic solvent is not used and there is no problem of waste liquid treatment and can be easily and efficiently manufactured at low cost. However, when the light emitting layer is designed in a single layer structure, for example, the light emitting layer is a hole transporting layer and a light emitting layer. When forming as a double layer and an electron carrying layer, the wet film manufacturing method is also preferable.

The vapor deposition method is not particularly limited and may be appropriately selected from those known according to the purpose. Examples thereof include a vacuum vapor deposition method, a resistive heating vapor deposition method, a chemical vapor deposition method, and a physical vapor deposition method. As a chemical vapor deposition method, a plasma CVD method, a laser CVD method, a thermal CVD method, a gas source CVD method, etc. are mentioned, for example.

As the wet film production method, a binder including a host and / or a polymer and the like and a 1,3,6,8-4 substituted pyrene compound of the present invention are mixed in a solvent to spin coating, inkjet, dip coating, and blade coating. It may be applied by a wet film production method such as a method. At this time, in order to increase the charge transporting property of the organic light emitting layer, when the above-mentioned material, which is mentioned as a hole transporting layer material and an electron transporting layer material, is simultaneously mixed into a solution to form a film, the organic light emitting layer has a function of a hole transporting layer or an electron transporting layer. Therefore, a hole transporting layer, an organic light emitting layer, an organic light emitting layer, an electron transporting layer, a hole transporting layer, an organic light emitting layer, and an electron carrying layer can also be comprised.

At this time, examples of the binder that can be used include polyvinylcarbazole, polycarbonate, polyvinyl chloride, polystyrene, polymethylmethacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, and phenoxy. Resin, polyamide, ethyl cellulose, vinyl acetate, ABS (acrylonitrile-butadiene-styrene) resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin and the like.

The organic EL display using the organic EL element of the present invention has high luminous efficiency, long driving life, and can be driven stably. The organic EL element can be used as a passive matrix panel or an active matrix panel (for example, Nikkei Electronics, March 13, 2000, 765, p. 55 to 62).

As a colorization method of the organic EL display, a tricolor emission method in which an organic EL element portion emitting three colors of red, green, and blue are respectively disposed on a substrate, and white light of a white light emitting organic EL element are classified into three primary colors through a color filter. And a color conversion method for converting blue light of a blue light emitting organic EL device into red and green color through a fluorescent dye layer (for example, Monthly Display, Sep. 2000, p. 33 to 37). . Among these, when the 1,3,6,8-4 substituted pyrene compound of the present invention is used alone or as a guest, the organic EL element portion that emits blue light of the organic EL display by the tricolor emission method is preferably used. Can be used.

The panel by the tricolor light emission method requires an organic EL element portion that emits three colors of red, green, and blue colors, respectively. In this case, the following combinations can be exemplified.

Blue light emitting element

As illustrated in the Examples, the configuration in which the 1,3,6,8-4 substituted pyrene compound of the present invention was used alone or as a guest (see Examples).

ㆍ green light emitting element

ITO (positive electrode) / NPD (hole transporting layer) / Alq (electron transporting layer and light emitting layer) / A1-Li (negative electrode)

ㆍ red light emitting element

ITO (positive electrode) / NPD (hole transport layer) / containing 1% by weight of 4-dicyanomethylene-6-cp-zoloridinostyryl-2-tert-butyl-4H-pyran (DCJTB) represented by the following formula Alq (electron transport layer and organic light emitting layer) / Al-Li (negative electrode)

DCJTB

4-dicyanomethylene-6-cp-zoloridinostyryl-2-tert-butyl-4H-pyran

The organic EL device of the present invention can be used for a passive matrix display and also for an active matrix display. The case where the organic electroluminescent element of this invention was used for the passive matrix display is shown in FIG. 1 is a structural example of a positive electrode / hole transporting layer / organic light emitting layer / electron transporting layer / negative electrode. In Fig. 1, the organic EL device comprises a positive electrode 2 containing ITO, a hole transporting layer 3, an organic light emitting layer 4, an electron transporting layer 5, and a negative electrode containing a metal on a glass substrate 1 ( 6) is laminated. The positive electrode 2 containing ITO is a row electrode, and the negative electrode 6 containing metal is a column electrode. In FIG. 1, red light emission 7, green light emission 8, and blue light emission 9 are realized by changing the organic light emitting layer forming material used for the organic light emitting layer 4. In FIG.

The case where the organic electroluminescent element of this invention is used for an active matrix display is shown in FIG. 2 is a structural example of a positive electrode / hole transporting layer / organic light emitting layer / electron transporting layer / negative electrode. In Fig. 2, the organic EL element comprises a drive circuit 21, a TFT (thin film transistor) circuit 22, a positive electrode 2 including ITO, a hole transport layer 3, and an organic light emitting layer on a glass substrate 1 ( 4), the electron transport layer 5 and the negative electrode 6 containing a metal are laminated | stacked. Also in FIG. 2, red luminescence (7), green luminescence (8), and blue luminescence (9) are realized by changing the organic luminescence layer forming material used for the organic luminescence layer (4).

Next, the Example and comparative example of this invention are demonstrated in detail.

<Example 1>

(Synthesis of 1,3,6,8-tetra (4-phenoxyphenyl) pyrene represented by the following formula)

According to the method described in Annalen der Chemie Vol. 531, p. 81, 1,3,6,8-tetrabromopyrene was obtained by reaction of 1 equivalent of pyrene and 4 times of bromine in nitrobenzene.

Then, 1 equivalent of 1,3,6,8-tetrabromopyrene, 4.4 equivalents of 4-phenoxyphenylboronic acid, 10 equivalents of 2 mol / L aqueous solution of sodium carbonate, 0.12 equivalents of tetrakis (triphenylphosphine ) Palladium (O) was added, and it reacted by heating under reflux for 3 hours using benzene as a solvent.

After the reaction was cooled, the precipitate formed by adding methanol to the reaction solution was washed with water and recrystallized from THF-methanol to obtain a crude product. The crude product was purified by vacuum sublimation to afford the desired compound.

The o-xylene solution of this compound showed strong blue fluorescence by ultraviolet light irradiation with a wavelength of 365 nm. The molecular weight of this compound by mass spectrum was 850, which was consistent with the value expected from the molecular formula (C ₆₂ H ₄₂ 0 ₄ ).

<Example 2>

(Synthesis of 1,3,6,8-tetrakis [3- (3-methyldiphenylamino) phenyl] pyrene represented by the following formula)

To 1 equivalent of 1,3,6,8-tetrabromopyrene obtained in the same manner as in Example 1, 4.4 equivalent of 3-chlorophenylboronic acid, 2 mol / L aqueous solution of 10 equivalents of sodium carbonate, and 0.12 equivalent of tetra Kis (triphenylphosphine) palladium (0) was added, and the reaction was carried out by refluxing with heating for 3 hours using benzene as a solvent, and then purified by precipitation and recrystallization to give 1,3,6,8-tetra (3-chlorophenyl Pyrene was obtained.

4.4 equivalents of 3-methyldiphenylamine, 10 equivalents of sodium tert-butoxide, 0.01 equivalents of palladium acetate, 0.04 equivalents to 1 equivalent of 1,3,6,8-tetra (3-chlorophenyl) pyrene tert-butylphosphine was added, followed by reaction under heating at reflux for 3 hours with o-xylene as a solvent.

After cooling, methanol was added to the reaction solution, and the resulting precipitate was washed with water and recrystallized from THF-methanol to obtain a crude product. The crude product was purified by vacuum sublimation to afford the desired compound.

The o-xylene solution of the compound showed strong blue fluorescence by ultraviolet light irradiation with a wavelength of 365 nm. The molecular weight by mass spectrum of this compound was 1230, which was consistent with the value expected from the molecular formula (C ₉₂ H ₇₀ N ₄ ).

<Example 3>

(Synthesis of 1,3,6,8-tetrakis [3,5-bis (3-methyldiphenylamino) phenyl] pyrene represented by the following formula)

Operation similar to Example 2 except having changed 3-chlorophenylboronic acid in Example 2 into 3, 5- dichlorophenylboronic acid and changing the addition amount of 3-methyldiphenylamine from 4.4 equivalent to 8.8 equivalent 1,3,6,8-tetrakis [3- (3-methyldiphenylamino) phenyl] pyrene was obtained.

The o-xylene solution of the compound showed strong blue fluorescence by ultraviolet light irradiation with a wavelength of 365 nm. The molecular weight of this compound by the mass spectrum was 1954, which was consistent with the value expected from the molecular formula (C ₁₄₄ H ₁₁₄ N ₈ ). The IR spectrum in KBr of this compound is shown in FIG. 4.

<Example 4>

(Manufacture of Laminated Organic EL Device)

1,3,6,8-tetra (4-phenoxyphenyl) pyrene was used for the organic light emitting layer as follows to manufacture a laminated organic EL device.

The glass substrate with an ITO electrode was wash | cleaned with water, acetone, and isopropyl alcohol, and each layer was laminated | stacked using the vacuum vapor deposition apparatus (1.33 * 10 <^-4> Pa, substrate temperature at room temperature).

Specifically, according to FIG. 3, NPD is 50 nm as the hole transport layer 3 on the glass substrate 1 with the electrode 2 containing ITO, 1,3,6 as the organic light emitting layer 4 thereon. 20 nm of 8-tetra (4-phenoxyphenyl) pyrene, 10 nm of BAlq as the first electron transport layer 51 thereon, 20 nm of Alq as the second electron transport layer 52 thereon, and 50 nm of the negative electrode 6 containing Al-Li alloy (Li: 0.5 weight%) was deposited on it.

When voltage was applied with ITO of the organic EL device as a positive electrode and Al-Li as a negative electrode, blue light emission was observed at a voltage of 5 V or more. At an applied voltage of 10 V, blue light emission with an emission luminance of 1470 cd / m ² was observed.

Example 5

The 1,3,6,8-tetra (4-phenoxyphenyl) pyrene layer of the organic light emitting layer is changed to a layer in which 1,3,6,8-tetra (4-phenoxyphenyl) pyrene and NPD are co-deposited. Other organic EL elements were manufactured in the same manner as in Example 4. NPD functions as a host and this layer was considered to be a hole transporting layer and an organic light emitting layer. The deposition rate ratio was NPD 90 for 1,3,6,8-tetra (4-phenoxyphenyl) pyrene 10 by weight ratio.

When voltage was applied with ITO of the organic EL device as a positive electrode and Al-Li as a negative electrode, blue light emission was observed at a voltage of 4 V or more. At an applied voltage of 10 V, blue light emission with an emission luminance of 3600 cd / m ² was observed.

<Example 6>

The 1,3,6,8-tetra (4-phenoxyphenyl) pyrene layer of the organic light emitting layer was changed to a layer in which 1,3,6,8-tetra (4-phenoxyphenyl) pyrene and CBP were co-deposited. Other organic EL elements were manufactured in the same manner as in Example 4. CBP functions as a host and this layer was considered to be an organic light emitting layer and an electron transporting layer. The deposition rate ratio was CBP 90 for 1,3,6,8-tetra (4-phenoxyphenyl) pyrene 10 in weight ratio.

When voltage was applied with ITO of the organic EL device as a positive electrode and Al-Li as a negative electrode, blue light emission was observed at a voltage of 4 V or more. At an applied voltage of 10 V, blue light emission of emission luminance 5010 cd / m ² was observed.

<Example 7>

The 1,3,6,8-tetra (4-phenoxyphenyl) pyrene layer of the organic light emitting layer was changed to a 1,3,6,8-tetrakis [3- (3-methyldiphenylamino) phenyl] pyrene layer. Except for the above, an organic EL device was manufactured in the same manner as in Example 4.

When voltage was applied with ITO of the organic EL device as a positive electrode and Al-Li as a negative electrode, blue light emission was observed at a voltage of 4 V or more. At an applied voltage of 10 V, blue light emission of emission luminance 4120 cd / m ² was observed.

<Example 8>

1,3,6,8-tetrakis [3- (3-methyldiphenylamino) phenyl] pyrene layer of the organic light emitting layer was replaced with 1,3,6,8-tetrakis [3- (3-methyldiphenylamino) An organic EL device was manufactured in the same manner as in Example 7, except that the phenyl] pyrene and BAlq were co-deposited. BAlq functions as a host, and this layer was considered to be an organic light emitting layer and an electron transporting layer. The deposition rate ratio was BAlq 90 relative to 1,3,6,8-tetrakis [3- (3-methyldiphenylamino) phenyl] pyrene 10 by weight ratio.

When voltage was applied with ITO of the organic EL device as a positive electrode and Al-Li as a negative electrode, blue light emission was observed at a voltage of 4 V or more. At an applied voltage of 10 V, blue light emission of emission luminance 5420 cd / m ² was observed.

Example 9

1,3,6,8-tetra (4-phenoxyphenyl) pyrene layer of the organic light emitting layer as a 1,3,6,8-tetrakis [3,5-bis (3-methyldiphenylamino) phenyl] pyrene layer An organic EL device was manufactured in the same manner as in Example 4 except for changing to.

When voltage was applied with ITO of the organic EL device as a positive electrode and Al-Li as a negative electrode, blue light emission was observed at a voltage of 4 V or more. At an applied voltage of 10 V, blue light emission of emission luminance 4180 cd / m ² was observed.

<Example 10>

The 1,3,6,8-tetrakis [3,5-bis (3-methyldiphenylamino) phenyl] pyrene layer of the organic light emitting layer was replaced with 1,3,6,8-tetrakis [3,5-bis (3). An organic EL device was manufactured in the same manner as in Example 9, except that the methyl-diphenylamino) phenyl] pyrene and BAlq were co-deposited. In this case, BAlq is the host. The deposition rate ratio was BAlq 90 for 1,3,6,8-tetrakis [3,5-bis (3-methyldiphenylamino) phenyl] pyrene 10 by weight ratio.

When voltage was applied with ITO of the organic EL device as a positive electrode and Al-Li as a negative electrode, blue light emission was observed at a voltage of 4 V or more. At an applied voltage of 10 V, blue light emission of emission luminance 5600 cd / m ² was observed.

<Example 11>

The 1,3,6,8-tetrakis [3,5-bis (3-methyldiphenylamino) phenyl] pyrene layer of the organic light emitting layer was replaced with 1,3,6,8-tetrakis [3,5-bis (3). An organic EL device was manufactured in the same manner as in Example 9, except that the methyl-diphenylamino) phenyl] pyrene and 1,3,6,8-tetrakis (diphenylamino) pyrene were changed to a layer deposited at the same time. 1,3,6,8-tetrakis [3,5-bis (3-methyldiphenylamino) phenyl] pyrene was considered to be a host and 1,3,6,8-tetrakis (diphenylamino) pyrene was a guest . The deposition rate ratio is 1,3,6,8-tetrakis (diphenylamino) relative to 1,3,6,8-tetrakis [3,5-bis (3-methyldiphenylamino) phenyl] pyrene 90 in weight ratio. Was pyrene 10.

When voltage was applied with ITO of the organic EL device as the positive electrode and Al-Li as the negative electrode, green light emission was observed at a voltage of 4 V or more. At an applied voltage of 10 V, green light emission with an emission luminance of 8900 cd / m ² was observed.

<Example 12>

The EL element manufactured in Example 6 was subjected to constant current continuous driving at an initial luminance of 150 cd / m ² . The time from the initial luminance to the luminance half life (luminance half life) was 600 hours.

Example 13

The EL element manufactured in Example 8 was subjected to constant current continuous driving at an initial luminance of 150 cd / m ² . The time from the initial luminance to the luminance half life (luminance half life) was 670 hours.

<Example 14>

The EL element manufactured in Example 10 was subjected to constant current continuous driving at an initial luminance of 150 cd / m ² . The time from the initial luminance to the luminance half life (luminance half life) was 640 hours.

<Example 15>

The EL element manufactured in Example 11 was subjected to constant current continuous driving at an initial luminance of 150 cd / m ² . The time from the initial luminance to the luminance half life (luminance half life) was 1040 hours.

Comparative Example 1

An organic EL device was manufactured in the same manner as in Example 4, except that 1,3,6,8-tetra (4-phenoxyphenyl) pyrene included in the organic light emitting layer was changed to 1,3,6,8-tetraphenylpyrene. Prepared.

When voltage was applied with ITO of the organic EL device as a positive electrode and Al-Li as a negative electrode, blue light emission was observed at a voltage of 5 V or more. At an applied voltage of 10 V, blue light emission of emission luminance 680 cd / m ² was observed.

Comparative Example 2

When the organic EL device manufactured in Comparative Example 1 was continuously driven at an initial luminance of 150 cd / m ² , the time from initial luminance to luminance half life (luminance half life) was 30 hours.

식 중, R은 서로 독립적으로 하기 화학식 2의 구조를 갖는다.
<화학식 2>

{식 중, R¹ 내지 R⁵는 서로 독립적으로 수소 또는 치환기를 나타내되, 단 R¹ 내지 R⁵ 중 하나 이상은 하기 화학식 3 내지 6으로 표시되는 기 중 어느 하나임}
<화학식 3>

<화학식 4>

<화학식 5>

<화학식 6>

{식 중, R⁶ 내지 R¹²는 서로 독립적으로 수소 또는 치환기를 나타냄}
(부기 2)
부기 1에 있어서, 상기 화학식 3의 R⁶ 및 R⁷이 모두 서로 독립적으로 치환기를 가질 수도 있는 방향족기인 1,3,6,8-4 치환 피렌 화합물.
(부기 3)
부기 1에 있어서, 상기 화학식 6의 R¹²가 치환기를 가질 수도 있는 방향족기인 1,3,6,8-4 치환 피렌 화합물.
(부기 4)
부기 1에 있어서, 유기 전계 발광 소자에서의 유기 발광층 형성 재료로서 사용되는 1,3,6,8-4 치환 피렌 화합물.
(부기 5)
부기 1에 있어서, 유기 전계 발광 소자에서의 호스트 또는 게스트로서의 유기 발광층 형성 재료로서 사용되는 1,3,6,8-4 치환 피렌 화합물.
(부기 6)
정극과 부극 사이에 유기 발광층을 가지며, 해당 유기 발광층이 하기 화학식 1로 표시되는 1,3,6,8-4 치환 피렌 화합물을 유기 발광층 형성 재료로서 함유하는 유기 전계 발광 소자.
<화학식 1>

식 중, R은 서로 독립적으로 하기 화학식 2의 구조를 갖는다.
<화학식 2>

{식 중, R¹ 내지 R⁵는 서로 독립적으로 수소 또는 치환기를 나타내되, 단 R¹ 내지 R⁵ 중 하나 이상은 하기 화학식 3 내지 6으로 표시되는 기 중 어느 하나임}
<화학식 3>

<화학식 4>

<화학식 5>

<화학식 6>

{식 중, R⁶ 내지 R¹²는 서로 독립적으로 수소 또는 치환기를 나타냄}
(부기 7)
부기 6에 있어서, 상기 화학식 1로 표시되는 1,3,6,8-4 치환 피렌 화합물이 호스트 또는 게스트로서의 유기 발광층 형성 재료인 유기 전계 발광 소자.
(부기 8)
부기 6에 있어서, 상기 유기 발광층이 상기 화학식 1로 표시되는 1,3,6,8-4 치환 피렌 화합물의 단독층을 포함하는 유기 전계 발광 소자.
(부기 9)
부기 6에 있어서, 상기 화학식 3의 R⁶ 및 R⁷이 모두 서로 독립적으로 치환기를 가질 수도 있는 방향족기인 유기 전계 발광 소자.
(부기 10)
부기 6에 있어서, 상기 화학식 6의 R¹²가 치환기를 가질 수도 있는 방향족기인 유기 전계 발광 소자.
(부기 11)
부기 6에 있어서, 상기 유기 발광층이 하기 화학식 7로 표시되는 방향족 아민 화합물을 하나 이상 함유하여 이루어지는 유기 전계 발광 소자.
<화학식 7>

식 중, Ar¹은 치환기를 가질 수도 있는 2, 3 또는 4가 방향족기를 나타내고, R¹⁷ 및 R¹⁸은 각각 독립적으로 치환기를 가질 수도 있는 1가 방향족기를 나타내며, n은 2 내지 4의 정수를 나타낸다.
(부기 12)
부기 11에 있어서, 화학식 7로 표시되는 방향족 아민 화합물이 하기 화학식 8로 표시되는 N,N'-디나프틸-N,N'-디페닐-[1,1'-비페닐]-4,4'-디아민인 유기 전계 발광 소자.
<화학식 8>

(부기 13)
부기 6에 있어서, 상기 유기 발광층이 하기 화학식 9로 표시되는 카르바졸 화합물을 하나 이상 함유하여 이루어지는 유기 전계 발광 소자.
<화학식 9>

식 중, Ar²는 치환기를 가질 수도 있는 2, 3 또는 4가 방향족기를 나타내고, R¹³ 및 R^13'는 각각 독립적으로 수소 원자, 할로겐 원자, 또는 치환될 수도 있는 알킬기, 아랄킬기, 알케닐기, 방향족기, 시아노기, 아미노기, 아실기, 알콕시카르보닐기, 카르복시기, 알콕시기, 알킬술포닐기, 수산기, 아미드기 또는 방향족 옥시기를 나타내며, n은 2 내지 4의 정수를 나타낸다.
(부기 14)
부기 13에 있어서, 화학식 9로 표시되는 카르바졸 화합물이 하기 화학식 10으로 표시되는 4,4'-비스(9-카르바졸릴)-비페닐인 유기 전계 발광 소자.
<화학식 10>

CBP
(부기 15)
부기 6에 있어서, 상기 유기 발광층이 하기 화학식 11로 표시되는 히드록시퀴놀린-옥시아릴 착체를 하나 이상 함유하여 이루어지는 유기 전계 발광 소자.
<화학식 11>

식 중, R¹⁴는 수소 또는 치환기를 가질 수도 있는 알킬기이고, R¹⁵는 치환기를 가질 수도 있는 방향족기를 나타내며, M은 3가의 금속을 나타내고, n은 1 또는 2를 나타낸다.
(부기 16)
부기 15에 있어서, 화학식 11로 표시되는 히드록시퀴놀린-옥시아릴 착체가 하기 화학식 12로 표시되는 알루미늄 히드록시퀴놀린-옥시비페닐 착체인 유기 전계 발광 소자.
<화학식 12>

(부기 17)
부기 6에 기재된 유기 전계 발광 소자를 이용한 유기 전계 발광 디스플레이.
(부기 18)
부기 7에 기재된 유기 전계 발광 소자를 이용한 유기 전계 발광 디스플레이.
(부기 19)
부기 9에 기재된 유기 전계 발광 소자를 이용한 유기 전계 발광 디스플레이.
(부기 20)
부기 10에 기재된 유기 전계 발광 소자를 이용한 유기 전계 발광 디스플레이. From the above results, the 1,3,6,8-4 substituted pyrene compound of the present invention, when used alone or as a guest, exhibits blue light emission with high color purity, high luminous efficiency, and is stable for long time driving. It became a formation material, and it turned out that the organic electroluminescent element of this invention has high luminous efficiency and long drive life.
Moreover, the invention shown in the following bookkeeping can be derived from the contents disclosed above.
(Book 1)
1,3,6,8-4 substituted pyrene compound represented by the following formula (1).
<Formula 1>

Wherein R has the structure of formula (2) independently of one another.
<Formula 2>

{Wherein, R ¹ to R ⁵ independently represent hydrogen or a substituent, provided that at least one of R ¹ to R ⁵ is any one of groups represented by the following Chemical Formulas 3 to 6}
<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

{Wherein R ⁶ to R ¹² independently represent hydrogen or a substituent}
(Book 2)
1,3,6,8-4 substituted pyrene compound according to Appendix 1, wherein R ⁶ and R ^{7 in} Formula 3 are both aromatic groups which may independently have a substituent.
(Supplementary Note 3)
The 1,3,6,8-4 substituted pyrene compound according to Appendix 1, wherein R ¹² in Chemical Formula 6 is an aromatic group which may have a substituent.
(Appendix 4)
The 1,3,6,8-4 substituted pyrene compound according to Appendix 1 which is used as an organic light emitting layer forming material in an organic electroluminescent element.
(Supplementary Note 5)
The 1,3,6,8-4 substituted pyrene compound according to Appendix 1 which is used as an organic light emitting layer forming material as a host or a guest in an organic electroluminescent device.
(Supplementary Note 6)
An organic electroluminescent device having an organic light emitting layer between a positive electrode and a negative electrode, wherein the organic light emitting layer contains a 1,3,6,8-4 substituted pyrene compound represented by the following formula (1) as an organic light emitting layer forming material.
<Formula 1>

Wherein R has the structure of formula (2) independently of one another.
<Formula 2>

{Wherein, R ¹ to R ⁵ independently represent hydrogen or a substituent, provided that at least one of R ¹ to R ⁵ is any one of groups represented by the following Chemical Formulas 3 to 6}
<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

{Wherein R ⁶ to R ¹² independently represent hydrogen or a substituent}
(Appendix 7)
The organic electroluminescent device according to Appendix 6, wherein the 1,3,6,8-4 substituted pyrene compound represented by Chemical Formula 1 is an organic light emitting layer forming material as a host or a guest.
(Appendix 8)
The organic electroluminescent device according to Appendix 6, wherein the organic light emitting layer comprises a single layer of a 1,3,6,8-4 substituted pyrene compound represented by Chemical Formula 1.
(Appendix 9)
The organic electroluminescent device according to Appendix 6, wherein R ⁶ and R ^{7 in} Formula 3 are each an aromatic group which may independently have a substituent.
(Book 10)
The organic electroluminescent device according to Appendix 6, wherein R ¹² of Formula 6 is an aromatic group which may have a substituent.
(Appendix 11)
The organic electroluminescent device according to Appendix 6, wherein the organic light emitting layer contains at least one aromatic amine compound represented by the following general formula (7).
<Formula 7>

In the formula, Ar ¹ represents a divalent, trivalent or tetravalent aromatic group which may have a substituent, R ¹⁷ and R ¹⁸ each independently represent a monovalent aromatic group which may have a substituent, and n represents an integer of 2 to 4. .
(Appendix 12)
In Appendix 11, the aromatic amine compound represented by the formula (7) is N, N'-dinaphthyl-N, N'-diphenyl- [1,1'-biphenyl] -4,4 represented by the following formula (8). An organic electroluminescent device which is' -diamine.
<Formula 8>

(Appendix 13)
The organic electroluminescent device according to Appendix 6, wherein the organic light emitting layer contains at least one carbazole compound represented by the following formula (9).
<Formula 9>

In the formula, Ar ² represents a di, tri or tetravalent aromatic group which may have a substituent, and R ¹³ and R ^{13 ′} each independently represent a hydrogen atom, a halogen atom, or an alkyl group, an aralkyl group, an alkenyl group, which may be substituted, An aromatic group, a cyano group, an amino group, an acyl group, an alkoxycarbonyl group, a carboxyl group, an alkoxy group, an alkylsulfonyl group, a hydroxyl group, an amide group, or an aromatic oxy group is shown, n shows the integer of 2-4.
(Book 14)
The organic electroluminescent device according to Appendix 13, wherein the carbazole compound represented by the formula (9) is 4,4'-bis (9-carbazolyl) -biphenyl represented by the following formula (10).
<Formula 10>

CBP
(Supplementary Note 15)
The organic electroluminescent device according to Appendix 6, wherein the organic light emitting layer contains at least one hydroxyquinoline-oxyaryl complex represented by the following formula (11).
<Formula 11>

In formula, R <^14> is hydrogen or the alkyl group which may have a substituent, R <^15> represents the aromatic group which may have a substituent, M represents a trivalent metal, n represents 1 or 2.
(Appendix 16)
The organic electroluminescent device according to Appendix 15, wherein the hydroxyquinoline-oxyaryl complex represented by the formula (11) is an aluminum hydroxyquinoline-oxybiphenyl complex represented by the following formula (12).
<Formula 12>

(Appendix 17)
An organic electroluminescent display using the organic electroluminescent element according to Appendix 6.
(Supplementary Note 18)
An organic electroluminescent display using the organic electroluminescent element according to Appendix 7.
(Appendix 19)
An organic electroluminescent display using the organic electroluminescent element according to Appendix 9.
(Book 20)
An organic electroluminescent display using the organic electroluminescent element of appendix 10.

When used alone or as a guest according to the present invention, an organic light emitting layer-forming material exhibiting blue light emission with high color purity, high luminous efficiency, and stable for long time driving, an organic EL element having high luminous efficiency and long driving life, and It is possible to provide a high performance organic EL display having high luminous efficiency and long driving life.

Claims (20)

1,3,6,8-4 substituted pyrene compound represented by the following formula (1). <Formula 1>

Wherein R has the structure of formula (2) independently of one another. <Formula 2>

{Wherein, R ¹ to R ⁵ independently represent hydrogen or a substituent, provided that at least one of R ¹ to R ⁵ is any one of groups represented by the following Chemical Formulas 3 to 6} <Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

{Wherein R ⁶ to R ¹² independently represent hydrogen or a substituent} The 1,3,6,8-4 substituted pyrene compound according to claim 1, wherein R ⁶ and R ^{7 in} Formula 3 are both aromatic groups which may independently have a substituent. The 1,3,6,8-4 substituted pyrene compound according to claim 1, wherein R ¹² in Formula 6 is an aromatic group which may have a substituent. The 1,3,6,8-4 substituted pyrene compound according to claim 1, which is used as an organic light emitting layer forming material in an organic electroluminescent device. The 1,3,6,8-4 substituted pyrene compound according to claim 1, which is used as an organic light emitting layer forming material as a host or a guest in an organic electroluminescent device. An organic electroluminescent device having an organic light emitting layer between a positive electrode and a negative electrode, wherein the organic light emitting layer contains a 1,3,6,8-4 substituted pyrene compound represented by the following formula (1) as an organic light emitting layer forming material. <Formula 1>

Wherein R has the structure of formula (2) independently of one another. <Formula 2>

{Wherein, R ¹ to R ⁵ independently represent hydrogen or a substituent, provided that at least one of R ¹ to R ⁵ is any one of groups represented by the following Chemical Formulas 3 to 6} <Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

{Wherein R ⁶ to R ¹² independently represent hydrogen or a substituent} The organic electroluminescent device according to claim 6, wherein the 1,3,6,8-4 substituted pyrene compound represented by Chemical Formula 1 is an organic light emitting layer forming material as a host or a guest. The organic electroluminescent device according to claim 6, wherein the organic light emitting layer comprises a single layer of a 1,3,6,8-4 substituted pyrene compound represented by Chemical Formula 1. The organic electroluminescent device according to claim 6, wherein R ⁶ and R ^{7 in} Formula 3 are each an aromatic group which may independently have a substituent. The organic electroluminescent device according to claim 6, wherein R ¹² in Formula 6 is an aromatic group which may have a substituent. delete delete delete delete delete delete delete delete delete delete

Images