JP6388114B2 - Method for producing cyclic aromatic compound used for material for organic electronics element - Google Patents

Description

  The present invention relates to an organic electronics element material, an organic electronics element, and an organic electronics device.

  Organic electronic elements such as organic electroluminescent elements, organic thin-film solar cells, and organic transistors are attracting attention as next-generation electronic materials because they are excellent in lightness, moldability, and flexibility. For example, organic electroluminescent elements ( Hereinafter, the “organic EL element” in some cases is expected to be applied to organic electronic devices such as lighting devices and display devices.

  The organic EL element has an electron transport material that mediates electron transport; a hole transport material that mediates hole transport; and a luminescent molecule (a luminescent dopant) such as a phosphorescent dopant or a fluorescent dopant, and is dispersed on the molecule. Three kinds of host materials (light-emitting layer host materials) capable of charge recombination are required. At present, it has become the mainstream to develop materials that have been specialized by refining the performance required for each material. For example, Alq3 (tris (8-hydroxyquinolyl) aluminum is used as the electron transport material. ), BAlq (bis (2-methyl-8-quinolyl) -4- (phenylphenolate) aluminum), etc., as the hole transport material, poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT). -PSS), triarylamine derivatives and the like, and CBP (4,4'-N, N-dicarbazole-biphenyl) and the like are known as the host materials. However, in such a heterojunction type organic EL element in which an organic compound layer is formed from a plurality of different materials, it is necessary to use different materials as materials for the electron transport layer, the hole transport layer, and the light emitting layer. For this reason, there is a problem that the manufacturing process is bulky and the manufacturing cost is increased. Furthermore, since an interface is generated between the layers, the interface causes problems of deterioration of the organic EL element and the stability of light emission is not sufficient.

  On the other hand, as an organic EL element having a simpler structure and easy to manufacture, a homojunction type using the same material as an electron transport material, a hole transport material, and a light emitting layer host material is known. Examples of materials that can be used as the material of the three layers include phenazaricin derivatives described in JP-A-2006-083167 (Patent Document 1), Hayato Hayato Tsuji et al., Advanced Materials, 2009, 21, 3776. -CZBDF (bis (carbazolyl) bendodifuran) described on page 3779 (Non-Patent Document 1).

  Further, the organic thin film solar cell has a structure having an organic compound layer between the cathode and the anode, and has attracted attention because it can reduce the power generation cost and the environmental load compared to the inorganic solar cell. ing. As the organic compound layer, a bulk heterojunction layer in which an electron donor layer and an electron acceptor layer are mixed is known.

  Furthermore, as a material for such an organic electronic element, for example, International Publication No. 2011-111719 (Patent Document 2), divalent aromatic hydrocarbon groups at positions 4 and 4 ′ of diphenylene, etc. Is described, and a condensed macrocyclic compound in which naphthylene is bonded is described in Japanese Patent Application Laid-Open No. 2012-121861 (Patent Document 3).

  Pisula et al., Chem. Asian. J. et al. 2007, pages 2, 51-56 (non-patent document 2) describe cyclic compounds composed of benzene and phenanthrene accumulated in layers. However, Non-Patent Document 2 does not describe any use of the compound as a material for an organic electronics element.

JP 2006-083167 A International Publication No. 2011-117719 JP 2012-121861 A

Hayato Hayato Tsuji et al., Advanced Materials, 2009, 21, 3776-3779. Pisula et al., Chem. Asian. J. et al. 2007, 2, 51-56

  The present invention has been made in view of the above problems, and a novel organic electronic device material that can be used as an electron transport material, a hole transport material, and a light emitting layer host material of an organic electroluminescence device, and An object of the present invention is to provide an organic electronic device and an organic electronic device used.

  As a result of intensive studies to achieve the above object, the present inventors can use a cyclic aromatic compound in which the 1-position and 3-position of phenylene are bonded to each other as a material for an organic electronics element. In particular, the present inventors have found that it can be used as any of an electron transport material, a hole transport material, and a light emitting layer host material of an organic EL device, and completed the present invention.

That is, the manufacturing method of the cyclic aromatic compound used for the organic electronics element material of the present invention,
The said cyclic aromatic compound is the following general formula (1) [In formula (1), n shows the integer in any one of 5-9. A cyclic aromatic compound represented by the formula:
Zero-valent nickel catalyst and the following general formula (2) [in the formula (2), X independently represents Cl, Br or I. And a halogenated benzene represented by the following formula, and the halogenated benzene is polymerized by a Yamamoto coupling reaction to obtain the cyclic aromatic compound.
It is characterized by this.

A method of manufacturing a cyclic aromatic compound of the present invention, the organic electronic device material is an anode, a cathode, and the organic electronic device comprising an organic compound layer disposed between the cathode and the anode it is preferably contained in the organic compound layer.

In the method for producing a cyclic aromatic compound of the present invention, the zero-valent nickel catalyst is preferably bis (1,5-cyclooctadiene) nickel .

  According to the present invention, a novel material for an organic electronics element that can be used as an electron transport material, a hole transport material, and a light emitting layer host material of an organic electroluminescence element, and an organic electronics element and an organic electronics device using the same Can be provided.

It is the schematic of the organic electroluminescent element for evaluation used for the organic electronics element evaluation of an Example. It is a schematic diagram which shows the longitudinal cross-section of the organic electroluminescent element for evaluation used for the organic electronics element evaluation of an Example. 2 is a graph showing a ¹ H-NMR spectrum of Compound 1 obtained in Synthesis Example 1. FIG. 2 is a graph showing a ¹ H-NMR spectrum of Compound 2 obtained in Synthesis Example 2. FIG. 6 is a graph showing a ¹ H-NMR spectrum of compound 3 obtained in Synthesis Example 3. 2 is a graph showing a ¹ H-NMR spectrum of Compound 4 obtained in Synthesis Example 4. FIG. 6 is a graph showing a ¹ H-NMR spectrum of compound 5 obtained in Synthesis Example 5. FIG. 2 is a graph showing a ¹³ C-NMR spectrum of Compound 1 obtained in Synthesis Example 1. FIG. 6 is a graph showing a ¹³ C-NMR spectrum of compound 3 obtained in Synthesis Example 3. 6 is a graph showing a ¹³ C-NMR spectrum of compound 5 obtained in Synthesis Example 5. FIG. It is a graph which shows the MALDI-TOF MS spectrum of the compounds 1-5 obtained by the synthesis examples 1-5. It is a graph which shows the spectrum obtained by the HPLC measurement of the compounds 1-5 obtained by the synthesis examples 1-5. 1 is a schematic diagram showing a longitudinal section of an organic electronics element obtained in Example 1. FIG. It is a graph which shows the result of having implemented the spectrum measurement about the organic electronics element obtained in Example 3. FIG. It is a graph which shows the result of having implemented the spectrum measurement about the organic electronics element obtained in Example 4. FIG.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

<Materials for organic electronics elements>
First, the organic electronics element material of the present invention will be described. The organic electronic device material of the present invention has the following general formula (1):

[In Formula (1), n shows the integer in any one of 5-9. ]
It contains the cyclic aromatic compound represented by these.

  In the cyclic aromatic compound represented by the general formula (1), the repeating number n of the m-phenylene group is an integer of 5-9. The cyclic aromatic compound represented by the general formula (1) is [5] -cyclometaphenylene when n is 5, [6] -cyclometaphenylene when n is 6, and when n is 7, 7] -cyclometaphenylene, when n is 8, [8] -cyclometaphenylene, and when n is 9, [9] -cyclometaphenylene. Among these, it is preferable that the repeating number n of the phenylene group is 5 or 6 from the viewpoint that the strain is small and the structure of the obtained compound tends to be rigid.

The cyclic aromatic compound according to the present invention can be identified by IR (infrared absorption spectrum), ¹ H-NMR, ¹³ C-NMR, MS (MALDI TOF), elemental analysis, and thermal decomposition temperature measurement. The cyclic aromatic compound according to the present invention can have a single crystal structure and can be identified by single crystal X-ray structure analysis.

  The cyclic aromatic compound according to the present invention includes, for example, the following general formula (2):

[In the formula (2), X represents a halogen atom. ]
It can obtain by carrying out the coupling reaction of the halogenated benzene represented by these.

  In the halogenated benzene represented by the general formula (2), examples of the halogen atom include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). Among these, the coupling reaction From the viewpoint of having sufficient reactivity, bromine (Br) is preferable.

  The coupling reaction may be any method capable of producing the cyclic aromatic compound according to the present invention, and a known coupling reaction can be appropriately employed. For example, Suzuki coupling reaction, Still A coupling reaction, a Kumada coupling reaction, an Ullmann reaction, a Yamamoto coupling reaction, a Negishi coupling reaction, an Hiyama coupling reaction, a reaction combining these reactions, and the like. Among these, it is preferable to use the Yamamoto coupling reaction from the viewpoint that the yield of the obtained cyclic aromatic compound is high and the material used for the reaction is easy to obtain.

  In the coupling method, an organic solvent can be used. Examples of the organic solvent include toluene, N, N-dimethylformamide (DMF), benzene, xylene, mesitylene, DMSO, and the like. You may use individually or in mixture of 2 or more types. Among these, it is preferable to use toluene, N, N-dimethylformamide, or benzene. In addition, when such an organic solvent is used, it is preferably used after sufficiently deoxygenated from the viewpoint of suppressing side reactions, although it varies depending on the halogenated benzene used and the coupling reaction employed. In addition, it is more preferable to use in an inert gas atmosphere such as nitrogen or argon under light shielding.

  Furthermore, in the synthesis of the cyclic aromatic compound according to the present invention, it is preferable to add an alkali or an appropriate catalyst as appropriate in order to advance the reaction. These alkalis and catalysts can be selected according to the coupling reaction employed. For example, the alkali includes potassium carbonate, sodium carbonate, cesium carbonate, potassium hydroxide, sodium hydroxide, tripotassium phosphate. , Potassium acetate, potassium fluoride, cesium fluoride, and the like. Examples of the catalyst include nickel catalysts such as bis (1,5-cyclooctadiene) nickel, copper catalysts, palladium catalysts, platinum catalysts, iron catalysts, and the like. Can be mentioned. Among such alkalis and catalysts, those sufficiently dissolved in the organic solvent used for the reaction are preferably used, and bis (1,5-cyclooctadiene) nickel is preferably used. Moreover, it is preferable to set it as 2-5 mol with respect to 1 mol of halogenated benzene represented by the said General formula (2) as the addition amount of the said alkali. The amount of the catalyst to be added is not particularly limited as long as it is an effective amount as a catalyst, but is 0.1 to 2 with respect to 1 mol of the halogenated benzene represented by the general formula (2). 5 mol is preferable. When the amount of such an alkali and catalyst added is less than the lower limit, the reaction efficiency tends to decrease. On the other hand, when the upper limit is exceeded, addition beyond that is wasted, and the economy tends to decrease. .

  The method of mixing such an alkali or catalyst is not particularly limited. For example, the alkali is slowly added while stirring the reaction solution containing the halogenated benzene and the organic solvent in an inert atmosphere such as argon or nitrogen. And / or a method of adding a catalyst solution, a method of slowly adding the reaction solution to a solution containing an alkali and / or a catalyst, and the like. The total concentration of the alkali and / or catalyst and the halogenated benzene represented by the general formula (2) in the mixed solution (reaction solution) obtained by the mixing is set to a high dilution condition in order to further promote cyclization. From this viewpoint, the content is preferably 1 to 15% by mass (5 to 50 mM).

  Further, the coupling reaction is preferably performed in an inert gas atmosphere under light shielding. Examples of the inert gas include nitrogen gas and argon gas. The temperature of the coupling reaction varies depending on the organic solvent used, but is preferably 20 to 80 ° C. The reaction time of the coupling reaction is not particularly limited, and may vary depending on the halogenated benzene used and the coupling reaction employed. The upper limit of the reaction time may be set when the target degree of polymerization is reached. It is preferable that it is about time.

  In addition, when stopping the said coupling reaction, although it changes also with the halogenated benzene to be used and the coupling reaction to be employ | adopted, it is preferable to add water, dilute hydrochloric acid, etc. to the said reaction liquid. In addition, after the coupling reaction, conventional separation operations such as acid washing, alkali washing, neutralization, water washing, organic solvent washing, reprecipitation, centrifugation, extraction, column chromatography, dialysis, etc., purification operations, drying, etc. It is preferable to appropriately perform a purification treatment by the above operation.

  As an example of a preferred embodiment of the method for synthesizing a cyclic aromatic compound according to the present invention, a nickel catalyst and 1,3-dibromobenzene in which X is Br in the above general formula (2) are mixed, and Yamamoto coupling is performed. A method for obtaining a cyclic aromatic compound according to the present invention by polymerizing 1,3-dibromobenzene by reaction will be described.

  As the nickel catalyst, known ones can be appropriately used. For example, bis (1,5-cyclooctadiene) nickel that is zero-valent nickel, 1,5-cyclooctadiene, 2,2 ′ -Dissolve nickel catalyst obtained by dissolving bipyridine in an equimolar ratio in an organic solvent, or bis (1,5-cyclooctadiene) nickel and triphenylphosphine in an equimolar ratio in an organic solvent. The nickel catalyst obtained by this can be used. The addition amount of such a nickel catalyst is not particularly limited, but is preferably 2 mol or more with respect to 1 mol of 1,3-dibromobenzene.

  The polymerization reaction is preferably performed in an organic solvent such as toluene or N, N-dimethylformamide. Further, such an organic solvent is preferably sufficiently deaerated from the viewpoint of suppressing side reactions.

  The mixing method of the nickel catalyst and 1,3-dibromobenzene is not particularly limited and is as described above. The total concentration of the nickel catalyst and 1,3-dibromobenzene in the mixed solution (reaction solution) obtained by the mixing is preferably 1 to 15% by mass.

  The polymerization reaction is preferably carried out in an inert gas atmosphere under light shielding, and the temperature of the polymerization reaction is preferably 20 to 80 ° C., although it varies depending on the organic solvent used. The reaction time of the polymerization reaction is not particularly limited, and the upper limit of the reaction time may be set when the target degree of polymerization is reached, but is preferably about 1 to 24 hours. Thus, since it is possible to use single bond formation that is simple and has mild reaction conditions for linking m-phenylenes, a crude product containing the cyclic aromatic compound according to the present invention can be obtained easily and efficiently. be able to. From the viewpoint of further improving the function as a material for an organic electronics element, the cyclic reporting group compound according to the present invention is obtained from the crude product using a two-liquid phase separation method or the following purification method, [5]- It is preferable to separate and purify into cyclometaphenylene, [6] -cyclometaphenylene, [7] -cyclometaphenylene, [8] -cyclometaphenylene, and [9] -cyclometaphenylene. Thus, the cyclic aromatic compound according to the present invention can be produced.

  In addition, each cyclic aromatic compound thus separated can be simply self-assembled to form a crystal having a π-stacked filling structure, so that it is known depending on the cyclic aromatic compound and the production method thereof. The crystal can be obtained by appropriately adopting the method. Examples of such a crystallization method include methods such as crystallization, sublimation, and vapor deposition.

  As the cyclic aromatic compound according to the present invention, it is preferable to further purify and use it from the viewpoint of suppressing the influence of a small amount of impurities as a material for an organic electronics element. The purity measured by HPLC, TGA, DSC, impurity metal analysis or the like is preferably 99.99% or more. As the purification method, a known method can be appropriately employed depending on the cyclic aromatic compound and the production method thereof, for example, gel filtration, silica gel column chromatography, high performance liquid chromatography, medium pressure column chromatography, etc. Examples include various chromatographies; recrystallization; sublimation purification; and a combination of these purification methods.

  The organic electronics element material of the present invention includes impurities derived from the reagents used in the synthesis of the cyclic aromatic compound within the range that does not impair the effects of the present invention, even if the material is composed of only the cyclic aromatic compound. Further, it may further contain impurities generated by purification.

<Organic electronics elements>
Next, the organic electronics element of the present invention will be described. The organic electronics element of the present invention is an organic electronics element comprising an anode, a cathode, and an organic compound layer disposed between the cathode and the anode, the organic compound layer comprising the material for an organic electronics element. It is characterized by containing.

  Examples of the organic electronics element include an organic EL element, an organic thin film solar cell, and an organic diode. The organic compound layer refers to a layer containing an organic compound. For example, in the layer configuration of the organic EL element, a hole transport layer, a light emitting layer, an electron transport layer, and the like can be given. In the case where an organic compound is contained, a hole blocking layer, a hole injection layer, an electron injection layer, and the like are also included in the organic compound layer according to the present invention. Examples of the layer configuration of the organic thin film solar cell include a hole transport layer, a p-type semiconductor layer, a power generation layer, an n-type semiconductor layer, and an electron transport layer.

  The present invention is characterized in that the organic electronic element material is contained in at least one of the plurality of organic compound layers. When the organic electronics element is an organic EL element, the organic electronic element material may be contained in at least one organic compound layer of a hole transport layer, a light emitting layer, and an electron transport layer. preferable. In the present invention, the organic electronics element material can be used as any of an electron transport material, a hole transport material, and a light emitting layer host material, and therefore the organic electronics element can be used in any of the three layers. Materials can be included.

<Organic EL device>
Hereinafter, an organic EL element will be described as a preferred embodiment of the organic electronic element of the present invention. Although the preferable specific example of the layer structure of the organic EL element of this invention is shown below, this invention is not limited to these.
(I) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode (iii) anode / hole transport layer / Light emitting layer / hole blocking layer / electron transport layer / electron injection layer (cathode buffer layer) / cathode (iv) anode / hole injection layer (anode buffer layer) / hole transport layer / light emitting layer / hole blocking layer / Electron transport layer / electron injection layer (cathode buffer layer) / cathode (v) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer (cathode buffer layer) / cathode (vi) anode / hole injection Layer (anode buffer layer) / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode.

[Light emitting layer]
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.

  The light emitting layer may be a single layer or a combination of a plurality of layers. In the organic EL device of the present invention, the blue light emitting layer has a maximum emission wavelength of 430 nm to 480 nm. The green light emitting layer preferably has a light emission maximum wavelength of 510 nm to 550 nm, and the red light emitting layer has a light emission maximum wavelength of 600 nm to 640 nm. Alternatively, a white light emitting layer may be formed by laminating at least three light emitting layers. Further, a non-light emitting intermediate layer may be provided between the light emitting layers.

  The total film thickness of the light emitting layer is not particularly limited, but it is possible to prevent film homogeneity, application of unnecessary high voltage during light emission, and improvement of stability of emission color against driving current. Therefore, it is preferable to adjust to the range of 2 nm to 5 μm, more preferable to adjust to the range of 2 nm to 200 nm, and particularly preferable to adjust to the range of 10 nm to 20 nm.

  The light emitting layer of the organic EL device of the present invention preferably contains a light emitting layer host material and at least one kind of light emitting dopant of phosphorescent light emitting dopant and fluorescent dopant. Moreover, you may further contain the hole transport material and electron transport material which are mentioned later.

  The light emitting layer can be formed by forming the light emitting layer host compound and the light emitting dopant by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, and an ink jet method. .

(Light emitting layer host material)
In the present invention, the light-emitting layer host material (hereinafter sometimes referred to as “host material”) is a compound having a mass ratio of 20% or more in the light-emitting layer, and a room temperature. A compound having a phosphorescence quantum yield of phosphorescence emission at (25 ° C.) of less than 0.1. Preferably, the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the mass ratio in the layer is 20% or more among the compounds contained in the said light emitting layer.

  As the host material, one type of host material may be used alone, or two or more types may be used in combination. When a plurality of types of host materials are used, the efficiency of the organic EL element can be increased by adjusting the movement of charges. In the present invention, it is preferable that the organic electronic device material of the present invention is used alone or in combination with another host material as the host material. In addition, when the material for an organic electronics element of the present invention is used as an electron transport material or a hole transport material to be described later, other materials may be used alone or in combination of two or more as the host material. .

As host materials other than the organic electronic device material of the present invention, the hole transport ability and the electron transport ability are prevented, the emission of light is prevented from being increased in wavelength, and the Tg (glass transition temperature) is high. ) Is preferred. Specifically, the following documents:
JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like. Among these, as other host materials, compounds having a carbazole ring as a partial structure; compounds having a polymerizable group and having a carbazole ring as a partial structure; polymers of these compounds are preferable, for example, CBP (4,4′-N, N-dicarbazole-biphenyl) is preferred.

(Luminescent dopant)
As the light-emitting dopant according to the present invention, a fluorescent dopant (also referred to as a fluorescent compound) or a phosphorescent dopant (also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like) can be used. From the viewpoint of obtaining an organic EL device with higher luminous efficiency, it is preferable to contain a phosphorescent dopant.

  The phosphorescent dopant is a compound in which light emission from an excited triplet is observed. Specifically, the phosphorescent dopant is a compound that emits phosphorescence at room temperature (25 ° C.), and phosphorescent phosphorescence at 25 ° C. A compound having a photon yield of 0.01 or more. Preferably, the phosphorescence quantum yield is 0.1 or more. In addition, the said phosphorescence quantum yield can be measured by the method as described in 398 page (1992 version, Maruzen) of Spectroscopic II of 4th edition Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence emitting dopant according to the present invention achieves the above phosphorescence quantum yield (0.01 or more) in any solvent. It only has to be done.

  There are two types of light emission principles of the phosphorescent dopant, and the first principle is that the recombination of carriers occurs on the host material to which carriers are transported to generate an excited state of the host material, and this energy Is transferred to the phosphorescent dopant to obtain light emission from the phosphorescent dopant. The second principle is a carrier trap type in which a phosphorescent dopant becomes a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained. In any of the above cases, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host material.

  The phosphorescent dopant according to the present invention can be appropriately selected from known ones used for the light emitting layer of the organic EL device, and preferably is a metal of Group 8 to Group 10 in the periodic table. More preferably an iridium compound (Ir complex), an osmium compound, a platinum compound (platinum complex compound), or a rare earth complex, and most preferably an iridium compound (Ir complex). .

  Moreover, as a phosphorescent dopant which concerns on this invention, the compound represented by following General formula (3) is preferable.

[In Formula (3), P and Q represent a carbon atom or a nitrogen atom, A1 represents an atomic group that forms an aromatic hydrocarbon ring or an aromatic heterocycle with PC, and A2 represents an aromatic group with QN. An atomic group forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring, P1-L1-P2 represents a bidentate ligand, P1 and P2 each independently represent a carbon atom, a nitrogen atom or an oxygen atom, L1 represents an atomic group forming a bidentate ligand together with P1 and P2, and M represents a group 8-10 metal element in the periodic table. r represents an integer of 1 to 3, s represents an integer of 0 to 2, and r + s is 2 or 3. ]
In the general formula (3), the aromatic hydrocarbon ring represented by A1 includes a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a chrysene ring, a naphthacene ring, and a triphenylene ring. , O-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring , Pyranthrene ring, anthraanthrene ring and the like. These rings may further have a substituent described later.

  In the general formula (3), examples of the aromatic heterocycle represented by A1 include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and a benzo Imidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indazole ring, indazole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, quinoline ring, And an isoquinoline ring, a phthalazine ring, a naphthyridine ring, a carbazole ring, a carboline ring, and a diazacarbazole ring (showing a ring in which one of the carbon atoms constituting the carboline ring is further substituted with a nitrogen atom). These rings may further have a substituent described later.

  Examples of the substituent that the aromatic hydrocarbon ring or aromatic heterocyclic ring may have include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, and a hexyl group). Octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg, vinyl group, allyl group etc.), alkynyl group (eg, Ethynyl group, propargyl group, etc.), aromatic hydrocarbon group (aromatic hydrocarbon ring group, aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl Group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, Ndenyl group, pyrenyl group, biphenylyl group, etc.), aromatic heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1, 2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, A quinolyl group, a benzofuryl group, a dibenzofuryl group, a benzothienyl group, a dibenzothienyl group, an indolyl group, a carbazolyl group, a carbolinyl group, a diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group is a nitrogen atom) Quinoxalinyl) , Pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, Pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio Group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (Eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, , Phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group) Group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, Cetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), acyloxy groups ( For example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonyl) Amino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octyl Sulfonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, Cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethyl) Ureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pi Lysylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group) Group), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (for example, phenyl) Sulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butyraryl) Group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg fluorine atom, chlorine atom, bromine atom etc.), fluorinated carbonization Hydrogen group (for example, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group) , Triphenylsilyl group, phenyldiethylsilyl group, etc.), phosphono group and the like. In addition, these substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

  In the general formula (3), the aromatic hydrocarbon ring and aromatic heterocycle represented by A2 have the same meanings as the aromatic hydrocarbon ring and aromatic heterocycle represented by A1.

  In the general formula (3), examples of the bidentate ligand represented by P1-L1-P2 include substituted or unsubstituted phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, Examples include pyraza ball, acetylacetone, and picolinic acid.

  Furthermore, in the general formula (3), M represents a transition metal element belonging to Group 8 to 10 in the periodic table (also simply referred to as a transition metal). Among them, iridium and platinum are preferable, and iridium is particularly preferable.

  These phosphorescent dopants are described in, for example, Inorg. Chem. 40, 1704-1711, and the like.

  Examples of the fluorescent dopant (fluorescent compound) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, and perylenes. And dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

  As the luminescent dopant according to the present invention, one of these luminescent dopants may be used alone, or two or more luminescent dopants may be used in combination, and an organic EL device with higher luminous efficiency is obtained, and From the viewpoint that an arbitrary emission color can be obtained, it is preferable to use a combination of a plurality of other light-emitting dopants with the phosphorescent light-emitting dopant.

(Hole transport layer)
The hole transport layer according to the present invention is a layer made of a hole transport material having a function of transporting holes. The hole transport layer may be a single layer or a combination of a plurality of layers.

  In the present invention, it is preferable to use the organic electronic device material of the present invention alone or in combination with another hole transport material as the hole transport material. When the organic electronic device material of the present invention is used as the host material or an electron transport material described later, other materials may be used alone or in combination of two or more as the hole transport material. Also good.

  As the hole transport material other than the material for an organic electronics element of the present invention, any material that has either hole injection or transport or electron barrier property may be used. There may be. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, or conductive polymer oligomers such as thiophene oligomers.

  As the hole transport material, the above-mentioned materials can be used. Among them, it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of the aromatic tertiary amine compound and the styrylamine compound include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N '-Bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1 -Bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl; 1,1-bis (4-di-p -Tolylaminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) Quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N -Diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenylcarbazole; described in US Pat. No. 5,061,569 Having one condensed aromatic ring in the molecule (for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD)); No. 688, 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) in which three triphenylamine units are linked in a starburst type ) And the like.

  In addition, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. Furthermore, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material. JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used.

  In the hole transport layer according to the present invention, the hole transport material is thinned by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Can be formed. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm.

  In addition, the hole transport layer according to the present invention may be a hole transport layer having a high p property doped with impurities. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like, specifically, poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate. In the present invention, such a hole transport layer having a high p property is preferable because an organic EL element with lower power consumption can be produced.

(Electron transport layer)
The electron transport layer according to the present invention is a layer made of a material having a function of transporting electrons. The electron transport layer may be a single layer or a combination of a plurality of layers.

  In the present invention, as the electron transport material (also serving as a hole blocking material) used for the electron transport layer adjacent to the cathode side with respect to the light emitting layer in the case of a single layer electron transport layer and a plurality of layers, the present invention It is preferable to use the organic electronics element material alone or in combination with other electron transport materials. Moreover, when using the organic electronic element material of the present invention as the host material or the hole transport material, other materials may be used alone or in combination of two or more as the electron transport material.

  The electron transport material other than the organic electronic element material of the present invention may have any function of transmitting electrons injected from the cathode to the light emitting layer, and can be arbitrarily selected from conventionally known compounds. Can be selected and used. Examples of such compounds include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like. In the oxadiazole derivative, a thiadiazole derivative in which an oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group may be used as the electron transport material. it can. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum , Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), bis (2-methyl-8-quinolinate) -4- ( Phenylphenolato) aluminum (BAlq), tris (8-quinolinolato) aluminum (Alq3) and the like, and metal complexes in which the central metal of these metal complexes is replaced with In, Mg, Cu, Ca, Sn, Ga or Pb , And can be used as the electron transport material.

  In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material. Further, a distyrylpyrazine derivative that can also be used as a host material of the light emitting layer can be used as the electron transport material, and similarly to the hole transport layer, an inorganic semiconductor such as n-type-Si or n-type-SiC. Can also be used as the electron transport material.

  The electron transport layer according to the present invention is formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. can do. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm.

  Moreover, as an electron carrying layer which concerns on this invention, it can also be set as an electron carrying layer with high n property which doped the impurity. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like. In the present invention, such an electron transport layer having a high n property is preferable because an organic EL element with lower power consumption can be produced.

[Injection layer: electron injection layer, hole injection layer]
The injection layer according to the present invention can be provided as necessary. For example, “Organic EL device and its forefront of industrialization” (issued on November 30, 1998 by NTS, Inc.), Part 2, Part 2 There are a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer) described in Chapter “Electrode Materials” (pages 123 to 166).

  The injection layer according to the present invention is a layer provided between the electrode and the organic compound layer for lowering the driving voltage and improving the light emission luminance, between the anode and the light emitting layer or the hole transport layer, and It can be provided between the cathode and the light emitting layer or the electron transport layer.

  The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 10 nm although it depends on the material.

[Blocking layer: hole blocking layer, electron blocking layer]
The blocking layer according to the present invention can be provided as necessary. For example, JP-A-11-204258, JP-A-11-204359, and “Organic EL element and its industrialization front line (November 30, 1998) There is a hole blocking layer described on page 237 of “NTT Corporation”.

  The hole blocking layer is a layer having the function of the electron transport layer in a broad sense, and is made of a hole blocking material having a function of transporting electrons and having a remarkably small ability to transport holes, and transports electrons. While blocking holes, the recombination probability of electrons and holes can be improved. Such a hole blocking layer is preferably provided adjacent to the light emitting layer.

  Further, in the present invention, when a plurality of light emitting layers having different emission colors are provided, it is preferable that the light emitting layer whose light emission maximum wavelength is the shortest is the closest to the anode among all the light emitting layers. Preferably, the hole blocking layer is additionally provided between the light emitting layer of the shortest wave and the light emitting layer next to the anode next to the light emitting layer of the shortest wave. Further, it is preferable that 50 mass% or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host material of the light emitting layer of the shortest wave.

The ionization potential is defined by the energy required to emit electrons at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level. For example, a method as shown below:
(1) Using Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), a molecular orbital calculation software manufactured by Gaussian, USA As a value obtained by rounding off the second decimal place of the value (eV unit converted value) calculated by performing structural optimization using B3LYP / 6-31G *. The reason why this calculated value is effective is that there is a high correlation between the calculated value obtained by this method and the experimental value;
(2) A method of direct measurement by photoelectron spectroscopy. For example, a method using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd., or a method using a method known as ultraviolet photoelectron spectroscopy;
It can ask for.

  On the other hand, the electron blocking layer is a layer having the function of the hole transport layer in a broad sense, and is made of a material having a function of transporting holes and a remarkably small ability to transport electrons, and transports holes. However, the probability of recombination of electrons and holes can be improved by blocking electrons. The film thickness of the hole blocking layer according to the present invention is preferably 3 nm to 100 nm, and more preferably 5 nm to 30 nm.

〔anode〕
As the anode according to the present invention, an electrode material made of a metal, an alloy, an electrically conductive compound and a mixture thereof having a large work function (4 eV or more) is preferably used. Specific examples of the electrode material include Au and the like. And conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) that can form a transparent conductive film may be used.

  The anode can be formed by thinning these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or the pattern accuracy is not necessary. If not (about 100 μm or more), a pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material. Moreover, when using the substance which can be apply | coated like an organic electroconductivity compound, it can also shape | mold using application methods (wet process, wet film-forming method), such as a printing system and a coating system.

  When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is several hundred Ω / sq. The following is preferred. The thickness of the anode is usually in the range of 10 nm to 1000 nm, preferably 10 nm to 200 nm, although it depends on the material.

〔cathode〕
As the cathode according to the present invention, a cathode having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.

Among these, from the point of durability against electron injection and oxidation, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

  The cathode can be formed by thinning these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is several hundred Ω / sq. The following is preferred. The thickness of the cathode is usually 10 nm to 5 μm, preferably 50 nm to 200 nm.

  In addition, as an organic EL element of this invention, it is preferable that either one of the said anode or the said cathode is transparent or translucent from a viewpoint which permeate | transmits the emitted light. In such an organic EL element, for example, after forming the electrode substance as the cathode so as to have a film thickness of 1 nm to 20 nm, the conductive transparent material described in the description of the anode is formed, and transparent or It can be obtained by producing a translucent cathode.

[Support substrate]
The organic EL element of the present invention preferably further comprises a support substrate (also referred to as a base, substrate, base material, support, etc.), and the support substrate is particularly limited to the types of glass, plastic and the like. In addition, it may be transparent or opaque, but it is preferably transparent when light is extracted from the support substrate side.

  Examples of the transparent support substrate (hereinafter sometimes referred to as “transparent substrate”) include glass, quartz, and a transparent resin film. A resin film is particularly preferable from the viewpoint that flexibility can be imparted to the organic EL element. Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, and cellulose acetate propionate (CAP). , Cellulose esters such as cellulose acetate phthalate (TAC), cellulose nitrate or derivatives thereof; polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol; syndiotactic polystyrene; polycarbonate; norbornene resin; polymethylpentene; Polyimide; Polyethersulfone (PES), Polyphenylene sulfide; Polysulfone Polyetherimide; Polyetherketoneimide; Polyamide; Fluororesin; Nylon; Polymethylmethacrylate; Acrylic or polyarylates; Cycloolefin resin such as Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Etc.

The surface of the resin film may be formed with an inorganic film, an organic film, or a hybrid film of both, and as such a film, the water vapor permeability measured by a method according to JIS K 7129-1992. (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is preferably a barrier film having a viscosity of 0.01 g / (m ² · 24 h) or less, and a method based on JIS K 7126-1987 The oxygen permeability measured in (1) is 10 ⁻³ ml / (m ² · 24 h · MPa) or less, and the water vapor permeability is 10 ⁻⁵ g / (m ² · 24 h) or less. Further preferred.

  The material of the film may be any material as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Moreover, in order to improve the brittleness of such a film, it is more preferable to have a structure in which a layer made of an organic material is laminated on these inorganic layers. Although there is no restriction | limiting in particular about the lamination | stacking order of the said inorganic layer and the said organic layer, It is preferable to laminate | stack both alternately several times.

  The method for forming the coating film on the surface of the resin film is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the molecular beam epitaxy method, the cluster ion beam method, the ion plating method, the plasma A polymerization method, an atmospheric pressure plasma polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in Japanese Patent Application Laid-Open No. 2004-68143. Is particularly preferred.

  Examples of the opaque support substrate include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.

(Sealing member)
In this invention, it is preferable to further provide the sealing member arrange | positioned so that a cathode or a cathode may be covered on the opposite side of the said support substrate. Such a sealing member may be a concave plate shape or a flat plate shape, and transparency and electrical insulation are not particularly limited. When the sealing member is processed into a concave plate shape, sandblasting, chemical etching, or the like is used.

  Specific examples of the sealing member include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.

As the sealing member, a polymer film and a metal film are preferable from the viewpoint that the organic EL element can be thinned. The polymer film preferably has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ ml / (m ² · 24 h · MPa) or less, and JIS K 7129- The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to 1992 is 1 × 10 ⁻³ g / (m ² · 24 h) or less. Further preferred.

  Such a sealing member can seal the layer structure of the organic EL element by adhering to the support substrate with an adhesive (sealant), for example. Specific examples of the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. An agent can be mentioned. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Furthermore, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

  As the adhesive, since the organic EL element may be deteriorated by heat treatment, an adhesive that can be adhesively cured at a temperature between room temperature and 80 ° C. is preferable. A desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.

  Such a sealing member can also be used as a sealing film by forming an inorganic or organic layer in contact with the support substrate on the cathode facing the support substrate or outside the cathode. In this case, the material for forming the sealing film may be any material that has a function of suppressing the intrusion of elements such as moisture and oxygen that cause deterioration, such as silicon oxide, silicon dioxide, and silicon nitride. Can be used. Furthermore, in order to improve the brittleness of such a film, it is preferable to have a structure in which a layer made of an organic material is laminated on these inorganic layers. The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster-ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

  In the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil is injected in a gas phase or a liquid phase. Is preferred. A vacuum is also possible. Moreover, a hygroscopic compound (water trapping agent) can also be enclosed inside.

  Examples of the hygroscopic compound include metal oxides (eg, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide), sulfates (eg, sodium sulfate, calcium sulfate, magnesium sulfate, sulfuric acid). Cobalt), metal halides (eg, calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide, etc.), perchloric acids (eg, perchlorine) Barium acid, magnesium perchlorate, etc.), and anhydrous salts are preferably used in sulfates, metal halides and perchloric acids.

[Protective film, protective plate]
In the present invention, a protective film or a protective plate may be further provided outside the sealing member on the side facing the support substrate from the viewpoint of increasing the mechanical strength of the organic EL element. In particular, when the sealing member is the sealing film, the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film or a protective plate. As the material of such a protective film or protective plate, the same glass plate, polymer plate / film, metal plate / film, etc. as those mentioned as the sealing member can be used, but the viewpoint of light weight and thin film formation. Therefore, it is preferable to use a polymer film.

[Light extraction]
The external extraction efficiency at 23 ° C. of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more. In the present invention, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

  Moreover, as an organic EL element of the present invention, a color conversion filter that converts a luminescent color from an organic EL element into multiple colors using a phosphor is used in combination with a hue improving filter such as a color filter. Also good. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

  In general, an organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1), and about 15% to 20% of light generated in the light emitting layer. It is said that only the light can be extracted. This is because light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the element side surface.

  As a method for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), A method for improving the efficiency by giving the substrate a light collecting property (Japanese Patent Laid-Open No. 63-314795), a method for forming a reflective surface on the side surface of the organic EL element (Japanese Patent Laid-Open No. 1-220394), light emission A method of introducing an antireflection film by introducing a flat layer having an intermediate refractive index between the layer and the transparent substrate (Japanese Patent Laid-Open No. Sho 62-172691), between the light emitting layer and the transparent substrate, A method of introducing a flat layer having a low refractive index (Japanese Patent Laid-Open No. 2001-202827), and forming a diffraction grating between any one of the substrate, the transparent electrode layer and the light emitting layer (including between the substrate and the outside). Method (Japanese Patent Laid-Open No. 11-28375) There is JP), and the like.

  In the present invention, these methods can be used in combination with the organic EL device of the present invention, or a method of introducing a flat layer having a lower refractive index than the substrate between the light emitting layer and the transparent substrate, or A method of forming a diffraction grating between any one of the substrate, the transparent electrode layer, and the light emitting layer (including between the substrate and the outside) can be suitably used. In the present invention, by combining these means, it is possible to obtain an organic EL device having further high luminance or durability.

  If a low refractive index medium (low refractive index layer) is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of the light, the light emitted from the transparent electrode will go to the outside as the refractive index of the medium decreases. The take-out efficiency is increased. Examples of the low refractive index layer include airgel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less. The thickness of the low refractive index layer is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index layer is about the wavelength of light and the electromagnetic wave exuded by evanescent enters the substrate.

  The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency. This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Of these, light that cannot go out due to total reflection between layers, etc. is diffracted by introducing a diffraction grating into any layer or medium (inside a transparent substrate or transparent electrode). I want to take it out.

  The introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.

  As described above, the position where the diffraction grating is introduced may be in any one of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated. At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium. The arrangement of the diffraction grating is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.

[Condenser sheet]
The organic EL device of the present invention is processed on the light extraction side of the substrate so as to provide, for example, a microlens array-like structure, or combined with a so-called condensing sheet, for example, with respect to a specific direction, for example, the device light emitting surface. By condensing in the front direction, the luminance in a specific direction can be increased.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  As the condensing sheet, it is possible to use, for example, a sheet that has been put to practical use in an LED backlight of a liquid crystal display device. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used. As the shape of the prism sheet, for example, the base material may be formed by forming a △ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.

  Moreover, in order to control the light emission angle from a light emitting element, you may use together a light diffusing plate and a film with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

[Method for producing organic EL element]
As an example of the method for producing the organic EL device of the present invention, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode Will be explained.

  First, a desired electrode material, for example, a thin film made of a material for an anode is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 nm to 200 nm. . Next, an organic compound film of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer is sequentially formed thereon. As the formation method of each of these layers, there are a vapor deposition method and a coating method (spin coating method, casting method, ink jet method, printing method) as described above, but it is easy to obtain a uniform film and a pinhole is generated. From the viewpoint of difficulty, film formation by a coating method such as a spin coating method, an ink jet method, or a printing method is preferable.

  In particular, when a compound having a carbazole ring as a partial structure, a compound having a polymerizable group, or a polymer of the compound is used as the host material, the light emitting layer is preferably formed by the coating method described above. Further, when the total number of layers existing between the anode and the cathode is 100%, 50% or more of the total number of layers is preferably formed by a coating method. For example, in the anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode mentioned as an example of the organic EL element, the hole injection layer In the case where the total number of layers / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer is 6, it is preferable that at least three layers are formed by a coating method.

  On the other hand, film formation by vapor deposition is preferable from the viewpoint that thinning is possible. When the material for an organic electronics element of the present invention is used as a material for each layer, a hole transport layer, a light-emitting layer, an electron transport layer All the layers may be formed by vapor deposition.

  When the constituent layers of the organic EL device of the present invention are formed by coating, examples of the liquid medium for dissolving or dispersing various organic EL device materials used for coating include ketones such as methyl ethyl ketone and cyclohexanone, and fatty acids such as ethyl acetate. Esters; Halogenated hydrocarbons such as dichlorobenzene; Aromatic hydrocarbons such as toluene, xylene, mesitylene, and cyclohexylbenzene; Aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane; Organic solvents such as DMF and DMSO Can be used. Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.

  After these layers are formed, a thin film made of a cathode material is formed thereon by 1 μm or less, preferably by a method such as vapor deposition or sputtering so that the film thickness is in the range of 50 nm to 200 nm. By providing, a desired organic EL element can be obtained. Further, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order.

  When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  Next, as another example of the method for producing the organic EL device of the present invention, an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode is produced. A method will be described.

  First, a desired electrode material, for example, a thin film made of a material for an anode is formed on a suitable substrate so as to have a thickness of 1 μm or less, preferably 10 nm to 200 nm, thereby producing an anode. Next, a thin film containing an organic compound such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, which is an organic EL element material, is formed thereon.

  Examples of methods for forming each of these layers include vapor deposition methods and coating methods (wet processes, wet film forming methods). Examples of the coating methods include spin coating, casting, die coating, blade coating, roll coating, There are inkjet methods, printing methods, spray coating methods, curtain coating methods, etc., but rolls such as die coating methods, roll coating methods, ink jet methods, spray coating methods can be used to form precise thin films and have high productivity. -A method with high suitability for the two-roll method is preferred. Different film formation methods may be applied for each layer.

  After the formation of these layers, a thin film made of a cathode material is formed thereon so as to have a thickness of 1 μm or less, preferably in the range of 50 to 200 nm, and a desired organic EL device can be obtained by providing a cathode. . Further, the order can be reversed, and the cathode, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode can be formed in this order.

  When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 V to 40 V with the anode as + and the cathode as-. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  The organic EL device of the present invention is preferably produced from the hole injection layer to the cathode consistently by one evacuation, but it may be taken out halfway and subjected to different film forming methods. At that time, it is preferable to perform the work in a dry inert gas atmosphere.

[Use]
The organic EL element of the present invention can be used for various organic electronic devices, and for example, can be used as a display device such as a display device, a display, and various light emitting light sources. For example, lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Although the light source of a sensor etc. are mentioned, It is not limited to this, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.

  In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like at the time of forming each constituent layer depending on the application. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire constituent layer may be patterned.

  The color emitted by the organic EL element of the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured by Minolta Sensing Co., Ltd. is applied to the CIE chromaticity coordinates.

When the organic EL element of the present invention is a white element, white means that the chromaticity in the CIE 1931 color system at 1000 cd / m ² is X = 0 when the 2 ° viewing angle front luminance is measured by the above method. .33 ± 0.07, Y = 0.33 ± 0.1.

-Display apparatus The said display apparatus is equipped with the organic EL element of this invention. The display device may be single color or multicolor, but here, the multicolor display device will be described. In the case of a multicolor display device, a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by vapor deposition, casting, spin coating, ink jet, printing, or the like. In the case of patterning only the light emitting layer, the method is not limited. However, the vapor deposition method, the ink jet method, the spin coating method, and the printing method are preferable.

  The configuration of the organic EL element included in the display device is selected from the configuration examples of the organic EL element of the present invention as necessary. Moreover, the manufacturing method of an organic EL element is as having shown to the one aspect | mode of the manufacturing method of the organic EL element of said this invention.

  In the case of applying a DC voltage to the obtained multicolor display device, light emission can be observed by applying a voltage of about 2V to 40V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.

  The multicolor display device can be used as a display device, a display, and various light emission sources. In a display device or display, full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.

  Examples of the display device and display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in an automobile. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.

  Light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. The present invention is not limited to these examples.

  Hereinafter, as an example of a display device including the organic EL element of the present invention, a display such as a mobile phone will be described among those that display image information by light emission of the organic EL element. The display generally includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like. The control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside, and the pixels for each scanning line respond to the image data signal by the scanning signal. The image information is sequentially emitted to scan the image and display the image information on the display unit A.

  The display unit A includes a wiring unit including a plurality of scanning lines and data lines orthogonal thereto, and a plurality of pixels surrounded by the scanning lines and data lines on the substrate. The scanning lines and the data lines of the wiring portion are each made of a conductive material, and the scanning lines and the data lines are orthogonal to each other in a lattice pattern and are connected to the pixels at the orthogonal positions. When a scanning signal is applied from the scanning line, the pixel receives an image data signal from the data line and emits light according to the received image data. Full-color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.

  Next, the light emission process of the pixel will be described. The pixel includes an organic EL element, a switching transistor, a driving transistor, a capacitor, and the like. A full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements for a plurality of pixels and arranging them on the same substrate.

  In the display, an image data signal is applied from the control unit B to the drain of the switching transistor via the data line. When a scanning signal is applied from the control unit B to the gate of the switching transistor via the scanning line, the switching transistor is turned on, and the image data signal applied to the drain is transmitted to the capacitor and the gate of the driving transistor. The By transmitting the image data signal, the capacitor is charged according to the potential of the image data signal, and the driving transistor is turned on. The drive transistor has a drain connected to the power supply line and a source connected to the electrode of the organic EL element, and current is supplied from the power supply line to the organic EL element in accordance with the potential of the image data signal applied to the gate. .

  When the scanning signal is moved to the next scanning line by the sequential scanning of the control unit B, the driving of the switching transistor is turned off. However, since the capacitor holds the potential of the charged image data signal even if the driving of the switching transistor is turned off, the driving of the driving transistor is kept on and the organic EL is applied until the next scanning signal is applied. The device continues to emit light. When a scanning signal is next applied by sequential scanning, the drive transistor is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element emits light.

  That is, the organic EL element emits light by providing a switching transistor and a drive transistor, which are active elements, for the organic EL element of each of the plurality of pixels, and emitting light from the organic EL element of each of the plurality of pixels. Such a light emitting method is called an active matrix method.

  Here, the light emission of the organic EL element may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or may be on / off of a predetermined light emission amount by a binary image data signal. . Further, the capacitor potential may be maintained until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied. In the present invention, not only the active matrix method described above, but also a passive matrix light emission drive in which the organic EL element emits light according to the data signal only when the scanning signal is scanned.

  In the passive matrix system, a plurality of scanning lines and a plurality of image data lines are provided in a lattice shape so as to face each other with pixels interposed therebetween. When the scanning signal of the scanning line is applied by sequential scanning, the pixels connected to the applied scanning line emit light according to the image data signal. In the passive matrix method, there is no active element in the pixel, and the manufacturing cost can be reduced.

-Illuminating device The said illuminating device is provided with the organic EL element of this invention. The illumination device may be used as an organic EL element in which the organic EL element of the present invention has a resonator structure. The purpose of use of the organic EL element having such a resonator structure is as an optical storage medium. Light sources of electrophotographic copying machines, light sources of optical communication processors, light sources of optical sensors, and the like, but are not limited thereto. Moreover, you may use for the said use by making a laser oscillation.

  The organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device that projects an image, or a type that directly recognizes a still image or a moving image. It may be used as a display.

  The driving method for use as a display for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, it is possible to produce a full-color display device by using two or more organic EL elements of the present invention having different emission colors. Moreover, the organic EL element material of the present invention can be applied to an organic EL element that emits substantially white light as a lighting device. A plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing. The combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of blue, green, and blue, or two using the relationship of complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.

  A combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent light emitting materials (light emitting dopants), a light emitting material that emits fluorescence or phosphorescent light, and a light emitting material. Any combination with a dye material that emits light as excitation light may be used, but in the white organic EL device according to the present invention, a plurality of light emitting dopants need only be mixed and mixed.

  As the lighting device, a mask is provided only when a light emitting layer, a hole transport layer, an electron transport layer, or the like is formed, and it may be simply arranged such as separately coating with the mask. Is not necessary, and for example, an electrode film can be formed on one surface by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, etc., and productivity is improved. According to this method, unlike a white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, the elements themselves are luminescent white.

  There is no restriction | limiting in particular as a luminescent material used for a light emitting layer, For example, if it is a backlight in a liquid crystal display element, the light emission dopant which concerns on this invention so that it may adapt to the wavelength range corresponding to CF (color filter) characteristic, Any one of known luminescent materials may be selected and combined to whiten.

  Hereinafter, an aspect of an illumination device including the organic EL element of the present invention will be described. As the lighting device, the non-light emitting surface of the organic EL element of the present invention is covered with a glass case, and a glass substrate (for example, a thickness of 300 μm) is used as a sealing member. (For example, Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, and is formed by curing and sealing by irradiating UV light from the glass substrate side. An apparatus can be mentioned. In such a lighting device, the organic EL element of the present invention is covered with a glass case and a glass substrate (in addition, the sealing work is a glove box under a nitrogen atmosphere (preferably without bringing the organic EL element into contact with the atmosphere) Is preferably performed in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more). The glass case is preferably filled with nitrogen gas and further provided with a water catching agent.

<Organic thin film solar cell>
The material for an organic electronics element of the present invention can also be used as a material for an organic compound layer of an organic thin film solar cell. As a preferable specific example of the layer structure of the organic thin film solar cell,
(I) anode / power generation layer / cathode (ii) anode / hole transport layer / power generation layer / cathode (iii) anode / hole transport layer / power generation layer / electron transport layer / cathode (iv) anode / hole transport layer / P-type semiconductor layer / power generation layer / n-type semiconductor layer / electron transport layer / cathode (v) anode / hole transport layer / first power generation layer / electron transport layer / intermediate electrode / hole transport layer / second power generation layer / Electron transport layer / cathode and the like.

  In the present invention, as the material for the hole transport layer, the p-type semiconductor layer, the power generation layer, the n-type semiconductor layer, and the electron transport layer, the organic electronic device material of the present invention is used alone or in combination with other materials. It is preferable to use it in combination with a material.

  As a material other than the material for an organic electronics element of the present invention, a known material can be appropriately used as a material for an organic compound layer of a conventional organic thin film solar cell. Moreover, as a formation method of each said layer, the conventionally well-known method, for example, the method similar to the method quoted as the formation method of each layer of the said organic EL element can be used suitably.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to a following example. In addition, the measurement of the compound obtained in each synthesis example and the evaluation of the element obtained in each example were performed by the following methods.

(Measurement of thermal decomposition temperature)
The obtained compound was held at 50 ° C. for 10 minutes, then heated at a heating rate of 10 ° C./min, helium gas was introduced, and TG-DTA2020SE (NETZSCH) and JMS-Q1050GCT (JEOL) were used. Then, thermogravimetric analysis (TG-DTA-MS) was performed, and the thermal decomposition temperature of the obtained compound was measured.

(Spectrum measurement)
IR (infrared absorption spectrum): The obtained compound was powdered and measured using Nicolet iS10 FTIR (Thermo Scientific).
¹ H-NMR, ¹³ C-NMR: Measured at 400 MHz using JNM-ECS400 (manufactured by JEOL) using CDCl ₃ or o-dichlorobenzene-d ₄ as a solvent.
^{In 1} H-NMR, the chemical shift of CDCl ₃ was δ 7.26, and the chemical shift of o-dichlorobenzene-d ₄ was δ 7.19.
MS (MALDI TOF): After adding 500% by weight of a matrix (tetracyanoquinodimethane) to the obtained compound and mixing, it was dispersed in cyclohexane and applied onto a substrate for measurement, and Microflex ( Measurement was performed by performing time-of-flight mass spectrometry (TOFMS) by matrix-assisted laser desorption / ionization (MALDI) using a Bruker Daltonics.

(Elemental analysis)
1 mg of the obtained compound was weighed with a precision balance, burned in a mixed gas atmosphere of helium and oxygen, and the generated H ₂ O, CO ₂ , N ₂ was converted into a CHN analyzer (JM-10, manufactured by Yanaco) and Quantification was performed using a halogen analyzer (HNS-15 / HSU-20, manufactured by Yanaco).

(Single crystal X-ray structure analysis)
Structural analysis was performed using XtaLAB P200 MM007HF-DWX (manufactured by Rigaku Corporation, detector: PILATUS200K) or SMART APEX II (manufactured by Bruker, detector: CCD).

(HPLC measurement)
High performance liquid chromatography (HPLC) measurement was performed using a Cosmosil Buckyprep column (diameter: 4.6 mm × 250 mm) under the conditions of eluent: methanol / chloroform = 50/50, 40 ° C., flow rate 1.0 mL / min. The eluate was detected by visible / ultraviolet spectroscopy (UV-vis) (detector: MD2018PLUS (manufactured by JASCO)).

(Organic electronics device evaluation)
As shown in FIGS. 1 and 2, the surface opposite to the glass substrate 103 of the obtained organic electronics element 101 is covered with a glass case 102, and an epoxy-based photocurable adhesive (LUXE manufactured by Toagosei Co., Ltd.) is used as a sealing material 104 around the surface. The glass substrate 103 and the glass case 102 were brought into close contact with each other using a track LC0629B) and cured by UV light and sealed to produce an organic electroluminescence device for evaluation (organic EL device). The glass case was filled with dry nitrogen gas 108, and a water capturing agent 109 was sealed. The light emitting surface of the evaluation element is the surface on the glass substrate 103 side.
-External extraction quantum efficiency About the produced evaluation element, external extraction quantum efficiency (%) when ^2.5 mA / cm < ² > constant current was applied at the temperature of 23 degreeC was measured. For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta) was used.
-Drive voltage The voltage at the time of the light emission start was measured about the produced evaluation element at the temperature of 23 degreeC. The voltage at the start of light emission was the voltage value when the current density was ^2.5 mA / cm ² . A spectral radiance meter CS-1000 was used for measuring the luminance.
-Spectral spectrum measurement About the produced evaluation element, the emission spectrum when ^2.5 mA / cm < ² > constant current was applied was measured at the temperature of 23 degreeC. In addition, the spectral radiance meter CS-1000 was used for the measurement.

(Synthesis Example 1: Compound 1 / [5] -cyclometaphenylene)
First, 2,2′-bipyridine (26.5 g, 170 mmol, purified by recrystallization with hexane, the same applies hereinafter), 1,5-cyclooctadiene (20.7 mL) in a nitrogen gas atmosphere under light shielding 169, 169 mmol) and bis (1,5-cyclooctadiene) nickel (0) (46.6 g, 169 mmol) were mixed with a solvent purifier using degassed toluene (350 mL, activated alumina and copper catalyst column). Purified product, the same applies hereinafter) and N, N-dimethylformamide (DMF) (350 mL, purified by a solvent purifier using a column of activated alumina and copper catalyst, the same applies hereinafter), and stirred at 80 ° C. for 50 minutes did. Next, while maintaining the temperature at 80 ° C., a toluene solution (1.40 L) of 1,3-dibromobenzene (10.2 mL, 84.7 mmol) was added dropwise to the mixture over 1 hour. The mixture was stirred as it was for 1 hour, allowed to cool to room temperature (25 ° C.), 1M hydrochloric acid (1 L) was added, and the mixture was stirred overnight. Subsequently, it isolate | separated into the toluene extract and the insoluble matter (crude product B) by filter filtration. The toluene extract was washed with water and brine, dried by adding magnesium sulfate, filtered to remove the magnesium sulfate, and then concentrated under reduced pressure to obtain [5], [7], [9] to 3.85 g of crude product A containing [14] -cyclometaphenylene was obtained.

  Chloroform (700 mL) was added to the obtained crude product A, and the extract obtained was recrystallized from toluene to obtain a solid of Compound 1. The yield was 1.10 g, and the yield was 17%.

The thermal decomposition temperature of the obtained compound 1 was 358 ° C. The results of IR measurement, ¹ H-NMR measurement, ¹³ C-NMR measurement, MS measurement and elemental analysis of the obtained compound 1 were as follows. The ¹ H-NMR spectrum, ¹³ C-NMR spectrum and MALDI-TOF MS spectrum of Compound 1 are shown in FIG. 3, FIG. 8 and FIG. 11, respectively. Moreover, the spectrum obtained by HPLC measurement about the obtained compound 1 is shown in FIG.

IR (powder):
3046 (w), 1604 (w), 1567 (w), 1488 (w), 1391 (w), 1315 (w), 1164 (w), 1068 (w), 925 (w), 899 (w), 815 (w), 772 (s), 737 (w), 699 (m), 633 (m), 609 (w) cm ⁻¹ ;
¹ H-NMR (400 MHz, CDCl ₃ ):
δ 8.52 (t, J = 2.0 Hz, 5H), 7.73 (dd, J = 2.0, 7.6 Hz, 10H), 7.51 (t, J = 7.6 Hz, 5H);
¹³ C-NMR (100 MHz, CDCl ₃ ):
δ 141.3, 134.6, 129.0, 124.2;
MS (MALDI-TOF):
m / z calcd for C ₃₀ H ₂₀ [M] ⁺ 380.2, found 380.3;
Anal. calcd for C ₃₀ H ₂₀ :
C: 94.70, H: 5.30, found C: 94.37, H: 5.45.

Further, the obtained compound 1 was subjected to single crystal X-ray structural analysis. Analysis conditions and results are shown below. From these results, the obtained compound 1 was [5] -cyclometaphenylene.
Chemical formula: C ₃₀ H ₂₀
Chemical formula amount: 380.49
Temperature: 90K
Wavelength: 1.54187mm
Crystal system: Monoclinic
Space group: P 2 ₁ / n
Lattice constant: a = 16.288 (18) Å α = 90 °
b = 5.4529 (7) Åβ = 107.144 (3) °
c = 22.623 (3) Å γ = 90 °
Volume: 1920.0 (5) ^{３ 3}
Z: 4
Density (calculated value): 1.316 Mg / m ³
Absorption coefficient: 0.565 mm ⁻¹
F (000): 800.00
Crystal size: 0.13x0.05x0.05mm ³
θ range for data collection: 3.96 ° to 74.23 °
Index range: −20 <= h <= 20, −6 <= k <= 5, −28 <= l <= 28
Reflections collected: 26741
Independent reflections:
3826 [R (int) = 0.0223]
Completeness to θ = 74.23 °: 97.8%
Absorption correction: Empirical
Max. and min. transmission:
0.978 and 0.910
Refinement method: Full-matrix last-squares on F ²
Data / Limit / Parameter: 3826/0/271
Goodness-of-fit on F ² : 1.105
Final R indicators [I> 2σ (I)]:
R ₁ = 0.0368, wR ₂ = 0.1020
R indicators (all data):
R ₁ = 0.0382, wR ₂ = 0.1042
Maximum value between peak and hole: 0.21 and -0.21 e. Å ^-3.

(Synthesis Example 2: Compound 2 / [6] -cyclometaphenylene)
First, 3.58 g of crude product B containing [6], [8] -cyclometaphenylene was obtained in the same manner as in Synthesis Example 1. Chlorobenzene (500 mL) was added to the obtained crude product B, and it was separated into a chlorobenzene extract (473 mg) and an insoluble matter (3.13 g) by filtration through a filter. Subsequently, the obtained insoluble matter was added to and dissolved in o-dichlorobenzene heated to 180 ° C., and separated into an o-dichlorobenzene extract and an insoluble matter by filter filtration. Subsequently, a solid was precipitated by repeating the recrystallization operation from the obtained o-dichlorobenzene extract, and the precipitated solid was collected by filtration to obtain 306 mg of a solid of Compound 2. In addition, the solid obtained from the o-dichlorobenzene extract after the solid was precipitated was sublimated to obtain 361 mg of Compound 2 solid. The total yield was 10%.

The thermal decomposition temperature of Compound 2 obtained was 451 ° C. Moreover, the results of IR measurement, ¹ H-NMR measurement, MS measurement, and elemental analysis of the obtained compound 2 were as follows. The ¹ H-NMR spectrum and MALDI-TOF MS spectrum of Compound 2 are shown in FIGS. 4 and 11, respectively. Moreover, the spectrum obtained by HPLC measurement about the obtained compound 2 is shown in FIG. In FIG. 12, a peak around 2.5 minutes appears because the solubility of compound 2 is low.

IR (powder):
3035 (w), 1602 (w), 1573 (w), 1489 (w), 1396 (w), 1301 (w), 1176 (w), 1090 (w), 916 (w), 891 (w), 812 (w), 776 (s), 723 (w), 701 (m), 628 (m), 615 (w) cm ⁻¹ ;
¹ H-NMR (400 MHz, o-dichlorobenzene-d ₄ ):
δ 8.18 (s, 6H), 7.63 (d, J = 7.6 Hz, 12H), 7.45 (t, J = 7.6 Hz, 6H);
MS (MALDI-TOF):
m / z calcd for C ₃₆ H ₂₄ [M] ⁺ 456.2, found 456.2;
Anal. calcd for C ₃₆ H ₂₄ :
C: 94.70, H: 5.30, found C: 94.69, H: 5.35.

Further, the obtained compound 2 was subjected to single crystal X-ray structural analysis. Analysis conditions and results are shown below. From these results, the obtained compound 2 was [6] -cyclometaphenylene.
Chemical formula: C ₃₆ H ₂₄
Chemical formula amount: 456.55
Temperature: 90K
Wavelength: 1.54178mm
Crystal system: Monoclinic
Space group: P 2 ₁ / c
Lattice constant: a = 12.2289 (3) Å α = 90 °
b = 15.382 (3) Åβ = 99.35 (3) °
c = 6.0239 (12) Å γ = 90 °
Volume: 1123.6 (4) Å ³
Z: 2
Density (calculated value): 1.349 Mg / m ³
Absorption coefficient: 0.579 mm ⁻¹
F (000): 480.0
Crystal size: 0.20x0.05x0.05mm ³
θ range for data collection: 3.65 ° to 67.33 °
Index range: −12 <= h <= 14, −18 <= k <= 18, −7 <= l <= 7
Reflections collected: 8005
Independent reflections:
1960 [R (int) = 0.0371]
Completeness to θ = 67.33 °: 97.0%
Absorption correction: Empirical
Refinement method: Full-matrix last-squares on F ²
Data / Limit / Parameter: 1960/0/163
^{Goodness-of-fit on F 2} : 1.015
Final R indicators [I> 2σ (I)]:
R ₁ = 0.0362, wR ₂ 0.0942
R indicators (all data):
R ₁ = 0.0410, wR ₂ = 0.0977
Maximum value between peak and hole: 0.177 and -0.211 e. Å ^-3.

(Synthesis Example 3: Compound 3 / [7] -cyclometaphenylene)
First, a toluene solution containing the crude product A was obtained in the same manner as in Synthesis Example 1. The toluene solution containing the obtained crude product A was subjected to gel permeation chromatography (GPC, apparatus: “LC-9104” manufactured by Japan Analytical Industries, Ltd.), column: JAIGEL 1H, 2H, 2.5H polystyrene column, eluent: chloroform The compound 3 solid was obtained by adding acetonitrile to chloroform at room temperature. The yield was 504 mg and the yield was 7%.

The thermal decomposition temperature of the obtained compound 3 was 440 ° C. Moreover, the results of IR measurement, ¹ H-NMR measurement, ¹³ C-NMR measurement, MS measurement and elemental analysis of the obtained compound 3 were as follows. The ¹ H-NMR spectrum, ¹³ C-NMR spectrum, and MALDI-TOF MS spectrum of Compound 3 are shown in FIGS. 5, 9, and 11, respectively. Moreover, the spectrum obtained by HPLC measurement about the obtained compound 3 is shown in FIG.

IR (powder):
3034 (w), 1603 (w), 1576 (w), 1485 (w), 1396 (w), 1300 (w), 1179 (w), 1092 (w), 924 (w), 893 (w), 885 (w), 805 (w), 786 (m), 774 (s), 702 (s), 644 (w), 627 (m) cm ⁻¹ ;
¹ H-NMR (400 MHz, CDCl ₃ ):
δ 8.04 (t, J = 2.0, Hz, 7H), 7.64 (dd, J = 2.0, 7.6 Hz, 14H), 7.55 (t, J = 7.6 Hz, 7H) );
¹³ C-NMR (100 MHz, CDCl ₃ ):
δ 141.8, 129.4, 126.7, 125.8;
MS (MALDI-TOF):
m / z calcd for C ₄₂ H ₂₈ [M] ⁺ 532.2, found 532.1;
Anal. _{calcd for C 42 H 28 · 0.04CHCl} 3 · 0.5CH 3 CN:
C: 92.65, H: 5.34, N: 1.26, Cl: 0.76, found C: 92.38, H: 5.38, N: 1.26, Cl: 0.57.

The obtained compound 3 was subjected to single crystal X-ray structural analysis. Analysis conditions and results are shown below. From these results, the obtained compound 3 was [7] -cyclometaphenylene.
Chemical formula: C ₈₆ H ₅₉ N
Formula weight: 1106.42
Temperature: 93K
Wavelength: 1.54187mm
Crystal system: Monoclinic
Space group: P 2 ₁ / n
Lattice constant: a = 16.7629 (11) Å α = 90 °
b = 13.5865 (8) Åβ = 99.125 (3) °
c = 26.032 (3) Å γ = 90 °
Volume: 5853.7 (8) Å ³
Z: 4
Density (calculated value): 1.255 Mg / m ³
Absorption coefficient: 0.543 mm ^-1
F (000): 2328
Crystal size: 0.20x0.20x0.20mm ³
θ range for data collection: 2.94 ° to 74.60 °
Index range:
−20 <= h <= 20, −16 <= k <= 16, −30 <= l <= 32
Reflections collected: 81527
Independent reflections:
11688 [R (int) = 0.0331]
Completeness to θ = 74.60 °: 97.6%
Max. and min. transmission:
0.897 and 0.658
Refinement method: Full-matrix last-squares on F ²
Data / Limit / Parameter: 11688/0/787
^{Goodness-of-fit on F 2} : 1.059
Final R indicators [I> 2σ (I)]:
R ₁ = 0.0430, wR ₂ = 0.1126
R indicators (all data):
R ₁ = 0.0449, wR ₂ = 0.1155
Maximum value between peak and hole: 0.88 and -0.41 e. Å ^-3.

(Synthesis Example 4: Compound 4 / [8] -cyclometaphenylene)
First, 3.58 g of crude product B containing [6], [8] -cyclometaphenylene was obtained in the same manner as in Synthesis Example 1. Chlorobenzene (500 mL) was added to the obtained crude product B, and it was separated into a chlorobenzene extract (473 mg) and an insoluble matter (3.13 g) by filtration through a filter. Subsequently, solid was precipitated by adding methanol to the obtained chlorobenzene extract, and the precipitated solid was collected by filtration to obtain a solid of Compound 4. The yield was 73.1 mg, and the yield was 1%.

The thermal decomposition temperature of the obtained compound 4 was 449 ° C. Moreover, the results of IR measurement, ¹ H-NMR measurement, MS measurement and elemental analysis of the obtained compound 4 were as follows. The ¹ H-NMR spectrum and MALDI-TOF MS spectrum of Compound 4 are shown in FIGS. 6 and 11, respectively. Moreover, the spectrum obtained by implementing HPLC measurement about the obtained compound 4 is shown in FIG. In FIG. 12, the peak around 2.5 minutes appears because the solubility of Compound 4 is low.

IR (powder):
3023 (w), 1603 (w), 1573 (w), 1481 (w), 1409 (w), 1397 (w), 1301 (w), 1167 (w), 1091 (w), 914 (w), 894 (w), 815 (w), 792 (s), 784 (s), 715 (w), 708 (m), 701 (m), 642 (w), 625 (m) cm ⁻¹ ;
¹ H-NMR (400 MHz, o-dichlorobenzene-d ₄ ):
δ 7.80 (s, 8H), 7.43 (d, J = 6.8 Hz, 16H), 7.37 (t, J = 6.8 Hz, 8H);
MS (MALDI-TOF):
m / z calcd for C ₄₈ H ₃₂ [M] ⁺ 608.3, found 608.5;
Anal. _{calcd for C 48 H 32 · 0.28C} 6 H 5 Cl · 0.66CH 3 OH:
C: 91.41, H: 5.49, N: 0.00, Cl: 1.50, found C: 91.02, H: 5.25, N: 0.36, Cl: 1.11.

The obtained compound 4 was subjected to single crystal X-ray structural analysis. Analysis conditions and results are shown below. From these results, the obtained compound 4 was [8] -cyclometaphenylene.
Chemical formula: C _48.5 H _39.03
Chemical formula amount: 669.84
Temperature: 93K
Wavelength: 1.54187mm
Crystal system: Tetragonal
Space group: P- 42 ₁ / c
Lattice constant: a = 17.550 (8) Å α = 90 °
b = 17.550 (8) Å β = 90 °
c = 5.619 (3) Å γ = 90 °
Volume: 1730.7 (14) ^{３ 3}
Z: 2
Density (calculated value): 1.285 Mg / m ³
Absorption coefficient: 0.613 mm ⁻¹
F (000): 708.00
Crystal size: 0.32x0.12x0.02mm ³
θ range for data collection: 68.09 °
Index range: -20 <= h <= 21, -21 <= k <= 20, -6 <= l <= 6
Reflections collected: 10198
Independent reflections:
1576 [R (int) = 0.0784]
Completeness to θ = 68.09 °: 97.6%
Max. and min. transmission:
0.988 and 0.722
Refinement method: Full-matrix last-squares on F ²
Data / Limit / Parameter: 1576/1/129
^{Goodness-of-fit on F 2} : 1.099
Final R indicators [I> 2σ (I)]: R ₁ = 0.0510
R indicators (all data): wR ₂ = 0.1309
Maximum value between peak and hole: 0.25 and -0.18 e. Å ^-3.

(Synthesis Example 5: Compound 5 / [9] -cyclometaphenylene)
First, a toluene solution containing the crude product A was obtained in the same manner as in Synthesis Example 1. The obtained toluene solution containing the crude product A is purified using gel filtration chromatography (GPC) and recrystallized from toluene to precipitate a solid. The precipitated solid is recovered by filtration, and the compound 5 solid is recovered. Got. The yield was 65.8 mg, and the yield was 1%.

The thermal decomposition temperature of the obtained compound 5 was 480 ° C. Further, IR measurement, ¹ H-NMR measurement, ¹³ C-NMR measurement, MS measurement and elemental analysis of the obtained compound 5 were as follows. The ¹ H-NMR spectrum, ¹³ C-NMR spectrum, and MALDI-TOF MS spectrum of Compound 5 are shown in FIGS. 7, 10, and 11, respectively. Moreover, the spectrum obtained by HPLC measurement about the obtained compound 5 is shown in FIG.

IR (powder):
3053 (w), 1598 (w), 1576 (w), 1472 (w), 1400 (w), 1387 (w), 1168 (w), 1091 (w), 892 (w), 806 (w), 787 (s), 782 (s), 728 (w), 707 (s), 629 (w), 619 (w) cm ⁻¹ ;
¹ H-NMR (400 MHz, CDCl ₃ ):
δ 7.77 (t, J = 1.6 Hz, 9H), 7.57 (dd, J = 1.6, 7.6 Hz, 18H), 7.51 (t, J = 7.6 Hz, 9H);
¹³ C-NMR (100 MHz, CDCl ₃ ):
δ 141.8, 129.0, 126.6, 126.3;
MS (MALDI-TOF):
m / z calcd for C ₅₄ H ₃₆ [M] ⁺ 684.3, found 684.2;
Anal. _{calcd for C 54 H 36 · 0.8C} 7 H 8 · 0.3H 2 O:
C: 93.70, H: 5.67, found C: 93.48, H: 5.65, N: 0.13.

The obtained compound 5 was subjected to single crystal X-ray structural analysis. Analysis conditions and results are shown below. From these results, the obtained compound 5 was [9] -cyclometaphenylene.
Chemical formula: C _57.49 H _43.69 Cl _1.04
Chemical formula amount: 771.42
Temperature: 93K
Wavelength: 1.54187mm
Crystal system: Monoclinic
Space group: P 2 ₁ / n
Lattice constant: a = 13.18 (3) Å α = 90 °
b = 24.710 (5) Åβ = 95.99 (3) °
c = 13.243 (3) Å γ = 90 °
Volume: 4266 (4) ^{３ 3}
Z: 4
Density (calculated value): 1.201 Mg / m ³
Absorption coefficient: 1.096 mm ⁻¹
F (000): 1625.24
Crystal size: 0.20x0.16x0.14mm ³
θ range for data collection: 3.803 to 74.580 °
Index range:
−16 <= h <= 16, −30 <= k <= 29, −16 <= l <= 16
Reflections collected: 29332
Independent reflections:
8380 [R (int) = 0.160]
Completeness to θ = 74.58 °: 95.9%
Max. and min. transmission:
0.858 and 0.808
Refinement method: Full-matrix last-squares on F ²
Data / Limit / Parameter: 8380/136/635
Goodness-of-fit on F ² : 1.100
Final R indicators [I> 2σ (I)]:
R ₁ = 0.0623, wR ₂ = 0.1756
R indicators (all data):
R ₁ = 0.0634, wR ₂ = 0.1769
Maximum value between peak and hole: 1.12 and -0.51 e. Å ^-3.

Example 1
Patterning was performed on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) having a thickness of 100 nm on a 100 mm × 100 mm × 1.1 mm glass substrate, and then isopropyl alcohol was used. Was subjected to ultrasonic cleaning, dried with dry nitrogen gas, UV ozone cleaning was performed for 5 minutes, and a transparent support substrate provided with an ITO transparent electrode (anode) was obtained. A solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water on the ITO transparent electrode of the transparent support substrate. A film was formed by spin coating at 3000 rpm for 30 seconds and then dried at 200 ° C. for 1 hour to provide a hole transport layer 1 having a thickness of 30 nm.

Then, this is attached to a vacuum deposition apparatus, the vacuum chamber is decompressed to 4 × 10 ⁻⁴ Pa, and the following conditions:
Hole transport layer 2 (HTL): NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl) is deposited to a film thickness of 1 nm / sec to a film thickness of 20 nm. ;
Light-emitting layer (HOST): Compound 2 ([6] -cyclometaphenylene (CMP)) and Ir (ppy) ₃ (tris- (2-phenylpyridine) iridium) obtained in Synthesis Example 2 were formed into a film of Compound 2. A film thickness of 40 nm is obtained by a binary co-evaporation method at a rate of 0.94 ｓｅｃ / sec and a film formation rate of Ir (ppy) ₃ of 0.06 Å / sec (content of Ir (ppy) ₃ is 6 vol%). Vapor deposition;
Electron transport layer 1 (ETL1): BAlq (bis (2-methyl-8-quinolyl) -4- (phenylphenolate) aluminum) is deposited to a film thickness of 1 nm / sec to a film thickness of 10 nm;
Electron transport layer 2 (ETL2): Alq3 (tris (8-hydroxyquinolyl) aluminum) is deposited to a film thickness of 1 nm / sec to a film thickness of 20 nm;
LiF (electron injection layer) is deposited at a film formation rate of 0.1 Å / sec to a film thickness of 0.5 nm;
Cathode: Al is vapor-deposited to a film thickness of 100 nm at a film formation rate of 4 mm / sec;
Each layer is laminated in order by vacuum evaporation method, and glass substrate / ITO transparent electrode (100 nm) / hole transport layer 1 (PEDOT / PSS, 30 nm) / hole transport layer 2 (NPD, 20 nm) / light emitting layer ( [6] -CMP: Ir (ppy) ₃ (6%), 40 nm) / electron transport layer 1 (BAlq, 10 nm) / electron transport layer 2 (Alq3, 20 nm) / LiF layer (0.5 nm) / cathode (Al , 100 nm) was produced in the order of organic electronics elements (organic EL elements). FIG. 13 shows a schematic diagram of a cross section of the obtained organic electronic element.

(Example 2)
In film formation of the hole transport layer 2 (HTL), the compound 2 obtained in Synthesis Example 2 was used instead of NPD, and in the film formation of the light emitting layer (HOST), CBP (4,4 ′ Glass substrate / ITO transparent electrode (100 nm) / hole transport layer 1 (PEDOT / PSS, 30 nm) / hole transport layer in the same manner as in Example 1 except that —N, N-dicarazole-biphenyl) was used. 2 ([6] -CMP, 20 nm) / light emitting layer (CBP: Ir (ppy) ₃ (6%), 40 nm) / electron transport layer 1 (BAlq, 10 nm) / electron transport layer 2 (Alq3, 20 nm) / LiF An organic electronic device was fabricated in the order of layer (0.5 nm) / cathode (Al, 100 nm).

(Comparative Example 1)
In the film formation of the light emitting layer (HOST), a glass substrate / ITO transparent electrode (100 nm) / hole transport layer 1 (PEDOT / PSS) was used in the same manner as in Example 1 except that CBP was used instead of Compound 2. 30 nm) / hole transport layer 2 (NPD, 20 nm) / light emitting layer (CBP: Ir (ppy) ₃ (6%), 40 nm) / electron transport layer 1 (BAlq, 10 nm) / electron transport layer 2 (Alq3, 20 nm) ) / LiF layer (0.5 nm) / cathode (Al, 100 nm) were laminated in this order.

  Table 1 shows the results of measuring the external extraction quantum efficiency and the driving voltage for the organic electronic elements obtained in Examples 1 and 2 and Comparative Example 1. In addition, the result shown in Table 1 is relative evaluation when each value of the organic electronics element obtained in Comparative Example 1 is 100. As is apparent from the results shown in Table 1, it was confirmed that when the organic electronic device material of the present invention was used as a light emitting layer host material, the driving voltage could be reduced to 0.77 compared to the conventional example (Examples). 1). Moreover, when the organic electronic device material of this invention was used as a positive hole transport material, it was confirmed that external extraction quantum efficiency can be improved to 1.8 compared with the past (Example 2).

(Example 3)
A glass substrate was prepared in the same manner as in Comparative Example 1 except that Compound 2 obtained in Synthesis Example 2 was used instead of BAlq and Alq3 in the formation of the electron transport layer 1 (ETL1) and the electron transport layer 2 (ETL2). / ITO transparent electrode (100 nm) / hole transport layer 1 (PEDOT / PSS, 30 nm) / hole transport layer 2 (NPD, 20 nm) / light emitting layer (CBP: Ir (ppy) ₃ (6%), 40 nm) / An organic electronic device (organic EL device) was fabricated in the order of an electron transport layer ([6] -CMP, 30 nm) / LiF layer (0.5 nm) / cathode (Al, 100 nm). In the formation of the electron transport layer, the compound 2 was deposited so as to have a film thickness of 30 nm at a film formation rate of 1 レ ー ト / sec.

(Example 4)
In the film formation of the hole transport layer 2 (HTL), the compound 2 obtained in Synthesis Example 2 was used instead of NPD, and in the film formation of the electron transport layer 1 (ETL1) and the electron transport layer (ETL2), BAlq and Alq3 were used. Instead, the glass substrate / ITO transparent electrode (100 nm) / hole transport layer 1 (PEDOT / PSS, 30 nm) / hole were used in the same manner as in Example 1 except that the compound 2 obtained in Synthesis Example 2 was used. Transport layer 2 ([6] -CMP, 20 nm) / Light-emitting layer ([6] -CMP: Ir (ppy) ₃ (6%), 40 nm) / Electron transport layer ([6] -CMP, 20 nm) / LiF ( An organic electronic device was fabricated in the order of 0.5 nm) / cathode (Al, 100 nm). In film formation of the electron transport layer, Compound 2 was vapor-deposited so as to have a film thickness of 20 nm at a film formation rate of 1 Å / sec.

FIG. 14 and FIG. 15 show the results of spectroscopic spectrum measurement for the organic electronics elements obtained in Example 3 and Example 4, respectively. As apparent from the results shown in FIGS. 14 to 15, when the organic electronic device material of the present invention is used as the electron transport material of the organic EL device, the hole transport material, the light emitting layer host material, and the electron transport material. In any case, green emission due to Ir (ppy) ₃ was observed, and it was confirmed that the compound had a light emitting functionality. From these results, it was confirmed that the material for organic electronics elements of the present invention is also effective as an electron transport material for organic EL elements. Further, it is also effective as a material for an interfaceless organic EL device having a configuration (seamless configuration) using the same material for all of the hole transport layer, the light emitting layer, and the electron transport layer, and it is possible to manufacture the interfaceless device. It was confirmed that the number of manufacturing steps of the organic EL element can be reduced. In addition, also when the compound 1 ([5] -CMP) is used as the material for an organic electronics element of the present invention, it can be used as an electron transport material, a hole transport material, and a light emitting layer host material similarly to the compound 2. Was confirmed.

  As described above, according to the present invention, a novel organic electronic device material that can be used as an electron transport material, a hole transport material, and a light emitting layer host material of an organic electroluminescence device, and an organic material using the same. It is possible to provide an electronic device and an organic electronic device.

  Moreover, the organic electronics element material of the present invention can be easily manufactured using inexpensive raw materials, and further used as an electron transport material, a hole transport material, and a light emitting layer host material of an organic EL element. In some cases, the number of manufacturing steps of the organic EL element can be reduced, which is very useful from the viewpoint of manufacturing cost.

  DESCRIPTION OF SYMBOLS 101 ... Organic electronics element, 102 ... Glass case, 103 ... Glass substrate, 104 ... Sealing material, 105 ... Cathode (Al), 106 ... Organic compound layer, 107 ... Anode (ITO transparent electrode), 108 ... Nitrogen gas, 109 ... Water trapping agent, 1 ... glass substrate, 2 ... ITO transparent electrode, 3 ... hole transport layer 1, 4 ... hole transport layer 2, 5 ... light emitting layer, 6 ... electron transport layer 1, 7 ... electron transport layer 2, 8 ... LiF layer, 9 ... cathode.

Claims (3)

A method for producing a cyclic aromatic compound used for a material for an organic electronics element,
The cyclic aromatic compound has the following general formula (1):
[In Formula (1), n shows the integer in any one of 5-9. ]
A cyclic aromatic compound represented by :
Zero-valent nickel catalyst and the following general formula (2):
[In formula (2), X represents Cl, Br, or I each independently. ]
Is mixed with a halogenated benzene represented by the following formula, and the halogenated benzene is polymerized by a Yamamoto coupling reaction to obtain the cyclic aromatic compound.
The manufacturing method of the cyclic aromatic compound characterized by the above-mentioned . Claim wherein the organic electronic device material is an anode, a cathode, and characterized by Rukoto be contained in the organic compound layer of an organic electronic device comprising an organic compound layer disposed between the cathode and the anode A method for producing the cyclic aromatic compound according to 1 . The method for producing a cyclic aromatic compound according to claim 1 or 2 , wherein the zero-valent nickel catalyst is bis (1,5-cyclooctadiene) nickel .