JP2009108096A - Tertiary amine compound, material for organic el element, and organic el element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain both improvement in luminance life span and heat-resistant of 100°C or higher in an organic electroluminescent (EL) element which comprises pinching a light-emitting layer between a pair of electrodes, the light-emitting layer comprising a mixture of a hole-transporting material, an electron-transporting material, and a light-emitting additive material. <P>SOLUTION: The organic electroluminescent element comprises pinching a light-emitting layer 50 between a pair of electrodes 20, 80, the light-emitting layer 50 comprising a mixture of a hole-transporting material comprising a tertiary amine compound, an electron-transporting material, and a light-emitting additive material, wherein the tertiary amine compound has two or more oxidation potentials determined by a cyclic voltammetry method, a potential difference between the first oxidation potential and the second oxidation potential in the oxidation potentials is at least 0.22 V, and a glass transition temperature is at least 100°C, and wherein the electron-transporting material has a glass transition temperature of at least 100°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a material for an organic EL (electroluminescence) device, an organic EL device, and a tertiary amine compound suitable for the material, and in particular, a mixed host in which a hole transport material and an electron transport material are mixed as a host of a light emitting layer. It relates to what was used.

  Since the organic EL element is self-luminous, it has excellent visibility and can be driven at a low voltage of several V to several tens of V. Therefore, the organic EL element can be reduced in weight including a driving circuit. Therefore, it can be expected to be used as a thin film display, lighting, and backlight. The organic EL element is also characterized by abundant color variations.

  In particular, performances such as a high viewing angle, high contrast, and low temperature operability are extremely promising for in-vehicle displays. However, in automotive applications, quality standards are extremely strict, and it has been difficult to put into practical use due to problems such as a decrease in luminance and heat resistance peculiar to organic EL.

  As a method for improving the luminance life, a method of applying a light-emitting layer formed by mixing a hole-transporting material as a host and an electron-transporting material and a light-emitting additive material as a dopant has been conventionally proposed (Patent Literature). 1).

  However, in this method, according to the study by the present inventors, the heat resistance of the hole transport material is insufficient depending on the material. For this reason, when exposed to a high temperature environment such as 100 ° C., dark spots and the like are generated. As a result, it was confirmed that the brightness was lowered.

  On the other hand, various hole injecting and transporting materials have been conventionally disclosed as a host of the light emitting layer (see Patent Documents 2 and 3), and among them, have a high glass transition temperature in order to improve high temperature durability. Materials are also disclosed. Specifically, a compound in which three or more triphenylamines are arranged in the molecule so as to have a glass transition temperature of 100 ° C. or higher has been proposed.

However, according to the study by the present inventors, even in the material having such a high glass transition temperature, the generation of dark spots can be suppressed, but the improvement of the luminance life was not observed.
JP-A-8-48656 JP 2000-156290 A International Publication No. 98/8360 Pamphlet

  The present invention has been made in view of the circumstances as described above, and an organic EL formed by sandwiching a light emitting layer formed by mixing a hole transporting material, an electron transporting material, and a light emitting additive material between a pair of electrodes. In the device, an object is to achieve both improvement in luminance life and securing heat resistance of 100 ° C. or higher.

  In order to achieve the above object, the present inventors paid attention to an organic EL element having a light emitting layer formed by mixing a hole transporting material, an electron transporting material, and a light emitting additive material.

  Luminance life is improved by the light emitting layer formed by mixing the hole transporting material, the electron transporting material, and the light emitting additive material, that is, the light emitting layer using the mixed host. This is because the transportation function can be shared.

  However, it was thought that the decrease in the luminance life in a high temperature environment occurs because the electron transporting material is easily excited in the host depending on the combination of the hole transporting material and the electron transporting material. This was considered to be due to the hole transport from the hole transport material to the electron transport material.

  FIG. 17 is a diagram schematically showing hole transport between the hole transporting material and the electron transporting material. The energy gap between the hole transporting material Ha and the electron transporting material Hb involved in the movement of holes is a difference ΔG1 in ionization potential between the materials Ha and Hb.

  Usually, in a mixed host of a light emitting layer, holes move from molecule to molecule between hole transport materials. At this time, the hole transporting molecule is oxidized when it receives holes from the neutral state, and when it moves to the partner hole transporting molecule, it is reduced and returns to the neutral state.

  However, some hole transport materials have a plurality of oxidation states. This oxidation state can be easily measured as a plurality of oxidation potentials by cyclic voltammetry. In such a plurality of oxidation potentials, the lowest oxidation potential is usually set to the first oxidation potential, the second oxidation potential, the third, etc., and this first oxidation potential is generally defined as the ionization potential.

  Here, the energy gap ΔG1 between the hole transporting material Ha and the electron transporting material Hb originally has an ionization potential of the hole transporting material, that is, the first oxidation potential, and an ionization potential of the electron transporting material, that is, the first oxidation potential. If the gap ΔG1 obtained by the ionization potential difference is large, it is considered that the transfer of holes from the hole transport material Ha to the electron transport material Hb is suppressed.

  However, when the values of the first oxidation potential E1 and the second oxidation potential E2 in the hole transport material Ha are close to each other, holes are generated from the first oxidation potential E1 to the second oxidation potential E2 in the hole transport material Ha. Moving. That is, the higher oxidation potential in the hole transporting and transporting material Ha also contributes to hole transport.

  At this time, the effective energy gap between the hole transporting material Ha and the electron transporting material Hb is as small as ΔG2, and exchange of holes from the hole transporting material Ha to the electron transporting material Hb is likely to occur.

  Therefore, in the light emitting layer, holes are transferred from the hole transporting material Ha to the electron transporting material Hb in spite of the fact that the holes are transported only by the molecules of the hole transporting material Ha, and in the electron transporting material Hb. As a result, electrons and holes recombine. Then, the electron transport material Hb is excited and deteriorates. As a result, it is considered that the luminance life is reduced.

  From such an estimation mechanism described with reference to FIG. 17, the present inventors can increase the potential difference between the first oxidation potential and the second oxidation potential of the hole transport material to some extent in the mixed host of the light emitting layer. Therefore, it was considered that a sufficient energy gap between the hole transporting material and the electron transporting material related to the movement of holes can be secured, and the exchange of holes between these two materials can be suppressed.

  Based on this idea, an experimental study was conducted focusing on the use of a tertiary amine compound as a hole transporting material serving as a mixed host of the light emitting layer.

  As a result, as the tertiary amine compound, there are a plurality of oxidation potentials determined by cyclic voltammetry, and a tertiary amine having a potential difference between the first oxidation potential and the second oxidation potential at a plurality of oxidation potentials greater than or equal to a certain value. It has been found that the brightness lifetime is improved in the case of a compound as compared with that of a conventional mixed host.

  That is, as in the invention described in claim 1 or 2, a hole transporting material composed of a tertiary amine compound, an electron transporting material, and a light emitting additive material are mixed between a pair of electrodes (20, 80). In the organic EL device having the light emitting layer (50) sandwiched therebetween, the hole transporting material can be constituted by the one represented by the following structural formula (3).

（構造式（３）において、Ｒ２、Ｒ３、Ｒ４、Ｒ５は同一でも異なってもよく水素原子、アルキル基もしくはアリール基であり、Ｒ１は下記構造式（４）で示される基である。）

(In Structural Formula (3), R 2, R 3, R 4 and R 5 may be the same or different and are a hydrogen atom, an alkyl group or an aryl group, and R 1 is a group represented by the following Structural Formula (4).)

（構造式（４）において、ｌは１以上の整数である。）
請求項３は、ホール輸送性材料として適した３級アミン化合物に関する発明である。このような３級アミン化合物をホール輸送性材料として用いることにより、従来の混合ホストのものに比べて輝度寿命が向上することが可能となる。

(In structural formula (4), l is an integer of 1 or more.)
A third aspect of the present invention relates to a tertiary amine compound suitable as a hole transporting material. By using such a tertiary amine compound as a hole transporting material, the luminance life can be improved as compared with that of a conventional mixed host.

  The tertiary amine compound represented by the structural formula (3) has a plurality of oxidation potentials determined by cyclic voltammetry, and the potential difference between the first oxidation potential and the second oxidation potential at these oxidation potentials is 0. It has a value of 22 V or higher and a glass transition temperature of 100 ° C. or higher. The electron transporting material has a glass transition temperature of 100 ° C. or higher.

  According to this, since the glass transition temperature of the hole transport material and the electron transport material in the light emitting layer (50) is 100 ° C. or higher, heat resistance of 100 ° C. or higher can be ensured.

  With such a potential difference relationship, the movement of holes from the first oxidation potential to the second oxidation potential can be suppressed in the hole transporting material, and the movement of holes to the electron transporting material can be suppressed. Therefore, it was considered that the deterioration of the electron transporting material could be suppressed, and it was confirmed that the luminance life could actually be improved.

  As described above, according to the present invention, an organic layer in which a light emitting layer (50) formed by mixing a hole transporting material, an electron transporting material, and a light emitting additive material is sandwiched between a pair of electrodes (20, 80). In an EL element, it is possible to achieve both improvement in luminance life and securing heat resistance of 100 ° C. or higher.

  Here, as the tertiary amine compound represented by the structural formula (3), more specifically, a compound represented by the following structural formula (6) can be employed.

また、ホール輸送性材料と電子輸送性材料と発光添加材料とを混合してなる発光層（５０）については、陰極（８０）側よりも陽極（２０）側においてホール輸送性材料の混合比率が大きくなるように、混合比率が異なる複数の層が積層された構造としたところ、輝度寿命の向上が図れることが確認できた。

In the light emitting layer (50) formed by mixing the hole transporting material, the electron transporting material, and the light emitting additive material, the mixing ratio of the hole transporting material is higher on the anode (20) side than on the cathode (80) side. It was confirmed that the luminance life could be improved when a structure in which a plurality of layers having different mixing ratios were laminated so as to be larger.

  In this case, mixed light emission such as white is also possible by selecting different light emitting additive materials (light emitting additive dyes) to be added to the plurality of layers for each of the plurality of layers.

  Further, in the case where the light emitting layer (50) has a structure in which a plurality of light emitting layers made of different light emitting additive dyes are stacked, the blue light emitting dye that emits blue light is used. When the light emitting layer was included, it was confirmed that the luminance life could be improved by arranging the blue light emitting layer on the cathode side and arranging the light emitting layer having longer wavelength light emission than the blue light emission on the anode side.

  In addition, the code | symbol in the bracket | parenthesis of each said means is an example which shows a corresponding relationship with the specific means as described in embodiment mentioned later.

(First embodiment)
DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments shown in the drawings will be described below. FIG. 1 is a diagram showing a schematic cross-sectional configuration of an organic EL element S1 according to an embodiment of the present invention. An anode 20 made of a transparent conductive film such as indium-tin oxide (hereinafter referred to as ITO) is formed on a substrate 10 made of transparent glass or the like.

  A hole injection layer 30 made of a hole injection material such as copper phthalocyanine (hereinafter referred to as CuPc) is formed on the anode 20 as an organic material having crystallinity. A hole transport layer 40 made of a hole transport material such as a secondary amine compound is formed.

  Here, when an ITO film is used as the anode 20, the average surface roughness Ra of the ITO film is preferably 2 nm or less, and the 10-point average surface roughness Rz is preferably 20 nm or less. These surface roughness Ra and Rz are defined in JIS (Japanese Industrial Standard).

  In order to form the hole injection layer 30 as the crystalline organic material located on the anode 20 in a stable film having high crystallinity, the surface roughness of the anode 20 is important. The Ra of the ITO film is set to 2 nm or less and Rz is set to 20 nm or less, as a result of the study by the present inventors.

  A light emitting layer 50 is formed on the hole transporting layer 40 by using a hole transporting material made of a tertiary amine compound and an electron transporting material as a host material, and mixing a light emitting additive material as a dopant. Has been.

  An electron transport layer 60 made of an electron transport material such as tris (8-quinolinolato) aluminum (hereinafter referred to as Alq3) is formed on the light emitting layer 50. Further, an electron injection layer 70 made of LiF (lithium fluoride) or the like is formed on the electron transport layer 60, and a cathode 80 made of a metal such as Al is formed thereon.

  Thus, the hole injection layer 30, the hole transport layer 40, the light emitting layer 50, the electron transport layer 60, and the electron injection layer 70 are laminated and sandwiched between the pair of electrodes 20 and 80, and the organic EL element S1 is formed.

  In this organic EL element S 1, an electric field is applied between the anode 20 and the cathode 80, holes from the anode 20 and electrons from the cathode 80 are injected and transported to the light emitting layer 50. Electrons and holes are recombined, and the light emitting layer 50 emits light by the energy at that time. The emitted light is taken out from the substrate 10 side and visually recognized, for example.

  The organic EL element S1 can be manufactured by sequentially forming the layers 20 to 80 on the substrate 10 by sputtering, vapor deposition, or the like. Here, organic layers such as the hole injection layer 30, the hole transport layer 40, the light emitting layer 50, and the electron transport layer 60 are formed by a vapor deposition method.

  Here, the light emitting layer 50 of the present embodiment is formed by mixing a hole transporting material composed of a tertiary amine compound, an electron transporting material, and a light emitting additive material, and 3 as a hole transporting material used here. The secondary amine compound and the electron transporting material have a glass transition temperature of 100 ° C. or higher for the purpose of ensuring heat resistance of 100 ° C. or higher.

  For the purpose of improving the luminance life, the tertiary amine compound as the hole transporting material in the light emitting layer 50 has a plurality of oxidation potentials determined by the cyclic voltammetry method and the first oxidation at the plurality of oxidation potentials. It is assumed that the potential difference between the potential and the second oxidation potential has a value of 0.22V or more. Hereinafter, the potential difference between the first oxidation potential and the second oxidation potential is referred to as “oxidation potential difference”.

  As the tertiary amine compound as a hole transporting material having such a glass transition temperature and an oxidation potential difference, a compound having four triphenylamines in the molecule is adopted.

  Furthermore, among the tertiary amine compounds having such a glass transition temperature and an oxidation potential difference, the tertiary amine compounds preferable for suppressing thermal decomposition by heating the material during the formation of the light emitting layer 50 include intramolecular Those having no substituent at the ortho position of the phenyl group of triphenylamine are employed.

  Further, as a similar tertiary amine compound, a compound having a substituent at the ortho position of the phenyl group of triphenylamine in the molecule and having a molecular weight of less than 1100 is employed.

  In the case of the light emitting layer 50 using a mixed host, although the luminance life is improved as compared with the light emitting layer of a single host, the light emission efficiency may be lowered depending on the combination of materials. In order to suppress this, the tertiary amine compound preferably has an ionization potential of 5.45 eV or more.

  Further, in order to more effectively suppress the decrease in luminance life, the tertiary amine compound has an oxidation-side curve shape and a reduction-side curve shape of an oxidation-reduction curve measured by a cyclic voltammetry method. It is preferable that it is symmetrical.

  Furthermore, in the light emitting layer 50 of this embodiment, in order to improve the luminance life, the electron transporting material preferably has a difference in ionization potential from the hole transporting material of 0.35 eV or more.

  In the present embodiment, the tertiary amine compound as the hole transporting material in the light emitting layer 50 described above has a unique manufacturing method as described below even when the relationship of the oxidation potential difference is not satisfied. By adopting it, it is possible to achieve both improvement in luminance life and ensuring heat resistance of 100 ° C. or higher.

  Such a unique manufacturing method relates to the manufacturing method of the light emitting layer 50 in the manufacturing method of the organic EL element S1. First, as a tertiary amine compound constituting the hole transporting material, triphenylamine is included in the molecule. And a glass transition temperature of 100 ° C. or higher.

  As the electron transporting material, a material having a difference in ionization potential from the hole transporting material of 0.35 eV or more and a glass transition temperature of 100 ° C. or more is used.

  Then, when forming the light emitting layer 50, when the electron transporting material is a thin film, when the peak of the fluorescence spectrum of the thin film is at a position 20 nm or more than the rising value of the spectrum, from the rising value. The film forming conditions of the electron transporting material are controlled so that the peak or shoulder of the fluorescence spectrum of the thin film appears at a position less than 20 nm. By adopting such a manufacturing method, it is possible to achieve both improvement in luminance life and securing heat resistance of 100 ° C. or higher.

  Specifically, when forming the light emitting layer 50, the film forming conditions of the electron transporting material can be controlled by controlling the material heating temperature of the electron transporting material.

  That is, the light emitting layer 50 is performed by ternary co-evaporation of a hole transport material, an electron transport material, and a light emission additive material, and is performed by setting the material heating temperature in each material. Vary material heating temperature.

  Accordingly, when the electron transporting material is a thin film, even if the peak of the fluorescence spectrum of the thin film is located at a position of 20 nm or more than the rising value of the spectrum, the rising of the electron transporting material by changing the heating temperature of the material. The peak or shoulder of the fluorescence spectrum of the thin film appears at a position less than 20 nm from the value.

  Moreover, what is represented by following Structural formula (1) is employable as a tertiary amine compound which is a hole transportable material of the light emitting layer 50 used in this original manufacturing method.

ここで、構造式（１）において、Ｒ１は下記構造式（２）で示される基である。

Here, in the structural formula (1), R1 is a group represented by the following structural formula (2).

ここで、構造式（２）中、ｎは０を含む０以上の整数であり、Ｌ１は飽和鎖式炭化水素、飽和環状炭化水素、飽和多環状炭化水素、フルオレンのいずれかであり、Ｌ２およびＬ３は不飽和鎖式炭化水素もしくは不飽和環状炭化水素であり、
Ｒ２、Ｒ３、Ｒ４、Ｒ５はアルキル基もしくはアリール基もしくは水素である。

Here, in Structural Formula (2), n is an integer of 0 or more including 0, L1 is any one of a saturated chain hydrocarbon, a saturated cyclic hydrocarbon, a saturated polycyclic hydrocarbon, and fluorene, and L2 and L3 is an unsaturated chain hydrocarbon or an unsaturated cyclic hydrocarbon,
R2, R3, R4, and R5 are an alkyl group, an aryl group, or hydrogen.

  Specific examples of the tertiary amine compound represented by the structural formula (1) include compounds 1 and 2 described later (see FIG. 2 described later).

  Furthermore, also in this unique manufacturing method, it is preferable to use a tertiary amine compound of the light emitting layer 50 having an ionization potential of 5.45 eV or more. Further, as the tertiary amine compound, it is preferable to use a compound in which the shape of the oxidation-side curve of the oxidation-reduction curve measured by the cyclic voltammetry method is symmetrical to the shape of the reduction-side curve.

[Examination example]
Here, the configuration and the like of the light emitting layer 50 in the present embodiment will be described in more detail with reference to an examination example verified using a specific compound. Note that the present embodiment is not limited to these examination examples.

[Constituent material of the light emitting layer used in the study example]
2 to 5 show compounds 1 to 10 as constituent materials of the light emitting layer 50 used in the study example. Here, compounds 1, 2, 3 (above, see FIG. 2), compounds 4, 5, 6 (above, see FIG. 3), and compound 7 (see FIG. 4) are hole transporting materials, and compound 8 ( 4 (see FIG. 4) and compound 10 (see FIG. 5) are electron-transporting materials, and compound 9 (see FIG. 5) is a styrylamine derivative that performs blue color development and a light-emitting additive material.

  Among these, a synthesis method is shown about compounds 1-7 other than compound 8, 9, 10 which is a well-known compound.

[Compound 1] (see FIG. 2)
Compound 1: Synthesis of 9,9-bis {4- [4 ′-(4-diphenylaminophenyl) triphenylamino]} fluorene.

  Acetanilide 20.3 g (0.15 mol), 4,4'-diiodobiphenyl 73.1 g (0.18 mol), anhydrous potassium carbonate 22.1 g (0.16 mol), copper powder 2.16 g (0. 034 mol) and 35 ml of nitrobenzene were mixed and reacted at 190 to 205 ° C. for 10 hours.

  The reaction product was extracted with 200 ml of toluene, and the insoluble matter was removed by filtration, followed by concentration to dryness. This was purified by column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate = 6/1), and 40.2 g (yield 64.8%) of N- (4′-iodo-4-biphenyl) acetanilide. Got.

  Subsequently, N- (4′-iodo-4-biphenyl) acetanilide 13.2 g (0.032 mol), diphenylamine 6.60 g (0.039 mol), anhydrous potassium carbonate 5.53 g (0.040 mol) and Copper powder 0.45g (0.007mol) and nitrobenzene 10ml were mixed, and it was made to react at 200-212 degreeC for 15 hours.

  The reaction product was extracted with 100 ml of toluene, insolubles were removed by filtration and then concentrated to an oily product. The oily substance was dissolved in 60 ml of isoamyl alcohol, added with 1 ml of water and 2.64 g (0.040 mol) of 85% potassium hydroxide, and hydrolyzed at 130 ° C. After isoamyl alcohol was distilled off by steam distillation, the product was extracted with 250 ml of toluene, washed with water, dried and concentrated.

  The concentrate was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), and 10.5 g (yield 72.2%) of N, N, N′-triphenylbenzidine was obtained. Obtained.

  Furthermore, N, N, N′-triphenylbenzidine 8.66 g (0.021 mol), 9,9-bis- (4-iodophenyl) fluorene 5.7 g (0.01 mol), anhydrous potassium carbonate 2. 90 g (0.021 mol), 0.32 g (0.005 mol) of copper powder, and 10 ml of nitrobenzene were mixed and reacted at 195 to 210 ° C. for 20 hours.

  The reaction product was extracted with 140 ml of toluene, insoluble matter was filtered off and concentrated, and 120 ml of n-hexane was added to take out crude crystals. The crude crystals were purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), 9,9-bis {4- [4 ′-(4-diphenylaminophenyl) triphenyl Amino]} fluorene (5.7 g, yield: 50.0%) was obtained.

[Compound 2] (see FIG. 2)
Compound 2: Regarding the synthesis of N, N′-bis [4- (4′-diphenylaminobiphenyl)]-N, N′-diphenyl-1,1′-bis (4-aminophenyl) -methylene.

  Acetanilide 20.3 g (0.15 mol), 4,4'-diiodobiphenyl 73.1 g (0.18 mol), anhydrous potassium carbonate 22.1 g (0.16 mol), copper powder 2.16 g (0. 034 mol) and 35 ml of nitrobenzene were mixed and reacted at 190 to 205 ° C. for 10 hours.

  The reaction product was extracted with 200 ml of toluene, and the insoluble matter was removed by filtration, followed by concentration to dryness. This was purified by column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate = 6/1), and 40.2 g of N- [4- (4′-iodobiphenyl)] acetanilide (yield 64.8%). )

  Subsequently, N- [4- (4′-iodobiphenyl)] acetanilide 13.2 g (0.032 mol), diphenylamine 6.60 g (0.039 mol), anhydrous potassium carbonate 5.53 g (0.040 mol) And 0.45 g (0.007 mol) of copper powder and 10 ml of nitrobenzene were mixed and reacted at 200-212 ° C. for 15 hours.

  The reaction product was extracted with 100 ml of toluene, insolubles were removed by filtration and then concentrated to an oily product. The oily substance was dissolved in 60 ml of isoamyl alcohol, added with 1 ml of water and 2.64 g (0.040 mol) of 85% potassium hydroxide, and hydrolyzed at 130 ° C. After isoamyl alcohol was distilled off by steam distillation, the product was extracted with 250 ml of toluene, washed with water, dried and concentrated.

  The concentrate was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), and 10.5 g (yield 72.2%) of N, N, N′-triphenylbenzidine was obtained. Obtained.

  Furthermore, N, N, N′-triphenylbenzidine 8.66 g (0.021 mol), (4,4′-diiodo) methylenebiphenyl 4.20 g (0.01 mol), anhydrous potassium carbonate 2.90 g (0 0.021 mol), 0.32 g (0.005 mol) of copper powder, and 10 ml of nitrobenzene were mixed and reacted at 195 to 210 ° C. for 20 hours.

  The reaction product was extracted with 140 ml of toluene, insoluble matter was filtered off and concentrated, and 120 ml of n-hexane was added to take out crude crystals. The crude crystals were purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), and N, N′-bis [4- (4′-diphenylaminobiphenyl)]-N, 4.95 g (yield; 50.0%) of N′-diphenyl-1,1′-bis (4-aminophenyl) -methylene was obtained.

[Compound 3] (see FIG. 2)
Compound 3: N, N′-bis [4- (4′-diphenylaminobiphenyl)]-N, N′-diphenyl- [1,1 ′-(3,3′-dimethyl) -biphenyl-4,4 ′ -Synthesis of diamine].

  Acetanilide 20.3 g (0.15 mol), 4,4'-diiodobiphenyl 73.1 g (0.18 mol), anhydrous potassium carbonate 22.1 g (0.16 mol), copper powder 2.16 g (0. 034 mol) and 35 ml of nitrobenzene were mixed and reacted at 190 to 205 ° C. for 10 hours.

  The reaction product was extracted with 200 ml of toluene, insolubles were removed by filtration, and then concentrated to dryness. This was purified by column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate = 6/1), and 40.2 g of N- [4- (4′-iodobiphenyl)] acetanilide (yield 64.8%). )

  Subsequently, N- [4- (4′-iodobiphenyl)] acetanilide 13.2 g (0.032 mol), diphenylamine 6.60 g (0.039 mol), anhydrous potassium carbonate 5.53 g (0.040 mol) And 0.45 g (0.007 mol) of copper powder and 10 ml of nitrobenzene were mixed and reacted at 200-212 ° C. for 15 hours.

  The reaction product was extracted with 100 ml of toluene, insolubles were removed by filtration and then concentrated to an oily product. The oily substance was dissolved in 60 ml of isoamyl alcohol, added with 1 ml of water and 2.64 g (0.040 mol) of 85% potassium hydroxide, and hydrolyzed at 130 ° C. After isoamyl alcohol was distilled off by steam distillation, the product was extracted with 250 ml of toluene, washed with water, dried and concentrated.

  The concentrate was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), and 10.5 g (yield 72.2%) of N, N, N′-triphenylbenzidine was obtained. Obtained.

  Furthermore, N, N, N′-triphenylbenzidine 8.66 g (0.021 mol), 3,3′-dimethyl-4,4′-diiodobiphenyl 4.34 g (0.01 mol), anhydrous potassium carbonate 2.90 g (0.021 mol), 0.32 g (0.005 mol) of copper powder, and 10 ml of nitrobenzene were mixed and reacted at 195 to 210 ° C. for 20 hours.

  The reaction product was extracted with 140 ml of toluene, insolubles were filtered off and concentrated, and then 120 ml of n-hexane was added to take out crude crystals. The crude crystals were purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), and N, N′-bis [4- (4′-diphenylaminobiphenyl)]-N, 4.31 g (yield; 43.0%) of N′-diphenyl- [1,1 ′-(3,3′-dimethyl) -biphenyl-4,4′-diamine] was obtained.

[Compound 4] (see FIG. 3)
Compound 4: Synthesis of N, N′-bis {4-[(1-naphthyl) phenylamino] phenyl)}-N, N′-diphenylbenzidine.

  Acetanilide 20.3 g (0.15 mol), 1,4-diiodobenzene 59.4 g (0.18 mol), anhydrous potassium carbonate 22.1 g (0.16 mol), copper powder 2.16 g (0.034) Mol) and 35 ml of nitrobenzene were mixed and reacted at 190 to 205 ° C. for 10 hours.

  The reaction product was extracted with 200 ml of toluene, insolubles were removed by filtration, and then concentrated to dryness. This was purified by column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate = 6/1) to obtain 30.3 g (yield 60%) of N- (4-iodophenyl) acetanilide.

  Subsequently, N- (4-iodophenyl) acetanilide 10.8 g (0.032 mol), (1-naphthyl) phenylamine 8.0 g (0.039 mol), anhydrous potassium carbonate 5.53 g (0.040 mol) ) And 0.45 g (0.007 mol) of copper powder and 10 ml of nitrobenzene were mixed and reacted at 200 to 212 ° C. for 15 hours.

  The reaction product was extracted with 100 ml of toluene, the insoluble matter was removed by filtration and then concentrated to an oily product. The oily substance was dissolved in 60 ml of isoamyl alcohol, added with 1 ml of water and 2.64 g (0.040 mol) of 85% potassium hydroxide, and hydrolyzed at 130 ° C.

  After isoamyl alcohol was distilled off by steam distillation, the product was extracted with 250 ml of toluene, washed with water, dried and concentrated. The concentrate is purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), and N, N′-diphenyl-N- (1-naphthyl) -1,4-phenylenediamine 8 0.6 g (yield 70.0%) was obtained.

  Furthermore, 8.11 g (0.021 mol) of N, N′-diphenyl-N- (1-naphthyl) -1,4-phenylenediamine, 4.06 g (0.01 mol) of 4,4′-diiodobiphenyl Then, 2.90 g (0.021 mol) of anhydrous potassium carbonate, 0.32 g (0.005 mol) of copper powder and 10 ml of nitrobenzene were mixed and reacted at 195 to 210 ° C. for 20 hours.

  The reaction product was extracted with 140 ml of toluene, insoluble matter was filtered off and concentrated, and 120 ml of n-hexane was added to take out crude crystals. The crude crystals are purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), N, N′-bis {4-[(1-naphthyl) phenylamino] phenyl)} 4.2 g (yield: 45.0%) of -N, N′-diphenylbenzidine was obtained.

[Compound 5] (see FIG. 3)
Compound 5: Synthesis of 4,4 ′, 4 ″ -tris [(1-naphthyl) phenylamino] triphenylamine.

  In a 200 ml reaction vessel, 28.7 g (0.046 mol) of 4,4 ′, 4 ″ -triiodotriphenylamine, 50.4 g (0.23 mol) of N- (1-naphthyl) -aniline and anhydrous potassium carbonate 44.2 g (0.32 mol), 4.32 g (0.068 mol) of copper powder and 50 ml of decalin were added, and the mixture was heated in an Ar atmosphere at an oil bath temperature of 220 ° C. for 24 hours.

  After completion of the reaction, 200 ml of toluene was added and filtered to remove insoluble matters, and the filtrate was washed with water and dried over sodium sulfate. After drying, the solvent was distilled off from this filtrate, and the residue was purified four times by silica gel column (developing solvent: n-hexane / toluene mixed solvent), recrystallized repeatedly from hexane / toluene mixed solvent and ethyl acetate, and vacuum dried. After that, 24.7 g (yield 60.0%) of 4,4 ′, 4 ″ -tris [(1-naphthyl) phenylamino] triphenylamine was obtained.

  By sublimation purification, 4,4 ′, 4 ″ -tris [(1-naphthyl) phenylamino] triphenylamine with high purity was obtained (sublimation purification yield: 70.0%).

[Compound 6] (see FIG. 3)
Compound 6: Synthesis of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine.

  4.6 g (0.021 mol) of (1-naphthyl) phenylamine, 4.06 g (0.01 mol) of 4,4′-diiodobiphenyl, 2.90 g (0.021 mol) of anhydrous potassium carbonate, copper powder 0.32 g (0.005 mol) and 10 ml of nitrobenzene were mixed and reacted at 195 to 210 ° C. for 20 hours.

  The reaction product was extracted with 140 ml of toluene, insoluble matter was filtered off and concentrated, and 120 ml of n-hexane was added to take out crude crystals. The crude crystals are purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine 6 g (yield; 45.0%) was obtained.

[Compound 7] (see FIG. 4)
Compound 7: Synthesis of N, N′-bis [4- (4′-diphenylaminobiphenyl)]-N, N′-diphenylbenzidine.

  Acetanilide 20.3 g (0.15 mol), 4,4'-diiodobiphenyl 73.1 g (0.18 mol), anhydrous potassium carbonate 22.1 g (0.16 mol), copper powder 2.16 g (0. 034 mol) and 35 ml of nitrobenzene were mixed and reacted at 190 to 205 ° C. for 10 hours.

  The reaction product was extracted with 200 ml of toluene, and the insoluble matter was removed by filtration, followed by concentration to dryness. This was purified by column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate = 6/1), and 40.2 g of N- [4- (4′-iodobiphenyl)] acetanilide (yield 64.8%). )

  Subsequently, N- [4- (4′-iodobiphenyl)] acetanilide 13.2 g (0.032 mol), diphenylamine 6.60 g (0.039 mol), anhydrous potassium carbonate 5.53 g (0.040 mol) and Copper powder 0.45g (0.007mol) and nitrobenzene 10ml were mixed, and it was made to react at 200-212 degreeC for 15 hours.

  The reaction product was extracted with 100 ml of toluene, insolubles were removed by filtration and then concentrated to an oily product. The oily substance was dissolved in 60 ml of isoamyl alcohol, added with 1 ml of water and 2.64 g (0.040 mol) of 85% potassium hydroxide, and hydrolyzed at 130 ° C. After isoamyl alcohol was distilled off by steam distillation, the product was extracted with 250 ml of toluene, washed with water, dried and concentrated.

  The concentrate was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), and 10.5 g (yield 72.2%) of N, N, N′-triphenylbenzidine was obtained. Obtained.

  Further, N, N, N′-triphenylbenzidine 8.66 g (0.021 mol), 4,4′-diiodobiphenyl 4.06 g (0.01 mol), anhydrous potassium carbonate 2.90 g (0.021 mol) Mol), 0.32 g (0.005 mol) of copper powder and 10 ml of nitrobenzene were mixed and reacted at 195 to 210 ° C. for 20 hours.

  The reaction product was extracted with 140 ml of toluene, insoluble matter was filtered off and concentrated, and 120 ml of n-hexane was added to take out crude crystals. The crude crystals were purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), and N, N′-bis [4- (4′-diphenylaminobiphenyl)]-N, 4.73 g (yield; 48.5%) of N′-diphenylbenzidine was obtained.

[Physical properties of the compounds used in the study examples]
Of the compounds 1 to 10 as described above, the physical property values of the compounds 1 to 8 and 10 excluding the compound 9 which is a light emitting additive material will be described.

  First, compounds 1 to 7 which are hole transporting materials will be described. Regarding the glass transition temperature (Tg), Compound 1 is 162 ° C, Compound 2 is 133 ° C, Compound 3 is 139 ° C, Compound 4 is 132 ° C, Compound 5 is 112 ° C, Compound 6 is 96 ° C, and Compound 7 is 144 ° C. It is. Compounds 1 to 5 and 7 excluding Compound 6 have a glass transition temperature of 100 ° C. or higher.

  Regarding the ionization potential (Ip) of compounds 1 to 7, compound 1 is 5.50 eV, compound 2 is 5.50 eV, compound 3 is 5.50 eV, compound 4 is 5.30 eV, compound 5 is 5.20 eV, compound 6 Is 5.47 eV, and compound 7 is 5.40 eV. Compounds 1 to 3 and 6 except for compounds 4, 5 and 7 have an ionization potential of 5.45 eV or more. In addition, the measurement of ionization potential used here the photoelectron measuring apparatus (AC-2) by a Riken Keiki.

  The oxidation potentials of the compounds 1 to 7 were measured by a generally known cyclic voltammetry method, that is, a method of giving a potential change to a solution containing a tertiary amine compound that is a hole transporting material of the light emitting layer 50.

  As a result, regarding the oxidation potential difference (potential difference between the first oxidation potential and the second oxidation potential), Compound 1 is 0.18V, Compound 2 is 0.2V, Compound 3 is 0.23V, Compound 4 is 0.51V, Compound 5 is 0.23V, Compound 6 is 0.25V, and Compound 7 is 0.19V. Compounds 3 to 6 excluding compounds 1, 2 and 7 have an oxidation potential difference of 0.22 V or more.

  Further, among compounds 1 to 7 which are tertiary amine compounds, those in which the shape of the oxidation-side curve and the shape of the reduction-side curve of the oxidation-reduction curve measured by cyclic voltammetry are symmetric are compound 4, Compounds 1 to 3, 6 and 7 except for 5.

  As an example of the measurement of the oxidation potential by the cyclic voltammetry method, the measurement result of Compound 3 is shown in FIG. 6, and the measurement result of Compound 4 is shown in FIG. Here, the measurement conditions of the cyclic voltammetry method are as follows.

  Reference electrode: saturated calomel electrode, working electrode: platinum electrode, counter electrode: platinum electrode, supporting electrolyte: tetra-n-butylammonium chlorate, measuring sample: 1 mmol / l measuring sample, and 0.1 mmol / l supporting electrolyte Methylene chloride solution, measurement conditions: Sweep speed 100 mV / sec (triangular wave) at room temperature.

  6 and 7, the difference between the smallest first oxidation potential E1 and the second smallest second oxidation potential E2 is the oxidation potential difference. Moreover, in the compound 3 shown in FIG. 6, the shape of the oxidation side curve of the measured oxidation-reduction curve and the shape of the reduction side curve are symmetrical, whereas in the compound 4 shown in FIG. The shape of the oxidation-side curve of the oxidation-reduction curve and the shape of the reduction-side curve are asymmetric.

  Among the above-mentioned tertiary amine compounds 1 to 7, those having a glass transition temperature of 100 ° C. or higher and an oxidation potential difference determined by a cyclic voltammetry method of 0.22 V or higher are compounds 3 and 4 5. And these compounds 3, 4, and 5 all have four triphenylamines in a molecule | numerator.

  Of these compounds 3, 4, and 5, those having no substituent at the ortho position of the phenyl group of triphenylamine in the molecule are compounds 4 and 5, and in the phenyl group of triphenylamine in the molecule. A compound having a substituent at the ortho position and having a molecular weight of less than 1100 is Compound 3.

  Next, compounds 8 and 10 which are electron transporting materials will be described. Regarding the glass transition temperature (Tg), Compound 8 is 175 ° C. and Compound 10 is 164 ° C., both of which have a glass transition temperature of 100 ° C. or higher.

  Regarding the ionization potential (Ip) of the compounds 8 and 10, the compound 8 is 5.85 eV, and the compound 10 is 5.75 eV. In the measurement of the ionization potential, a photoelectron measuring device (AC-2) manufactured by Riken Keiki Co., Ltd. was used here.

[Results of study on luminance life and heat resistance]
Next, using the compounds 1 to 10 shown in FIGS. 2 to 5, an organic EL element S <b> 1 was produced, and the luminance life, high temperature storage (heat resistance), luminous efficiency, and the like were verified. The results are shown in the tables of FIGS.

  Specifically, in FIG. 8 and FIG. 9, the following items are shown for each example. The hole transport material, the electron transport material, the light emission additive material, and the material heating temperature, the luminance life, the high temperature storage, and the light emission efficiency of the electron transport material when the light emitting layer 50 is formed by vapor deposition. , Oxidation potential difference (unit: V), oxidation-reduction curve symmetry, Tg (unit: ° C), Ip (unit: eV).

Here, the luminance lifetime is the luminance when the element manufactured in each example was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive in an environment of 85 ° C., and the driving time after 400 hours. The initial luminance is represented by normalized luminance standardized as 1.

The high temperature storage is a heat resistance of 100 ° C. or higher, and “×” is given for those in which dark spots are generated by a storage test at 100 ° C., and “◯” is given for those where no dark spots are generated. The light emission efficiency is an initial light emission efficiency, that is, a value (unit: cd / A) when the initial luminance is 400 cd / m ² .

  The oxidation potential difference, oxidation-reduction curve symmetry, Tg, and Ip are respectively the oxidation potential difference of the hole transport material of each example, the oxidation-side curve shape of the oxidation-reduction curve measured by the cyclic voltammetry method, and the reduction-side curve. Symmetry with the shape of the curve, glass transition temperature, and ionization potential. Here, the symmetry of the redox curve symmetry is “◯”, and the asymmetric one is “x”.

  Next, specific embodiments will be described with respect to the individual examination examples shown in FIGS.

(Examination Example 1-1)
An ITO film (transparent electrode) was formed as the anode 20 on the glass substrate 10, and the surface thereof was polished so that Ra was about 1 nm and Rz was about 10 nm.

  On the anode 20, a 10 nm hole injection layer 30 made of CuPc as an organic material having crystallinity was formed. On the hole injection layer 30, 20 nm of the compound 1 (refer FIG. 2) which is a tertiary amine compound as the hole transport layer 40 was formed.

  In addition, as the light emitting layer 50, a compound 1 as a tertiary amine compound, a compound 8 as an electron transporting material (see FIG. 4), and a compound 9 as a light emitting additive material (see FIG. 5) are respectively 60: A 20 nm film was formed at a weight ratio of 20: 3. Here, the material heating temperature of the compound 8, which is an electron transporting material, was set to 260 ° C.

  Tris (8-quinolinolato) aluminum 20 nm was formed as the electron transport layer 60, LiF was formed on the electron injection layer 70, and Al was formed on the cathode 80, and sealed in a sealed can in a dry nitrogen atmosphere to obtain an organic EL device.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 1-2)
In the same element structure as in the above Study Example 1-1, the element was formed by setting the material heating temperature of the compound 8 which is an electron transporting material as high as 280 ° C. when forming the light emitting layer 50.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 2-1)
Except that the tertiary amine compound used for the hole transport layer 40 and the light emitting layer 50 was replaced with the compound 2 (see FIG. 2) in the element structure and element formation conditions of the above Example 1-1, the above Example 1-1 A device was fabricated in the same manner as described above.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Study Example 2-2)
Except that the tertiary amine compound used in the hole transport layer 40 and the light emitting layer 50 was replaced with the compound 2 (see FIG. 2) in the element structure and element formation conditions of the above-described Example 1-2, the above Example 1-2 A device was fabricated in the same manner as described above.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 3-1)
Except that the tertiary amine compound used for the hole transport layer 40 and the light emitting layer 50 was replaced with the compound 3 (see FIG. 2) in the element structure and element formation conditions of the above Example 1-1, the above Example 1-1 A device was fabricated in the same manner as described above.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 3-2)
Except that the tertiary amine compound used for the hole transport layer 40 and the light-emitting layer 50 was replaced with the compound 3 (see FIG. 2) in the element structure and element formation conditions of the above-described Example 1-2, the above Example 1-2 A device was fabricated in the same manner as described above.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Study Example 4-1)
Except that the tertiary amine compound used for the hole transport layer 40 and the light emitting layer 50 was replaced with the compound 4 (see FIG. 3) in the element structure and element formation conditions of the above Example 1-1, the above Example 1-1 A device was fabricated in the same manner as described above.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 4-2)
In the element structure and element formation conditions of the above-described Investigation Example 1-2, except that the tertiary amine compound used for the hole transport layer 40 and the light emitting layer 50 is changed to the compound 4 (see FIG. 3), the above Investigation Example 1-2 A device was fabricated in the same manner as described above.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 5-1)
In the device structure and device formation conditions of the above-mentioned Study Example 1-1, the tertiary amine compound used for the hole transport layer 40 and the light emitting layer 50 is replaced with the compound 5 (see FIG. 3) which is a starbust triphenylamine derivative. A device was fabricated in the same manner as in Examination Example 1-1 except that.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 5-2)
In the device structure and device formation conditions of the above-described Study Example 1-2, the tertiary amine compound used for the hole transport layer 40 and the light emitting layer 50 is replaced with the compound 5 (see FIG. 3) which is a starbust triphenylamine derivative. A device was fabricated in the same manner as in Examination Example 1-2 except that.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 6-1)
Other than changing the tertiary amine compound used for the hole transport layer 40 and the light emitting layer 50 to the compound 6 (see FIG. 3) which is a triphenylamine derivative in the element structure and the element formation conditions of the examination example 1-1. Were fabricated in the same manner as in Examination Example 1-1.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Further, dark spots were generated in the storage test under the environment of 100 ° C.

(Examination Example 6-2)
Other than changing the tertiary amine compound used for the hole transport layer 40 and the light emitting layer 50 to the compound 6 (see FIG. 3) which is a triphenylamine derivative in the device structure and the device formation conditions of the examination example 1-2. Were fabricated in the same manner as in Study Example 1-2 above.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Further, dark spots were generated in the storage test under the environment of 100 ° C.

(Examination Example 7-1)
Other than changing the tertiary amine compound used for the hole transport layer 40 and the light emitting layer 50 to the compound 7 (see FIG. 4) which is a triphenylamine derivative in the element structure and the element formation conditions of the examination example 1-1. Were fabricated in the same manner as in Example 1-1 above.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the time exceeded 500 hours.

(Examination Example 7-2)
Other than changing the tertiary amine compound used for the hole transport layer 40 and the light emitting layer 50 to the compound 7 (see FIG. 4) which is a triphenylamine derivative in the device structure and the device formation conditions of the examination example 1-2. Were fabricated in the same manner as in Study Example 1-2 above.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 8-1)
The device was fabricated in the same manner as in Study Example 1-1 except that the electron transporting material used for the light emitting layer 50 was changed to Compound 10 (see FIG. 5) in the device structure and device formation conditions of Study Example 1-1. Produced. Here, the material heating temperature of the electron transporting material was set to 350 ° C.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 8-2)
The device was fabricated in the same manner as in Study Example 2-1, except that the electron transport material used for the light emitting layer 50 was changed to Compound 10 (see FIG. 5) in the device structure and device formation conditions of Study Example 2-1. Produced. Here, the material heating temperature of the electron transporting material was set to 350 ° C.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 8-3)
The device was fabricated in the same manner as in Study Example 3-1, except that the electron transport material used for the light emitting layer 50 was changed to Compound 10 (see FIG. 5) in the device structure and device formation conditions of Study Example 3-1. Produced. Here, the material heating temperature of the electron transporting material was set to 350 ° C.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 8-4)
The device was fabricated in the same manner as in Study Example 4-1, except that the electron transporting material used for the light emitting layer 50 was changed to Compound 10 (see FIG. 5) in the device structure and device formation conditions of Study Example 4-1. Produced. Here, the material heating temperature of the electron transporting material was set to 350 ° C.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 8-5)
The device was fabricated in the same manner as in Study Example 5-1, except that the electron transport material used for the light emitting layer 50 was changed to Compound 10 (see FIG. 5) in the device structure and device formation conditions of Study Example 5-1. Produced. Here, the material heating temperature of the electron transporting material was set to 350 ° C.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 8-6)
In the same element structure as in Examination Example 8-3, the element 10 was formed by setting the material heating temperature of the compound 10 which is an electron transporting material as high as 380 ° C. when the light emitting layer 50 was formed.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

  Next, based on the results shown in FIGS. 8 and 9, feature points and the like in each study example will be described.

  As shown in FIG. 8, in Examination Examples 3-1, 4-1, 5-1, 8-4, and 8-5, the tertiary amine compound and the electron transporting material as the hole transporting material have a glass transition. The temperature is 100 ° C. or higher, and the oxidation potential difference of the tertiary amine compound as the hole transporting material is 0.22 V or higher. Thereby, in these examples, it is possible to achieve both improvement of the luminance life and securing heat resistance of 100 ° C. or more.

  This is because the glass transition temperature of the hole transporting material and the electron transporting material in the light emitting layer 50 is 100 ° C. or higher and the relationship between the oxidation potential difference of 0.22 V or higher is used. This is considered to be because the movement of holes from the first oxidation potential to the second oxidation potential in the conductive material is suppressed, the movement of holes to the electron transport material is suppressed, and the deterioration of the electron transport material can be suppressed.

  Incidentally, in the study examples 1-1, 8-1 and the like using the hole transporting material having an oxidation potential difference of less than 0.22 V, the light emitting layer 50 serving as a mixed host has a low luminance life.

  Usually, the reason why the luminance lifetime is improved by the light emitting layer using the mixed host is considered to be that the hole transport and the electron transport functions can be shared in the light emitting layer. The effect of the luminance life improvement by the light emitting layer using the mixed host was examined.

  In the examination examples 1-1, 2-1, 3-1, 4-1, 5-1, 6-1, and 7-1 shown in FIG. The result is shown in FIG.

  In FIG. 10, the luminance life and luminous efficiency in the examination examples 1-1, 2-1, 3-1, 4-1, 5-1, 6-1 and 7-1 are shown in the “mixed layer present” column. is there. In addition, for each of these examination examples, an element having “no mixed layer”, that is, a light emitting layer of a single host that is not a mixed host, was manufactured, and its luminance life and luminous efficiency were examined.

  This “without mixed layer” is the same as that in each of the examination examples 1-1, 2-1, 3-1, 4-1, 5-1, 6-1, 7-1. The compound 8 and the compound 9 which is a light-emitting additive material are all the same except that they are formed with a weight ratio of 100: 5 to 200 nm.

  As can be seen from FIG. 10, in any case, the luminance life is improved by using the light emitting layer as a mixed host. Here, in the organic EL element in which the light-emitting layer is a mixed host layer, that is, a layer formed by mixing a hole-transporting material composed of a tertiary amine compound, an electron-transporting material, and a light-emitting additive material, a mechanism that suppresses a decrease in luminance. Is estimated as follows.

  When the light emitting layer is a single host material, it is considered that light is emitted by the following formula.

(Chemical formula 12)
H ⁺ + H ⁻ + D → (H * + D) → H + D * → H + D
Here, H is a charge (hole or electron) transport material molecule that is a host material molecule, D is a light-emitting additive material molecule that is a guest material molecule, and * is a singlet excited state.

Since the host material is single, charge transfer from each polar ion H ⁺ , H ^{− of} the host material molecule to the guest material molecule D to emit light, or charge transfer from the excited state H * of the host material molecule to the guest material molecule D As a result, the guest molecule becomes an excited state D * and emits light.

  On the other hand, when the light emitting layer is a mixed host layer, it is considered that light is emitted according to the following formula.

(Chemical Formula 13)
Ha ⁺ + Hb ⁻ + D → Ha + Hb + D * → Ha + Hb + D
Here, Ha and Hb are host material molecules, Ha is a hole transporting material molecule, and Hb is an electron transporting material molecule. D represents a light emitting additive material molecule which is a guest material molecule, and * represents a singlet excited state.

  Since the host materials Ha and Hb have a very large energy band shift, mutual charge transfer does not occur. For this reason, the host material does not enter an excited state, and as a result of charge transfer to the guest material molecule D, the guest molecule becomes an excited state D * and emits light.

  As described above, in the mixed host layer, the host molecules Ha and Hb are not excited, and therefore the host material is hardly deteriorated. This is presumed to be one cause of the improvement of the luminance life due to the mixed host layer.

  However, even when the light emitting layer is a mixed host layer, the electron transporting material may be easily excited depending on the combination of the hole transporting material and the electron transporting material in the host. In the present embodiment, such combinations can be eliminated as much as possible, excitation of the electron transporting material can be suppressed, and the luminance life can be improved.

  That is, the oxidation potential difference of the tertiary amine compound as the hole transporting material is a value of 0.22 V or more as in Examples 3-1, 4-1, 5-1, 8-4, and 8-5 described above. For example, the deterioration of the electron transporting material can be suppressed and the luminance life can be improved.

  Further, when the tertiary amine compound and the electron transporting material as the hole transporting material have a glass transition temperature of 100 ° C. or higher, high temperature storage is good, and dark spots are not generated even when exposed to 100 ° C. or higher. . Actually, in compound 6 (see FIG. 3) having a glass transition temperature of less than 100 ° C., dark spots are generated during high temperature storage.

  The result of investigating the cause of this dark spot is shown in FIG. FIG. 11 is a diagram schematically showing a cross-sectional shape of the device of Study Example 6-1 using Compound 6 above after being stored at 120 ° C. for 500 hours using a scanning electron microscope. is there.

  From this observation result, it was found that the layer (the hole transport layer 40 and the light emitting layer 50) in which the hole transporting material exists was partially hollowed out. In the hollow portion K1, no current flows, so that it becomes a non-light emitting region and is considered to be recognized as a dark spot. This is presumed to be due to the fact that the environmental temperature is higher than the glass transition temperature of the material, so that crystallization accompanied by volume change has progressed.

  In addition, the compounds 3 to 5 used as the hole transporting materials in the examination examples 3-1, 4-1, 5-1, 8-4, and 8-5 shown in FIGS. In the molecule, it is assumed that it has four triphenylamines, and it is possible to appropriately realize that the glass transition temperature is 100 ° C. or higher and that the above-described oxidation potential difference is satisfied.

  In this way, the tertiary amine compound having four triphenylamines in the molecule has a glass transition temperature of 100 ° C. or higher, and easily realizes the relationship between the oxidation potential differences and the molecular design of the material. A wide variety of compounds can be realized.

  Further, as a tertiary amine compound having a glass transition temperature of 100 ° C. or higher, a compound in which triphenylamine is simply multimerized as in Compound 7 (see FIG. 4) can be considered. Compound 7 has a glass transition temperature of 100 ° C. or higher, but has a small oxidation potential difference of 0.19V. Therefore, the luminance life is low as shown in Examination Example 7-1.

  This is because, when triphenylamine is simply multimerized, conjugation (resonance) is extended, so that the first oxidation potential and the second oxidation potential are considered to be close to each other. In contrast, a higher oxidation potential difference is obtained if the material has a structure that can increase the steric hindrance or break the conjugation, such as the compounds 1 to 5.

  Here, as one of the methods for cleaving the conjugation, a steric hindrance can be provided by introducing a substituent into the ortho position of the phenyl group of triphenylamine as in compound 3 (see FIG. 2). However, this part is thermally weak, and particularly when the molecular weight is large, the material is thermally decomposed by heating during vapor deposition.

  Therefore, for example, as the compounds 4 and 5 (see FIG. 3), the tertiary amine compound of the light emitting layer 50 is preferably one having no substituent at the ortho position of the phenyl group of triphenylamine. A tertiary amine compound that does not have a substituent at the ortho position is generally difficult to be thermally decomposed, and temperature control during film formation is easy, so that stable film formation is easily achieved.

  However, according to the study by the present inventors, even a tertiary amine compound having a substituent at the ortho position in the phenyl group of triphenylamine is not affected by thermal decomposition as long as the molecular weight is less than 1100. It was experimentally found that stable film formation was possible. For example, compound 3 (see FIG. 2).

  Incidentally, the present inventors investigated a compound 11 as shown in FIG. 12 as a tertiary amine compound having a substituent at the ortho position in the phenyl group of triphenylamine. This compound 11 has a molecular weight of 1102.

  In the case of this compound 11, the degree of vacuum fluctuated greatly during vapor deposition, and the material heating temperature also fluctuated. This is presumed to be due to the generation of gas accompanying the material decomposition of the compound 11 and the heat generation of the material. The vapor deposition rate at this time is 0.1 nm / sec, which is a lower value than the vapor deposition rate during normal production.

  Therefore, in the case of a tertiary amine compound having a substituent at the ortho position in the phenyl group of triphenylamine, it is considered that a film cannot be formed unless the molecular weight is less than 1100.

  In addition, in the case where the ionization potential of the tertiary amine compound in the light-emitting layer 50 is 5.45 eV or more as in Study Examples 1-1, 2-1, 3-1, etc., the light emission efficiency is high, and Study Example 4-1. When the ionization potential of the tertiary amine compound in the light emitting layer 50 is less than 5.45 eV, such as 5-1 or 5-1, the luminous efficiency is low.

  Thus, it has been found that there is a correlation between the ionization potential of the tertiary amine compound and the light emission efficiency in the light emitting layer 50 as a mixed host. This can be confirmed also in the table of FIG. 10 above, and it is also understood that this is a phenomenon unique to the mixed host.

  That is, if the light emitting layer 50 is a mixed host, the luminance life is improved, but if the ionization potential of the tertiary amine compound is small, the light emission efficiency is lowered.

  This is presumably because if the ionization potential of the tertiary amine compound which is a hole transporting material is small, the movement of holes from the hole transporting material to the light emitting additive material which is a dopant (guest molecule) is not smooth.

  Therefore, in the light emitting layer 50 serving as a mixed host, it is preferable to use a tertiary amine compound having an ionization potential of 5.45 eV or more because the light emission efficiency can be ensured more reliably than in the past.

  Further, when the study example 3-1 and the study examples 4-1 and 5-1 are compared, the former has a slightly longer luminance life than the latter. One reason for this is that the former tertiary amine compound has good redox curve symmetry, while the latter tertiary amine compound is asymmetric.

  As described above, the hole transporting material is oxidized when it receives holes from the neutral state, and when it passes the holes to the other party, it is reduced and returns to the neutral state. In such a hole transporting material, if the redox curve symmetry is good, the hole transporting material can easily restore the original hole transporting function after the hole transporting material has passed the hole.

  Incidentally, when the oxidation-reduction curve symmetry is asymmetric, the hole transport capability is lowered since the hole transport function is difficult to restore after the hole transport material passes the hole. Then, the resistance of the hole transporting material in the light emitting layer 50 is increased, and the light emission distribution is shifted. As a result, the luminous efficiency is lowered and the luminance life is lowered.

  As described above, in order to more effectively suppress the decrease in luminance life, it is also necessary that the oxidation-reduction curve of the tertiary amine compound of the light emitting layer 50 has good symmetry.

  As described above, the ionization potential of the electron transporting material is 5.85 eV for compound 8 (see FIG. 4) and 5.75 eV for compound 10 (see FIG. 5).

  Here, in Examination Examples 3-1, 4-1, 8-4, etc., the difference in ionization potential between the electron transporting material and the hole transporting material is 0.35 eV or more, and the ionization potential Luminance life is improved as compared with Study Example 8-3 in which the difference is less than 0.35 eV.

  About this examination example, although the effect in the case where the oxidation potential difference of the hole transport material is 0.22 V or more has been mainly described so far, as shown in examination examples 1-2, 2-2, and 7-2, Even when the oxidation potential difference is less than 0.22 V, improvement in luminance life and securing of heat resistance of 100 ° C. or higher are compatible.

  This is due to the adoption of the unique manufacturing method of the present embodiment described above. That is, in these examination examples 1-2, 2-2, and 7-2, as a tertiary amine compound constituting the hole transporting material, it has four triphenylamines in the molecule and a glass transition temperature of 100 ° C. or higher. Some compounds 1, 2, and 7 are used.

  Further, as the electron transporting material to be combined, compounds 8 and 10 having a difference in ionization potential from the hole transporting material of 0.35 eV or more and a glass transition temperature of 100 ° C. or more are used.

  And in these examination examples 1-2, 2-2, and 7-2, compared with examination examples 1-1, 2-1, and 7-1 having the same material configuration, the material heating temperature of the electron transporting material is 260. The temperature is increased from ℃ to 280 ℃.

  Thus, by raising the material heating temperature of the electron transporting material, the phenomenon shown in FIG. FIG. 13 is a diagram showing a fluorescence spectrum for each material heating temperature when Compound 8 (see FIG. 4), which is an electron transporting material, is formed on a glass substrate as a thin film (thickness of about 100 nm).

  The material heating temperature is 260 ° C. and 280 ° C. As shown in FIG. 13, when the material heating temperature is 260 ° C., the peak of the fluorescence spectrum of the thin film made of compound 8 appears at a position 20 nm or more from the rising value of the spectrum.

  On the other hand, when the material heating temperature is as high as 280 ° C., the shoulder SH of the fluorescence spectrum of the thin film made of the compound 8 appears at a position less than 20 nm from the rising value of the spectrum.

  It has been confirmed that the tendency shown in FIG. 13 is also observed when the electron transporting material is in the form of the light emitting layer 50, that is, in the form of an element. Further, as shown in FIG. 13, the peak may appear at a position less than 20 nm from the rising value instead of the shoulder.

  Thus, when forming the light emitting layer 50, the film-forming conditions of the electron transporting material such as the material heating temperature are controlled, and the fluorescence spectrum has a peak or shoulder in the fluorescence spectrum when the electron transporting material is a thin film. What is necessary is just to make it express in the position below 20 nm from the rise value of a spectrum.

  Thereby, the unique manufacturing method of the present embodiment is realized, and as shown in Examination Examples 1-2, 2-2, and 7-2, it is possible to achieve both improvement in luminance life and ensuring heat resistance of 100 ° C. or more. Can be planned.

  Thus, changing the fluorescence spectrum in the electron transporting material is considered to bring about the following effects.

  The electron transporting material of the light emitting layer 50 used in this study example is compounds 8 and 10 (see FIGS. 4 and 5), and these electron transporting materials have a structure including a polycyclic aromatic group. . The polycyclic aromatic group is planar, and in the solid state, as a result of the interaction of the planar portion between molecules, the fluorescence spectrum tends to shift to the longer wavelength side.

  This indicates that higher vibrational levels contribute in the state where electrons exist in the electron transporting material molecule. Due to the contribution of this vibration level, an effective energy gap with the hole transporting material is reduced, and holes are easily transferred from the hole transporting material to the electron transporting material in the light emitting layer.

  As a result, the electron transporting material is considered to be in an excited state, resulting in a decrease in luminance. Therefore, by shifting the fluorescence spectrum in the electron transporting material to the short wavelength side as described above, the contribution of the high vibration level is suppressed, and as a result, the electron transport from the hole transporting material in the light emitting layer is suppressed. It is considered that the transfer of holes to the functional material is suppressed. And it is considered that the luminance life can be improved.

  Incidentally, in Study Example 8-6, the compound 10 (see FIG. 5), which is an electron transporting material, was used to increase the material heating temperature from 350 ° C. to 380 ° C., and in the fluorescence spectrum of the thin film comprising the compound 10 The peak or shoulder of the fluorescence spectrum is expressed at a position less than 20 nm from the value at the rise of the spectrum.

  However, in Study Example 8-6, the difference in ionization potential between the compound 3 which is a hole transporting material and the compound 10 which is an electron transporting material is as small as 0.25 eV. That is, the requirements for electron transporting materials are not satisfied in the above-mentioned original manufacturing method. For this reason, even if the material heating temperature is increased as compared with Study Example 8-3, which is a combination of the same materials, the luminance life is hardly improved.

(Second Embodiment)
The second embodiment of the present invention will be described mainly with respect to differences from the first embodiment.

  The organic EL device of the present embodiment has the same configuration as that of the organic EL device shown in FIG. 1, that is, as shown in FIG. 1, between the pair of electrodes 20 and 80, the hole injection layer 30 and the hole transport. An organic EL device in which the layer 40, the light emitting layer 50, the electron transport layer 60, and the electron injection layer 70 are stacked and sandwiched can be obtained.

  Here, in the present embodiment, as the tertiary amine compound in the light emitting layer 50 obtained by mixing a hole transporting material composed of a tertiary amine compound, an electron transporting material, and a light emitting additive material, the molecular structure unique to the present embodiment. The thing which has is adopted.

  That is, in the light emitting layer 50 of the present embodiment, the electron transporting material has a glass transition temperature of 100 ° C. or higher, and the tertiary amine compound constituting the hole transporting material is represented by the following structural formula (3). It is a compound represented.

ここで、構造式（３）において、Ｒ１は下記構造式（４）もしくは下記構造式（５）で示される基である。

Here, in the structural formula (3), R1 is a group represented by the following structural formula (4) or the following structural formula (5).

これら構造式（４）、（５）中、ｌ、ｍ₁、ｍ₂、ｎ₁およびｎ₂は１以上の整数であり、ｘは１以上の整数であり、ｙは０または１以上の整数であり、Ｌ１およびＬ２はアセン化合物であり、Ｒ２、Ｒ３、Ｒ４、Ｒ５はアルキル基もしくはアリール基もしくは水素である。

In these structural formulas (4) and (5), l, m ₁ , m ₂ , n ₁ and n ₂ are integers of 1 or more, x is an integer of 1 or more, and y is 0 or an integer of 1 or more. L1 and L2 are acene compounds, and R2, R3, R4, and R5 are an alkyl group, an aryl group, or hydrogen.

  In addition, an acene compound has a molecular skeleton as shown in the following chemical formula 17, for example, and has a benzene ring bonded linearly.

この構造式（３）に示される３級アミン化合物は、サイクリックボルタンメトリー法により求められる酸化電位が複数存在するとともにこれら複数の酸化電位における第１酸化電位と第２酸化電位との電位差が０．２２Ｖ以上の値を有し、且つガラス転移温度が１００℃以上のものである。

The tertiary amine compound represented by the structural formula (3) has a plurality of oxidation potentials determined by cyclic voltammetry, and the potential difference between the first oxidation potential and the second oxidation potential at these oxidation potentials is 0. It has a value of 22 V or higher and a glass transition temperature of 100 ° C. or higher.

  The tertiary amine compound represented by the structural formula (3) has been found as a result of experimental studies by the present inventors. The background of the results of the study is as follows.

  In the said 1st Embodiment, the compound (refer said Chemical formula 10) shown by Structural formula (1) was used as a specific tertiary amine compound. In the tertiary amine compound represented by the structural formula (1), R1 having a benzene ring bonded on both sides is a saturated hydrocarbon.

  On the other hand, in the tertiary amine compound represented by the structural formula (3) used in this embodiment, R1 having a benzene ring bonded on both sides does not contain a saturated hydrocarbon.

  As described above, it is considered that when the triphenylamine is simply multimerized like the compound 7 (see FIG. 4), the conjugation is extended, and as a result, the first oxidation potential and the second oxidation potential are close to each other. Specifically, Compound 7 has a structure without R1 in Structural Formula (1) or Structural Formula (3).

  At this time, resonance is likely to occur between the two central benzene rings in the compound 7, and as a result, the oxidation potential difference is considered to be small.

  Here, by introducing a saturated hydrocarbon between the central benzene rings as in the tertiary amine compound of the structural formula (1) in the first embodiment, resonance between the two central benzene rings is achieved. Can be cut. As a result, it is considered that a relatively high oxidation potential difference can be obtained as compared with the case where there is no saturated hydrocarbon.

  Therefore, the present inventors can obtain the same result by introducing a compound comprising a benzene ring instead of a saturated hydrocarbon as a group introduced between the central benzene rings in order to cut the resonance. I thought.

  As a result of synthesizing and experimentally examining a tertiary amine compound in which a compound comprising a benzene ring is introduced between the central benzene rings, that is, a tertiary amine compound represented by the structural formula (3), the above structural formula (1) It was found that an oxidation potential difference equivalent to or rather large as shown in FIG. This is the reason why the tertiary amine compound represented by the structural formula (3) has been adopted in this embodiment.

  Here, as the tertiary amine compound represented by the structural formula (3), more specifically, a compound represented by the following structural formula (6) can be employed.

この構造式（６）で示される化合物は、Ｎ，Ｎ’−ビス（４−ジフェニルアミノビフェニル−４’−イル）−Ｎ，Ｎ’−ジフェニル−４，４’−ジアミノ−ｐ−ターフェニルであり、以下、上記化合物１〜１１からの連番として、化合物１２ということとする。

The compound represented by the structural formula (6) is N, N′-bis (4-diphenylaminobiphenyl-4′-yl) -N, N′-diphenyl-4,4′-diamino-p-terphenyl. In the following, the serial number from the above compounds 1 to 11 will be referred to as compound 12.

  In this compound 12, R1 in the structural formula (3) is one benzene ring, and three benzene rings are bonded in series at the center of the molecule. Including the case of this compound 12, in the structural formula (3), three or more benzene rings are bonded in series at the center of the molecule.

  In such a structure in which three or more benzene rings are connected in series, the twist between the benzene rings is larger than that in the case of two, and as a result, the above-described resonance is less likely to occur. It is done.

  As described above, in this embodiment, the tertiary amine compound represented by the structural formula (3) and the electron transporting material having a glass transition temperature of 100 ° C. or higher as used in the first embodiment (FIG. Compound 8 shown in FIG. 4, Compound 10 shown in FIG. 5, etc.) are used as the mixed host of the light emitting layer 50.

  According to this, since the glass transition temperature of the hole transport material and the electron transport material in the light emitting layer 50 is 100 ° C. or higher, heat resistance of 100 ° C. or higher can be ensured.

  Also in this embodiment, since the oxidation potential difference in the tertiary amine compound can have a value of 0.22 V or more, the movement of holes from the first oxidation potential to the second oxidation potential in the hole transport material. Therefore, it is considered that the movement of holes to the electron transporting material can be suppressed, and the deterioration of the electron transporting material can be suppressed, and the luminance life can be actually improved.

  Thus, according to the present embodiment, in the organic EL element in which the light emitting layer 50 formed by mixing the hole transporting material, the electron transporting material, and the light emitting additive material is sandwiched between the pair of electrodes 20 and 80. In addition, it is possible to achieve both improvement in luminance life and securing heat resistance of 100 ° C. or higher.

  In addition, since the tertiary amine compound represented by the structural formula (3) in this embodiment has an oxidation potential difference of 0.22 V or more, the oxidation potential difference is less than 0.22 V in the first embodiment. As in the case of Study Examples 1-2, 2-2, and 7-2 (see FIG. 8 above), it is not necessary to employ a unique manufacturing method in the manufacture of the organic EL element.

  That is, in this embodiment, by adopting a manufacturing method in a normal organic EL element, it is possible to achieve both improvement in luminance life and securing heat resistance of 100 ° C. or higher.

  In other words, “a tertiary amine compound constituting the hole transporting material having four triphenylamines in the molecule and having a glass transition temperature of 100 ° C. or higher is used as the electron transporting material. When the electron transporting material is a thin film using a material having a difference in ionization potential of 0.35 eV or more and a glass transition temperature of 100 ° C. or more, the peak of the fluorescence spectrum of the thin film When the light emitting layer is formed, the electron transporting material is formed so that the peak or shoulder of the fluorescence spectrum of the thin film appears at a position less than 20 nm from the rising value when the position is 20 nm or more from the value. The object of the present invention can be achieved without employing the manufacturing method of “controlling the conditions”.

  Moreover, in the light emitting layer 50 of this embodiment, when the mixed host which used the tertiary amine compound shown by the said Structural formula (3) as the hole transportable material is used, a brightness lifetime improves rather than the light emitting layer of a single host. At the same time, the luminous efficiency is not lowered. This is because the ionization potential of the tertiary amine compound represented by the structural formula (3) is 5.45 eV or more.

  Further, the tertiary amine compound represented by the structural formula (3) of the present embodiment has a symmetrical shape of the oxidation-side curve and the reduction-side curve of the oxidation-reduction curve measured by a cyclic voltammetry method. It is.

  Further, also in the light emitting layer 50 of the present embodiment, the difference in ionization potential between the electron transporting material and the hole transporting material is 0.35 eV or more in order to improve the luminance life as in the first embodiment. It is preferable that.

[Examination example]
Here, the configuration and the like of the light emitting layer 50 in the present embodiment will be described in more detail with reference to an examination example verified using a specific compound. Note that the present embodiment is not limited to these examination examples.

[Constituent material of the light emitting layer used in the study example]
The hole transporting material in the light emitting layer 50 used in this examination example is the one represented by the above structural formula (3), that is, the tertiary amine compound of Compound 12. The electron transporting material in the light emitting layer 50 is the compound 8 (see FIG. 4), and the light emitting additive material is the compound 9 (see FIG. 5) which is a styrylamine derivative that performs blue color development.

  Here, a synthesis method for the tertiary amine compound of Compound 12 will be described.

[Compound 12]
Compound 12: Synthesis of N, N′-bis (4-diphenylaminobiphenyl-4′-yl) -N, N′-diphenyl-4,4′-diamino-p-terphenyl.

  Acetanilide 20.3 g (0.15 mol), 4,4'-diiodobiphenyl 73.1 g (0.18 mol), anhydrous potassium carbonate 22.1 g (0.16 mol), copper powder 2.16 g (0. 034 mol) and 35 ml of nitrobenzene were mixed and reacted at 190 to 205 ° C. for 10 hours.

  The reaction product was extracted with 200 ml of toluene, and the insoluble matter was removed by filtration, followed by concentration to dryness. This was purified by column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate = 6/1), and 37.2 g (yield 60%) of N- (4′-iododiphenyl-4-yl) acetanilide was obtained. Obtained.

  Then, N- (4′-iododiphenyl-4-yl) acetanilide 13.2 g (0.032 mol), diphenylamine 6.60 g (0.039 mol), anhydrous potassium carbonate 5.53 g (0.040 mol) And 0.45 g (0.007 mol) of copper powder and 10 ml of nitrobenzene were mixed and reacted at 200-212 ° C. for 15 hours.

  The reaction product was extracted with 100 ml of toluene, insolubles were removed by filtration and then concentrated to an oily product. The oily substance was dissolved in 60 ml of isoamyl alcohol, added with 1 ml of water and 2.64 g (0.040 mol) of 85% potassium hydroxide, and hydrolyzed at 130 ° C. After isoamyl alcohol was distilled off by steam distillation, the product was extracted with 250 ml of toluene, washed with water, dried and concentrated.

  The concentrate was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), and 9.2 g of 4-diphenylamino-4′-phenylaminobiphenyl (yield: 70.0%) Got.

  Furthermore, 8.7 g (0.021 mol) of 4-diphenylamino-4′-phenylaminobiphenyl, 4.8 g (0.01 mol) of 4,4′-diiodo-p-terphenyl, 2.90 g of anhydrous potassium carbonate (0.021 mol), 0.32 g (0.005 mol) of copper powder, and 10 ml of nitrobenzene were mixed and reacted at 195 to 210 ° C. for 20 hours.

  The reaction product was extracted with 140 ml of toluene, insoluble matter was filtered off and concentrated, and 120 ml of n-hexane was added to take out crude crystals. The crude crystals were purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/2), and N, N′-bis (4-diphenylaminobiphenyl-4′-yl) -N, 4.7 g (yield; 45.0%) of N′-diphenyl-4,4′-diamino-p-terphenyl was obtained.

[Physical properties of the compounds used in the study examples]
The physical property values of the compounds 8, 12 excluding the compound 9, which is a light-emitting additive material, among the compounds 8, 9, 12 as described above will be described.

  First, regarding the glass transition temperature (Tg), the compound 12 is 151 ° C., the compound 8 is 175 ° C. as described above, and the glass transition temperature of the compounds 8 and 12 serving as the host of the light emitting layer 50 satisfies 100 ° C. or more. is doing.

  Regarding the ionization potential (Ip), the compound 12 satisfies 5.46 eV and 5.45 eV or more, and the compound 8 is 5.85 eV as described above. The ionization potential was measured using a photoelectron measuring device (AC-2) manufactured by Riken Keiki, as described above.

  The oxidation potential of the compound 12 was measured by a generally known cyclic voltammetry method, that is, a method in which a potential change was applied to a solution containing a tertiary amine compound that is a hole transporting material of the light emitting layer 50, as described above. . As a result, the oxidation potential difference (potential difference between the first oxidation potential and the second oxidation potential) of the compound 12 is 0.22, which satisfies the oxidation potential difference of 0.22 V or more.

  Further, when the oxidation-reduction curve was measured by the cyclic voltammetry method for the compound 12 which is a tertiary amine compound, the shape of the oxidation-side curve and the shape of the reduction-side curve of the oxidation-reduction curve are symmetrical. Met.

[Results of study on luminance life and heat resistance]
Next, using these compounds 8, 9, and 12, an organic EL element S1 was produced, and the luminance life, high-temperature storage stability (heat resistance), luminous efficiency, and the like were verified. The results are shown in the table of FIG.

  As in the first embodiment, specifically, FIG. 14 shows the following items for each example. The hole transport material, the electron transport material, the light emission additive material, and the material heating temperature, the luminance life, the high temperature storage, and the light emission efficiency of the electron transport material when the light emitting layer 50 is formed by vapor deposition. , Oxidation potential difference (unit: V), oxidation-reduction curve symmetry, Tg (unit: ° C), Ip (unit: eV).

Here, in the same manner as in the first embodiment, the luminance lifetime is determined by performing an endurance test on an element manufactured in each example with an initial luminance of 400 cd / m ² and a 1/64 duty drive in an environment of 85 ° C. Is the normalized luminance with the initial luminance normalized to 1 after 400 hours.

As in the first embodiment, the high temperature storage was conducted by examining the heat resistance of 100 ° C. or higher. “X” indicates that a dark spot was generated by a storage test at 100 ° C. “○”. The light emission efficiency is an initial light emission efficiency, that is, a value (unit: cd / A) when the initial luminance is 400 cd / m ² .

  In addition, the oxidation potential difference, the oxidation-reduction curve symmetry, Tg, and Ip are the oxidation potential difference of the hole transport material of each example and the oxidation side of the oxidation-reduction curve measured by the cyclic voltammetry method, respectively, as in the first embodiment. These are the symmetry between the shape of the curve and the shape of the curve on the reduction side, the glass transition temperature, and the ionization potential. Here, the symmetry of the redox curve symmetry is “◯”, and the asymmetric one is “x”.

  Next, a specific embodiment will be described for each example of study of the present embodiment shown in FIG.

(Examination Example 9-1)
An ITO film (transparent electrode) was formed as the anode 20 on the glass substrate 10, and the surface thereof was polished so that Ra was about 1 nm and Rz was about 10 nm.

  On the anode 20, a 10 nm hole injection layer 30 made of CuPc as an organic material having crystallinity was formed. On the hole injection layer 30, 20 nm of the compound 12 which is a tertiary amine compound was formed as the hole transport layer 40.

  In addition, as the light emitting layer 50, a compound 12 as a tertiary amine compound, a compound 8 as an electron transporting material (see FIG. 4), and a compound 9 as a light emitting additive material (see FIG. 5) are respectively 60: A 20 nm film was formed at a weight ratio of 20: 3. Here, the material heating temperature of the compound 8, which is an electron transporting material, was set to 260 ° C.

  Tris (8-quinolinolato) aluminum 20 nm was formed as the electron transport layer 60, LiF was formed on the electron injection layer 70, and Al was formed on the cathode 80, and sealed in a sealed can in a dry nitrogen atmosphere to obtain an organic EL device.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 9-2)
In the same element structure as in the above examination example 9-1, when the light emitting layer 50 was formed, the material heating temperature of the compound 8 which is an electron transporting material was set as high as 280 ° C. to form an element.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the time exceeded 500 hours.

  Next, based on the results shown in FIG. 14, feature points and the like in each study example of the present embodiment are summarized.

  As shown in FIG. 14, in Examination Examples 9-1 and 9-2, the tertiary amine compound and the electron transporting material as the hole transporting material have glass transition temperatures of 151 ° C. and 175 ° C., respectively, and The oxidation potential difference of the tertiary amine compound as the hole transporting material is 0.22V.

  That is, in these examination examples 9-1 and 9-2, the tertiary amine compound as the hole transporting material and the glass transition temperature of the electron transporting material are 100 ° C. or more, and the tertiary amine as the hole transporting material. It is satisfied that the oxidation potential difference of the compound is 0.22V or more. Thereby, in these examples, it is possible to achieve both improvement of the luminance life and securing heat resistance of 100 ° C. or more.

  Regarding the improvement of the luminance life in the examination examples 9-1 and 9-2 of the present embodiment, the examination example 1-1 using the hole transporting material having an oxidation potential difference of less than 0.22 V in the first embodiment. It is clear from the comparison with 8-1 etc.

  This is because the glass transition temperature of the hole transporting material and the electron transporting material in the light emitting layer 50 is 100 ° C. or higher and the relationship between the oxidation potential difference of 0.22 V or higher is used. This is considered to be because the movement of holes from the first oxidation potential to the second oxidation potential in the conductive material is suppressed, the movement of holes to the electron transport material is suppressed, and the deterioration of the electron transport material can be suppressed.

  In Study Examples 9-1 and 9-2, the light emitting layer 50 serving as a mixed host uses a tertiary amine compound having an ionization potential of 5.46 eV and an ionization potential of 5.45 eV or more. . Thereby, luminous efficiency can be ensured more reliably than in the past.

  This is apparent from a comparison with the study examples 4-1 and 5-1, in which the ionization potential of the tertiary amine compound of the light emitting layer 50 is less than 5.45 eV in the first embodiment.

  Further, in Examination Examples 9-1 and 9-2, since the redox curve symmetry of the tertiary amine compound is good, a long luminance life can be secured. This is clear from the comparison with Examination Examples 4-1 and 5-1 in which the redox curve symmetry of the tertiary amine compound is asymmetric in the first embodiment.

  In addition, the physical properties and characteristics are the same as compared with the two Examination Examples 9-1 and 9-2 of the present embodiment. In these examples, the use of the compound 12 allows the above-described effects to be achieved regardless of the production method. It has been realized.

  As described above, according to the present embodiment, in the light emitting layer 50 composed of the mixed host, the electron transporting material has a glass transition temperature of 100 ° C. or higher, and the tertiary amine constituting the hole transporting material. By making the compound a compound represented by the structural formula (3), it is possible to achieve both improvement in luminance life and securing heat resistance of 100 ° C. or higher.

(Third embodiment)
Further, in the light emitting layer 50 formed by mixing the hole transporting material, the electron transporting material, and the light emitting additive material, the mixing ratio is such that the mixing ratio of the hole transporting material is larger on the anode 20 side than on the cathode 80 side. It was confirmed that the luminance life could be improved when a plurality of layers having different thicknesses were laminated.

  In this case, mixed light emission such as white is also possible by selecting different light emitting additive materials (light emitting additive dyes) to be added to the plurality of layers for each of the plurality of layers.

  Further, in the case where the light emitting layer 50 has a structure in which a plurality of light emitting layers made of different light emitting additive dyes are stacked, a blue light emitting layer in which the light emitting additive dye emits blue light. It was also confirmed that the luminance life can be improved by arranging the blue light emitting layer on the cathode side and arranging the light emitting layer having longer wavelength light emission than blue light emission on the anode side.

[Examination example]
Hereinafter, the configuration and the like of the light emitting layer 50 in the present embodiment will be described in more detail with reference to examination examples verified using specific compounds. Note that the present embodiment is not limited to these examination examples.

  The hole transporting material in the light emitting layer 50 used in this examination example is the one represented by the above structural formula (3), that is, the tertiary amine compound of Compound 12. Further, the electron transporting material in the light emitting layer 50 is the compound 8 (see FIG. 4), and the light emitting additive material is the compound 9 (see FIG. 5) which is a styrylamine derivative that performs blue color development and the following chemical structure. Compound 13 represented by Formula 22, that is, rubrene.

次に、これら化合物８、９、１２、１３を用いて、有機ＥＬ素子Ｓ１を作製し、輝度寿命や高温保存性（耐熱性）、発光効率等について検証した。その結果は、図１５、図１６の表に示してある。

Next, using these compounds 8, 9, 12, and 13, an organic EL element S1 was produced, and the luminance life, high-temperature storage stability (heat resistance), luminous efficiency, and the like were verified. The results are shown in the tables of FIGS.

  Specifically, FIG. 15 and FIG. 16 show the following items for each example. The hole transport material, the electron transport material, the light emission additive material, and the material heating temperature, the luminance life, the high temperature storage, and the light emission efficiency of the electron transport material when the light emitting layer 50 is formed by vapor deposition. .

  15 and 16, for each example, the mixing ratio of the electron transporting material and the hole transporting material at the site on the anode 20 side in the light emitting layer 50, the electron transporting material and the hole transport at the site on the cathode 80 side. The mixing ratio with the functional material is shown.

Here, in the same manner as in the first embodiment, the luminance lifetime is determined by performing an endurance test on an element manufactured in each example with an initial luminance of 400 cd / m ² and a 1/64 duty drive in an environment of 85 ° C. Is the normalized luminance with the initial luminance normalized to 1 after 400 hours.

As in the first embodiment, the high temperature storage was conducted by examining the heat resistance of 100 ° C. or higher, and “x” indicates that a dark spot was generated by a storage test at 100 ° C., and no occurrence occurred. “○”. The light emission efficiency is an initial light emission efficiency, that is, a value (unit: cd / A) when the initial luminance is 400 cd / m ² .

  Next, a specific implementation will be described for each example of examination of this embodiment shown in FIGS. 15 and 16.

(Examination Example 10-1)
An ITO film (transparent electrode) was formed on the glass substrate 10 as the anode 20, and the surface thereof was polished to make Ra about 1 nm and Rz about 10 nm.

  On the anode 20, a 10 nm hole injection layer 30 made of CuPc as an organic material having crystallinity was formed. On the hole injection layer 30, 20 nm of the compound 12 which is a tertiary amine compound was formed as the hole transport layer 40.

  In addition, as the light emitting layer 50, a compound 12 as a tertiary amine compound, a compound 8 as an electron transporting material (see FIG. 4), and a compound 9 as a light emitting additive material (see FIG. 5) are respectively 60: A 20 nm film was formed at a weight ratio of 20: 3. Here, the material heating temperature of the compound 8, which is an electron transporting material, was set to 260 ° C.

  Tris (8-quinolinolato) aluminum 20 nm was formed as the electron transport layer 60, LiF was formed on the electron injection layer 70, and Al was formed on the cathode 80, and sealed in a sealed can in a dry nitrogen atmosphere to obtain an organic EL device.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 10-2)
An ITO film (transparent electrode) was formed on the glass substrate 10 as the anode 20, and the surface thereof was polished to make Ra about 1 nm and Rz about 10 nm.

  On the anode 20, a 10 nm hole injection layer 30 made of CuPc as an organic material having crystallinity was formed. On the hole injection layer 30, 20 nm of the compound 12 which is a tertiary amine compound was formed as the hole transport layer 40.

  In addition, as the light emitting layer 50, a compound 12 as a tertiary amine compound, a compound 8 as an electron transporting material (see FIG. 4), and a compound 9 as a light emitting additive material (see FIG. 5) are respectively 60: After forming 10 nm with a weight ratio of 30: 3, another 10 nm was formed with a weight ratio of 60: 15: 3. Here, the material heating temperature of the compound 8, which is an electron transporting material, was set to 260 ° C.

  Tris (8-quinolinolato) aluminum 20 nm was formed as the electron transport layer 60, LiF was formed on the electron injection layer 70, and Al was formed on the cathode 80, and sealed in a sealed can in a dry nitrogen atmosphere to obtain an organic EL device.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

  Further, in this Study Example 10-2, the mixing ratio is different in the light emitting layer so that the mixing ratio of the hole transporting material is larger on the anode 20 side than on the cathode 80 side in comparison with the above Study Example 10-1. A structure in which a plurality of layers are stacked is provided, whereby the luminance life is improved.

  Incidentally, a hole transporting material having four triphenylamines in the molecule as described in the present application generally has a high carrier density and a relatively high mobility. For this reason, the change in hole mobility from the hole transport layer 40 to the light emitting layer 50 is extremely large, and the holes are rapidly decelerated in this portion. At that time, it is considered that holes also move to the electron transporting material in the light emitting layer.

  For this reason, the probability of holes moving to the electron transporting material in the light-emitting layer is reduced and the luminance life is improved by making the mixing ratio of the hole transporting material stepwise and suppressing a sudden change in hole mobility. It is thought that.

(Examination Example 11-1)
An ITO film (transparent electrode) was formed on the glass substrate 10 as the anode 20, and the surface thereof was polished to make Ra about 1 nm and Rz about 10 nm.

  On the anode 20, a 10 nm hole injection layer 30 made of CuPc as an organic material having crystallinity was formed. On the hole injection layer 30, 20 nm of the compound 12 which is a tertiary amine compound was formed as the hole transport layer 40.

  In addition, as the light-emitting layer 50, a compound 12 that is a tertiary amine compound, a compound 8 that is an electron-transporting material (see FIG. 4), and a compound 13 that is a light-emitting additive material (see the above chemical formula 22) are each 60 After forming 10 nm by a weight ratio of 20: 3, a compound 12 as a tertiary amine compound, a compound 8 as an electron transporting material (see FIG. 4), and a compound 9 as a light emitting additive material (see FIG. 5) , 60: 20: 3, and a further 10 nm was formed. Here, the material heating temperature of the compound 8, which is an electron transporting material, was set to 260 ° C.

  Tris (8-quinolinolato) aluminum 20 nm was formed as the electron transport layer 60, LiF was formed on the electron injection layer 70, and Al was formed on the cathode 80, and sealed in a sealed can in a dry nitrogen atmosphere to obtain an organic EL device. This organic EL element exhibited white light emission by a mixed color of blue light emission and yellow light emission.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

(Examination Example 11-2)
An ITO film (transparent electrode) was formed on the glass substrate 10 as the anode 20, and the surface thereof was polished to make Ra about 1 nm and Rz about 10 nm.

  On the anode 20, a 10 nm hole injection layer 30 made of CuPc as an organic material having crystallinity was formed. On the hole injection layer 30, 20 nm of the compound 12 which is a tertiary amine compound was formed as the hole transport layer 40.

  In addition, as the light-emitting layer 50, a compound 12 that is a tertiary amine compound, a compound 8 that is an electron-transporting material (see FIG. 4), and a compound 13 that is a light-emitting additive material (see the above chemical formula 22) are each 60 After forming 10 nm by a weight ratio of 30: 3, a compound 12 as a tertiary amine compound, a compound 8 as an electron transporting material (see FIG. 4), and a compound 9 as a light emitting additive material (see FIG. 5) , 60: 15: 3, and a further 10 nm was formed. Here, the material heating temperature of the compound 8, which is an electron transporting material, was set to 260 ° C.

  Tris (8-quinolinolato) aluminum 20 nm was formed as the electron transport layer 60, LiF was formed on the electron injection layer 70, and Al was formed on the cathode 80, and sealed in a sealed can in a dry nitrogen atmosphere to obtain an organic EL device. This organic EL element exhibited white light emission by a mixed color of blue light emission and yellow light emission.

This device was subjected to an endurance test with an initial luminance of 400 cd / m ² and a 1/64 duty drive under an environment of 85 ° C. The result was as shown in FIG. Furthermore, in a storage test under an environment of 100 ° C., no significant dark spots were generated even when the duration exceeded 500 hours.

  From these examination examples 11-1 and 11-2, it was confirmed that the effects of the present embodiment were also exhibited in the structure in which the light emitting layers having different emission colors were laminated.

It is a schematic sectional drawing of the organic EL element which concerns on 1st Embodiment of this invention. It is a figure which shows the chemical structure of the compounds 1-3 used for the examination example of the said 1st Embodiment. It is a figure which shows the chemical structure of the compounds 4-6 used for the examination example of the said 1st Embodiment. It is a figure which shows the chemical structure of the compounds 7 and 8 used for the examination example of the said 1st Embodiment. It is a figure which shows the chemical structure of the compounds 9 and 10 used for the examination example of the said 1st Embodiment. It is a figure which shows the measurement result by the cyclic voltammetry method about the compound 3 shown in FIG. It is a figure which shows the measurement result by the cyclic voltammetry method about the compound 4 shown in FIG. It is a graph which shows the result of the examination example of the said 1st Embodiment. It is a graph which shows the result of the examination example of the said 1st Embodiment following FIG. It is a graph which shows the result of having investigated the improvement effect of the brightness lifetime at the time of using a light emitting layer as a mixed host compared with the case of a single host. It is a figure which shows the result of having investigated the cause of the dark spot. 2 is a diagram showing a chemical structure of Compound 11. FIG. It is a figure which shows the fluorescence spectrum for every material heating temperature when the compound 8 which is an electron transport material is formed as a thin film on a glass substrate. It is a graph which shows the result of the example of examination of 2nd Embodiment of this invention. It is a graph which shows the result of the example of examination of 3rd Embodiment of this invention. It is a graph which shows the result of the examination example of 3rd Embodiment of this invention following FIG. It is a figure which shows typically about the transport of the hole between the hole transportable material and electron transportable material in a mixed host.

Explanation of symbols

  20 ... anode, 50 ... light emitting layer, 80 ... cathode.

Claims (3)

Organics in an organic EL device having a light emitting layer (50) formed by mixing a hole transporting material composed of a tertiary amine compound, an electron transporting material, and a light emitting additive material between a pair of electrodes (20, 80). A material for an EL element,
The hole transport material is represented by the following structural formula (3).

(In Structural Formula (3), R 2, R 3, R 4 and R 5 may be the same or different and are a hydrogen atom, an alkyl group or an aryl group, and R 1 is a group represented by the following Structural Formula (4).)

(In structural formula (4), l is an integer of 1 or more.) In an organic EL element having a light emitting layer (50) formed by mixing a hole transporting material composed of a tertiary amine compound, an electron transporting material and a light emitting additive material between a pair of electrodes (20, 80),
The organic EL device, wherein the hole transporting material is composed of a tertiary amine compound represented by the following structural formula (3).

(In Structural Formula (3), R 2, R 3, R 4 and R 5 may be the same or different and are a hydrogen atom, an alkyl group or an aryl group, and R 1 is a group represented by the following Structural Formula (4).)

(In structural formula (4), l is an integer of 1 or more.) A tertiary amine compound represented by the following structural formula (3).

(In Structural Formula (3), R 2, R 3, R 4 and R 5 may be the same or different and are a hydrogen atom, an alkyl group or an aryl group, and R 1 is a group represented by the following Structural Formula (4).)

(In structural formula (4), l is an integer of 1 or more.)

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