JP2010006818A - Compound and organic electroluminescence element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound that gives an organic electroluminescence element having excellent heat resistance and a long life, and an organic thin film and the organic electroluminescence element using the compound. <P>SOLUTION: The compound represented by general formula (I'), the organic thin film made of the compound and the organic electroluminescence element in which at least one organic compound layer sandwiched between a pair of electrodes contains the compound are provided. In the formula, Ar<SP>1</SP>' indicates a 6-30C trivalent aromatic group; X<SP>1</SP>' and X<SP>2</SP>' each indicates an aryl group; D<SP>1</SP>indicates a 16-60C monovalent aromatic group having 4 or more carbon rings; D<SP>1</SP>, Ar<SP>1</SP>', X<SP>1</SP>' and X<SP>2</SP>' each may have or may not have a substituent, but D<SP>1</SP>does not include a group indicated by metadiphenylphenyl- or this group added with a substituent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a compound, an organic thin film using the same, and an organic electroluminescence device (hereinafter, electroluminescence is abbreviated as “EL”). More specifically, the present invention relates to a compound that has excellent heat resistance and provides a long-life organic EL device, an organic thin film that is excellent in heat resistance having a glass transition temperature of 90 ° C. or higher, and is composed of the compound. The present invention relates to an organic EL element having excellent heat resistance and a long lifetime contained in a hole injecting and transporting layer.

EL elements using electroluminescence are highly visible due to self-emission and are completely solid elements, so they have features such as excellent impact resistance, so they are attracting attention as light emitting elements in various display devices. Has been.
This EL element includes an inorganic EL element using an inorganic compound as a light emitting material and an organic EL element using an organic compound. Among these, the organic EL element can significantly reduce the applied voltage. Since it is easy to downsize, consumes little power, can emit surface light, and can easily emit light of three primary colors, its practical application research has been actively conducted as a next-generation light-emitting device.
The structure of this organic EL element is basically the structure of an anode / organic light emitting layer / cathode, which is appropriately provided with a hole injection / transport layer or an electron injection layer, such as an anode / hole injection / transport layer / organic light emission. Layers / cathodes and anodes / hole injection / transport layers / organic light emitting layers / electron injection layers / cathodes are known.

で表される化合物などが開示されている。しかしながら、これらの化合物は、発光効率が低く、かつ印加電圧が高い上、ガラス転移温度が約６０℃程度と低く、保存温度８５℃で素子の効率が低下したり、寿命が短くなるなど、耐熱性，寿命及び発光効率共に、必ずしも充分に満足しうるものではなかった。 For practical use of such an organic EL element, driving stability and storage stability under a high temperature environment such as outdoors or in a vehicle are required. When an organic EL element is used outdoors or in a vehicle-mounted device, generally high temperature storage stability at 75 ° C. is required. However, when the conventional organic EL device is stored at a high temperature of about 75 ° C., there is a problem that the emission color changes and the emission efficiency is lowered. For this reason, it was inevitable that the use of the organic EL element was limited.
Therefore, various attempts have been made so far to improve the thermal stability of the organic EL element, and for example, light emitting materials made of amine derivatives have been proposed (Patent Documents 1 and 2). Specifically, the formula

And the like are disclosed. However, these compounds have low luminous efficiency, high applied voltage, low glass transition temperature of about 60 ° C., low device efficiency at a storage temperature of 85 ° C., and short lifetime. The properties, lifetime, and luminous efficiency were not always satisfactory.

Japanese Patent No. 2712634 JP-A-6-240245

  An object of the present invention is to provide a compound that provides an organic EL device having excellent heat resistance and a long life under such circumstances, an organic thin film comprising the compound, and an organic EL device using the compound. It is.

  As a result of intensive studies to achieve the above object, the present inventors have found that the object can be achieved by a compound having a specific structure. The present invention has been completed based on such findings.

（式中、Ａｒ¹ は炭素数６〜３０の二価又は三価の芳香族基、Ｘ¹ 及びＸ² は、それぞれスチリル基，スチリルアリール基，ジアリールアミノ基又はジアリールアミノアリール基、ｎは０又は１を示す。Ｄ¹ はＸ¹ 及びＸ² のいずれかがスチリル基又はスチリルアリール基の場合、４環以上の炭素環を有する炭素数１６〜６０の一価の芳香族基を示し、その他の場合は５環以上の炭素環を有する炭素数２０〜６０の一価の芳香族基を示す。Ｄ¹ ，Ａｒ¹ ，Ｘ¹ 及びＸ² は、それぞれ置換基を有していてもよく、有さなくてもよい。） That is, the present invention
(1) General formula (I)

(In the formula, Ar ¹ is a divalent or trivalent aromatic group having 6 to 30 carbon atoms, X ¹ and X ² are a styryl group, a styrylaryl group, a diarylamino group or a diarylaminoaryl group, and n is 0. Or D ¹ represents a monovalent aromatic group having 16 to 60 carbon atoms having 4 or more carbocyclic rings when either X ¹ or X ² is a styryl group or a styryl aryl group; In the case of, it represents a monovalent aromatic group having 20 to 60 carbon atoms and having 5 or more carbocycles, D ¹ , Ar ¹ , X ¹ and X ² may each have a substituent, You do not have to have it.)

（式中、Ａｒ¹'は炭素数６〜３０の三価の芳香族基、Ｘ¹'及びＸ²'は、それぞれアリール基、スチリル基，スチリルアリール基，ジアリールアミノ基又はジアリールアミノアリール基を示す。Ｄ¹ はＸ¹'及びＸ²'のいずれかがアリール基、スチリル基又はスチリルアリール基の場合、４環以上の炭素環を有する炭素数１６〜６０の一価の芳香族基を示す。Ｄ¹ ，Ａｒ¹'，Ｘ¹'及びＸ²'は、それぞれ置換基を有していてもよく、有さなくてもよい。ただし、Ｄ¹ は

で示される基及びこれに置換基を付加した基を含まない。）
で表される化合物、
（２）上記化合物からなるガラス転移温度９０℃以上の有機薄膜、及び
（３）一層以上の有機化合物層を、陽極と陰極とで構成された一対の電極で挟持してなる有機ＥＬ素子において、有機化合物層の少なくとも一層が、上記化合物を含有することを特徴とする有機ＥＬ素子、
を提供するものである。 Or general formula (I ′)

(In the formula, Ar ¹ ′ is a trivalent aromatic group having 6 to 30 carbon atoms, and X ¹ ′ and X ² ′ are an aryl group, a styryl group, a styryl aryl group, a diarylamino group or a diarylaminoaryl group, respectively. D ¹ represents a monovalent aromatic group having 16 to 60 carbon atoms and having 4 or more carbocyclic rings when either X ¹ ′ or X ² ′ is an aryl group, a styryl group or a styryl aryl group. D ¹ , Ar ¹ ′, X ¹ ′ and X ² ′ may or may not have a substituent, provided that D ¹ is

And a group having a substituent added thereto are not included. )
A compound represented by
(2) In an organic EL device comprising an organic thin film composed of the above compound having a glass transition temperature of 90 ° C. or higher, and (3) one or more organic compound layers sandwiched between a pair of electrodes composed of an anode and a cathode, An organic EL device characterized in that at least one of the organic compound layers contains the above compound,
Is to provide.

The compound of the present invention is excellent in heat resistance (storage temperature 85 ° C. or more) and can provide a practical organic EL device having a long life.
An organic EL device using the compound of the present invention is excellent in heat resistance and has a long life, and thus is suitably used for, for example, a display of an information device or a backlight.

で表される構造を有するものである。
上記一般式（Ｉ）において、Ａｒ¹ は炭素数６〜３０の二価又は三価の芳香族基、Ｘ¹ 及びＸ² は、それぞれスチリル基，スチリルアリール基，ジアリールアミノ基又はジアリールアミノアリール基、ｎは０又は１を示す。Ｄ¹ はＸ¹ 及びＸ² のいずれかがスチリル基又はスチリルアリール基の場合、４環以上の炭素環を有する炭素数１６〜６０の一価の芳香族基を示し、その他の場合は５環以上の炭素環を有する炭素数２０〜６０の一価の芳香族基を示す。 The compounds of the present invention have the general formula (I)

It has the structure represented by these.
In the general formula (I), Ar ¹ is a divalent or trivalent aromatic group having 6 to 30 carbon atoms, and X ¹ and X ² are a styryl group, a styrylaryl group, a diarylamino group, or a diarylaminoaryl group, respectively. , N represents 0 or 1. D ¹ represents a monovalent aromatic group having 16 to 60 carbon atoms having 4 or more carbocyclic rings when either X ¹ or X ² is a styryl group or a styryl aryl group, and in other cases, 5 rings A monovalent aromatic group having 20 to 60 carbon atoms and having the above carbocycle is shown.

で表される構造を有するものである。
上記一般式（Ｉ）において、Ａｒ¹'は炭素数６〜３０の三価の芳香族基、Ｘ¹'及びＸ²'は、それぞれアリール基、スチリル基，スチリルアリール基，ジアリールアミノ基又はジアリールアミノアリール基を示す。Ｄ¹ はＸ¹'及びＸ²'のいずれかがアリール基、スチリル基又はスチリルアリール基の場合、４環以上の炭素環を有する炭素数１６〜６０の一価の芳香族基を示す。Ｄ¹ ，Ａｒ¹'，Ｘ¹'及びＸ²'は、それぞれ置換基を有していてもよく、有さなくてもよい。ただし、Ｄ¹ は

で示される基及びこれに置換基を付加した基を含まない。 In addition, the compound of the present invention has the general formula (I ′)

It has the structure represented by these.
In the general formula (I), Ar ¹ ′ is a trivalent aromatic group having 6 to 30 carbon atoms, and X ¹ ′ and X ² ′ are an aryl group, a styryl group, a styrylaryl group, a diarylamino group, or a diaryl, respectively. An aminoaryl group is shown. D ¹ represents a monovalent aromatic group having 16 to 60 carbon atoms and having 4 or more carbocyclic rings when either X ¹ ′ or X ² ′ is an aryl group, a styryl group or a styryl aryl group. D ¹ , Ar ¹ ′, X ¹ ′ and X ² ′ may or may not have a substituent. However, D ¹ is

And a group having a substituent added thereto are not included.

（ｍは１〜３の整数であり、置換基が導入されていても良い）のいずれかで示される一価の基、又はビフェニル，ターフェニル，クォーターフェニル，キンクフェニル，ナフタレン，アズレン，アセナフテン，アントラセン，フルオレン，ナフタセン，ピレン，トリフェニレン，クリセン，ピセン，ペリレン，フルオランテン，ペンタセン及びコロネンの中から選ばれた化合物の一価又は二価の残基を含むものが好ましく、さらに好ましくはナフタレン，アズレン，アセナフテン，アントラセン，フルオレン，ナフタセン，ピレン，トリフェニレン，クリセン，ピセン，ペリレン，フルオランテン，ペンタセン及びコロネンの中から選ばれた化合物の一価又は二価の残基とフェニレン、ビフェニレン及びターフェニレンの中から選ばれた一価又は二価の残基とを合わせ含むものである。 D ¹ is

(M is an integer of 1 to 3, and a substituent may be introduced), or a bivalent group, biphenyl, terphenyl, quarterphenyl, kinkphenyl, naphthalene, azulene, acenaphthene, Those containing a monovalent or divalent residue of a compound selected from anthracene, fluorene, naphthacene, pyrene, triphenylene, chrysene, picene, perylene, fluoranthene, pentacene, and coronene are preferable, and naphthalene, azulene, A monovalent or divalent residue selected from acenaphthene, anthracene, fluorene, naphthacene, pyrene, triphenylene, chrysene, picene, perylene, fluoranthene, pentacene and coronene, and phenylene, biphenylene and terphenylene Monovalent It is intended to include combination of the divalent residues.

Each of D ¹ , Ar ¹ , X ¹ , X ² , Ar ¹ ′, X ¹ ′ and X ² ′ may or may not have an appropriate substituent. Examples of suitable substituents include fluorine, chlorine, bromine, iodine halogen atoms, hydroxyl groups, cyano groups, nitro groups, trifluoromethyl groups, alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups,- NR ¹ R ² , —COOR ³ , —COR ⁴ , —SO ₂ R ⁵ , —CONR ⁶ R ⁷ , —SO ₂ NR ⁸ R ⁹ , an alkylenedioxy group, an alkylenedithio group, a substituted or unsubstituted styryl group, such as -CR ¹⁰ = CR ¹¹ R ¹² can be exemplified.
Here, as the alkyl group, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable. The alkyl group of the alkoxy group and the alkylthio group is the same as the above alkyl group.

The aryl group may be any of a carbocyclic aryl group and a heterocyclic aryl group. Examples thereof include a phenyl group, a naphthyl group, an anthryl group, an acenaphthenyl group, a fluorenyl group, a phenanthryl group, an indenyl group, and a pyrenyl group. Group, pyridyl group, pyrimidyl group, furyl group, pyranyl group, thienyl group, quinolyl group, benzofuryl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, quinoxalyl group, benzimidazolyl group, pyrazolyl group, dibenzofuryl Group, dibenzothienyl group and the like. These aryl groups may be introduced with appropriate substituents (halogen atom, hydroxyl group, cyano group, nitro group, alkyl group, aryl group, alkoxy group, amino group, etc.). Examples of the aryl group of the aryloxy group include the same aryl groups as those described above.
Further, R ¹ and R ² in -NR ¹ R ² are each a hydrogen atom, an alkyl group, an acyl group (acetyl group, benzoyl group), or an aryl group and may be the same with or different from each other, R ¹ and R ² may be bonded to each other, and together with the nitrogen atom to which they are bonded, a ring such as a piperidyl group or a morpholyl group may be formed. Moreover, you may form a ring with the carbon atom on an aryl group like a eurolidyl group. The alkyl group and aryl group of R ¹ and R ² are the same as the above-described alkyl group and aryl group.

R ³ , R ⁴ and R ⁵ in —COOR ³ , —COR ⁴ and —SO ₂ R ⁵ each represents an alkyl group or an aryl group, and this alkyl group and aryl group are the same as the above-described alkyl group and aryl group. It is.
R ⁶ and R ⁷ , and R ⁸ and R ⁹ in —CONR ⁶ R ⁷ and —SO ₂ NR ⁸ R ⁹ are the same as those described above for R ¹ and R ² except that they form a ring together with the carbon atom on the aryl group. It is the same.
Examples of the alkylenedioxy group include a methylenedioxy group, and examples of the alkylenedithio group include a methylenedithio group.
As the substituent of the styryl group, or description all of the substituents can be exemplified, further, R ^10, R ¹¹ and R ¹² in the -CR ¹⁰ = CR ¹¹ R ¹² are each a hydrogen atom or a substituent As this substituent, all the substituents described above can be exemplified.

Specific examples of the compound represented by the general formula (I), particularly D ¹ is selected from naphthalene, azulene, acenaphthene, anthracene, fluorene, naphthacene, pyrene, triphenylene, chrysene, picene, perylene, fluoranthene, pentacene and coronene. Specific examples including a monovalent or divalent residue of the selected compound and a monovalent or divalent residue selected from phenylene, biphenylene and terphenylene are shown below.
(1) Compound represented by general formula (Ia):

Indicating the type of X ¹ in the formula (I-a) represented by the compound E1~E10 in Table 1.

(2) Compound represented by general formula (Ib):

Table 2 shows the types of X ¹ in the compounds E11 to E20 represented by the general formula (Ib).

(3) Compound represented by general formula (Ic):

Table 3 shows types of X ¹ in the compounds E21 to E30 represented by the general formula (Ic).

(4) Compound represented by general formula (Id):

Table 4 shows types of X ¹ in the compounds E31 to E40 represented by the general formula (Id).

(5) Compound represented by general formula (Ie):

The general formula (I-e) type of X ¹ and X ² in the compound E41~E47 represented by shown in Table 5.

(6) Compound represented by general formula (If):

The general formula (I-f) type of X ¹ and X ² in the compound E48~E52 represented by shown in Table 6.

(7) Compound represented by general formula (Ig):

Table 7 shows the types of X ¹ and X ² in the compounds E53 to E57 represented by the general formula (Ig).

(8) Compound represented by general formula (Ih):

The general formula (I-h) types of X ¹ and X ² in the compound E58~E63 represented by shown in Table 8.

(9) Compound represented by general formula (Ii):

Table 9 shows the types of X ¹ and X ² in the compounds E64 to E67 represented by the general formula (Ii).

この一般式（Ｉ’−ａ）で表される化合物Ｅ６８〜Ｅ８６におけるＸ¹ 及びＸ² の種類を第１０表に示す。 Specific examples of the compound represented by formula (I ′) are shown below.
(10) Compound represented by general formula (I′-a):

Table 10 shows the types of X ¹ and X ² in the compounds E68 to E86 represented by the general formula (I′-a).

この一般式（Ｉ’−ｂ）で表される化合物Ｅ８７〜Ｅ１０５におけるＸ¹ 及びＸ² の種類を第１０表に示す。 (11) Compound represented by general formula (I′-b):

Table 10 shows the types of X ¹ and X ² in the compounds E87 to E105 represented by the general formula (I′-b).

この一般式（Ｉ’−ｃ）で表される化合物Ｅ１０６〜Ｅ１２４におけるＸ¹ 及びＸ² の種類を第１０表に示す。 (12) Compound represented by general formula (I′-c):

Table 10 shows the types of X ¹ and X ² in the compounds E106 to E124 represented by the general formula (I′-c).

この一般式（Ｉ’−ｄ）で表される化合物Ｅ１２５〜Ｅ１４３におけるＸ¹ 及びＸ² の種類を第１０表に示す。 (13) Compound represented by general formula (I′-d):

Table 10 shows the types of X ¹ and X ² in the compounds E125 to E143 represented by the general formula (I′-d).

この一般式（Ｉ’−ｅ）で表される化合物Ｅ１４４〜Ｅ１６２におけるＸ¹ 及びＸ² の種類を第１０表に示す。 (14) Compound represented by general formula (I′-e):

Table 10 shows the types of X ¹ and X ² in the compounds E144 to E162 represented by the general formula (I′-e).

この一般式（Ｉ’−ｆ）で表される化合物Ｅ１６３〜Ｅ１８１におけるＸ¹ 及びＸ² の種類を第１０表に示す。 (15) Compound represented by general formula (I′-f):

Table 10 shows the types of X ¹ and X ² in the compounds E163 to E181 represented by the general formula (I′-f).

Since the compound of the present invention represented by the general formula (I) or (I ′) has high fluorescence and can form an organic thin film having a glass transition temperature of 90 ° C. or higher, the luminous efficiency is good. In addition, an organic EL device having excellent heat resistance (storage temperature of 85 ° C. or higher) and a long life can be provided. In particular, D ¹ is selected from those having 5 or more carbon rings, more preferably selected from naphthalene, azulene, acenaphthene, anthracene, fluorene, naphthacene, pyrene, triphenylene, chrysene, picene, perylene, fluoranthene, pentacene and coronene. By using a compound containing a monovalent or divalent residue of a compound and a monovalent or divalent residue selected from phenylene, biphenylene and terphenylene, the above characteristics can be more effectively obtained. It can be demonstrated.
The organic thin film of the present invention has a glass transition temperature of 90 ° C. or higher comprising the compound represented by the general formula (I) or (I ′), and in particular, a light emitting layer and a hole injection layer of an organic EL device And as a hole transport layer.
This organic thin film can be formed by thinning the compound of the general formula (I) or (I ′) by a known method such as a vapor deposition method, a spin coating method, or a casting method.

Next, the organic EL element of the present invention will be described.
The organic EL device of the present invention is an organic EL device in which one or more organic compound layers are sandwiched between a pair of electrodes composed of an anode and a cathode. ) Or (I ′). In particular, an element in which the compound is contained in at least one organic compound layer selected from the light emitting layer, the hole injection layer, and the hole transport layer is preferable.
There are various configurations for the organic EL device using the compound of the present invention. Basically, a configuration in which a light emitting layer is sandwiched between a pair of electrodes (anode and cathode) is used as needed. Thus, a hole injection / transport layer or an electron injection layer may be interposed. Examples of the intervening method include mixing into a polymer and simultaneous vapor deposition. Specifically, (1) anode / light emitting layer / cathode, (2) anode / hole injection transport layer / light emitting layer / cathode, (3) anode / hole injection transport layer / light emitting layer / electron injection layer / cathode, (4) The structure of anode / light emitting layer / electron injection layer / cathode can be mentioned. The hole injecting and transporting layer and the electron injecting layer are not always necessary. However, the presence of these layers further improves the light emitting performance.

In addition, it is preferable that all of the elements having the above-described structure are supported by a substrate, and the substrate is not particularly limited, and is made of a conventionally used EL element, for example, glass, transparent plastic, quartz or the like. Things can be used.
As the anode in this EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and dielectric transparent materials such as CuI, ITO, SnO ₂ and ZnO. The anode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. When taking out light emission from this electrode, it is desirable to make the transmittance greater than 10%, and the sheet resistance as the electrode is preferably several hundred Ω / □ or less.
Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm.

On the other hand, as the cathode, those using an electrode material of a metal, an alloy, an electrically conductive compound and a mixture thereof having a small work function (4 eV or less) are used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, Al / Al ₂ O ₃ , indium, and the like. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as an electrode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 1 μm, preferably 50 to 200 nm. In this EL element, it is convenient that either one of the anode or the cathode is transparent or translucent, since the emitted light is transmitted, and thus the emission efficiency of emitted light is good.

The compound of the present invention represented by the general formula (I) or (I ′) can be used for the light emitting layer of the EL device having the above-described configuration. When the compound is used as the light emitting layer, it can be formed by thinning the compound of the general formula (I) or (I ′) by a known method such as vapor deposition, spin coating, or casting. However, a molecular deposited film is particularly preferable. Here, the molecular deposition film refers to a thin film formed by deposition from the gas phase state of the compound or a film formed by solidification from the solution state or liquid phase state of the compound. As shown, this molecular deposited film can be distinguished from a thin film (accumulated molecular film) formed by the LB method. In addition, as disclosed in JP-A-59-194393, the light emitting layer is prepared by dissolving a binder such as a resin and the compound in a solvent to obtain a solution, which is then spin-coated. It can be formed into a thin film by, for example.
There is no restriction | limiting in particular about the film thickness of the light emitting layer formed in this way, Although it can select suitably according to a condition, Usually, it selects in the range of 5 nm-5 micrometers.
The light emitting layer in this EL element has (1) an injection function capable of injecting holes from the anode or the hole injecting and transporting layer when an electric field is applied, and injecting electrons from the cathode or the electron injecting layer; 2) Transport function to move injected charges (electrons and holes) by the force of electric field, (3) Providing a field for recombination of electrons and holes inside the light emitting layer, and light emitting function to connect this to light emission Have.

Note that there may be a difference in the ease with which holes are injected and the ease with which electrons are injected, and the transport ability represented by the mobility of holes and electrons may be large or small. It is preferable to move the charge.
Since the compound represented by the general formula (I) or (I ′) used in the light emitting layer generally has an ionization energy of less than about 6.0 eV, if an appropriate anode metal or anode compound is selected, a relatively positive hole is obtained. Easy to inject. Further, since the electron affinity is greater than about 2.8 eV, if an appropriate cathode metal or cathode compound is selected, electrons can be injected relatively easily and the ability to transport electrons and holes is also excellent. Furthermore, since the fluorescence in the solid state is strong, the ability to convert the excited state formed at the time of recrystallization of electrons and holes of the compound, its aggregate or crystal into light is great.

An organic compound layer other than the light emitting layer, for example, a hole injection layer or a hole transport layer (these are collectively referred to as a hole injection transport layer) is represented by the general formula (I) or (I ′). When the compound of the present invention is used, the light emitting layer may not contain the compound represented by the general formula (I) or (I ′), and a conventionally known compound as a light emitting material, for example, many Compounds having good thin film forming properties such as fluorescent brighteners such as ring-condensed aromatic compounds, benzoxazole-based, benzothiazole-based, and benzimidazole-based compounds, metal chelated oxanoid compounds, and distyrylbenzene-based compounds can be used.
As described above, the structure of the EL device using the compound of the present invention has various modes, and the hole injecting and transporting layer in the EL device having the structure of (2) or (3) is composed of a hole transporting compound. This layer has a function of transmitting holes injected from the anode to the light emitting layer. By interposing this hole injection transport layer between the anode and the light emitting layer, a large number of positive electrodes can be obtained at a lower electric field. Holes are injected into the light emitting layer. In addition, electrons injected from the cathode or the electron injection layer into the light emitting layer are accumulated near the interface in the light emitting layer due to an electron barrier existing at the interface between the light emitting layer and the hole injecting and transporting layer. The EL element is improved in efficiency and has excellent light emitting performance.

The hole transfer compound used in the hole injecting and transporting layer is disposed between two electrodes to which an electric field is applied, and when holes are injected from the anode, the holes are appropriately transferred to the light emitting layer. A compound having a hole mobility of at least 10 ⁻⁶ cm ² / (V · sec) when an electric field of 10 ⁴ to 10 ⁶ V / cm is applied is preferable. Such a hole transport compound is not particularly limited as long as it has the above-mentioned preferable properties, and is conventionally used as a charge transport material for holes in photoconductive materials or EL element holes. Any known material used for the injecting and transporting layer can be selected and used.

  Examples of the charge transport material include compounds of the present invention represented by the general formula (I) or (I ′), triazole derivatives (described in US Pat. No. 3,112,197), oxadi Azole derivatives (described in US Pat. No. 3,189,447), imidazole derivatives (described in Japanese Patent Publication No. 37-16096), polyarylalkane derivatives (US Pat. No. 3,615, No. 402, No. 3,820,989, No. 3,542,54, No. 45-555, No. 51-10983, No. 51-93224, 55-17105, 56-4148, 55-108667, 55-156953, 56-36656, etc.), pyrazoline derivatives and pyrazolone derivatives (U.S. Pat. Nos. 3,180,729, 4,278,746, JP-A 55-88064, 55-88065, 49-105537, 55-51086 No. 56-80051, No. 56-88141, No. 57-45545, No. 54-112737, No. 55-74546, etc.), phenylenediamine derivatives (US patents) 3,615,044, JP-B 51-10105, 46-3712, 47-25336, JP-54-53435, 54-110536, 54 -119925), arylamine derivatives (US Pat. Nos. 3,567,450, 3,180,703, 3,240,597, 3) No. 4,658,520, No. 4,232,103, No. 4,175,961, No. 4,012,376, Japanese Examined Patent Publication No. 49-35702, No. 39-27577. , JP-A-55-144250, JP-A-56-119132, JP-A-56-22437, West German Patent No. 1,110,518, etc.), amino-substituted chalcone derivatives (US) Patent No. 3,526,501, etc.), oxazole derivatives (described in US Pat. No. 3,257,203), styryl anthracene derivatives (Japanese Patent Laid-Open No. 56-46234) ), Fluorenone derivatives (described in JP-A No. 54-110837, etc.), hydrazone derivatives (US Pat. No. 3,717,462 specification, JP-A No. 54-59143), 55-5 No. 2063, No. 55-52064, No. 55-46760, No. 55-85495, No. 57-11350, No. 57-148749, etc.), stilbel derivatives ( JP-A-61-210363, 61-228451, 61-14642, 61-72255, 62-47646, 62-36684, 62-10652 62-30255, 60-93445, 60-94462, 60-174749, 60-175052, etc.).

  These compounds can be used as hole transport compounds, but the following porphyrin compounds (described in JP-A-63-295695 etc.), aromatic tertiary amine compounds and styrylamine compounds (US) Japanese Patent No. 4,127,412, JP-A-53-27033, 54-58445, 54-149634, 54-64299, 55-79450, 55 -144250, 56-119132, 61-295558, 61-98353, 63-295695, etc.), especially the aromatic tertiary amine compounds are used. It is preferable.

  Representative examples of the porphyrin compound include porphyrin; 5,10,15,20-tetraphenyl-21H, 23H-porphyrin copper (II); 5,10,15,20-tetraphenyl-21H, 23H-porphyrin zinc ( II); 5,10,15,20-tetrakis (pentafluorophenyl) -21H, 23H-porphyrin; silicon phthalocyanine oxide; aluminum phthalocyanine chloride; phthalocyanine (metal free); dilithium phthalocyanine; copper tetramethylphthalocyanine; Examples thereof include chromium phthalocyanine; zinc phthalocyanine; lead phthalocyanine; titanium phthalocyanine oxide; magnesium phthalocyanine; copper octamethylphthalocyanine. As typical examples of the aromatic tertiary compound and the styrylamine compound, N, N, N ′, N′-tetraphenyl- (1,1′-biphenyl) -4,4′-diamine; N, N '-Bis (3-methylphenyl) -N, N'-diphenyl- [1,1'-biphenyl] -4,4'-diamine; 2,2-bis (4-di-p-tolylaminophenyl) propane 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl- (1,1′-biphenyl) -4,4′-diamine 1,1-bis (4-di-p-tolylaminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl); Phenylmethane; N, N ' Diphenyl-N, N′-di (4-methoxyphenyl)-(1,1′-biphenyl) -4,4′-diamine; N, N, N ′, N′-tetraphenyl-4,4′-diamino Diphenyl ether; 4,4′-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamine) -4 ′-[4 (di-p- Tolylamine) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbene; N-phenylcarbazole and the like.

などのニトロ置換フルオレノン誘導体、 The hole injecting and transporting layer in the EL device may be composed of one or more of these hole transporting compounds, or a hole injecting and transporting layer made of a compound different from the above layer. May be laminated.
On the other hand, the electron injecting layer (electron injecting and transporting layer) in the EL device having the configuration (3) is made of an electron transfer compound and has a function of transmitting electrons injected from the cathode to the light emitting layer. Yes. There is no restriction | limiting in particular about such an electron transfer compound, Arbitrary things can be selected and used from a conventionally well-known compound. Preferred examples of the electron transfer compound include

Nitro-substituted fluorenone derivatives, such as

などのチオピランジオキシド誘導体、

Thiopyran dioxide derivatives such as

などのジフェニルキノン誘導体〔「ポリマー・プレプリント（Polymer Preprints), ジャパン」第３７巻，第３号，第６８１ページ（１９８８年）などに記載のもの〕、あるいは

Diphenylquinone derivatives such as those described in “Polymer Preprints, Japan” Vol. 37, No. 3, page 681 (1988), or the like

などの化合物〔「ジャーナル・オブ・アプライド・フィジックス（J.Apply.Phys．）」第２７巻，第２６９頁（１９８８年）などに記載のもの〕や、アントラキノジメタン誘導体（特開昭５７−１４９２５９号公報，同５８−５５４５０号公報，同６１−２２５１５１号公報，同６１−２３３７５０号公報，同６３−１０４０６１号公報などに記載のもの）、フレオレニリデンメタン誘導体（特開昭６０−６９６５７号公報，同６１−１４３７６４号公報，同６１−１４８１５９号公報などに記載のもの）、アントロン誘導体（特開昭６１−２２５１５１号公報，同６１−２３３７５０号公報などに記載のもの）

Compounds described in “Journal of Applied Physics”, Vol. 27, p. 269 (1988), etc., and anthraquinodimethane derivatives (Japanese Patent Laid-Open No. 57). 149259, 58-55450, 61-225151, 61-233750, 63-104061, etc.), fluorenylidenemethane derivatives (JP-A-60- 69657, 61-143762, 61-148159, etc.), anthrone derivatives (as described in JP-A-61-225151, 61-233750, etc.)

（式中、Ａｒ² 〜Ａｒ⁴ 及びＡｒ⁶ はそれぞれ独立に置換又は無置換のアリール基を示し、Ａｒ⁵ は置換又は無置換のアリーレン基を示す。）
で表される電子伝達化合物が挙げられる。ここで、アリール基としてはフェニル基，ナフチル基，ビフェニル基，アントラニル基，ペリレニル基，ピレニル基等が挙げられ、アリーレン基としてはフェニレン基，ナフチレン基，ビフェニレン基，アントラセニレン基，ペリレニレン基，ピレニレン基等が挙げられる。また、置換基としては炭素数１〜１０のアルキル基，炭素数１〜１０のアルコキシ基又はシアノ基等が挙げられる。この一般式（II）又は（III)で表される化合物は、薄膜形成性のものが好ましい。 In addition, the following general formula (II) or (III)

(In the formula, Ar ^{2 to} Ar ⁴ and Ar ⁶ each independently represent a substituted or unsubstituted aryl group, and Ar ⁵ represents a substituted or unsubstituted arylene group.)
The electron transfer compound represented by these is mentioned. Here, examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, an anthranyl group, a perylenyl group, and a pyrenyl group. The arylene group includes a phenylene group, a naphthylene group, a biphenylene group, an anthracenylene group, a peryleneylene group, and a pyrenylene group. Etc. Moreover, as a substituent, a C1-C10 alkyl group, a C1-C10 alkoxy group, a cyano group, etc. are mentioned. The compound represented by the general formula (II) or (III) is preferably a thin film-forming compound.

などが挙げられる。 Specific examples of the compound represented by the general formula (II) or (III) include

Etc.

Oxadiazole derivatives disclosed in “Appl. Phys. Lett.” Vol. 55, page 1489 (1989) can also be mentioned.
The hole injecting and transporting layer and the electron injecting layer are layers having one of electrification injecting property, transporting property, and barrier property. In addition to the organic materials described above, crystallinity such as Si, SiC, CdS, etc. An inorganic material such as an amorphous material can also be used.
Hole injection / transport layers and electron injection layers using organic materials can be formed in the same manner as the light-emitting layer, and hole injection / transport layers and electron injection layers using inorganic materials can be formed by vacuum evaporation or sputtering. However, it is preferable to use either an organic or inorganic material by vacuum deposition for the same reason as in the case of the light emitting layer.

Next, an example of a suitable method for manufacturing the EL element of the present invention will be described for each element of each configuration. The production method of the above-mentioned EL element composed of anode / light emitting layer / cathode will be described. First, a desired electrode material, for example, a thin film composed of an anode material is formed on a suitable substrate in a range of 1 μm or less, preferably 10 to 200 nm. After forming an anode by a method such as vapor deposition or sputtering so that the film thickness becomes a thin film, a thin film made of a light emitting material is formed thereon, and a light emitting layer is provided. As a method for thinning the light emitting material, for example, there are a spin coating method, a casting method, a vapor deposition method, etc., but a vapor deposition method is preferable because a homogeneous film is easily obtained and pinholes are not easily generated. .
When this vapor deposition method is used for thinning the light emitting material, the vapor deposition conditions vary depending on the type of organic compound used in the light emitting layer to be used, the target crystal structure of the molecular deposited film, the association structure, etc. Desirably, the boat heating temperature is 50 to 400 ° C., the degree of vacuum is 10 ⁻⁵ to 10 ⁻³ Pa, the deposition rate is 0.01 to 50 nm / sec, the substrate temperature is −50 to + 300 ° C., and the film thickness is 5 nm to 5 μm. . Next, after the formation of the light emitting layer, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 50 to 200 nm. By providing this, a desired EL element can be obtained. In the production of this EL element, the production order can be reversed, and the cathode, the light emitting layer, and the anode can be produced in this order.

  In addition, as a manufacturing method in the case of an element composed of an anode / light emitting layer / cathode, a hole injecting and transporting material, a light emitting material, and an electron injecting material mixed between a pair of electrodes and sandwiched between electrodes to form a light emitting layer. For example, a thin film made of an anode material is formed on a suitable substrate, and a solution made of a binder such as a hole injection / transport material, a light emitting material, an electron injection material, or polyvinylcarbazole is applied, or There is one in which a thin film is formed from this solution by a dip coating method to form a light emitting layer, and a thin film made of a cathode material is formed thereon. Here, on the produced light emitting layer, the element material used as the material of a light emitting layer may be vacuum-deposited, and the thin film which consists of a substance for cathodes may be formed on it. Alternatively, a hole injecting and transporting material, an electron injecting material, and a light emitting material may be co-evaporated to form a light emitting layer, and a thin film made of a cathode material may be formed thereon.

Next, a method for producing an EL device comprising an anode / hole injection / transport layer / light emitting layer / cathode will be described. First, an anode is formed in the same manner as in the case of the EL device, and then a hole is formed thereon. A thin film made of a transfer compound is formed by spin coating or the like, and a hole injection transport layer is provided. The conditions at this time may conform to the conditions for forming the thin film of the light emitting material. Next, a desired EL element is obtained by sequentially providing a light emitting layer and a cathode on the hole injecting and transporting layer in the same manner as in the production of the EL element. Also in the production of this EL element, it is also possible to produce in the order of the cathode, the light emitting layer, the hole injection transport layer, and the anode by reversing the production order.
Further, a method for producing an EL device comprising an anode / hole injection / transport layer / light emitting layer / electron injection layer / cathode will be described. First, in the same manner as in the production of the EL device, the anode and hole injection / transport are performed. After sequentially providing a layer and a light emitting layer, a thin film made of an electron transfer compound is formed on the light emitting layer by a spin coat method or the like to provide an electron injection layer, and then a cathode is formed on the EL element. A desired EL element can be obtained by providing in the same manner as in the production.
Also in the production of this EL element, the production order may be reversed, and the anode, the electron injection layer, the light emitting layer, the hole injection transport layer, and the anode may be produced in this order.

When a direct current voltage is applied to the organic EL device of the present invention thus obtained, the light emission is transparent or translucent when a voltage of about 1 to 30 V is applied with the positive polarity of the anode and the negative polarity of the cathode. It can be observed from the electrode side. Further, even when a voltage is applied with the reverse polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.
Such an organic EL device of the present invention has good luminous efficiency, excellent heat resistance (storage temperature of 85 ° C. or higher) and a long life.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Example 1 Production of Compound E1 (1) Intermediate (1)
Under an argon stream, 100 ml of anhydrous tetrahydrofuran (THF) solution containing 79 g (0.5 mol) of bromobenzene was added to 14 g (0.58 mol) of magnesium, and refluxed for 1 hour to prepare a Grignard reagent.
140 g (0.5 mol) of 1-bromopyrene, 3 g (5 mmol) of Ni (dppp) Cl ₂ (where dppp means diphenylphosphinopropane) are dissolved in 200 ml of anhydrous THF, and the Grignard reagent prepared above is dissolved. The solution was added dropwise at room temperature and refluxed for 3 hours. Water was added to the reaction product and extracted with dichloromethane, and the solvent was distilled off to obtain a yellow solid. This was purified by column chromatography (silica gel, hexane / dichloromethane) to obtain 42 g (yield 30%) of an intermediate (1) having the following structure as a pale yellow solid.

(2) Intermediate (2)
11.2 g (40 mmol) of the intermediate (1) obtained in the above (1) was suspended in 300 ml of dry dimethylformamide (DMF), and 8 g (45 mmol / mm) of N-bromosuccinimide (NBS) / DMF was suspended therein. 50 ml) was added and stirred at room temperature for 3 hours and allowed to stand overnight. Water was added to the reaction product, and the resulting solid was filtered off, washed with methanol, and then recrystallized with 100 ml of toluene to give 6.5 g of an intermediate (2) of the following structure of yellow needle crystals (yield 45%) Got.

(3) Intermediate (3)
Diphenylamine 51.2 g (0.3 mol), 1,4-dibromobenzene 71.4 g (0.3 mol), potassium tertiary butoxide (tBuOK) 34.6 g (0.36 mol), PdCl ₂ (PPh ₃ ) ₂ 4.2 g (5.9 mmol) and 1.2 liters of xylene were mixed and stirred at 130 ° C. overnight.
After completion of the reaction, the organic layer was concentrated to obtain about 100 g of brown crystals. After purification by column chromatography (silica gel, hexane / toluene), 28 g (yield 29%) of the target intermediate (3) having the following structure was obtained.

(4) Compound E1
Under an argon stream, 0.14 g (5.6 mmol) of magnesium was added with 5 ml of anhydrous THF containing 1.8 g (5 mmol) of the above intermediate (2) and refluxed for 1 hour to prepare a Grignard reagent. 1.62 g (5 mmol) of the intermediate (3) and 0.03 g (0.05 mmol) of Ni (dppp) Cl ₂ were dissolved in 20 mL of anhydrous THF, and the Grignard reagent prepared above was added dropwise at room temperature. Reflux for hours. Water was added to the reaction product and extracted with dichloromethane, and the solvent was distilled off to obtain a yellow solid. This was purified by column chromatography (silica gel, hexane / dichloromethane) to obtain 0.56 g (yield 25%) of yellow solid E1.
As a result of measuring a field desorption mass spectrum (FD-MS), 521 peaks were obtained with respect to C ₄₀ H ₂₇ N = 521, and thus E1 having the following structure was identified.

Example 2 Production of Compound E11 (1) Intermediate (4)
Under an argon stream, a solution of anhydrous THF in 100 ml containing 79 g (0.5 mol) of bromobenzene in 14 g (0.58 mmol) of magnesium was added and refluxed for 1 hour to prepare a Grignard reagent. 84 g (0.25 mol) of 9,10-dibromoanthracene and 3 g (5 mmol) of Ni (dppp) Cl ₂ were dissolved in 20 ml of anhydrous THF, and the previously prepared Grignard reagent was added dropwise at room temperature and refluxed for 3 hours. Water was added to the reaction product and extracted with dichloromethane, and the solvent was distilled off to obtain a yellow solid. This was purified by column chromatography (silica gel, hexane / dichloromethane) to obtain 12 g (yield 15%) of an intermediate (4) having the following structure as a yellow solid.

(2) Intermediate (5)
51.2 g (0.3 mol) of diphenylamine, 93.6 g (0.3 mol) of 4,4-dibromobenzene, 34.6 g (0.36 mol) of tBuOK, 4.2 g of PdCl ₂ (PPh ₃ ) ₂ 9 mmol) and 1.2 liters of xylene were mixed and stirred at 130 ° C. overnight.
After completion of the reaction, the organic layer was concentrated to obtain brown crystals. After purification by column chromatography (silica gel, hexane / toluene), 30 g (yield 25%) of the target intermediate (5) having the following structure was obtained.

(3) Compound E11
Under an argon stream, 0.14 g (5.8 mmol) of magnesium was added with 5 ml of anhydrous THF containing 1.7 g (0.5 mmol) of intermediate (4) and refluxed for 1 hour to prepare a Grignard reagent. The above intermediate (5) (2.0 g, 5 mmol) and Ni (dppp) Cl ₂ (0.03 g, 0.05 mmol) were dissolved in anhydrous THF (20 ml), and the previously prepared Grignard reagent was added dropwise at room temperature. Reflux for hours. Water was added to the reaction product and extracted with dichloromethane, and the solvent was distilled off to obtain a yellow solid. This was purified by column chromatography (silica gel hexane / dichloromethane) to obtain 0.58 g (yield 20%) of yellow solid E11.
As a result of measuring FD-MS, 573 peaks were obtained with respect to C ₄₄ H ₃₁ N = 573, and thus E11 having the following structure was identified.

Example 3 Production of Compound E61 (1) Intermediate (6)
Under an argon stream, a solution of 50 ml of anhydrous THF containing 16.7 g (50 mmol) of the intermediate (4) of Example 2 (1) was added to 1.4 g (58 mmol) of magnesium and refluxed for 1 hour to prepare a Grignard reagent. . 7.8 g (25 mmol) of 4,4′-dibromobiphenyl and 0.3 g (0.5 mmol) of Ni (dppp) Cl ₂ were dissolved in 50 mL of anhydrous THF, and the previously prepared Grignard reagent was added dropwise at room temperature. Refluxed for 3 hours. Water was added to the reaction product and extracted with dichloromethane, and the solvent was distilled off to obtain a yellow solid. This was purified by column chromatography (silica gel, hexane / dichloromethane) to obtain 62.4 g (yield 20%) of an intermediate having the following structure as a yellow solid.

(2) Intermediate (7)
Under an argon stream, a solution of 100 g of anhydrous THF containing 24 g (50 mmol) of the above intermediate (6) in 1.4 g (58 mmol) of magnesium was added and refluxed for 1 hour to prepare a Grignard reagent. 3.7 g (50 mmol) of N, N-dimethylformamide was dissolved in 50 ml of anhydrous THF, and the Grignard reagent prepared previously was added dropwise at 0 ° C. and refluxed at room temperature for 1 hour. The reaction mixture was poured into 100 ml of 3N hydrogen chloride water. After extraction with diethyl ether, the solvent was distilled off to obtain a yellow solid. This was purified by column chromatography (silica gel, hexane / ethyl acetate) to obtain 15.2 g (yield 70%) of an intermediate (7) having the following structure as a yellow solid.

(3) Intermediate (8)
200 g (0.8 mol) of α-bromodiphenylmethane and 200 g (1.2 mol) of triethyl phosphite were charged and heated to 100 ° C. The temperature gradually increased due to spontaneous heat generation, and bromoethylene began to distill. The mixture was heated at 140 ° C. for 3 hours. The low boiling point substance was distilled off from the reaction product with a vacuum pump to obtain 270 g of the target intermediate (8) having the following structure (purity by gel permeation chromatography method: 86%).

(4) Compound E61
Under an argon stream, 4.3 g (10 mmol) of the intermediate (7) and 3.0 g (10 mmol) of the intermediate (8) were dissolved in 50 ml of dimethyl sulfoxide (DMSO), and 1.1 g of tBuOK ( 10 mmol) and stirred at room temperature for 18 hours. Water was added to the reaction product and extracted with dichloromethane, and the solvent was distilled off to obtain a yellow solid. This was purified by column chromatography (silica gel, hexane / dichloromethane) to obtain 2.9 g (yield 50%) of yellow solid E61.
As a result of measuring FD-MS, 584 peaks were obtained with respect to C ₄₆ H ₃₂ N = 584, and thus E61 having the following structure was identified.

Example 4 Production of Organic EL Element A glass substrate having an ITO (indium tin oxide) anode formed thereon was prepared. This was subjected to a cleaning treatment using both ultraviolet rays and ozone, and then a compound E1 was deposited on the ITO anode to a thickness of 80 nm to form a light emitting layer. Next, an Al—Li alloy (Li 3 atomic%) was heated to form a cathode with a thickness of 50 nm on the light emitting layer, thereby producing an organic EL device. Note that a vacuum deposition method was used for forming the compound E1 and the Al—Li alloy.
When a DC voltage of 6 V was applied to the organic EL device thus obtained using an ITO anode as a positive electrode and an Al—Li alloy cathode as a negative electrode, a current of 10 mA / cm ² flowed and a luminance of 240 cd / m ² was obtained. Obtained.
Next, after sealing this element with a glass cap and storing it at 80 ° C. for 500 hours, when a DC voltage was applied in the same manner as described above, the decrease in luminance was only 15%.

Examples 5 to 20 and Comparative Examples 1 to 3 Production of Organic EL Device In Example 4, the same operation as in Example 4 was performed except that the compound shown in Table 11 was used instead of compound E1. The results are shown in Table 11.
In addition, the compounds C1, C2, and C3 used in Comparative Examples 1 to 3 have the following structures.

From Table 10, it can be seen that the device of the comparative example using the compounds C1 to C3 (prior art) is not practical because the brightness is drastically decreased in the storage test at 80 ° C.
On the other hand, it can be seen that the device of the example using the compound of the present invention has a small decrease in luminance in a storage test at 80 ° C. and is practical.
It has been found by DSC that the glass transition temperatures of compounds C1 to C3 are less than 80 ° C. On the other hand, since the compound of the present invention has a glass transition temperature higher than 80 ° C. by 10 ° C. or more, the high-temperature storage stability is good.

Example 21
A glass substrate having an ITO anode formed thereon was prepared. This was subjected to a cleaning treatment using both ultraviolet rays and ozone, and then a compound E67 was deposited on the ITO anode to a thickness of 80 nm to form a light emitting layer. Further, Alq (Al 8-hydroxyquinoline coordination complex) was deposited to a thickness of 10 nm as a compound for the electron transport layer. Thereafter, LiF was vapor-deposited as an electron injection layer to a thickness of 0.5 nm, and then aluminum was vapor-deposited as a cathode to a thickness of 100 nm to produce an organic EL device.
When a direct current voltage of 8.3 V was applied to the device using an ITO anode as a positive electrode and an Al cathode as a negative electrode, a luminance of 500 cd / m ² was obtained. Further, when the half-life was determined at an initial voltage of 8.3 V, it was 2100 hours.

Examples 22, 23 and Comparative Examples 4-6
In Example 21, the same operation as in Example 21 was carried out except that the compound shown in Table 12 was used instead of compound E67. The results are shown in Table 12.

第１２表から、化合物Ｃ１〜Ｃ３を用いた比較例の素子に比べ、本発明の化合物を用いた実施例の素子は長寿命であることが分かる。

From Table 12, it can be seen that the device of the example using the compound of the present invention has a longer life compared to the device of the comparative example using the compounds C1 to C3.

Example 24 Preparation of Compound E87 (1) 9-Bromo-10-phenylanthracene 9-Phenylanthracene (15 g, 59 mmol) was suspended in carbon tetrachloride (400 mL) and bromine (3 mL, 59 mL) at room temperature. Mmol) of carbon tetrachloride (50 milliliters) was added dropwise and refluxed for 6 hours. The reaction mixture was allowed to cool, and the resulting solid was filtered off and recrystallized from toluene to give white plate crystals (14 g) of 9-bromo-10-phenylanthracene (same structure as intermediate (4) of Example 2). 73%).
(2) Compound E87
Under an argon atmosphere, magnesium (0.26 g, 11 mmol) was suspended in anhydrous THF (10 ml) and activated by adding a small amount of 1,2-dibromoethane. While the reaction mixture was refluxed, 3,5-diphenylbromobenzene (2.8 g, 9 mmol) in anhydrous THF (10 ml) was gradually added dropwise and refluxed for 2 hours to prepare a Grignard reagent. In a separate flask, 9-bromo-10-phenylanthracene (3 g, 9 mmol) and bis (triphenylphosphine) palladium dichloride (0.13 g, 0.2 mmol, 2% Pd) were added in anhydrous THF under an argon atmosphere. (50 milliliters), diisobutylaluminum hydride / toluene solution (1 mole / liter, 0.2 milliliter, 0.2 millimol) was added, and then Grignard reagent was added dropwise, refluxed for 6 hours and left overnight. . The reaction mixture was diluted with methanol, and the resulting solid was filtered off and recrystallized from toluene to give a white solid (3.9 g, 89%).
Elemental analysis value; C, 94.50; H, 5.42%, calculated value as C ₃₈ H ₂₆ ; C, 94.57; H, 5.43%
FD-MS; measured value m / z = 482 (M ⁺ , 1OO); calculated value as C ₃₈ H ₂₆ = 482
From the above, it was identified as E87 having the following structure.

Example 25 Preparation of compound E88 In Example 24, except that 3,5-di (1-naphthyl) bromobenzene (3.7 g, 9 mmol) was used instead of 3,5-diphenylbromobenzene, the same procedure was followed. To give a white solid (4.0 g, 76%).
Elemental analysis value: C, 94.40; H, 5.22%, calculated value as C ₄₆ H ₃₀ ; C, 94.81; H, 5.19%
FD-MS; measured value m / z = 582 (M ⁺ , 1OO); calculated value as C ₄₆ H ₃₀ = 582
From this, it was identified as E88 having the following structure.

Example 26 Preparation of Compound E92 Magnesium (0.46 g, 19 mmol, 1.1 eq) was suspended in anhydrous THF (20 mL) under an argon atmosphere and activated by adding a small amount of 1,2-dibromoethane. . While refluxing the reaction mixture, anhydrous THF (20 ml) of bromophenylanthracene (5.3 g, 16 mmol, 5 eq) was gradually added dropwise and refluxed for 2 hours to prepare a Grignard reagent. In a separate flask, the above tribromobenzene (1 g, 3.2 mmol) and bis (triphenylphosphine) palladium dichloride (0.13 g, 0.2 mmol, 2% Pd) were added in anhydrous THF (50 mL) under an argon atmosphere. ), And a diisobutylaluminum hydride / toluene solution (1 mol / liter, 0.2 milliliter, 0.2 millimol) was added, and then the Grignard reagent was added dropwise, refluxed for 6 hours, and left overnight. The reaction mixture was diluted with methanol, and the resulting solid was filtered off and recrystallized from toluene to give a white solid (1.7 g, 65%).
Elemental analysis value; C, 94.88; H, 5.01%, calculated value as C ₆₆ H ₄₂ ; C, 94.93; H, 5.07%
FD-MS; measured value m / z = 834 (M ⁺ , 1OO); calculated value as C ₆₆ H ₄₂ = 834
From the above, it was identified as E92 having the following structure.

Example 27 Preparation of Compound E95 Magnesium (0.26 g, 11 mmol) was suspended in anhydrous THF (10 ml) under an argon atmosphere and activated by adding a small amount of 1,2-dibromoethane. While refluxing the reaction mixture, 3,5-bis (3-phenylphenyl) bromobenzene (4.1 g, 9 mmol) in anhydrous THF (20 ml) was gradually added dropwise and refluxed for 2 hours to give a Grignard reagent. Prepared. In a separate flask, under argon, 9-bromo-10-phenylanthracene (3 g, 9 mmol) prepared in Example 24 and bis (triphenylphosphine) palladium dichloride (0.13 g, 0.2 mmol, 2% Pd) is dissolved in anhydrous THF (50 ml), diisobutylaluminum hydride / toluene solution (1 mol / liter, 0.2 ml, 0.2 mmol) is added, and then Grignard reagent is added dropwise and refluxed for 6 hours. Left overnight. The reaction mixture was diluted with methanol, and the resulting solid was filtered off and recrystallized from toluene to give a white solid (4.4 g, 77%).
Elemental analysis value; C, 94.71; H, 5.02%, calculated value as C ₅₀ H ₃₄ ; C, 94.60; H, 5.40%
FD-MS; measured value m / z = 634 (M ⁺ , 1OO); calculated value as C ₅₀ H ₃₄ = 634
From the above, it was identified as E95 having the following structure.

Example 28 Preparation of Compound E97 In Example 27, instead of 3,5-bis (3-phenylphenyl) bromobenzene, 3,5-bis (4-phenylphenyl) bromobenzene (4.1 g, 9 A white solid (4.6 g, 81%) was obtained in the same manner except that mmol) was used.
Elemental analysis; C, 94.52; H, 5.39 %, calculated for _{C 50 H 34; C, 94.60} ; H, 5.40%
FD-MS; measured value m / z = 634 (M ⁺ , 1OO); calculated value as C ₅₀ H ₃₄ = 634
From the above, it was identified as E97 having the following structure.

Example 29 Production of Organic EL Element A glass substrate with ITO transparent electrode having a thickness of 25 mm × 75 mm × 1.1 mm (manufactured by Geomatic) was ultrasonically cleaned in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. I asked a question. A glass substrate with a transparent electrode line after washing is mounted on a substrate holder of a vacuum deposition apparatus, and N, N with a film thickness of 60 nm is first formed on the surface where the transparent electrode line is formed so as to cover the transparent electrode. A '-bis (N, N'-diphenyl-4-aminophenyl) -N, N-diphenyl-4,4'-diamino-1,1'-biphenyl film (TPD232 film) was formed. This TPD232 film functions as a first hole injection layer (hole transport layer). Next, a 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl film (NPD film) having a thickness of 20 nm was formed on the TPD232 film. This NPD film functions as a second hole injection layer (hole transport layer). Further, the compound (E85) having a thickness of 40 nm was deposited on the NPD film to form a film. This film functions as a light emitting layer. On this film, a tris (8-quinolinol) aluminum film (Alq film) having a thickness of 20 nm was formed. This Alq film functions as an electron injection layer. Thereafter, Li (Li: manufactured by Saesgetter) and Alq were binary evaporated to form an Alq: Li film as an electron injection layer (cathode). Metal Al was vapor-deposited on this Alq: Li film to form a metal cathode to form an organic EL device.
The performance was evaluated about the obtained organic EL element. When a direct current voltage of 6 V was applied with the ITO anode as the positive electrode and the Al cathode as the negative electrode, blue light emission with a luminance of 120 cd / m ² , a maximum light emission luminance of 23000 cd / m ² and a light emission efficiency of 2.4 cd / A was obtained. Further, the spectrum was in the vicinity of a peak wavelength of 450 nm, and the color purity was excellent.
Next, after sealing this element with a glass cap and storing it at 80 ° C. for 500 hours, when a DC voltage was applied in the same manner as described above, the decrease in luminance was only 3%. These results are shown in Table 13.

Examples 30 to 37 Production of Organic EL Element In Example 29, an organic EL element was produced in the same manner except that the compound shown in Table 13 was used as the light emitting material instead of the compound (E85). Performance was evaluated. The results are shown in Table 13.

第１３表から、本発明の化合物を用いた有機ＥＬ素子は、発光輝度、発光効率に優れた青色発光し、８０℃の保存試験において、輝度の低下が小さく、実用的であることが分かる。

From Table 13, it can be seen that the organic EL device using the compound of the present invention emits blue light with excellent light emission luminance and light emission efficiency, and is practical with little decrease in luminance in a storage test at 80 ° C.

Claims (7)

A compound represented by formula (I ′).

(In the formula, Ar ¹ ′ represents a trivalent aromatic group having 6 to 30 carbon atoms, X ¹ ′ and X ² ′ each represents an aryl group. D ¹ represents 16 carbon atoms having four or more carbocyclic rings. Represents a monovalent aromatic group of ˜60, D ¹ , Ar ¹ ′, X ¹ ′ and X ² ′ may or may not have a substituent, provided that D ¹ Is

And a group having a substituent added thereto are not included. ) D ¹ is

The compound according to claim 1, wherein the compound is a monovalent group represented by any one of (m is an integer of 1 to 3, and a substituent may be introduced). D ¹ is a compound selected from biphenyl, terphenyl, quarterphenyl, kinkphenyl, naphthalene, azulene, acenaphthene, anthracene, fluorene, naphthacene, pyrene, triphenylene, chrysene, picene, perylene, fluoranthene, pentacene and coronene. The compound according to claim 1 or 2, comprising a monovalent or divalent residue. An organic thin film having a glass transition temperature of 90 ° C. or higher, comprising the compound according to claim 1. The organic electroluminescent element formed by sandwiching one or more organic compound layers between a pair of electrodes composed of an anode and a cathode, wherein at least one of the organic compound layers is a compound according to any one of claims 1 to 3. An organic electroluminescence device comprising: The organic electroluminescence device according to claim 5, wherein at least one of the organic compound layers is a light emitting layer. 6. The organic electroluminescence device according to claim 5, wherein at least one of the organic compound layers is a hole injection layer or a hole transport layer.