JP5040216B2 - Organic compound, charge transport material, material for organic electroluminescence device, charge transport material composition, and organic electroluminescence device - Google Patents

Description

  The present invention relates to a novel organic compound, a charge transport material, and a material for an organic electroluminescent device. Specifically, the organic compound has a high triplet excitation energy level and is stable even when subjected to repeated electrical oxidation and reduction. The present invention relates to a charge transport material, an organic electroluminescent device material, and a charge transport material composition containing the organic compound. The present invention also relates to a high-efficiency and long-life organic electroluminescence device using this organic compound.

  An electroluminescent device using an organic thin film has been developed. An electroluminescent element using an organic thin film, that is, an organic electroluminescent element, usually has an organic layer including an anode, a cathode, and at least a light emitting layer provided between both electrodes on a substrate. As the organic layer, in addition to the light emitting layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like are used. Usually, these layers are laminated to be used as an organic electroluminescent element. Conventionally, organic electroluminescent devices have used fluorescent light emission, but in an attempt to increase the light emission efficiency of the device, it has been studied to use phosphorescent light emission instead of fluorescent light. However, even if phosphorescence is used, sufficient luminous efficiency has not been obtained yet.

The layer of the organic electroluminescent element contains a charge transport material. JP-A-2004-244400 proposes the following materials as materials having a high T1 level and positive and negative charge transportability.

As a result of arranging the phenylene group in a propeller type, these materials realize high luminous efficiency when used as a material for an organic electroluminescent element exhibiting blue phosphorescence.
However, the above materials have problems of electrochemical or photochemical degradation (such as intramolecular cyclization), and have problems in practicality.
JP 2004-244400 A

  The present invention relates to an organic compound and a charge transport material having a high triplet excitation energy level and excellent electrochemical durability, a charge transport material composition comprising the organic compound, and a high brightness using the organic compound It is an object of the present invention to provide an organic electroluminescence device having high efficiency and long life.

  As a result of intensive studies by the present inventors, an organic compound having the following specific structure has a high triplet excitation energy level, and is an organic compound that is stable even after repeated electrical oxidation and reduction. It has been found that by using an organic compound, a highly efficient and long-life device can be obtained in an organic electroluminescent device, particularly a phosphorescent organic electroluminescent device.

The present invention has been achieved on the basis of such findings, and the gist of the present invention is characterized by having one or more partial structures represented by the following general formula (I) or (II) in one molecule. And an organic compound (claims 1 and 2 ).

  Another gist of the present invention is to contain a charge transport material (Claim 5) and a material for an organic electroluminescent element (Claim 6), which are composed of the organic compound, and the organic compound and a solvent. A charge transport material composition characterized in that (Claim 7).

  Still another subject matter of the present invention is an organic electroluminescence device having an anode, a cathode, and a light emitting layer provided between the two electrodes on a substrate, wherein the organic electroluminescent device has a layer containing this organic compound. The present invention resides in an electroluminescent element (claim 9).

（一般式（Ｉ）中、Ｒ ^１３ 、Ｒ ^２３ 、及びＲ ^３３ は、各々独立して炭素数１〜３０のアルキル基、炭素数１〜３０のアルコキシ基、炭素数６〜３０のアリールオキシ基、フェニル基、或いは、ベンゼン環を２〜８個連結してなる１価の基を表す。）

（一般式（II）中、Ｒ ^１３ 、Ｒ ^２３ 、及びＲ ^３３ は、各々独立して炭素数１〜３０のアルキル基、炭素数１〜３０のアルコキシ基、炭素数６〜３０のアリールオキシ基、フェニル基、或いは、ベンゼン環を２〜８個連結してなる１価の基を表す。）

(In general formula (I), R < ^13> , R < ^23> , and R ^<33> are respectively independently a C1-C30 alkyl group, a C1-C30 alkoxy group, and a C6-C30 aryloxy group. , A phenyl group, or a monovalent group formed by connecting 2 to 8 benzene rings .

(In general formula (II), R < ^13> , R < ^23> , and R ^<33> are respectively independently a C1-C30 alkyl group, a C1-C30 alkoxy group, and a C6-C30 aryloxy group. , A phenyl group or a monovalent group formed by connecting 2 to 8 benzene rings.)

The organic compound of the present invention has a high triplet excitation energy level and is stable even when it is repeatedly subjected to electrical oxidation and reduction.
Therefore, according to the charge transport material and organic electroluminescent device material comprising the organic compound, the charge transport material composition containing the organic compound, and the organic electroluminescent device using the organic compound, high brightness, high efficiency and A long-life organic electroluminescent device is provided.

  Therefore, an organic electroluminescent device using the organic compound of the present invention is a light source (for example, a flat panel display (for example, for OA computers or wall-mounted televisions), an in-vehicle display device, a mobile phone display, or a surface light emitter (for example, It can be applied to light sources for copying machines, backlight sources for liquid crystal displays and instruments), display panels, and marker lamps, and its technical value is great.

  In addition, the charge transport material comprising the organic compound of the present invention and the charge transport material composition containing this charge transport material have essentially excellent electrochemical durability, and thus are not limited to organic electroluminescent devices, but other It can also be used effectively for electrophotographic photoreceptors and the like.

  Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. It is not specified in the contents.

[Organic compounds]
The organic compound of the present invention has one or more partial structures represented by the following general formula (I) (hereinafter sometimes referred to as “partial structure (I)”) in one molecule.

（一般式（Ｉ）中、Ｒ^１２〜Ｒ^１４、Ｒ^２１〜Ｒ^２５、Ｒ^３１〜Ｒ^３５、Ｒ^４１〜Ｒ^４５及びＲ^５１〜Ｒ^５５は、各々独立して水素原子或いは任意の置換基を表す。ただし、Ｒ^１２〜Ｒ^５５は、それぞれ隣接するＲ^１２〜Ｒ^５５と結合して環を形成していても良く、該環は置換基を有していても良い。）

(In the general formula (I), R ^{12 to} R ¹⁴ , R ^{21 to} R ²⁵ , R ^{31 to} R ³⁵ , R ^{41 to} R ⁴⁵ and R ^{51 to} R ⁵⁵ are each independently a hydrogen atom or an arbitrary substituent. However, R ^{12 to} R ⁵⁵ may be bonded to adjacent R ^{12 to} R ⁵⁵ to form a ring, and the ring may have a substituent.)

[1] Structural features As shown in the general formula (I), the organic compound of the present invention is formed on one benzene ring (the benzene ring having R ^{12 to} R ¹⁴ in the general formula (I)). , A disubstituted amino group and two phenyl groups (in general formula (I), a phenyl group having R ^{41 to} R ⁴⁵ and a phenyl group having R ^{51 to} R ⁵⁵ ) are adjacent to each other at the substitution position (ortho position). A compound having a linked structure. For this reason, a phenomenon in which a disubstituted amino group, which is a charge transporting group, interacts within a molecule or between molecules to form a more stable excitation energy level, that is, a substantial triplet excitation level is low. In addition, the possibility of degradation due to intramolecular cyclization can be eliminated, so that high-efficiency and long-life devices are provided for organic electroluminescent devices, especially phosphorescent organic electroluminescent devices. It is speculated that it can be done.

[2] R ^{12 to} R ¹⁴ , R ^{21 to} R ²⁵ , R ^{31 to} R ³⁵ , R ^{41 to} R ⁴⁵ , R ^{51 to} R ⁵⁵
In the general formula (I), R ^{12 to} R ¹⁴ , R ^{21 to} R ²⁵ , R ^{31 to} R ³⁵ , R ^{41 to} R ⁴⁵ , and R ^{51 to} R ⁵⁵ each independently represent a hydrogen atom or an arbitrary substituent. To express.
Specific examples of the optional substituent are preferably an alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, and an alkyl group having 1 to 30 carbon atoms. Alkoxy group, aryloxy group having 6 to 30 carbon atoms, heteroaryloxy group having 5 to 30 carbon atoms, alkylthio group having 1 to 30 carbon atoms, arylthio group having 6 to 30 carbon atoms, heteroarylthio group having 5 to 30 carbon atoms , An alkoxycarbonyl group having 1 to 30 carbon atoms, an aryloxycarbonyl group having 6 to 30 carbon atoms, a heteroaryloxycarbonyl group having 5 to 30 carbon atoms, a halogen atom, an arylamino group having 6 to 30 carbon atoms, and a member having 5 to 30 carbon atoms Heteroarylamino group, an alkylamino group having 1 to 30 carbon atoms, and an aromatic heterocyclic group having 5 to 30 members, more preferably an alkyl having 1 to 30 carbon atoms. , An alkoxy group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms and an aromatic heterocyclic group of membered 5-30.

From the viewpoint of a high triplet excited level and a viewpoint of avoiding a decrease in electrical resistance due to a bias of charge distribution, more preferably unsubstituted or an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, carbon 6 to 30 monocyclic rings such as aryloxy groups, benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, and fluoranthene rings Or a monovalent group derived from 2 to 5 condensed rings, or a monovalent group formed by linking a plurality of them (for example, a biphenyl group, a terphenyl group, etc.). Particularly preferably, when the durability against benzene is emphasized, a monovalent group derived from a benzene ring (phenyl group) or a monovalent group formed by linking 2 to 8 benzene rings (for example, A biphenyl group, a terphenyl group).
On the other hand, when high triplet excitation levels are emphasized, an unsubstituted or alkoxy group having 1 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms are particularly preferable.

  The above substituents may further have an arbitrary number of substituents at arbitrary positions. The substituent is preferably an alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or 6 carbon atoms. 30 to 30 aryloxy groups, 5 to 30 heteroaryloxy groups, 1 to 30 carbon alkylthio groups, 6 to 30 arylthio groups, 5 to 30 heteroarylthio groups, 1 to 30 carbon atoms Alkoxycarbonyl group, aryloxycarbonyl group having 6 to 30 carbon atoms, heteroaryloxycarbonyl group having 5 to 30 carbon atoms, halogen atom, alkoxy group having 1 to 30 carbon atoms, arylamino group having 6 to 30 carbon atoms, number of members Examples thereof include 5-30 heteroarylamino groups, alkylamino groups having 1-30 carbon atoms, and aromatic heterocyclic groups having 5-30 members, more preferably 1-1 carbon atoms. An alkyl group having 0, an alkoxy group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 5 to 30 members, more preferably an alkyl having 1 to 30 carbon atoms. A monovalent group (for example, a biphenyl group, a terphenyl group, etc.) formed by connecting 1 to 8 benzene rings, a substituent, a group, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, or An arylamino group (such as a diphenylamino group), or an N-carbazolyl group which may have a substituent. Examples of the substituent for the arylamino group and N-carbazolyl group include an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and an aryl group having 6 to 30 carbon atoms.

R ^{21 to} R ¹⁴ , R ^{21 to} R ²⁵ , R ^{31 to} R ³⁵ , R ^{41 to} R ⁴⁵ , and R ^{51 to} R ⁵⁵ may be bonded to each other and have a substituent. A good ring may be formed. Here, “adjacent” does not necessarily refer to a substituent substituted on an adjacent carbon atom on the same benzene ring, but refers to a state in which they can be bonded to each other in terms of molecular structure. In the case where this ring further has a substituent, examples of the substituent include those exemplified as the substituent that R ^{12 to} R ^{14 and the} like may further have.

In particular, it is preferable that the general formula (I) is represented by the following general formula (II) by combining R ²⁵ and R ³¹ to form a ring.

（一般式（II）中、Ｒ^１２〜Ｒ^１４、Ｒ^２１〜Ｒ^２４、Ｒ^３２〜Ｒ^３５、Ｒ^４１〜Ｒ^４５及びＲ^５１〜Ｒ^５５は、一般式（Ｉ）におけると同義である。）

(In the general formula ^{(II), R 12 ~R 14} , R 21 ~R 24, R 32 ~R 35, R 41 ~R 45 and ^R 51 ^{to R 55} are the same meaning as in formula (I). )

In addition, it is preferable that R ¹³ is an arbitrary substituent because durability against electrical redox is improved. When R ¹³ is a substituent, it is preferably an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, a phenyl group, or 2 benzene rings. -8 monovalent groups formed by linking (for example, biphenyl group, terphenyl group, etc.), more preferably an aromatic group, most preferably a phenyl group or a phenoxy group.

Further, it is preferable that R ²³ and / or R ³³ is an arbitrary substituent because durability against electrical oxidation is improved. When R ²³ and R ³³ are substituents, they are preferably formed by linking 1 to 8 alkyl groups having 1 to 30 carbon atoms, alkoxy groups having 1 to 30 carbon atoms, phenyl groups, or benzene rings. It is a monovalent group (for example, biphenyl group, terphenyl group, etc.), more preferably an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group, and most preferably a phenyl group or a phenoxy group.

The total molecular weight of R ^{12 to} R ¹⁴ , R ^{21 to} R ²⁵ , R ^{31 to} R ³⁵ , R ^{41 to} R ⁴⁵ and R ^{51 to} R ⁵⁵ is preferably 2000 or less, more preferably 1000 or less. If this upper limit is exceeded, it may be difficult to remove the impurity components, the vaporization temperature will rise, making it difficult to form a film by the vapor deposition method, or the solubility may be reduced, and the film formation by the wet method may be hindered. Yes, not preferred.

[3] Molecular Weight of Partial Structure (I) The molecular weight of the partial structure (I) is preferably 3000 or less, and more preferably 1500 or less. If the molecular weight of the partial structure (I) exceeds this upper limit, it becomes difficult to remove the impurity component, the vaporization temperature rises, making it difficult to form a film by the vapor deposition method, or the solubility is lowered and the wet method is used. There is a risk that film formation may be hindered.

[4] Number of Partial Structures (I) in One Molecule The organic compound of the present invention may have one or more partial structures (I) in one molecule, and the number is not particularly limited. The number of partial structures (I) in one molecule is preferably in the range of 1 to 10, more preferably in the range of 1 to 3, and particularly preferably 1 or 2. When the number of the partial structures (I) exceeds this upper limit, it becomes difficult to remove the impurity components, the vaporization temperature rises, making it difficult to form a film by the vapor deposition method, or the solubility is lowered and the wet method is used. There is a risk that film formation may be hindered. In addition, when it has two or more partial structures (I) in 1 molecule, these partial structures may share a part. If it shows concretely, the compound of the formula (I-3) shown by the below-mentioned Example (synthesis example) has two partial structures (I).

  The compound of the present invention is particularly a compound having a structure represented by the general formula (I) (that is, consisting of only a partial structure of the general formula (I)) or only two structures represented by the general formula (I). It is preferable that it is a compound which consists of. Specifically, the former includes compounds of formula (I-1) and formula (I-2) shown in Examples (synthesis examples) described later, and the latter includes formula (I-3) and formula (I-3). The compound of (I-4) is mentioned.

[5] Molecular Weight of Organic Compound The molecular weight of the organic compound of the present invention is preferably 5000 or less, and more preferably 3000 or less. If the molecular weight of the organic compound exceeds this upper limit, it will be difficult to remove the impurity components, the vaporization temperature will rise, making it difficult to form a film by the vapor deposition method, or the solubility will be reduced to form a film by a wet method. There is a risk of trouble, which is not preferable. Further, the molecular weight of the organic compound is preferably 300 or more, and more preferably 500 or more. If the molecular weight of the organic compound is below this lower limit, the heat resistance is lowered, the practicality is limited, the vaporization temperature is lowered and the film formation by the vapor deposition method becomes difficult, the film quality in the film formation by the wet method There is a risk that it may be hindered by a decrease, etc., which is not preferable.

[6] Examples of organic compounds Specific examples of organic compounds of the present invention are shown below, but the present invention is not limited thereto. In the following examples, Me: methyl group, n-Bu: n-butyl group, Ph: phenyl group, n-Octyl: n-octyl group, n-Desyl: n-decyl group, t-Bu: t- It is a butyl group.

[7] Synthesis method (raw material, catalyst, solvent, temperature, pressure, molar ratio, isolation method, purification method)
The organic compound of the present invention can be synthesized by a combination of known methods.
As a synthetic raw material, the following can be used, for example.

などの置換ホウ素原子、−ＭｇＸ基、−ＺｎＸ基、−ＳｎＸ_２基などのハロゲン化金属元素、又は塩素、臭素、ヨウ素などのハロゲン原子を表す。Ｒはメチル基、ｔｅｒｔ−ブチル基、ｉｓｏ−プロピル基、シクロヘキシル基などのアルキル基、或いはフェニル基、メシチル基などのアリール基である。
−ＯＴｓは−ＯＳＯ_２ＣＦ_３、−ＯＳＯ_２Ｃ_６Ｈ_４ＣＦ_３又は−ＯＳＯ_２Ｃ_６Ｈ_４ＣＨ_３を表す。 Specific examples of the synthesis method are shown below.
Of course, if the intermediate is generally available, the pre-synthesis step can be omitted.
In the following reaction formula, Ar represents an arbitrary monovalent aromatic ring group which may have a substituent.
Ar ₂ N— may be an N-carbazolyl group.
X represents chlorine, bromine, halogen atom or -OSO ₂ CF _3, such as _{iodine, -OSO 2 C 6 H 4 CH} 3, and _{-OSO 2 C 6 H 4 CF 3} .
Y represents -B (OH) ₂ , -B (OR) ₂ ,

Represents a substituted boron atom such as, a metal halide element such as —MgX group, —ZnX group, and —SnX ₂ group, or a halogen atom such as chlorine, bromine, and iodine. R is an alkyl group such as a methyl group, a tert-butyl group, an iso-propyl group, or a cyclohexyl group, or an aryl group such as a phenyl group or a mesityl group.
-OTs represents _{-OSO 2 CF 3, -OSO 2 C} 6 H 4 CF 3 or _{-OSO 2 C 6 H 4 CH 3} .

<Example 1>

  In the method of Example 1, aniline is converted into dichloromethane, N, N-dimethylformamide, chlorobenzene, toluene in the presence of an excess amount of chlorine, bromine, iodine, N-bromosuccinimide, N-chlorosuccinimide and the like in an inert gas atmosphere. In a solvent such as diethyl ether, halogenation is carried out by mixing for about 1 to 24 hours under a temperature condition of about -20 to + 80 ° C. to obtain the target product example 1.

  Then, under an inert gas atmosphere, the target product example 1 is converted to aryl boronic acid, aryl boronic acid ester, aryl tin chloride, aryl zinc chloride, aryl magnesium bromide, aryl magnesium iodide, etc. (1.0 to 3 with respect to X). 0.0 equivalents) and a zero-valent palladium catalyst such as tetrakis (triphenylphosphine) palladium (0.0001 to 0.2 equivalents relative to X), tert-butoxy sodium, tert-butoxy potassium, cesium carbonate, Bases such as sodium carbonate, potassium carbonate, tripotassium phosphate, triethylamine, potassium hydroxide, sodium hydroxide (2 to 10 equivalents relative to X), water, methanol, ethanol, normal hexanol, ethylene glycol, ethylene glycol mono Ethyl et Solvents such as tellurium, diethyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, N, N-dimethylformamide, cyclohexane, cyclohexanone, ethyl benzoate, ethyl acetate And about 0.01 to 100 liters / mole) and the like, and the mixture is stirred for about 1 to 60 hours under the temperature condition of −40 to 150 ° C. to obtain the target product example 2.

  As another method for obtaining the target product example 2, it can be synthesized using a known coupling reaction. As a known coupling method, specifically, “Palladium in Heterocyclic Chemistry: A guide for the Synthetic Chemist” (2nd edition, 2002, Jie Jack Li and Gordon W. Gribble, Pergamon), “Transition metal is "Organic synthesis to open up its various reaction modes and latest results" (1997, Kenjiro, Kagaku Dojinsha), "Under Borhard Shore Modern Organic Chemistry" (2004, KPCVollhardt, Kagaku Dojinsha)) The cited ring-to-ring (coupling) reaction, such as a coupling reaction between an aryl halide and an aryl borate, can be used.

  The target product example 3 can be obtained from the target product example 2 by the following methods (1) to (3).

(1) 2 to 100 equivalents of an aryl halide (Ar-X, preferably X = Br, I) and target product example 2 with respect to target product example 2 are combined with copper powder, copper wire, copper halide (CuX). (X = Cl, Br, I)), copper catalysts such as copper oxide (CuO) (about 0.1 to 5 equivalents relative to X), potassium carbonate, calcium carbonate, potassium phosphate, cesium carbonate, tert- In the presence of a basic substance such as butoxy sodium (about 1 to 100 equivalents relative to the halogen atom), in an inert gas stream, no solvent, or an aromatic solvent such as nitrobenzene, an alcohol solvent such as tetraglyme or polyethylene glycol ( Usually, a method of stirring and mixing in a temperature range of 20 to 300 ° C. in 0.1 to 100 liters per 1 mol of the target product example 2 for 1 to 60 hours.

(2) The target product example 2 is converted into a bivalent palladium catalyst such as Pd ₂ (dba) ₃ (Pd = palladium, dba = dibenzylideneacetone), Pd (dba) ₂ , palladium acetate, and BINAP (= 2, 2 ′ -Bis (diphenylphosphino-1,1'-binaphthyl)), tri (tert-butyl) phosphine, triphenylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) ) Zero-valent palladium complexes such as propane, 1,3-bis (diphenylphosphino) butane, dppf (= 1,1′-bis (diphenylphosphino) ferrocene), or PdCl ₂ (dppf ) Catalysts such as palladium chloride complexes such as ₂ (about 0.001-1 equivalent to X), ter Tetrahydrofuran, dioxane, dimethoxyethane, N, N-dimethyl in the presence of a basic substance (usually 2 to 100 equivalents relative to X) such as potassium t-butoxy, sodium tert-butoxy, potassium carbonate, cesium carbonate, triethylamine. Stir in a solvent such as formamide, dimethyl sulfoxide, xylene, toluene, triethylamine, pyridine, etc. (usually 0.1 to 100 liters per 1 mole of the target compound 2) at 0 to 200 ° C. for 1 to 60 hours. how to.

(3) 2 to 100 equivalents of aryl boronic acid or aryl boronic acid ester with respect to the target product example 2 and the target product example 2 are mixed with a monovalent copper catalyst such as CuCl, CuBr, or CuI (usually, target product example) 2 to 0.001 to 5 equivalents), and in the presence of oxygen, a solvent such as methanol, ethanol, normal butanol, ethylene glycol, ethylene glycol monoethyl ether (usually with respect to 1 mol of the target product example 2, 0.1 to 100 liters) in a temperature range of -10 to 200 ° C. for 1 to 60 hours.

<Example 2>

In the method of Example 2, target product example 4 is obtained in the same manner as the synthesis method of target product example 1 described above, except that the equivalent of the halogenating agent is 0.5 to 1.5 equivalents relative to aniline. Can do.
The target product example 5 can be obtained in the same manner as the target product example 2.
Target product example 6 can be obtained in the same manner as the synthesis method of target product example 1 except that the equivalent of the halogenating agent is 1.5 to 5 equivalents relative to aniline.
The target product example 7 can be obtained in the same manner as the target product example 2.
The target product example 8 can be obtained in the same manner as the target product example 3.

<Example 3>

The target product example 9 can be obtained in the same manner as the target product example 4.
The target product example 10 can be obtained in the same manner as the target product example 2.
The target product example 11 can be obtained in the same manner as the target product example 6.
The target product example 12 can be obtained in the same manner as the target product example 2.
The target product example 13 can be obtained by p-toluenesulfonylation or trifluoromethanesulfonylation reaction of a phenolic hydroxyl group known as a conventional method.
The object example 14 can be obtained by the following methods (1) and (2).

(1) 1 to 20 equivalents of diarylamine with respect to the target product example 13 and the target product example 13, copper powder, copper wire, copper halide (CuX (X = Cl, Br, I)), copper oxide Copper catalysts such as (CuO) (about 0.1 to 5 equivalents with respect to the target product example 13) and basic substances such as potassium carbonate, calcium carbonate, potassium phosphate, cesium carbonate, tert-butoxy sodium (target product examples) In the presence of 1 to 100 equivalents to 13), in an inert gas stream, no solvent, or an aromatic solvent such as nitrobenzene, an alcohol solvent such as tetraglyme or polyethylene glycol (usually 1 mol of the target product 13) And 100 to 100 liters) in a temperature range of 20 to 300 ° C. and stirring and mixing for 1 to 60 hours.

(2) The target product example 13 was converted to a divalent palladium catalyst such as Pd ₂ (dba) ₃ (Pd = palladium, dba = dibenzylideneacetone), Pd (dba) ₂ , palladium acetate, and BINAP (= 2, 2 ′ -Bis (diphenylphosphino-1,1'-binaphthyl)), tri (tert-butyl) phosphine, triphenylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) ) Zero-valent palladium complexes such as propane, 1,3-bis (diphenylphosphino) butane, dppf (= 1,1′-bis (diphenylphosphino) ferrocene), or PdCl ₂ (dppf ) Catalysts such as palladium chloride complexes such as ₂ (about 0.001 to 1 equivalent with respect to the target product example 13) ) And tert-butoxypotassium, tert-butoxysodium, potassium carbonate, cesium carbonate, triethylamine and the like in the presence of 2 to 100 equivalents of tetrahydrofuran, dioxane, dimethoxyethane, N , N-dimethylformamide, dimethyl sulfoxide, xylene, toluene, triethylamine, pyridine and the like (usually 0.1 to 100 liters per 1 mole of the target compound 13) at 0 to 200 ° C. for 1 to 60 hours. Over stirring.

In addition, for the introduction of an amino group, the method described in the section of “Fourth Edition Experimental Chemistry Course 20” (edited by Chemical Society of Japan, Maruzen), Chapter 6 (Amine) can be applied.
Examples of other synthesis schemes are shown below.

<Example 4>

<Example 5>

<Example 6>

  In addition, the structure shown in the above synthesis method example can be converted into a compound having a higher molecular weight by using any known linking means.

  In the formation of a direct bond between aryl groups, as a known coupling method, specifically, “Palladium in Heterocyclic Chemistry: A guide for the Synthetic Chemist” (2nd edition, 2002, Jie Jack Li and Gordon W. Gribble , Pergamon), “Organic synthesis pioneered by transition metals, its various reaction forms and latest results” (1997, Shinjiro, Kagaku Dojinsha), “Bolhard Shore under modern organic chemistry” (2004, KPCVollhardt, A ring-to-ring (coupling) reaction, such as a coupling reaction between an aryl halide and an aryl borate) described or cited in Chemical Dojinsha)) or the like.

  As a purification method of the synthesized compound, “Separation and purification technology handbook” (1993, edited by The Chemical Society of Japan), “High-level separation of trace components and difficult-to-purify substances by chemical conversion method” (1988, ) Issued by IPC), or the methods described in the section “Separation and purification” in “Experimental Chemistry Course (4th edition) 1” (1990, edited by The Chemical Society of Japan) Is available.

  Specifically, extraction (including suspension washing, boiling washing, ultrasonic washing, acid-base washing), adsorption, occlusion, melting, crystallization (including recrystallization from solvent, reprecipitation), distillation (atmospheric pressure) Distillation, vacuum distillation), evaporation, sublimation (atmospheric pressure sublimation, vacuum sublimation), ion exchange, dialysis, filtration, ultrafiltration, reverse osmosis, pressure osmosis, zone lysis, electrophoresis, centrifugation, flotation separation, sedimentation separation, Magnetic separation, various chromatography (shape classification: column, paper, thin layer, capillary. Mobile phase classification: gas, liquid, micelle, supercritical fluid. Separation mechanism: adsorption, distribution, ion exchange, molecular sieve, chelate, gel filtration , Exclusion, affinity) and the like.

The product confirmation and purity analysis methods include gas chromatograph (GC), high performance liquid chromatograph (HPLC), high speed amino acid analyzer (AAA), capillary electrophoresis measurement (CE), size exclusion chromatograph (SEC), Gel permeation chromatograph (GPC), cross-fractionation chromatograph (CFC) mass spectrometry (MS, LC / MS, GC / MS, MS / MS), nuclear magnetic resonance apparatus (NMR ( ¹ HNMR, ¹³ CNMR)), Fourier transform Infrared spectrophotometer (FT-IR), UV-visible near-infrared spectrophotometer (UV.VIS, NIR), electron spin resonance apparatus (ESR), transmission electron microscope (TEM-EDX), electron beam microanalyzer (EPMA), Metal element analysis (ion chromatography, inductively coupled plasma-emission spectroscopy (ICP-AES) atomic absorption analysis) (AAS) X-ray fluorescence analyzer (XRF)), non-metallic element analysis, trace component analysis (ICP-MS, GF-AAS, GD-MS) and the like can be applied as necessary.

[8] Use of organic compound Since the organic compound of the present invention has high charge transportability, it is suitable as a charge transport material for an electrophotographic photoreceptor, an organic electroluminescent element, a photoelectric conversion element, an organic solar cell, an organic rectifying element, and the like. Can be used for
In addition, since it has a high triplet excitation level, an organic electroluminescent device that has excellent heat resistance and can be stably driven (emitted) for a long period of time by using the charge transport material of the present invention made of the organic compound of the present invention. Therefore, the organic compound and the charge transport material of the present invention are particularly suitable as an organic electroluminescent element material.

[Charge transport material composition]
The charge transport material composition of the present invention contains the above-described organic compound of the present invention and a solvent, and is preferably used for an organic electroluminescent device.

[1] Solvent The solvent contained in the charge transport material composition of the present invention is not particularly limited as long as it is a solvent in which the charge transport material of the present invention which is a solute dissolves well.

  Since the charge transport material of the present invention has very high solubility, various solvents can be applied. For example, aromatic hydrocarbons such as toluene, xylene, methicylene, cyclohexylbenzene and tetralin; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene and anisole , Phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and other aromatic ethers; phenyl acetate, phenyl propionate, methyl benzoate, benzoic acid Aromatic esters such as ethyl, propyl benzoate and n-butyl benzoate; ketones having an alicyclic ring such as cyclohexanone and cyclooctanone; aliphatic ketones such as methyl ethyl ketone and dibutyl ketone; methyl ethyl ketone and cyclohexano Alcohol having an alicyclic ring such as ruthenium or cyclooctanol; Aliphatic alcohol such as butanol or hexanol; Aliphatic ether such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether or propylene glycol-1-monomethyl ether acetate (PGMEA); Ethyl acetate In addition, aliphatic esters such as n-butyl acetate, ethyl lactate, and n-butyl lactate can be used. Of these, aromatic hydrocarbons such as toluene, xylene, methicylene, cyclohexylbenzene, tetralin and the like are preferable in that they have low water solubility and are not easily altered.

  Since organic electroluminescent devices use many materials such as cathodes that deteriorate significantly due to moisture, the presence of moisture in the composition causes moisture to remain in the dried film, degrading the device characteristics. The possibility is considered and it is not preferable.

  Examples of the method for reducing the amount of water in the composition include nitrogen gas sealing, use of a desiccant, dehydration of the solvent in advance, use of a solvent having low water solubility, and the like. In particular, it is preferable to use a solvent having low water solubility because the solution film can prevent whitening by absorbing moisture in the atmosphere during the wet film-forming process. From such a viewpoint, the charge transport material composition to which the present embodiment is applied includes, for example, a solvent having a water solubility at 25 ° C. of 1% by weight or less, preferably 0.1% by weight or less. It is preferable to contain 10% by weight or more in the product.

  Further, in order to reduce deterioration in film formation stability due to solvent evaporation from the composition during wet film formation, the solvent of the charge transport material composition has a boiling point of 100 ° C. or higher, preferably 150 ° C. or higher. More preferably, it is effective to use a solvent having a boiling point of 200 ° C. or higher. In order to obtain a more uniform film, it is necessary for the solvent to evaporate from the liquid film immediately after film formation at an appropriate rate. For this purpose, the boiling point is usually 80 ° C. or higher, preferably 100 ° C. or higher. It is effective to use a solvent having a boiling point of 120 ° C. or more, usually less than 270 ° C., preferably less than 250 ° C., more preferably less than 230 ° C.

  A solvent that satisfies the above-mentioned conditions, ie, solute solubility, evaporation rate, and water solubility conditions, may be used alone. However, if a solvent that satisfies all the conditions cannot be selected, two or more solvents may be mixed. It can also be used.

[2] Luminescent Material The charge transport material composition of the present invention, particularly the charge transport material composition used as a composition for an organic electroluminescence device, preferably contains a luminescent material.

The light emitting material refers to a component that mainly emits light in the charge transport material composition of the present invention, and corresponds to a dopant component in an organic electroluminescent device. That is, the amount of light emitted from the charge transport material composition (unit: cd / m ² ) is usually 10 to 100%, preferably 20 to 100%, more preferably 50 to 100%, and most preferably 80 to 100%. Is identified as light emission from a component material, it is defined as the light emission material.

Any known material can be applied as the light-emitting material, and a fluorescent light-emitting material or a phosphorescent light-emitting material can be used singly or as a mixture of a plurality of materials. From the viewpoint of internal quantum efficiency, a phosphorescent light-emitting material is preferable.
The maximum emission peak wavelength of this luminescent material is preferably in the range of 390 to 490 nm.

  For the purpose of improving the solubility in a solvent, it is also important to reduce the symmetry and rigidity of the light emitting material molecule or introduce a lipophilic substituent such as an alkyl group.

  Examples of fluorescent dyes that emit blue light include perylene, pyrene, anthracene, coumarin, p-bis (2-phenylethenyl) benzene, and derivatives thereof. Examples of the green fluorescent dye include quinacridone derivatives and coumarin derivatives. Examples of yellow fluorescent dyes include rubrene and perimidone derivatives. Examples of red fluorescent dyes include DCM compounds, benzopyran derivatives, rhodamine derivatives, benzothioxanthene derivatives, azabenzothioxanthene and the like.

  Examples of the phosphorescent material include organometallic complexes containing a metal selected from Groups 7 to 11 of the periodic table.

Preferred examples of the metal in the phosphorescent organometallic complex containing a metal selected from Groups 7 to 11 of the periodic table include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold. Preferred examples of these organometallic complexes include compounds represented by the following general formula (V) or formula (VI).
ML _(q−j) L ′ _j (V)
(In general formula (V), M represents a metal, q represents the valence of the metal, L and L ′ represent a bidentate ligand, and j represents 0, 1 or 2.)

（一般式（VI）中、Ｍ^ｄは金属を表し、Ｔは炭素又は窒素を表す。Ｒ^９２〜Ｒ^９５は、それぞれ独立に置換基を表す。ただし、Ｔが窒素の場合は、Ｒ^９４及びＲ^９５は無い。）

(In the general formula (VI), ^{M d} represents a metal, T is ^.R 92 ^{to R 95} that represents a carbon or nitrogen, each independently represent a substituent. However, when T is ^{nitrogen, R 94} and R ⁹⁵ is not.)

Hereinafter, the compound represented by the general formula (V) will be described first.
In the general formula (V), M represents an arbitrary metal, and specific examples of preferable ones include the metals described above as the metal selected from Groups 7 to 11 of the periodic table.
Moreover, the bidentate ligands L and L ′ in the general formula (V) each represent a ligand having the following partial structure.

As L ′, the followings are particularly preferable from the viewpoint of the stability of the complex.

  In the partial structures of L and L ′, the ring A1 represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and these may have a substituent. Ring A2 represents a nitrogen-containing aromatic heterocyclic group, and these may have a substituent.

  When the rings A1 and A2 have a substituent, preferred substituents include halogen atoms such as fluorine atoms; alkyl groups such as methyl groups and ethyl groups; alkenyl groups such as vinyl groups; methoxycarbonyl groups and ethoxycarbonyl groups. Alkoxycarbonyl groups; alkoxy groups such as methoxy groups and ethoxy groups; aryloxy groups such as phenoxy groups and benzyloxy groups; dialkylamino groups such as dimethylamino groups and diethylamino groups; diarylamino groups such as diphenylamino groups; carbazolyl groups; An acyl group such as an acetyl group; a haloalkyl group such as a trifluoromethyl group; a cyano group; an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, and a phenanthyl group.

  More preferable examples of the compound represented by the general formula (V) include compounds represented by the following general formulas (Va), (Vb), and (Vc).

（一般式（Ｖａ）中、Ｍ^ａはＭと同様の金属を表し、ｗは上記金属の価数を表す。また、環Ａ１は置換基を有していてもよい芳香族炭化水素基を表し、環Ａ２は置換基を有していてもよい含窒素芳香族複素環基を表す。）

(In general formula (Va), M ^a represents the same metal as M, w represents the valence of the metal, and ring A1 represents an aromatic hydrocarbon group which may have a substituent. Ring A2 represents a nitrogen-containing aromatic heterocyclic group which may have a substituent.

（一般式（Ｖｂ）中、Ｍ^ｂはＭと同様の金属を表し、ｗは上記金属の価数を表す。また、環Ａ１は置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表し、環Ａ２は置換基を有していてもよい含窒素芳香族複素環基を表す。）

(In the general formula (Vb), M ^b represents the same metal as M, w represents the valence of the metal. Further, the ring A1 is an aromatic optionally substituted hydrocarbon group or a substituted Represents an aromatic heterocyclic group which may have a group, and ring A2 represents a nitrogen-containing aromatic heterocyclic group which may have a substituent.)

（一般式（Ｖｃ）中、Ｍ^ｃはＭと同様の金属を表し、ｗは上記金属の価数を表す。また、ｊは０、１又は２を表す。さらに、環Ａ１及び環Ａ１’は、それぞれ独立に、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表す。また、環Ａ２及び環Ａ２’は、それぞれ独立に、置換基を有していてもよい含窒素芳香族複素環基を表す。）

(In the general formula (Vc), M ^c represents the same metal as M, w represents the valence of the metal, j represents 0, 1 or 2. Furthermore, ring A1 and ring A1 ′ represent Each independently represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, and ring A2 and ring A2 ′ are each independently Represents a nitrogen-containing aromatic heterocyclic group which may have a substituent.

  In the general formulas (Va), (Vb), and (Vc), the group of the ring A1 and the ring A1 ′ is preferably a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a thienyl group, a furyl group, a benzo group, for example. Examples include thienyl group, benzofuryl group, pyridyl group, quinolyl group, isoquinolyl group, carbazolyl group and the like.

  In addition, the group of ring A2 and ring A2 ′ is preferably a pyridyl group, pyrimidyl group, pyrazyl group, triazyl group, benzothiazole group, benzoxazole group, benzimidazole group, quinolyl group, isoquinolyl group, quinoxalyl group, A phenanthridyl group and the like can be mentioned.

  Furthermore, the substituents that the compounds represented by the general formulas (Va), (Vb), and (Vc) may have include halogen atoms such as fluorine atoms; alkyl groups such as methyl groups and ethyl groups; vinyls Alkenyl groups such as methoxy groups; alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups; alkoxy groups such as methoxy groups and ethoxy groups; aryloxy groups such as phenoxy groups and benzyloxy groups; dialkyls such as dimethylamino groups and diethylamino groups An amino group; a diarylamino group such as a diphenylamino group; a carbazolyl group; an acyl group such as an acetyl group; a haloalkyl group such as a trifluoromethyl group; a cyano group;

  When the said substituent is an alkyl group, the carbon number is 1 or more and 6 or less normally. Furthermore, when the substituent is an alkenyl group, the carbon number is usually 2 or more and 6 or less. When the substituent is an alkoxycarbonyl group, the carbon number is usually 2 or more and 6 or less. Further, when the substituent is an alkoxy group, the carbon number is usually 1 or more and 6 or less. Moreover, when a substituent is an aryloxy group, the carbon number is 6 or more and 14 or less normally. Furthermore, when the substituent is a dialkylamino group, the carbon number is usually 2 or more and 24 or less. Further, when the substituent is a diarylamino group, the carbon number is usually 12 or more and 28 or less. Furthermore, when the substituent is an acyl group, the carbon number is usually 1 or more and 14 or less. Moreover, when a substituent is a haloalkyl group, the carbon number is 1 or more and 12 or less normally.

  These substituents may be connected to each other to form a ring. As a specific example, a substituent of the ring A1 and a substituent of the ring A2 are bonded, or a substituent of the ring A1 ′ and a substituent of the ring A2 ′ are bonded. Two fused rings may be formed. Examples of such a condensed ring group include a 7,8-benzoquinoline group.

  Among them, as a substituent for ring A1, ring A1 ′, ring A2 and ring A2 ′, an alkyl group, alkoxy group, aromatic hydrocarbon group, cyano group, halogen atom, haloalkyl group, diarylamino group, carbazolyl group are more preferable. Is mentioned.

In general formula (Va), (Vb), preferably as ^{M a, M b, M c} in (Vc), ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum or gold.

  Specific examples of the organometallic complex represented by the general formula (V), (Va), (Vb) or (Vc) are shown below, but are not limited to the following compounds (in the following, Ph is phenyl Represents a group).

Among the organometallic complexes represented by the general formulas (V), (Va), (Vb), and (Vc), in particular, as the ligand L and / or L ′, a 2-arylpyridine-based ligand, , 2-arylpyridine, compounds having an arbitrary substituent bonded thereto, and compounds formed by condensing an arbitrary group thereto are preferable.
In addition, compounds described in WO2005 / 019373 can also be used.

Next, the compound represented by the general formula (VI) will be described.
In the general formula (VI), M ^d represents a metal, and specific examples thereof include the metals described above as the metal selected from Groups 7 to 11 of the periodic table. Among these, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum or gold is preferable, and divalent metals such as platinum and palladium are particularly preferable.

In the general formula (VI), R ⁹² and R ⁹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, a cyano group, an amino group, an acyl group, an alkoxycarbonyl group, or a carboxyl group. Represents an alkoxy group, an alkylamino group, an aralkylamino group, a haloalkyl group, a hydroxyl group, an aryloxy group, an aromatic hydrocarbon group or an aromatic heterocyclic group.

Further, when T is carbon, R ⁹⁴ and R ⁹⁵ each independently represent a substituent represented by the same examples as R ⁹² and R ⁹³ . Further, as described above, when T is nitrogen, R ⁹⁴ and R ⁹⁵ are absent.

R ^{92 to} R ⁹⁵ may further have a substituent. In this case, the substituent which may further be present is not particularly limited, and any group can be used as the substituent.
Furthermore, R ^{92 to} R ⁹⁵ may be linked to each other to form a ring, and this ring may further have an arbitrary substituent.

  Specific examples (T-1, T-10 to T-15) of the organometallic complex represented by the general formula (VI) are shown below, but are not limited to the following exemplified compounds. In the following, Me represents a methyl group, and Et represents an ethyl group.

[3] Other components In the charge transport material composition of the present invention, particularly the charge transport material composition used as the composition for an organic electroluminescent device, in addition to the solvent and the light emitting material described above, if necessary, Various other solvents may be included. Examples of such other solvents include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and dimethyl sulfoxide.
Moreover, various additives, such as a leveling agent and an antifoamer, may be included.

  In addition, when two or more layers are laminated by a wet film-forming method, in order to prevent these layers from being compatible with each other, a photo-curing resin or a thermosetting resin is used for the purpose of curing and insolubilizing after film formation. Can also be contained.

[4] Material Concentration and Compounding Ratio in Charge Transport Material Composition Charge transport material composition, particularly charge transport material in organic electroluminescence device composition, light emitting material and components which can be added as required (leveling agent, etc.) ) And the like are usually 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, still more preferably 0.5% by weight or more, most preferably 1% by weight. %, Usually 80% by weight or less, preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less, and most preferably 20% by weight or less. If this concentration is below the lower limit, it is difficult to form a thick film when forming a thin film, and if it exceeds the upper limit, it may be difficult to form a thin film.

  In the charge transport material composition of the present invention, particularly the composition for an organic electroluminescence device, the light-emitting material / charge transport material weight mixing ratio is usually 0.1 / 99.9 or more, more preferably 0. 0.5 / 99.5 or more, more preferably 1/99 or more, most preferably 2/98 or more, usually 50/50 or less, more preferably 40/60 or less, still more preferably. Is 30/70 or less, most preferably 20/80 or less. If this ratio falls below the lower limit or exceeds the upper limit, the luminous efficiency may be significantly reduced.

[5] Method for Preparing Charge Transport Material Composition The charge transport material composition of the present invention, particularly the composition for an organic electroluminescent device, includes a charge transport material, a light emitting material, and a leveling agent or antifoam that can be added as necessary. It is prepared by dissolving a solute composed of various additives such as an agent in an appropriate solvent. In order to shorten the time required for the dissolution step and to keep the solute concentration in the composition uniform, the solute is usually dissolved while stirring the liquid. The dissolution step may be performed at room temperature, but when the dissolution rate is slow, it can be heated and dissolved. After completion of the dissolution step, a filtration step such as filtering may be performed as necessary.

[6] Properties and physical properties of the charge transport material composition (moisture concentration)
When an organic electroluminescent device is produced by forming a layer by a wet film forming method using the charge transport material composition (composition for an organic electroluminescent device) of the present invention, moisture is contained in the composition for organic electroluminescent device to be used. If present, moisture is mixed into the formed film and the uniformity of the film is impaired. Therefore, it is preferable that the water content in the charge transport material composition of the present invention, particularly the composition for organic electroluminescent elements, is as low as possible. . In general, since organic electroluminescent devices use many materials such as cathodes that deteriorate significantly due to moisture, when moisture is present in the charge transport material composition, moisture remains in the dried film. There is a possibility of deteriorating the characteristics of the element, which is not preferable.

  Specifically, the amount of water contained in the charge transport material composition of the present invention, particularly the organic electroluminescent device composition, is usually 1% by weight or less, preferably 0.1% by weight or less, more preferably 0.8%. 01% by weight or less.

  As a method for measuring the water concentration in the charge transport material composition, the method described in Japanese Industrial Standard “Method for Measuring Water of Chemical Products” (JIS K0068: 2001) is preferable. For example, the Karl Fischer reagent method (JIS K0211-1348). ) And the like.

(Uniformity)
The charge transport material composition of the present invention, particularly the composition for an organic electroluminescence device, is uniform at room temperature in order to improve stability in a wet film forming process, for example, ejection stability from a nozzle in an ink jet film forming method. It is preferably a liquid. The uniform liquid at normal temperature means that the composition is a liquid composed of a uniform phase and does not contain a particle component having a particle size of 0.1 μm or more in the composition.

(Physical properties)
Regarding the viscosity of the charge transport material composition of the present invention, particularly the composition for organic electroluminescence device, in the case of extremely low viscosity, for example, uneven coating surface due to excessive liquid film flow in the film forming process, Nozzle discharge failure or the like is likely to occur, and when the viscosity is extremely high, nozzle clogging or the like in the ink-jet film formation is likely to occur. For this reason, the viscosity at 25 ° C. of the composition of the present invention is usually 2 mPa · s or more, preferably 3 mPa · s or more, more preferably 5 mPa · s or more, and usually 1000 mPa · s or less, preferably 100 mPa · s or less. More preferably, it is 50 mPa · s or less.

  In addition, when the surface tension of the charge transport material composition of the present invention, particularly the composition for organic electroluminescent elements is high, the wettability of the film-forming liquid with respect to the substrate is lowered, the leveling property of the liquid film is poor, and when dried Therefore, the surface tension at 20 ° C. of the composition of the present invention is usually less than 50 mN / m, preferably less than 40 mN / m.

  Furthermore, when the vapor pressure of the charge transport material composition of the present invention, particularly the composition for organic electroluminescent elements, is high, problems such as changes in solute concentration due to evaporation of the solvent are likely to occur. For this reason, the vapor pressure at 25 ° C. of the composition of the present invention is usually 50 mmHg or less, preferably 10 mmHg or less, more preferably 1 mmHg or less.

[7] Method for Preserving Charge Transport Material Composition The charge transport material composition of the present invention is preferably filled in a container capable of preventing the transmission of ultraviolet rays, such as a brown glass bottle, and stored tightly. The storage temperature is usually −30 ° C. or higher, preferably 0 ° C. or higher, and usually 35 ° C. or lower, preferably 25 ° C. or lower.

[Organic electroluminescence device]
The organic electroluminescent element of the present invention has at least an anode, a cathode and a light emitting layer on a substrate, and has a layer containing the organic compound of the present invention. The layer containing the organic compound is preferably the light emitting layer. The layer containing the organic compound is preferably doped with an organometallic complex. As the organometallic complex, those exemplified as the light emitting material can be used.

  1 to 8 are schematic sectional views showing structural examples suitable for the organic electroluminescence device of the present invention. In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a light emitting layer, 5 represents an electron injection layer, and 6 represents a cathode.

[1] Substrate The substrate 1 serves as a support for the organic electroluminescent element, and quartz or glass plates, metal plates, metal foils, plastic films, sheets, and the like are used. In particular, a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polysulfone is preferable. When using a synthetic resin substrate, it is necessary to pay attention to gas barrier properties. If the gas barrier property of the substrate is too small, the organic electroluminescent element may be deteriorated by the outside air that has passed through the substrate, which is not preferable. For this reason, a method of providing a gas barrier property by providing a dense silicon oxide film or the like on at least one surface of the synthetic resin substrate is also a preferable method.

[2] Anode An anode 2 is provided on the substrate 1. The anode 2 plays a role of hole injection into a layer on the light emitting layer side (such as the hole injection layer 3 or the light emitting layer 4).

  This anode 2 is usually a metal such as aluminum, gold, silver, nickel, palladium, platinum, a metal oxide such as an oxide of indium and / or tin, a metal halide such as copper iodide, carbon black, or A conductive polymer such as poly (3-methylthiophene), polypyrrole, or polyaniline is used.

  In general, the anode 2 is often formed by sputtering, vacuum deposition, or the like. In addition, when forming an anode using fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, or conductive polymer fine powder, an appropriate binder resin solution is used. The anode 2 can also be formed by dispersing and coating the substrate 1. Further, in the case of a conductive polymer, a thin film can be directly formed on the substrate 1 by electrolytic polymerization, or the anode 2 can be formed by applying a conductive polymer on the substrate 1 (Appl. Phys. Lett. 60, 2711, 1992).

The anode 2 usually has a single-layer structure, but it can also have a laminated structure made of a plurality of materials if desired.

  The thickness of the anode 2 varies depending on the required transparency. When transparency is required, the visible light transmittance is usually 60% or more, preferably 80% or more. In this case, the thickness of the anode is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably about 500 nm or less. When it may be opaque, the thickness of the anode 2 is arbitrary, and the anode 2 may be the same as the substrate 1. Furthermore, it is also possible to laminate different conductive materials on the anode 2 described above.

  The surface of the anode is treated with ultraviolet (UV) / ozone, oxygen plasma, or argon plasma for the purpose of removing impurities adhering to the anode and adjusting the ionization potential to improve hole injection. Is preferred.

[3] Hole Injection Layer Since the hole injection layer 3 is a layer that transports holes from the anode 2 to the light emitting layer 4, the hole injection layer 3 preferably contains a hole transporting compound.

  In the hole injection layer 3, a cation radical obtained by removing one electron from an electrically neutral compound accepts one electron from a nearby electrically neutral compound, whereby holes move. When the cation radical compound is not included in the hole injection layer 3 when the element is not energized, the cation radical of the hole transport compound is generated when the hole transport compound gives electrons to the anode 2 during energization, Holes are transported by transferring electrons between the cation radical and an electrically neutral hole transporting compound.

  When the hole injection layer 3 contains a cation radical compound, cation radicals necessary for hole transport are present at a concentration higher than that generated by oxidation by the anode 2, and the hole transport performance is improved. It is preferable that the hole injection layer 3 contains a cation radical compound. When an electrically neutral hole transporting compound is present in the vicinity of the cation radical compound, electrons are transferred smoothly, so that the hole injection layer 3 contains a cation radical compound and a hole transporting compound. Is more preferable.

  Here, the cation radical compound is a cation radical that is a chemical species obtained by removing one electron from a hole transporting compound, and an ionic compound composed of a counter anion, and already has holes (free carriers) that are easy to move. Yes.

  Further, by mixing an electron-accepting compound with the hole-transporting compound, one-electron transfer from the hole-transporting compound to the electron-accepting compound occurs, and the above-described cation radical compound is generated. For this reason, it is preferable that the hole injection layer 3 contains a hole transporting compound and an electron accepting compound.

  Summarizing the above preferred materials, the hole injection layer 3 preferably contains a hole transporting compound, and more preferably contains a hole transporting compound and an electron accepting compound. The hole injection layer 3 preferably contains a cation radical compound, and more preferably contains a cation radical compound and a hole transporting compound.

  Furthermore, the hole injection layer 3 may contain a binder resin that does not easily trap charges and a coating property improving agent as necessary.

  However, as the hole injection layer 3, the electron accepting compound alone or the electron accepting compound and the hole transporting compound are used to form a film on the anode 2 by a wet film forming method, and the direct injection of the present invention is performed directly from above. It is also possible to laminate the charge transport material composition by coating or vapor deposition. In this case, a part or all of the charge transport material composition of the present invention interacts with the electron accepting compound, thereby forming a hole transport layer 10 having excellent hole injectability as shown in FIGS. Is done.

(Hole transporting compound)
As the hole transporting compound, a compound having an ionization potential of 4.5 eV to 6.0 eV is preferable.

  Examples of the hole transporting compound include an aromatic amine compound, a phthalocyanine derivative, a porphyrin derivative, an oligothiophene derivative, a polythiophene derivative and the like in addition to the charge transport material of the present invention. Of these, aromatic amine compounds are preferred from the viewpoints of amorphousness and visible light transmittance.

  Among the aromatic amine compounds, aromatic tertiary amine compounds such as the charge transport material of the present invention are particularly preferable. Here, the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and includes a compound having a group derived from an aromatic tertiary amine.

  The type of the aromatic tertiary amine compound is not particularly limited, but a polymer compound having a weight average molecular weight of 1,000 or more and 1,000,000 or less (a polymerization organic compound in which repeating units are linked) is more preferable from the viewpoint of the surface smoothing effect.

  Preferable examples of the aromatic tertiary amine polymer compound include a polymer compound having a repeating unit represented by the following general formula (VII).

（一般式（VII）中、Ａｒ^２１，Ａｒ^２２は各々独立して、置換基を有していてもよい芳香族炭化水素基、又は置換基を有していてもよい芳香族複素環基を表す。Ａｒ^２３〜Ａｒ^２５は、各々独立して、置換基を有していてもよい２価の芳香族炭化水素基、又は置換基を有していてもよい２価の芳香族複素環基を表す。Ｙは、下記の連結基群の中から選ばれる連結基を表す。また、Ａｒ^２１〜Ａｒ^２５のうち、同一のＮ原子に結合する二つの基は互いに結合して環を形成してもよい。）

(In General Formula (VII), Ar ²¹ and Ar ²² each independently represents an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. Ar ^{23 to} Ar ²⁵ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, or a divalent aromatic heterocyclic group which may have a substituent. Y represents a linking group selected from the following group of linking groups, and among Ar ^{21 to} Ar ²⁵ , two groups bonded to the same N atom are bonded to each other to form a ring. May be.)

（上記各式中、Ａｒ^３１〜Ａｒ^４１は、各々独立して、置換基を有していてもよい芳香族炭化水素環、又は置換基を有していてもよい芳香族複素環由来の１価又は２価の基を表す。Ｒ^１０１及びＲ^１０２は、各々独立して、水素原子又は任意の置換基を表す。））

(In the above formulas, Ar ^{31 to} Ar ⁴¹ are each independently 1 derived from an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocyclic ring which may have a substituent. And R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or an arbitrary substituent.)

As Ar ^{21 to} Ar ²⁵ and Ar ^{31 to} Ar ⁴¹ , any monovalent or divalent group derived from any aromatic hydrocarbon ring or aromatic heterocyclic ring is applicable. These may be the same or different from each other. Moreover, you may have arbitrary substituents.

  Examples of the aromatic hydrocarbon ring include a 5- or 6-membered monocyclic ring or a 2-5 condensed ring. Specific examples include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.

  The aromatic heterocycle includes a 5- or 6-membered monocyclic ring or a 2-4 condensed ring. Specific examples include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, Thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring , Synoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like.

Moreover, as Ar < ²³ > -Ar < ²⁵ >, Ar < ³¹ > -Ar < ³⁵ >, Ar < ³⁷ > -Ar < ⁴⁰ >, the bivalent origin derived from the 1 type or 2 or more types of aromatic hydrocarbon ring and / or aromatic heterocycle which were illustrated above is shown. Two or more groups may be linked and used.

The group derived from the aromatic hydrocarbon ring and / or aromatic heterocycle of Ar ^{21 to} Ar ⁴¹ may further have a substituent. The molecular weight of the substituent is usually 400 or less, preferably about 250 or less. Although the kind in particular of substituent is not restrict | limited, As an example, 1 type, or 2 or more types chosen from the following substituent group D is mentioned.

[Substituent group D]
An alkyl group having usually 1 or more, usually 10 or less, preferably 8 or less, such as a methyl group or an ethyl group; an alkenyl group having 2 or more, usually 11 or less, preferably 5 or less carbon atoms, such as a vinyl group. An alkynyl group having usually 2 or more, usually 11 or less, preferably 5 or less, such as an ethynyl group; an alkoxy having a carbon number of usually 1 or more, usually 10 or less, preferably 6 or less, such as a methoxy group or an ethoxy group; A group; an aryloxy group such as a phenoxy group, a naphthoxy group, a pyridyloxy group, etc., usually 4 or more, preferably 5 or more, usually 25 or less, preferably 14 or less; a carbon such as a methoxycarbonyl group or an ethoxycarbonyl group An alkoxycarbonyl group having a number of usually 2 or more, usually 11 or less, preferably 7 or less; a dimethylamino group, a diethylamino group or the like, and usually having 2 or more carbon atoms Usually 20 or less, preferably 12 or less dialkylamino group; diphenylamino group, ditolylamino group, N-carbazolyl group, etc., and usually diarylamino having 10 or more carbon atoms, preferably 12 or more, usually 30 or less, preferably 22 or less Group: an arylalkylamino group having 6 or more carbon atoms, preferably 7 or more, usually 25 or less, preferably 17 or less, such as a phenylmethylamino group; an acetyl group, a benzoyl group or the like, and usually having 2 or more carbon atoms, Usually an acyl group of 10 or less, preferably 7 or less; a halogen atom such as a fluorine atom or a chlorine atom; a haloalkyl group having a carbon number of usually 1 or more, usually 8 or less, preferably 4 or less, such as a trifluoromethyl group; An alkylthio group having 1 to 10 carbon atoms, preferably 6 or less, preferably 6 or less; An arylthio group having usually 4 or more, preferably 5 or more, usually 25 or less, preferably 14 or less, such as a ruthio group, a naphthylthio group, or a pyridylthio group; Or more, preferably 3 or more, usually 33 or less, preferably 26 or less silyl group; trimethylsiloxy group, triphenylsiloxy group, etc., the carbon number is usually 2 or more, preferably 3 or more, usually 33 or less, preferably 26 or less. A siloxy group; a cyano group; an aromatic hydrocarbon ring group having usually 6 or more, usually 30 or less, preferably 18 or less, such as a phenyl group or a naphthyl group; a carbon number such as a thienyl group or a pyridyl group. An aromatic heterocyclic group of 3 or more, preferably 4 or more, usually 28 or less, preferably 17 or less.

Ar ²¹ and Ar ²² are preferably monovalent groups derived from a benzene ring, a naphthalene ring, a phenanthrene ring, a thiophene ring, or a pyridine ring from the viewpoint of the solubility, heat resistance, and hole injection / transport properties of the polymer compound. More preferred are a phenyl group and a naphthyl group.

Ar ^{23 to} Ar ²⁵ are preferably divalent groups derived from a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring from the viewpoint of heat resistance and hole injection / transport properties including redox potential. More preferably a group, a biphenylene group, or a naphthylene group.

As R ¹⁰¹ and R ¹⁰² , a hydrogen atom or an arbitrary substituent is applicable. These may be the same or different from each other. The type of the substituent is not particularly limited, and examples of applicable substituents include alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, silyl groups, siloxy groups, aromatic hydrocarbon groups, aromatic heterocyclic rings. Group and halogen atom. Specific examples thereof include the groups exemplified in the above substituent group D.

  Specific examples of the aromatic tertiary amine polymer compound having a repeating unit represented by the general formula (VII) include those described in WO2005 / 089024, and preferred examples thereof are also the same. Although the compound (PB-1) represented by Structural Formula is mentioned, it is not limited to them at all.

  Preferable examples of other aromatic tertiary amine polymer compounds include polymer compounds containing a repeating unit represented by the following general formula (VIII) and / or general formula (IX).

（一般式（VIII）、（IX）中、Ａｒ^４５，Ａｒ^４７及びＡｒ^４８は各々独立して、置換基を有していてもよい芳香族炭化水素基、又は置換基を有していてもよい芳香族複素環基を表す。Ａｒ^４４及びＡｒ^４６は各々独立して、置換基を有していてもよい２価の芳香族炭化水素基、又は置換基を有していてもよい２価の芳香族複素環基を表す。また、Ａｒ^４５〜Ａｒ^４８のうち、同一のＮ原子に結合する２つの基は互いに結合して環を形成してもよい。Ｒ^１１１〜Ｒ^１１３は各々独立して、水素原子又は任意の置換基を表す。）

(In the general formulas (VIII) and (IX), Ar ⁴⁵ , Ar ⁴⁷ and Ar ⁴⁸ may each independently have an aromatic hydrocarbon group which may have a substituent, or a substituent. Each of Ar ⁴⁴ and Ar ⁴⁶ independently represents a divalent aromatic hydrocarbon group which may have a substituent, or a divalent which may have a substituent; In addition, two groups bonded to the same N atom among Ar ^{45 to} Ar ⁴⁸ may be bonded to each other to form a ring, and R ^{111 to} R ¹¹³ are each independently And represents a hydrogen atom or an arbitrary substituent.

Specific examples of Ar ⁴⁵ , Ar ⁴⁷ , Ar ⁴⁸ and Ar ⁴⁴ , Ar ⁴⁶ , preferred examples, examples of substituents that may be included, and examples of preferred substituents are Ar ²¹ , Ar ²² and Ar ²³ to Ar respectively. Same as Ar ²⁵ . R ^{111 to} R ¹¹³ are preferably a hydrogen atom or a substituent described in [Substituent group D], and more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aromatic hydrocarbon group, It is an aromatic hydrocarbon group.

  Specific examples of the aromatic tertiary amine polymer compound containing a repeating unit represented by the general formula (VIII) and / or (IX) include those described in WO2005 / 089024, and preferable examples thereof are also included. Although it is the same, it is not limited to them at all.

  Moreover, when forming a positive hole injection layer with a wet film forming method, the positive hole transport compound which is easy to melt | dissolve in a various solvent is preferable. As the aromatic tertiary amine compound, for example, a binaphthyl compound (Japanese Patent Laid-Open No. 2004-014187) and an asymmetric 1,4-phenylenediamine compound (Japanese Patent Laid-Open No. 2004-026732) are preferable.

  In addition, compounds that are easily soluble in various solvents may be appropriately selected from aromatic amine compounds that have been conventionally used as a hole injection / transport thin film purification material in organic electroluminescent devices. Examples of the aromatic amine compound applicable to the hole-transporting compound of the hole-injecting layer include conventionally known compounds that have been utilized as a hole-injecting / transporting layer-forming material in organic electroluminescence devices. It is done. For example, an aromatic diamine compound in which a tertiary aromatic amine unit such as 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane is linked (JP 59-194393 A); 4,4′- An aromatic amine compound containing two or more tertiary amines represented by bis [N- (1-naphthyl) -N-phenylamino] biphenyl and having two or more condensed aromatic rings substituted with nitrogen atoms No. 5-23481); an aromatic triamine compound having a starburst structure as a derivative of triphenylbenzene (US Pat. No. 4,923,774); N, N′-diphenyl-N, N′-bis (3- Aromatic diamine compounds such as methylphenyl) biphenyl-4,4′-diamine (US Pat. No. 4,764,625); α, α, α ′, α′-tetramethyl-α, α′- (4-di (p-tolyl) aminophenyl) -p-xylene (Japanese Patent Laid-Open No. 3-269084); sterically asymmetric triphenylamine derivative as a whole molecule (Japanese Patent Laid-Open No. 4-129271); pyrenyl A compound in which a plurality of aromatic diamino groups are substituted on the group (Japanese Patent Laid-Open No. 4-175395); an aromatic diamine compound in which a tertiary aromatic amine unit is linked with an ethylene group (Japanese Patent Laid-Open No. 4-264189); a styryl structure An aromatic diamine having a thiophene group (JP-A-4-290851); a compound in which an aromatic tertiary amine unit is linked by a thiophene group (JP-A-4-304466); a starburst type aromatic triamine compound (JP-A-4-30481) 308688); benzylphenyl compound (Japanese Patent Laid-Open No. 4-364153); Compounds in which thiones are linked (JP-A-5-25473); triamine compounds (JP-A-5-239455); bisdipyridylaminobiphenyl (JP-A-5-320634); N, N, N-triphenylamine Derivatives (JP-A-6-1972); Aromatic diamines having a phenoxazine structure (JP-A-7-138562); Diaminophenylphenanthridine derivatives (JP-A-7-252474); 2-311591); silazane compounds (US Pat. No. 4,950,950); silanamine derivatives (JP-A-6-49079); phosphamine derivatives (JP-A-6-25659); quinacridone compounds, etc. Can be mentioned. These aromatic amine compounds may be used in combination of two or more as required.

  Preferred specific examples of the phthalocyanine derivative or porphyrin derivative applicable to the hole transporting compound of the hole injection layer include porphyrin, 5,10,15,20-tetraphenyl-21H, 23H-porphyrin, 5,10 , 15,20-tetraphenyl-21H, 23H-porphyrin cobalt (II), 5,10,15,20-tetraphenyl-21H, 23H-porphyrin copper (II), 5,10,15,20-tetraphenyl- 21H, 23H-porphyrin zinc (II), 5,10,15,20-tetraphenyl-21H, 23H-porphyrin vanadium (IV) oxide, 5,10,15,20-tetra (4-pyridyl) -21H, 23H -Porphyrin, 29H, 31H-phthalocyanine copper (II), phthalocyanine zinc (II), lid Cyanine titanium, phthalocyanine oxide magnesium, phthalocyanine lead, phthalocyanine copper (II), 4,4 ', 4 ", 4' '' - tetraaza-29H, 31H-phthalocyanine, and the like.

  Further, preferred specific examples of the oligothiophene derivative applicable as the hole transporting compound of the hole injection layer include α-terthiophene and its derivatives, α-sexithiophene and its derivatives, and oligothiophene containing a naphthalene ring. Derivatives (JP-A-6-256341) and the like.

  Further, preferred specific examples of the polythiophene derivative applicable as the hole transporting compound in the present invention include poly (3,4-ethylenedioxythiophene) (PEDOT), poly (3-hexylthiophene) and the like.

  The molecular weight of these hole transporting compounds is usually 9000 or less, preferably 5000 or less, and usually 200 or more, preferably 400 or more, except in the case of a polymer compound (a polymerizable compound in which repeating units are continuous). Range. If the molecular weight of the hole-transporting compound is too high, synthesis and purification are difficult and not preferable. On the other hand, if the molecular weight is too low, the heat resistance may be lowered, which is also not preferable.

  The hole transporting compound used as the material for the hole injection layer may contain any one of these compounds alone, or may contain two or more. In the case of containing two or more kinds of hole transporting compounds, the combination is arbitrary, but one or more kinds of aromatic tertiary amine polymer compounds and one or two kinds of other hole transporting compounds. It is preferable to use the above together.

(Electron-accepting compound)
The electron-accepting compound is preferably a compound having an oxidizing power and the ability to accept one electron from the above-described hole transporting compound, specifically, a compound having an electron affinity of 4 eV or more is preferable, and 5 eV or more. The compound which is the compound of these is further more preferable.

  Examples include onium salts substituted with an organic group such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, iron (III) chloride (JP-A-11-251067), ammonium peroxodisulfate and the like. Examples thereof include valent inorganic compounds, cyano compounds such as tetracyanoethylene, aromatic boron compounds such as tris (pentafluorophenyl) borane (Japanese Patent Laid-Open No. 2003-31365), fullerene derivatives, iodine and the like.

  Of the above compounds, onium salts substituted with organic groups and high valent inorganic compounds are preferred because of their strong oxidizing power, and organic groups are substituted because they are soluble in various solvents and applicable to wet coating. Preferred are onium salts, cyano compounds, and aromatic boron compounds.

  Specific examples of an onium salt substituted with an organic group, a cyano compound, and an aromatic boron compound suitable as an electron-accepting compound include those described in WO 2005/089024, and suitable examples thereof are also the same. Although the compound (A-2) represented by the following structural formula is mentioned, it is not limited to them at all.

(Cation radical compound)
The cation radical compound is an ionic compound composed of a cation radical which is a chemical species obtained by removing one electron from a hole transporting compound and a counter anion. However, when the cation radical is derived from a hole transporting polymer compound, the cation radical has a structure in which one electron is removed from the repeating unit of the polymer compound.

  The cation radical is preferably a chemical species obtained by removing one electron from the aforementioned compound in the hole transporting compound, and is preferably a chemical species obtained by removing one electron from a compound more preferable as the hole transporting compound. From the viewpoints of visible light transmittance, heat resistance, solubility, and the like.

  The cation radical compound can be generated by mixing the hole transporting compound and the electron accepting compound. That is, by mixing the hole transporting compound and the electron accepting compound, electron transfer occurs from the hole transporting compound to the electron accepting compound, and the cation radical and the counter anion of the hole transporting compound are included. A cation ion compound is formed.

  Cationic radical compounds derived from polymer compounds such as PEDOT / PSS (Adv. Mater., 2000, 12, 481) and emeraldine hydrochloride (J. Phys. Chem., 1990, 94, 7716) It is also produced by oxidative polymerization (dehydrogenation polymerization), that is, by oxidizing the monomer chemically or electrochemically with peroxodisulfate in an acidic solution. In the case of this oxidative polymerization (dehydrogenation polymerization), the monomer is oxidized to be polymerized, and the cation radical is formed by removing one electron from the repeating unit of the polymer with an anion derived from an acidic solution as a counter anion. Produces.

  The hole injection layer 3 is formed on the anode 2 by a wet film forming method or a vacuum deposition method.

  ITO (indium tin oxide), which is generally used as the anode 2, has a surface roughness of about 10 nm (Ra) and, in addition, often has protrusions locally, resulting in short-circuit defects. There was a problem that it was easy to produce. When the hole injection layer 3 formed on the anode 2 is formed by the wet film forming method, the generation of device defects due to the unevenness of the surface of the anode as compared with the case of forming by the vacuum deposition method. Has the advantage of reducing.

  In the case of layer formation by a wet film-forming method, a predetermined amount of one or more of the aforementioned materials (hole transporting compound, electron accepting compound, cation radical compound) is not trapped as necessary. Add binder resin and coatability improver, dissolve in solvent, prepare coating solution, by wet film forming method such as spin coating, spray coating, dip coating, die coating, flexographic printing, screen printing, inkjet method etc. It is applied on the anode and dried to form the hole injection layer 3.

  As the solvent used for the layer formation by the wet film forming method, any solvent can be used as long as it can dissolve the above-mentioned materials (hole transporting compound, electron accepting compound, cation radical compound). Is not particularly limited, but generates a deactivating substance or deactivating substance that may deactivate each material (hole transporting compound, electron accepting compound, cation radical compound) used in the hole injection layer The thing which does not contain is preferable.

  Preferred solvents that satisfy these conditions include, for example, ether solvents and ester solvents. Specifically, examples of the ether solvent include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1, 3 -Aromatic ethers such as dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and the like. Examples of the ester solvent include aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and benzoic acid. Examples include aromatic esters such as n-butyl. Any one of these may be used alone, or two or more may be used in any combination and ratio.

  Examples of solvents that can be used in addition to the ether solvents and ester solvents described above include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and amides such as N, N-dimethylformamide and N, N-dimethylacetamide. System solvents, dimethyl sulfoxide and the like. Any one of these may be used alone, or two or more may be used in any combination and ratio. Moreover, you may use 1 type, or 2 or more types among these solvents in combination with 1 type or 2 or more types among the above-mentioned ether type solvent and ester type solvent. In particular, aromatic hydrocarbon solvents such as benzene, toluene, and xylene have a low ability to dissolve electron accepting compounds and cation radical compounds, and are therefore preferably used in a mixture with ether solvents and ester solvents.

  The concentration of the solvent in the coating solution is usually 10% by weight or more, preferably 30% by weight or more, more preferably 50% by weight or more, and usually 99.999% by weight or less, preferably 99.99% by weight or less. Preferably it is the range of 99.9 weight% or less. When two or more kinds of solvents are mixed and used, the total of these solvents is set to satisfy this range.

In the case of forming a layer by vacuum deposition, one or more of the aforementioned materials (hole transporting compound, electron accepting compound, cation radical compound) are put in a crucible installed in a vacuum vessel ( When two or more materials are used, put them in each crucible), and after evacuating the inside of the vacuum vessel to about 10 ⁻⁴ Pa with an appropriate vacuum pump, heat the crucible (if using two or more materials, each Heat the crucible) and evaporate by controlling the amount of evaporation (if more than one material is used, evaporate by controlling the amount of evaporation independently) and place it positively on the anode of the substrate placed facing the crucible A hole injection layer is formed. In addition, when using 2 or more types of materials, they can also be put into a crucible, can be heated and evaporated, and can be used for hole injection layer formation.

The film thickness of the hole injection layer 3 that may be formed in this manner is usually in the range of 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
The hole injection layer 3 may be omitted as shown in FIG.

[4] Light-Emitting Layer A normal light-emitting layer 4 is provided on the hole injection layer 3. The light emitting layer 4 is a layer containing a light emitting material, and between the electrodes to which an electric field is applied, holes injected from the anode 2 through the hole injection layer 3 and electrons injected from the cathode 6 through the electron transport layer 5 It is a layer that is excited by recombination and becomes a main light emitting source. The light-emitting layer 4 preferably contains a light-emitting material (dopant) and one or more host materials, and the light-emitting layer 4 more preferably contains the organic compound of the present invention as a host material, and is formed by a vacuum evaporation method. However, it is particularly preferable that the layer be formed by a wet film forming method using the charge transport material composition of the present invention.

  Here, the wet film forming method is a method of forming a film by applying the charge transporting material composition of the present invention containing the above solvent by spin coating, spray coating, dip coating, die coating, flexographic printing, screen printing, or ink jet method. Is.

  In addition, the light emitting layer 4 may contain other materials and components as long as the performance of the present invention is not impaired.

  In general, when the same material is used in the organic electroluminescent element, the thinner the film thickness between the electrodes, the larger the effective electric field, so that the injected current increases, so the driving voltage decreases. For this reason, the driving voltage of the organic electroluminescence device decreases when the total film thickness between the electrodes is thin, but if it is too thin, a short circuit occurs due to the protrusion caused by the electrode such as ITO. Necessary.

  In the present invention, in addition to the light emitting layer 4, when the organic layer such as the hole injection layer 3 and the electron transport layer 5 described later is provided, the light emitting layer 4 and other organic materials such as the hole injection layer 3 and the electron transport layer 5 The total film thickness combined with the layer is usually 30 nm or more, preferably 50 nm or more, more preferably 100 nm or more, usually 1000 nm or less, preferably 500 nm or less, more preferably 300 nm or less. In addition, when the conductivity of the hole injection layer 3 other than the light emitting layer 4 and the electron injection layer 5 described later is high, the amount of charge injected into the light emitting layer 4 increases. It is also possible to reduce the drive voltage while increasing the thickness to reduce the thickness of the light emitting layer 4 and maintaining the total thickness to some extent.

  Therefore, the thickness of the light emitting layer 4 is usually 10 nm or more, preferably 20 nm or more, and usually 300 nm or less, preferably 200 nm or less. When the element of the present invention has only the light emitting layer 4 between the anode and the cathode, the thickness of the light emitting layer 4 is usually 30 nm or more, preferably 50 nm or more, usually 500 nm or less, preferably 300 nm or less. is there.

[5] Electron Injection Layer The electron injection layer 5 plays a role of efficiently injecting electrons injected from the cathode 6 into the light emitting layer 4. In order to perform electron injection efficiently, the material for forming the electron injection layer 5 is preferably a metal having a low work function, and alkali metals such as sodium and cesium, and alkaline earth metals such as barium and calcium are used.
The film thickness of the electron injection layer 5 is preferably 0.1 to 5 nm.

Alternatively, an ultrathin insulating film (0.1 to 5 nm) such as LiF, MgF ₂ , Li ₂ O, CsCO ₃ may be inserted at the interface between the cathode 6 and the light emitting layer 4 or the electron transport layer 8 described later. (Appl. Phys. Lett., 70, 152, 1997; JP-A-10-74586; IEEE Trans. Electron. Devices, 44, 1245, 1997); SID 04 Digest, page 154).

  Further, organic electron transport materials represented by metal complexes such as nitrogen-containing heterocyclic compounds such as bathophenanthroline and aluminum complexes of 8-hydroxyquinoline described later are doped with alkali metals such as sodium, potassium, cesium, lithium and rubidium. (Described in JP-A-10-270171, JP-A 2002-1000047, JP-A 2002-1000048, and the like) makes it possible to improve electron injection / transport properties and achieve excellent film quality. Therefore, it is preferable. The film thickness in this case is usually 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.

The electron injection layer 5 is formed by laminating on the light emitting layer 4 by a wet film forming method or a vacuum deposition method in the same manner as the light emitting layer 4. In the case of the vacuum vapor deposition method, the vapor deposition source is put in a crucible or metal boat installed in a vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 ⁻⁴ Pa with an appropriate vacuum pump, and then the crucible or metal boat is Evaporate by heating to form an electron injection layer on the substrate placed facing the crucible or metal boat.

The alkali metal is deposited using an alkali metal dispenser in which nichrome is filled with an alkali metal chromate and a reducing agent. By heating the dispenser in a vacuum container, the alkali metal chromate is reduced and the alkali metal is evaporated. In the case of co-evaporating the organic electron transport material and the alkali metal, the organic electron transport material is put in a crucible installed in a vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 ⁻⁴ Pa with a suitable vacuum pump. Each crucible and dispenser are simultaneously heated and evaporated to form an electron injection layer on the substrate placed facing the crucible and dispenser.

At this time, co-evaporation is uniformly performed in the film thickness direction of the electron injection layer 5, but there may be a concentration distribution in the film thickness direction.
The electron injection layer 5 may be omitted as shown in FIGS.

[6] Cathode The cathode 6 plays a role of injecting electrons into a layer on the light emitting layer side (such as the electron injection layer 5 or the light emitting layer 4). The material used for the cathode 6 can be the material used for the anode 2, but a metal having a low work function is preferable for efficient electron injection, such as tin, magnesium, indium, calcium, A suitable metal such as aluminum or silver or an alloy thereof is used. Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.

  The film thickness of the cathode 6 is usually the same as that of the anode 2. For the purpose of protecting the cathode made of a low work function metal, further laminating a metal layer having a high work function and stable to the atmosphere on the cathode increases the stability of the device. For this purpose, metals such as aluminum, silver, copper, nickel, chromium, gold, platinum are used.

[7] Other Constituent Layers While the description has been made centering on the element having the layer structure shown in FIG. 1, the performance between the anode 2 and the cathode 6 and the light emitting layer 4 in the organic electroluminescent element of the present invention is described. In addition to the layers described above, any layer may be included, and any layer other than the light emitting layer 4 may be omitted.

  Examples of the layer that may be included include the electron transport layer 7. The electron transport layer 7 is provided between the light emitting layer 4 and the electron injection layer 5 as shown in FIG. 2 for the purpose of further improving the light emission efficiency of the device.

The electron transport layer 7 is formed of a compound capable of efficiently transporting electrons injected from the cathode 6 between electrodes to which an electric field is applied in the direction of the light emitting layer 4. As the electron transporting compound used for the electron transport layer 7, the electron injection efficiency from the cathode 6 or the electron injection layer 5 is high, and the injected electrons can be efficiently transported with high electron mobility. It must be a compound.
Materials satisfying such conditions include metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), metal complexes of 10-hydroxybenzo [h] quinoline, oxadiazole derivatives, Styryl biphenyl derivative, silole derivative, 3- or 5-hydroxyflavone metal complex, benzoxazole metal complex, benzothiazole metal complex, trisbenzimidazolylbenzene (US Pat. No. 5,645,948), quinoxaline compound No. 207169), phenanthroline derivatives (Japanese Patent Laid-Open No. 5-331459), 2-t-butyl-9,10-N, N′-dicyanoanthraquinonediimine, n-type hydrogenated amorphous silicon carbide, n-type sulfide Examples include zinc and n-type zinc selenide.

  The lower limit of the thickness of the electron transport layer 7 is usually 1 nm, preferably about 5 nm, and the upper limit is usually about 300 nm, preferably about 100 nm.

  The electron transport layer 7 is formed by laminating on the light emitting layer 4 by a wet film forming method or a vacuum deposition method in the same manner as the hole injection layer 3. Usually, a vacuum deposition method is used.

  Moreover, it is preferable in this invention to have the positive hole transport layer 10, and it is preferable that the positive hole transport layer 10 contains the organic compound of this invention. Moreover, the compound illustrated as a hole transportable compound of the said positive hole injection layer can also be used. Alternatively, a polymer material such as polyarylene ether sulfone containing polyvinyl carbazole, polyvinyl triphenylamine, or tetraphenylbenzidine may be used. The hole transport layer 10 is formed by laminating these materials on the hole injection layer by a wet film formation method or a vacuum deposition method. The film thickness of the hole transport layer 10 thus formed is usually 10 nm or more, preferably 30 nm. However, it is usually 300 nm or less, preferably 100 nm or less.

  In particular, when a phosphorescent material or a blue light emitting material is used as the light emitting substance, it is also effective to provide the hole blocking layer 8 as shown in FIG. The hole blocking layer 8 has a function of confining holes and electrons in the light emitting layer 4 and improving luminous efficiency. That is, the hole blocking layer 8 is generated by blocking the holes moving from the light emitting layer 4 from reaching the electron transport layer 7, thereby increasing the recombination probability with electrons in the light emitting layer 4. There is a role of confining excitons in the light emitting layer 4 and a role of efficiently transporting electrons injected from the electron transport layer 8 toward the light emitting layer 4.

  The hole blocking layer 8 prevents the holes moving from the anode 2 from reaching the cathode 6 and can efficiently transport the electrons injected from the cathode 6 toward the light emitting layer 4. The compound is laminated on the light emitting layer 4 so as to be in contact with the interface of the light emitting layer 4 on the cathode 6 side.

  The physical properties required for the material constituting the hole blocking layer 8 include high electron mobility, low hole mobility, a large energy gap (difference between HOMO and LUMO), and excited triplet level (T1). Is high.

  Examples of the hole blocking layer material satisfying such conditions include mixed arrangements of bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanolato) aluminum, and the like. Ligand complexes, metal complexes such as bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolinato) aluminum binuclear metal complexes, styryl compounds such as distyrylbiphenyl derivatives ( JP-A-11-242996), triazole derivatives such as 3- (4-biphenylyl) -4-phenyl-5 (4-tert-butylphenyl) -1,2,4-triazole (JP-A-7-41759) And phenanthroline derivatives such as bathocuproine (Japanese Patent Laid-Open No. 10-79297).

  Furthermore, a compound having at least one pyridine ring substituted at the 2,4,6-positions described in WO2005 / 022962 is also preferable as the hole blocking material.

  The film thickness of the hole blocking layer 8 is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less.

  The hole blocking layer 8 can also be formed by the same method as the hole injection layer 3, but a vacuum deposition method is usually used.

  The electron transport layer 7 and the hole blocking layer 8 may be appropriately provided as necessary. 1) Only the electron transport layer, 2) Only the hole blocking layer, 3) Stack of hole blocking layer / electron transport layer, 4) There are usages such as not using. Further, as shown in FIG. 7, the electron injection layer 5 may be omitted and the hole blocking layer 8 and the electron transport layer 7 may be laminated, or only the electron transport layer 7 may be used as shown in FIG.

  For the same purpose as the hole blocking layer 8, it is also effective to provide an electron blocking layer 9 between the hole injection layer 3 and the light emitting layer 4 as shown in FIG. The electron blocking layer 9 increases the probability of recombination with holes in the light emitting layer 4 by blocking the electrons moving from the light emitting layer 4 from reaching the hole injection layer 3, thereby generating excitons generated. Has a role of confining the light in the light emitting layer 4 and a role of efficiently transporting holes injected from the hole injection layer 3 in the direction of the light emitting layer 4.

  The characteristics required for the electron blocking layer 9 include high hole transportability, a large energy gap (difference between HOMO and LUMO), and a high excited triplet level (T1). Further, when the light emitting layer 4 is formed by a wet film forming method, it is preferable that the electron blocking layer 9 is also formed by a wet film forming method because the device manufacturing becomes easy.

  For this reason, it is preferable that the electron blocking layer 9 also has wet film forming compatibility. As a material used for such an electron blocking layer 9, a copolymer of dioctylfluorene and triphenylamine typified by F8-TFB is used. (Described in WO 2004/084260).

  The structure opposite to that shown in FIG. 1, that is, the cathode 6, the electron injection layer 5, the light emitting layer 4, the hole injection layer 3, and the anode 2 can be laminated on the substrate 1 in this order. It is also possible to provide the organic electroluminescent element of the present invention between two substrates, at least one of which is highly transparent. Similarly, it is also possible to laminate in a structure opposite to the above-described respective layer configurations shown in FIGS.

Further, a structure in which a plurality of layers shown in FIG. 1 are stacked (a structure in which a plurality of light emitting units are stacked) may be employed. In that case, instead of the interfacial layer (between the light emitting units) (when the anode is ITO and the cathode is Al, the two layers), for example, V ₂ O ₅ is used as the charge generation layer (CGL). This is more preferable from the viewpoint of luminous efficiency and driving voltage.

  The present invention can be applied to any of an organic electroluminescent element having a single element, an element having a structure arranged in an array, and a structure having an anode and a cathode arranged in an XY matrix.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

[Synthesis example]
The synthesis example of the compound used for the charge transport material of the present invention is shown below.
In the following synthesis examples, the glass transition temperature was determined by DSC measurement, the vaporization temperature was determined by TG-DTA measurement, and the melting point was determined by DSC measurement or TG-DTA measurement.

(Synthesis Example 1: Synthesis of the organic compound (I-1) of the present invention having the partial structure (I))

In a nitrogen stream, 2,4,6-triphenylaniline (2.50 g), 4-iodotoluene (10.18 g), copper powder (0.99 g), potassium carbonate (4.30 g), and tetraglyme (6 ml) ) Was stirred at 180 ° C. for 6.8 hours. Dichloromethane (50 ml) was added to the reaction mixture for extraction, and the solution components were separated by filtration and concentrated. The solid content obtained by dissolving in toluene was washed with brine. After separating the toluene solution, adding anhydrous magnesium sulfate and activated clay, the filtrate obtained by filtration was concentrated, purified by silica gel column chromatography and sublimation purification, and used as a target organic electroluminescent device material ( I-1) (1.21 g) was obtained.
This had a glass transition point of 80 ° C., a melting point of 202 ° C., and a boiling point of 344 ° C.
DEI-MS m / z = 501 (M ⁺ )

(Synthesis Example 2: Synthesis of the organic compound (I-2) of the present invention having the partial structure (I))

Place 2,4,6-triphenylaniline (2.48 g), 2,2'-dibromobiphenyl, and sodium tert-butoxy (1.79 g) in a 50 ml 2-neck round bottom flask, and purge the system with nitrogen Then, tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.40 g) and toluene (15.6 ml) were added, and tri (tert-butyl) phosphine (0.39 ml) was injected while stirring. And stirred at 80 to 85 ° C. for 6.5 hours. Ethanol (50 ml) was added to the reaction mixture and stirred, and then the precipitate was separated by filtration, extracted with chloroform (300 ml), and activated clay was added to the extracted solution and stirred. The solid was removed by filtration and then concentrated, and this was purified by column chromatography, followed by recrystallization from chloroform-ethanol and purification by sublimation to obtain the desired organic compound (I-2) (0.65 g). It was.
The glass transition point of this product was not detected, the melting point was 362 ° C., and the sublimation temperature at a pressure of 1 × 10 ⁻³ Pa was 250 to 300 ° C.
DEI-MS m / z = 471 (M ⁺ )

(Synthesis Example 3: Synthesis of the organic compound (I-2) of the present invention having the partial structure (I))

  Bromine (14.3 g) was added dropwise over 30 minutes to a methylene chloride solution (250 mL) of 1,3,5-triphenylbenzene (25 g) at room temperature. After stirring for 12 hours, the remaining bromine was removed with a 5 wt% aqueous sodium thiosulfate solution (100 mL x 3), washed with a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. . The residue was recrystallized from hexane-methylene chloride to obtain Compound (I-2a) (31.6 g).

  In a nitrogen stream, compound (I-2a) (9.0 g), potassium iodide (39 g), copper (I) iodide (22 g), and DMF (35 ml) were stirred for 10 hours under heating and reflux. The reaction mixture was added to 0.07N hydrochloric acid (270 ml) and stirred, and then the precipitate was filtered off and washed with methanol. Chloroform (150 ml) was added to the obtained solid content, and the mixture was stirred for 30 minutes under reflux with heating to dissolve the soluble component, and then the solution component was filtered and concentrated. The obtained solid was purified by recrystallization from methanol to obtain compound (I-2b).

  Under a nitrogen atmosphere, a mixture of copper iodide (132 mg), potassium carbonate (0.96 g), compound (I-2b) (3.0 g), carbazole (1.39 g), and diethylbenzene (20 ml) was added with water under reflux. The mixture was stirred for 16 hours while removing water, allowed to cool to room temperature, methylene chloride was added, and the mixture was filtered. The solvent was distilled off from the filtrate under reduced pressure, and the residue was subjected to silica gel column chromatography using hexane-methylene chloride as a developing solvent to obtain the target organic compound (I-2).

(Synthesis Example 4: Synthesis of the organic compound (I-3) of the present invention having the partial structure (I))

In a nitrogen stream, the intermediate product compound (I-2b) (6.05 g) synthesized in Synthesis Example 3, N, N′-diphenylbenzidine (1.68 g), copper powder (0.89 g), potassium carbonate ( 2.76 g) and tetraglyme (7 ml) were stirred at 210 ° C. for 9.5 hours, allowed to cool, and after adding copper powder (0.89 g) and potassium carbonate (2.76 g), 210 g Stir at 0 ° C. for 10.5 hours. Chloroform (250 ml) and activated clay were added to the reaction mixture and stirred, and the solution components were filtered and concentrated. The solid content obtained by dissolving in chloroform (50 ml) was added to methanol (200 ml) and stirred. Thereafter, the precipitate was filtered off and washed with methanol. The obtained solid was purified by silica gel column chromatography and recrystallization from a toluene-ethanol solution to obtain the target organic compound (I-4) (0.66 g).
This had a glass transition temperature of 157 ° C., a crystallization temperature of 304 ° C., a melting point of 333 ° C., and a vaporization temperature of 511 ° C.

(Synthesis Example 5: Synthesis of the organic compound (I-4) of the present invention having the partial structure (I))

2,4,6-triphenylaniline (2.5 g), 4-iodobiphenyl (13 g), copper (0.98 g), potassium carbonate (4.27 g), and tetraethylene glycol dimethyl ether (20 ml) The mixture was stirred for 11 hours under heating and refluxing and allowed to cool to room temperature. This was dissolved in chloroform, insoluble matter was removed, and the filtrate was concentrated and crystallized with methanol. Thereafter, the residue was purified by column chromatography (hexane / methylene chloride = 3/1) and washed with ethyl acetate. The obtained crystals were purified by sublimation to obtain the target organic compound (I-4) (1.56 g) as white crystals.
This had a melting point of 263 ° C. and a glass transition temperature of 111 ° C.
From DEI-MS (m / z = 625), it was confirmed to be the target product.

(Synthesis Example 6: Synthesis of the organic compound (I-5) of the present invention having the partial structure (I))

  2,4,6-Tribromoaniline (7.0 g), p-tolylboronic acid (11.5 g), and toluene (175 ml) were stirred under a nitrogen atmosphere. Separately, an aqueous solution obtained by dissolving potassium carbonate (26.4 g) in water (100 ml) and degassing was prepared and added to the system. Tetrakis (triphenylphosphine) palladium (2.2 g) was added, and the mixture was stirred for 7 hours under reflux with heating, and allowed to cool to room temperature. The organic layer was extracted and concentrated, further dissolved in toluene, and treated with activated clay. Thereafter, the residue was purified by column chromatography (hexane / methylene chloride = 7/3), the solvent was removed, and the residue was dried under reduced pressure to obtain candy-like compound (I-5a) (6.2 g).

Compound (I-5a) (1.23 g) obtained above, 4-iodo-4′-methylbiphenyl (5 g), copper (0.43 g), potassium carbonate (1.88 g), and tetraethylene glycol dimethyl ether (10 ml) was stirred at 200 ° C. with heating under reflux for 10 hours and allowed to cool to room temperature. This was dissolved in chloroform, insoluble matter was removed, and the filtrate was concentrated and crystallized with methanol. Thereafter, the residue was purified by column chromatography (hexane / methylene chloride = 7/3) and recrystallized from methanol / acetone / methylene chloride. The obtained crystal (0.7 g) was purified by sublimation to obtain the target organic compound (I-5) (0.58 g) as white crystals.
The vaporization temperature of this product was 439 ° C., and the glass transition temperature was 115 ° C.
From DEI-MS (m / z = 695), it was confirmed to be the target product.

(Synthesis Example 7: Synthesis of the organic compound (I-6) of the present invention having the partial structure (I))

  m-Dibromobenzene (14.4 g) and 3-biphenylboronic acid (10 g) were dissolved in toluene (120 ml) and stirred under a nitrogen atmosphere. Separately, potassium carbonate (19 g) was dissolved in water (68 ml) to prepare a degassed aqueous solution, which was added to the system. Tetrakis (triphenylphosphine) palladium (0.9 g) was added, and the mixture was stirred with heating under reflux for 6 hours, and then allowed to cool to room temperature. The organic layer was extracted, concentrated, purified by column chromatography (hexane), the solvent was removed, and the residue was dried under reduced pressure to obtain transparent candy-like compound (I-6a) (8.7 g).

  The compound (I-6a) (2.5 g), potassium iodide (13.4 g) and copper iodide (7.72 g) obtained above were dispersed in dimethylformamide (13 ml) and heated under reflux for 10 hours. Stir and allow to cool to room temperature. This was poured into 1N hydrochloric acid (10 ml) and water (100 ml) to precipitate crystals. The crystals were separated by filtration and dissolved in chloroform (150 ml) to remove insolubles. The chloroform solution was concentrated and dried under reduced pressure to obtain transparent candy-like compound (I-6b) (3.6 g).

Compound (I-6b) (3.6 g) obtained above, 2,4,6-triphenylaniline (0.8 g), copper (0.32 g), potassium carbonate (1.39 g), tetraethylene glycol Dimethyl ether (10 ml) was stirred with heating at 200 ° C. for 10 hours and allowed to cool to room temperature. This was dissolved in chloroform, insoluble matter was removed, and the filtrate was concentrated and crystallized with methanol. Then, it refine | purified by column chromatography (hexane / methylene chloride = 7/3), and heat-washed with methanol. The obtained crystals (1.33 g) were purified by sublimation to obtain the target organic compound (I-6) (0.9 g) as white crystals.
The vaporization temperature of this product was 470 ° C., the melting point was 233 ° C., and the glass transition temperature was 96.7 ° C.
From DEI-MS (m / z = 776), it was confirmed to be the target product.

(Synthesis Example 8: Synthesis of the organic compound (I-7) of the present invention having the partial structure (I))

  In a nitrogen stream, a mixed solution of 2,4,6-tribromoaniline (9.89 g), phenylboronic acid (14.27 g), and dimethoxyethane (120 ml) was added to tetrakis (triphenylphosphine) palladium (2. 08 g) and a 2M aqueous solution of potassium carbonate (29.02 g) were sequentially added, and the mixture was stirred under heating under reflux for 5 hours. Toluene and brine were added to the resulting solution and mixed well. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. This was purified by silica gel column chromatography and methanol suspension washing to obtain yellowish white crystalline compound (I-7a) (7.31 g).

In a nitrogen stream, compound (I-7a) (2.29 g), 4-iodo-4′-methylbiphenyl (5.03 g), copper powder (0.906 g), potassium carbonate (3.94 g), and tetraglyme (16 ml) of the mixture was stirred at 200 ° C. for 17.2 hours. Toluene and brine were added to the resulting solution and mixed well. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. This was purified by silica gel column chromatography, methanol suspension washing, drying under reduced pressure at 100 ° C. and sublimation purification under high vacuum (maximum heating temperature 330 ° C.) to obtain the desired organic compound (I-7) (2. 05g) was obtained as white crystals.
This had a glass transition point of 114 ° C., a melting point of 242 ° C., and a vaporization start temperature of 436 ° C.
From DEI-MS m / z = 653 (M ^<+> ), it confirmed that it was the target object.

(Synthesis Example 9: Synthesis of the organic compound (I-8) of the present invention having the partial structure (I))

  In a nitrogen stream, tetrakis (triphenylphosphine) palladium (0.584 g) was added to a mixed solution of 2,6-dibromoaniline (3.17 g), 3-biphenylboronic acid (6.51 g), and dimethoxyethane (51 ml). ) And a 2M aqueous solution of potassium carbonate (8.74 g) were sequentially added, and the mixture was stirred for 5.9 hours under heating under reflux. Dichloromethane (150 ml) and brine (100 ml) were added to the resulting solution and mixed well. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. This was purified by silica gel column chromatography to obtain white crystalline compound (I-8a) (3.54 g).

Compound (I-8a) (3.54 g), 2,2′-dibromobiphenyl (2.78 g), and tert-butoxy sodium (2.05 g) were added, and the system was purged with nitrogen, and then dehydrated toluene (27 ml) ) And tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.26 g) was added while stirring. Subsequently, tri (tert-butyl) phosphine (0.45 ml) was injected, and the mixture was stirred at 80 ° C. for 1.4 hours, 110 ° C. for 25 minutes, and heated under reflux for 5 hours. Here, 2,2′-dibromobiphenyl (0.32 g) was further added, followed by further stirring for 105 minutes. Dichloromethane (120 ml) and brine (50 ml) were added to the resulting reaction mixture and mixed well, and then the organic layer was separated, anhydrous magnesium sulfate and activated clay were added and mixed well, filtered, and the filtrate was concentrated. . This was purified by silica gel column chromatography, drying under reduced pressure at 60 ° C., and sublimation purification (highest heating temperature 250 ° C.) under high vacuum to obtain a colorless amorphous solid (0 0.8 g) was obtained.
This had a glass transition point of 67 ° C., a melting point of 167 ° C., and a vaporization start temperature of 369 ° C.
From DEI-MS m / z = 547 (M ^<+> ), it confirmed that it was the target object.

  Tables 1a, 1b, and 1c below compare the triplet excitation energy level (T1 level) and the glass transition temperature (Tg) of the organic compound of the present invention produced in the above synthesis example and the reference compound. Show. The compound of the present invention was found to be a compound having a high T1 level and a high Tg.

[Manufacture and evaluation of organic electroluminescence devices]
Example 1
An organic electroluminescent element having the structure shown in FIG. 7 was produced by the following method.
An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate 1 having a thickness of 150 nm (sputtered film; sheet resistance 15 Ω) is patterned into a 2 mm wide stripe using normal photolithography and hydrochloric acid etching. Thus, an anode 2 was formed. The patterned ITO substrate was cleaned in the order of ultrasonic cleaning with acetone, water with pure water, and ultrasonic cleaning with isopropyl alcohol, then dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.

  As a material for the hole injection layer 3, a non-conjugated polymer compound (PB-1 (weight average molecular weight: 29400, number average molecular weight: 12600)) having an aromatic amino group having the structural formula shown below and the structure shown below Using the electron-accepting compound (A-2) of the formula, spin coating was performed under the following conditions.

Spin coating conditions Solvent Ethyl benzoate Coating solution concentration 2.0% by weight
PB-1: A-2 10: 2 (weight ratio)
Spinner speed 1500rpm
Spinner rotation time: 30 seconds Drying condition: 230 ° C. × 15 minutes By the above spin coating, a uniform thin hole injection layer 3 having a film thickness of 30 nm was formed.

Next, the substrate on which the hole injection layer 3 was formed was placed in a vacuum evaporation apparatus. After roughly exhausting the apparatus with an oil rotary pump, the apparatus was exhausted with an oil diffusion pump until the degree of vacuum in the apparatus was about 2.0 × 10 ⁻⁵ Pa or less. The organic compound (I-1) of the present invention shown below, which was placed in a ceramic crucible arranged in the above apparatus, was heated by a tantalum wire heater around the crucible and deposited. The degree of vacuum at the time of vapor deposition was 5.7 × 10 ⁻⁵ Pa, the vapor deposition rate was 0.13 nm / sec, and a hole transport layer 10 having a thickness of 40 nm was obtained.

  Subsequently, the compound (E-1) shown below as the main component (host material) of the light emitting layer 4 and the organic iridium complex (D-1) shown below as the subcomponent (dopant) were placed in separate ceramic crucibles. Film formation was performed by a binary simultaneous vapor deposition method.

The crucible temperature of the compound (E-1) is 342 to 346 ° C., the deposition rate is 0.08 nm / sec, the crucible temperature of the compound (D-1) is controlled to 251 to 254 ° C., and the compound ( The light emitting layer 4 containing 6 wt% of D-1) was laminated on the hole transport layer 10. The degree of vacuum at the time of vapor deposition was 6.3 × 10 ⁻⁵ Pa.

Next, a pyridine derivative (HB-1) shown below was laminated as the hole blocking layer 8 at a crucible temperature of 241 to 245 ° C. with a deposition rate of 0.11 nm / second and a film thickness of 5 nm. The degree of vacuum at the time of vapor deposition was 5.5 × 10 ⁻⁵ Pa.

Next, an aluminum 8-hydroxyquinoline complex (ET-1) shown below was deposited as an electron transport layer 7 on the hole blocking layer 8 in the same manner. At this time, the crucible temperature of the aluminum 8-hydroxyquinoline complex is controlled in the range of 290 to 294 ° C., the vacuum during deposition is 5.5 × 10 ⁻⁵ Pa, the deposition rate is 0.13 nm / second, and the film thickness is Was 30 nm.

The substrate temperature during vacuum deposition of the hole transport layer 10, the light emitting layer 4, the hole blocking layer 8, and the electron transport layer 7 was kept at room temperature.
Here, the element that has been deposited up to the electron transport layer 7 is once taken out from the vacuum deposition apparatus into the atmosphere, and a 2 mm wide striped shadow mask is used as a cathode deposition mask. The device was placed in close contact with each other so as to be orthogonal to each other, placed in another vacuum vapor deposition apparatus, and evacuated until the degree of vacuum in the apparatus was 2.0 × 10 ⁻⁴ Pa or less in the same manner as the organic layer.

As the cathode 6, first, lithium fluoride (LiF) was vapor deposited at a deposition rate of 0.01 nm / second, a degree of vacuum of 2.2 × 10 ⁻⁴ Pa, and a thickness of 0.5 nm using a molybdenum boat. A film was formed on the substrate. Next, aluminum was similarly heated by a molybdenum boat to form an aluminum layer having a film thickness of 80 nm at a deposition rate of 0.4 nm / second and a degree of vacuum of 7.4 × 10 ⁻⁶ Pa, thereby completing the cathode 6. The substrate temperature at the time of vapor deposition of the above two-layered cathode 6 was kept at room temperature.

As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained.
The light emission characteristics of this element are shown in Table 2.
In Table 2, the maximum light emission luminance is the value at a current density of 0.25 A / cm ² , the light emission efficiency, the luminance / current, the voltage is the value at a luminance of 100 cd / m ² , the voltage @ 2500 cd, the luminance / current @ 2500 cd is the luminance 2500 cd. Each value in / m ² is shown.
The maximum wavelength of the emission spectrum of the device was 514 nm, which was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.31, 0.62).

(Example 2)
An organic electroluminescent device having the structure shown in FIG. 8 was produced.
An organic electroluminescence device having a light emitting area portion of 2 mm × 2 mm in size was obtained in the same manner as in Example 1 except that the hole blocking layer 8 was not laminated.
The light emission characteristics of this element are shown in Table 2.
In Table 2, the maximum light emission luminance is the value at a current density of 0.25 A / cm ² , the light emission efficiency, the luminance / current, the voltage is the value at a luminance of 100 cd / m ² , the voltage @ 2500 cd, the luminance / current @ 2500 cd is the luminance 2500 cd. Each value in / m ² is shown.
The maximum wavelength of the emission spectrum was 514 nm, and it was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.31, 0.62).

(Example 3)
An organic electroluminescence device having a light emitting area portion of 2 mm × 2 mm in size was produced in the same manner as in Example 1 except that the organic compound (I-3) of the present invention shown below was used for the hole transport layer 10. did.
The light emission characteristics of this element are shown in Table 2.
In Table 2, the maximum light emission luminance is the value at a current density of 0.25 A / cm ² , the light emission efficiency, the luminance / current, the voltage is the value at a luminance of 100 cd / m ² , the voltage @ 2500 cd, the luminance / current @ 2500 cd is the luminance 2500 cd. Each value in / m ² is shown.
The maximum wavelength of the emission spectrum was 514 nm, and it was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.31, 0.62).

Example 4
An organic electroluminescent element having a light emitting area portion of 2 mm × 2 mm in size was produced in the same manner as in Example 3 except that the hole blocking layer 6 was not laminated.
The light emission characteristics of this element are shown in Table 2.
In Table 2, the maximum light emission luminance is the value at a current density of 0.25 A / cm ² , the light emission efficiency, the luminance / current, the voltage is the value at a luminance of 100 cd / m ² , the voltage @ 2500 cd, the luminance / current @ 2500 cd is the luminance 2500 cd. Each value in / m ² is shown.
The maximum wavelength of the emission spectrum was 514 nm, and it was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.31, 0.62).

(Example 5)
An organic electroluminescent device having a light emitting area portion of 2 mm × 2 mm in size was produced in the same manner as in Example 1 except that the organic compound (I-4) of the present invention shown below was used for the hole transport layer 4. did.
The light emission characteristics of this element are shown in Table 2.
In Table 2, the maximum light emission luminance is the value at a current density of 0.25 A / cm ² , the light emission efficiency, the luminance / current, the voltage is the value at a luminance of 100 cd / m ² , the voltage @ 2500 cd, the luminance / current @ 2500 cd is the luminance 2500 cd. Each value in / m ² is shown.
The maximum wavelength of the emission spectrum was 514 nm, and it was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.30, 0.62).

(Example 6)
Example 1 except that the organic compound (I-7) of the present invention shown below and the compound (E-2) shown below as the main component (host material) of the light emitting layer 5 were used for the hole transport layer 4. Similarly, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was manufactured.
The light emission characteristics of this element are shown in Table 2.
In Table 2, the maximum light emission luminance is the value at a current density of 0.25 A / cm ² , the light emission efficiency, the luminance / current, the voltage is the value at a luminance of 100 cd / m ² , the voltage @ 2500 cd, the luminance / current @ 2500 cd is the luminance 2500 cd. Each value in / m ² is shown.
The maximum wavelength of the emission spectrum was 514 nm, and it was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.30, 0.62).

(Example 7)
An organic electroluminescent element having a light emitting area portion of 2 mm × 2 mm in size was produced in the same manner as in Example 6 except that the hole blocking layer 6 was not laminated.
The light emission characteristics of this element are shown in Table 2.
In Table 2, the maximum light emission luminance is the value at a current density of 0.25 A / cm ² , the light emission efficiency, the luminance / current, the voltage is the value at a luminance of 100 cd / m ² , the voltage @ 2500 cd, the luminance / current @ 2500 cd is the luminance 2500 cd. Each value in / m ² is shown.
The maximum wavelength of the emission spectrum was 514 nm, and it was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.30, 0.62).

(Example 8)
An organic electroluminescent device having a light emitting area portion of 2 mm × 2 mm in size was produced in the same manner as in Example 6 except that the organic compound (I-5) of the present invention shown below was used for the hole transport layer 4. did.
The light emission characteristics of this element are shown in Table 2.
In Table 2, the maximum light emission luminance is the value at a current density of 0.25 A / cm ² , the light emission efficiency, the luminance / current, the voltage is the value at a luminance of 100 cd / m ² , the voltage @ 2500 cd, the luminance / current @ 2500 cd is the luminance 2500 cd. Each value in / m ² is shown.
The maximum wavelength of the emission spectrum was 513 nm, which was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.30, 0.62).

Example 9
An organic electroluminescent element having a light emitting area portion of 2 mm × 2 mm in size was produced in the same manner as in Example 8 except that the hole blocking layer 6 was not laminated.
The light emission characteristics of this element are shown in Table 2.
In Table 2, the maximum light emission luminance is the value at a current density of 0.25 A / cm ² , the light emission efficiency, the luminance / current, the voltage is the value at a luminance of 100 cd / m ² , the voltage @ 2500 cd, the luminance / current @ 2500 cd is the luminance 2500 cd. Each value in / m ² is shown.
The maximum wavelength of the emission spectrum was 513 nm, which was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.30, 0.62).

(Example 10)
For the hole transport layer 4, the arylamine compound (H-1) shown below is used, and the organic compound (I-2) of the present invention shown below is used as the main component (host material) of the light emitting layer 5. An organic electroluminescent element having a light emitting area portion of 2 mm × 2 mm in size was produced in the same manner as in Example 1 except that the organic iridium complex (D-2) shown below was used as (dopant).
Table 3 shows the light emission characteristics of the device.
In Table 3, luminance / current indicates a value at a luminance of 100 cd / m ² .
The maximum wavelength of the emission spectrum was 500 nm, which was identified as that from the organic iridium complex (D-2). The chromaticity was CIE (x, y) = (0.24, 0.48).

(Example 11)
Implemented except that (PPD) shown in Comparative Example 1 described later was used for the hole transport layer 4 and the organic compound (I-8) of the present invention shown below was used as the main component (host material) of the light emitting layer 5. In the same manner as in Example 1, an organic electroluminescent device having a light emitting area portion having a size of 2 mm × 2 mm was produced.
The light emission characteristics of this element are shown in Table 4.
In Table 4, the luminance / current are at luminance 100 cd / ^{m 2,} luminance / current @ 2500 cd are at luminance 2500 cd / ^{m 2,} luminance / current @ 2.5 mA is at a current density of 2.5 mA / cm ² Each value is shown.
The maximum wavelength of the emission spectrum was 513 nm, which was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.30, 0.62).

(Example 12)
The device manufactured in Example 3 was subjected to a driving test under the following conditions, and the driving time when the luminance / initial luminance was 0.5 and the device manufactured in Comparative Example 1 described later were driven under the same conditions. Table 5 shows the relative time when the drive time when the brightness / initial brightness = 0.5 is 1.0.
Temperature: Room temperature
Initial luminance: 5,000 cd / m ²
Drive system: DC drive (DC drive)

(Example 13)
The element manufactured in Example 5 was subjected to a driving test under the same conditions as in Example 12, and the driving time when luminance / initial luminance = 0.5 was the same as the element manufactured in Comparative Example 4 described later. Table 5 shows the relative time when driving was performed under the conditions, and the driving time at the time when luminance / initial luminance = 0.5 was set to 1.0.

(Comparative Example 1)
An organic electroluminescent device having a light emitting area portion of 2 mm × 2 mm in the same manner as in Example 1 except that the following compound (PPD) was used instead of the organic compound (I-1) of the present invention. Obtained.
The light emission characteristics of this element are shown in Table 2.
In Table 2, the maximum light emission luminance is the value at a current density of 0.25 A / cm ² , the light emission efficiency, the luminance / current, the voltage is the value at a luminance of 100 cd / m ² , the voltage @ 2500 cd, the luminance / current @ 2500 cd is the luminance 2500 cd. Each value in / m ² is shown.
The maximum wavelength of the emission spectrum was 514 nm, and it was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.31, 0.62).

(Comparative Example 2)
An organic electroluminescent device having a light emitting area portion of 2 mm × 2 mm in the same manner as in Example 2 except that the compound (PPD) shown above was used instead of the organic compound (I-1) of the present invention. Obtained.
The light emission characteristics of this element are shown in Table 2.
In Table 2, the maximum light emission luminance is the value at a current density of 0.25 A / cm ² , the light emission efficiency, the luminance / current, the voltage is the value at a luminance of 100 cd / m ² , the voltage @ 2500 cd, the luminance / current @ 2500 cd is the luminance 2500 cd. Each value in / m ² is shown.
The maximum wavelength of the emission spectrum was 514 nm, and it was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.31, 0.62).

(Comparative Example 3)
Aside from using the compound (PPD) shown in the above Comparative Example 1 instead of the organic compound (I-7) of the present invention and the compound (E-2) described above as the main component (host material) of the light emitting layer 5, In the same manner as in Example 6, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was manufactured.
The light emission characteristics of this element are shown in Table 2.
In Table 2, the maximum light emission luminance is the value at a current density of 0.25 A / cm ² , the light emission efficiency, the luminance / current, the voltage is the value at a luminance of 100 cd / m ² , the voltage @ 2500 cd, the luminance / current @ 2500 cd is the luminance 2500 cd. Each value in / m ² is shown.
The maximum wavelength of the emission spectrum was 512 nm, which was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.31, 0.62).

(Comparative Example 4)
An organic compound having a light emitting area of 2 mm × 2 mm in the same manner as in Example 7, except that the compound (PPD) shown in Comparative Example 1 was used instead of the organic compound (I-7) of the present invention. An electroluminescent device was manufactured.
The light emission characteristics of this element are shown in Table 2.
In Table 2, the maximum light emission luminance is the value at a current density of 0.25 A / cm ² , the light emission efficiency, the luminance / current, the voltage is the value at a luminance of 100 cd / m ² , the voltage @ 2500 cd, the luminance / current @ 2500 cd is the luminance 2500 cd. Each value in / m ² is shown.
The maximum wavelength of the emission spectrum was 512 nm, which was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.31, 0.62).

(Comparative Example 5)
An organic electroluminescent element having a light emitting area portion of 2 mm × 2 mm in size was obtained in the same manner as in Example 10 except that the compound (CBP) shown below was used instead of the organic compound (I-7) of the present invention. Manufactured.
Table 3 shows the light emission characteristics of the device.
In Table 3, luminance / current indicates a value at a luminance of 100 cd / m ² .
The maximum wavelength of the emission spectrum was 498 nm, which was identified as that from the organic iridium complex (D-2). The chromaticity was CIE (x, y) = (0.20, 0.42).

(Comparative Example 6)
An organic compound having a light emitting area of 2 mm × 2 mm in the same manner as in Example 11 except that the compound (CBP) shown in Comparative Example 5 was used instead of the organic compound (I-8) of the present invention. An electroluminescent device was manufactured.
The light emission characteristics of this element are shown in Table 4.
In Table 4, the luminance / current are at luminance 100 cd / ^{m 2,} luminance / current @ 2500 cd are at luminance 2500 cd / ^{m 2,} luminance / current @ 2.5 mA is at a current density of 2.5 mA / cm ² Each value is shown.
The maximum wavelength of the emission spectrum was 512 nm, which was identified as that from the organic iridium complex (D-1). The chromaticity was CIE (x, y) = (0.31, 0.62).

  As is clear from the above results, the organic electroluminescent device using the organic compound of the present invention as a hole transporting material can obtain uniform light emission because the organic compound of the present invention has excellent charge transportability, and the luminous efficiency. It was high and could be driven at a low voltage.

It is typical sectional drawing which showed an example of the organic electroluminescent element of this invention. It is typical sectional drawing which showed another example of the organic electroluminescent element of this invention. It is typical sectional drawing which showed another example of the organic electroluminescent element of this invention. It is typical sectional drawing which showed another example of the organic electroluminescent element of this invention. It is typical sectional drawing which showed another example of the organic electroluminescent element of this invention. It is typical sectional drawing which showed another example of the organic electroluminescent element of this invention. It is typical sectional drawing which showed another example of the organic electroluminescent element of this invention. It is typical sectional drawing which showed another example of the organic electroluminescent element of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection layer 4 Light emitting layer 5 Electron injection layer 6 Cathode 7 Electron transport layer 8 Hole blocking layer 9 Electron blocking layer 10 Hole transport layer

Claims (10)

An organic compound having one or more partial structures represented by the following general formula (I) in one molecule.

(In general formula (I), R < ^13> , R < ^23> , and R ^<33> are respectively independently a C1-C30 alkyl group, a C1-C30 alkoxy group, and a C6-C30 aryloxy group. , A phenyl group, or a monovalent group formed by connecting 2 to 8 benzene rings . Organic compounds you characterized as having 1 or more partial structures represented by the following general formula (II) in one molecule.

(In the general formula ^{(II), R 13, R} 23, 及 Beauty R ³³ are each independently an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, 6 to 30 carbon atoms aryloxy Represents a monovalent group formed by linking 2 to 8 groups, a phenyl group, or a benzene ring. In the general formula (I) or (II), R ¹³ Is an aromatic group and R ²³ And R ³³ Are each independently an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. In the general formula (I) or (II), R ¹³ , R ²³ And R ³³ Are each independently a phenyl group or a phenoxy group, The organic compound according to claim 3, wherein   A charge transport material comprising the organic compound according to any one of claims 1 to 4.   An organic electroluminescent element material comprising the organic compound according to claim 1.   A charge transport material composition comprising the organic compound according to any one of claims 1 to 4 and a solvent.   The charge transport material composition according to claim 7, further comprising a light emitting material.   5. An organic electroluminescence device having an anode, a cathode, and a light emitting layer provided between both electrodes on a substrate, comprising a layer containing the organic compound according to any one of claims 1 to 4. An organic electroluminescent element. The organic electroluminescent device according to claim 9 , wherein the layer containing the organic compound is a hole transport layer.

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