JP4848198B2 - Organic electroluminescence device - Google Patents

Description

  The present invention relates to a light emitting device capable of emitting light by converting electric energy into light, and more particularly to an organic electroluminescent device.

Organic electroluminescent elements (hereinafter sometimes referred to as “organic EL elements”) are capable of obtaining light emission with high luminance at a low voltage, and thus are attracting attention as promising display elements and are actively researched and developed. Further improvements such as durability, light emission efficiency, and reduction in driving voltage are required. Regarding light-emitting materials, elements containing phosphorescent materials such as tetradentate platinum complexes such as phenylpyridine platinum complexes and phenoxypyridine platinum complexes (Patent Documents 1, 2, and 3) have achieved high efficiency and are attracting attention. . In order to further reduce durability, luminous efficiency, and driving voltage, it has been strongly desired to develop a host material combined with these phosphorescent materials, particularly an electron transporting host material.
On the other hand, nitrogen-containing heterocyclic compounds are known as host materials in combination with phosphorescent materials (Patent Documents 4 and 5), but further improvements have been desired from the viewpoint of durability and the like.
International Publication No. 05/042550 Pamphlet International Publication No. 05/042444 Pamphlet International Patent Publication No. 04/108857 Pamphlet JP 2005-320277 A JP 2005-255986 A

  An object of the present invention is to provide an organic electroluminescence device having a low driving voltage and a small voltage increase width.

式中、R ₈ 、R ₉ 、R ₁₀ 、R ₁₁ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ 、R ₁₆ およびR ₁₇ は水素原子あるいは置換基を表す。R ₈ 、R ₉ 、R ₁₀ 、R ₁₁ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ 、R ₁₆ およびR ₁₇ が置換基を表す場合、さらに置換基を有していてもよく、R ₉ とR ₁₀ 、R ₁₀ とR ₁₁ 、R ₁₃ とR ₁₄ あるいはR ₁₅ とR ₁₆ は互いに結合し、環を形成してもよい。
〔２〕上記一般式（IV）において、R ₈ 、R ₉ 、R ₁₀ およびR ₁₁ は水素原子、アルキル基又はシアノ基を表し、R ₁₂ およびR ₁₇ はアリール基又はヘテロ環基を表し、R ₁₃ 、R ₁₄ 、R ₁₅ およびR ₁₆ は水素原子、アルキル基、シアノ基又はトリフルオロメチル基を表す、上記〔１〕に記載の有機電界発光素子。
〔３〕一対の電極間に、発光層を含む有機化合物層を有する有機電界発光素子であって、下記一般式（V）で表される化合物の少なくとも一種を正孔ブロック層に含有することを特徴とする有機電界発光素子。

式中、R ₈ 、R ₉ 、R ₁₀ 、R ₁₁ 、R ₁₃ 、R ₁₄ 、R ₁₅ 、R ₁₆ 、R ₁₇ 、R ₁₈ 、R ₁₉ 、R ₂₀ 、R ₂₁ 、R ₂₂ 、R ₂₃ 、R ₂₄ 、R ₂₅ およびR ₂₆ は水素原子あるいは置換基を表す。R ₈ 、R ₉ 、R ₁₀ 、R ₁₁ 、R ₁₃ 、R ₁₄ 、R ₁₅ 、R ₁₆ 、R ₁₇ 、R ₁₈ 、R ₁₉ 、R ₂₀ 、R ₂₁ 、R ₂₂ 、R ₂₃ 、R ₂₄ 、R ₂₅ およびR ₂₆ が置換基を表す場合、さらに置換基を有していてもよく、R ₉ とR ₁₀ 、R ₁₀ とR ₁₁ 、R ₁₃ とR ₁₄ 、R ₁₅ とR ₁₆ 、R ₁₇ とR ₁₈ 、R ₁₈ とR ₁₉ 、R ₁₉ とR ₂₀ 、R ₂₀ とR ₂₁ 、R ₂₂ とR ₂₃ 、R ₂₃ とR ₂₄ 、R ₂₄ とR ₂₅ あるいはR ₂₅ とR ₂₆ は互いに結合し、環を形成してもよい。
〔４〕上記一般式（V）において、R ₈ 、R ₉ 、R ₁₀ およびR ₁₁ は水素原子、アルキル基又はシアノ基を表し、R ₁₃ 、R ₁₄ 、R ₁₅ およびR ₁₆ は水素原子、アルキル基、シアノ基又はトリフルオロメチル基を表し、R ₁₇ 、R ₁₈ 、R ₁₉ 、R ₂₀ 、R ₂₁ 、R ₂₂ 、R ₂₃ 、R ₂₄ 、R ₂₅ およびR ₂₆ は水素原子、アルキル基、ハロゲン原子又はシアノ基を表す、上記〔３〕に記載の有機電界発光素子。
〔５〕一対の電極間に、発光層を含む有機化合物層を有する有機電界発光素子であって、正孔ブロック層に一般式（IV）又は（V）で表される化合物の少なくとも一種を含み、さらに発光層に少なくとも一種の三重項発光材料を含有することを特徴とする上記〔１〕〜〔４〕のいずれか一項に記載の有機電界発光素子。
〔６〕前記発光層に含まれる少なくとも一種の三重項発光材料が、白金錯体またはイリジウム錯体であることを特徴とする上記〔５〕に記載の有機電界発光素子。
本発明は、上記〔１〕〜〔６〕項に関するものであるが、その他の事項についても参考のために記載した。
（１）一対の電極間に、発光層を含む有機化合物層を有する有機電界発光素子であって、下記一般式（I）で表される化合物の少なくとも一種を有機化合物層に含有することを特徴とする有機電界発光素子。
This object has been achieved by the following means. Ie
[1] An organic electroluminescent device having an organic compound layer including a light emitting layer between a pair of electrodes, wherein the hole blocking layer contains at least one compound represented by the following general formula (IV): Organic electroluminescent element characterized.

In the formula, R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ represent a hydrogen atom or a substituent. When R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ represent a substituent, they may further have a substituent, and R ₉ and R ₁₀ , R ₁₀ and R ₁₁ , R ₁₃ and R ₁₄ or R ₁₅ and R ₁₆ may be bonded to each other to form a ring.
[2] In the general formula (IV), R ₈ , R ₉ , R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group or a cyano group, R ₁₂ and R ₁₇ represent an aryl group or a heterocyclic group, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are the organic electroluminescent elements according to the above [1], wherein each represents a hydrogen atom, an alkyl group, a cyano group or a trifluoromethyl group.
[3] An organic electroluminescent device having an organic compound layer including a light emitting layer between a pair of electrodes, wherein the hole blocking layer contains at least one compound represented by the following general formula (V): Organic electroluminescent element characterized.

In the formula, R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ represent a hydrogen atom or a substituent. _{R 8, R 9, R 10} , R 11, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25 And R ₂₆ represents a substituent, it may further have a substituent, R ₉ and R ₁₀ , R ₁₀ and R ₁₁ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ , R ₁₈ and R ₁₉ , R ₁₉ and R ₂₀ , R ₂₀ and R ₂₁ , R ₂₂ and R ₂₃ , R ₂₃ and R ₂₄ , R ₂₄ and R ₂₅ or R ₂₅ and R ₂₆ are bonded to each other to form a ring May be.
[4] In the general formula (V), R ₈ , R ₉ , R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group or a cyano group, and R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ represent a hydrogen atom and an alkyl group. Group, cyano group or trifluoromethyl group, R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are hydrogen atom, alkyl group, halogen atom Or the organic electroluminescent element as described in said [3] showing a cyano group.
[5] An organic electroluminescent device having an organic compound layer including a light emitting layer between a pair of electrodes, wherein the hole blocking layer contains at least one compound represented by the general formula (IV) or (V) The organic electroluminescent device according to any one of [1] to [4], wherein the light emitting layer further contains at least one triplet light emitting material.
[6] The organic electroluminescent element as described in [5] above, wherein the at least one triplet light emitting material contained in the light emitting layer is a platinum complex or an iridium complex.
The present invention relates to the items [1] to [6] above, but other matters are also described for reference.
(1) An organic electroluminescent device having an organic compound layer including a light emitting layer between a pair of electrodes, wherein the organic compound layer contains at least one compound represented by the following general formula (I) An organic electroluminescent element.

In the formula, R ₁ represents a substituent, and Q represents an atomic group consisting of carbon or nitrogen constituting a substituted or unsubstituted pyrazole ring together with a carbon atom. m represents an integer of 0 or more, and n represents an integer of 2 or more. However, the sum of m and n is 6 or less.
(2) General formula (I) is following general formula (II) or general formula (III), The organic electroluminescent element of Claim 1 characterized by the above-mentioned.

In the formula, R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent. R _1, m and n have the same meanings as R _1, m and n in the general formula (I). When R ₁ , R ₂ , R ₃ and R ₄ represent a substituent, they may further have a substituent, R ₁ and R ₃ , R ₁ and R ₂ , R ₁ and R ₄ or R ₃ and R ₄ may be bonded to each other to form a ring.

In the formula, R ₅ , R ₆ and R ₇ represent a hydrogen atom or a substituent. R _1, m and n have the same meanings as R _1, m and n in the general formula (I). When R ₁ , R ₅ , R ₆ and R ₇ represent a substituent, they may further have a substituent, R ₁ and R ₅ , R ₁ and R ₆ , R ₁ and R ₇ , R ₅ and R ₆ or R ₆ and R ₇ may be bonded to each other to form a ring.
(3) The organic electroluminescence device as described in (1), wherein the general formula (I) is the following general formula (IV).

In the formula, R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ represent a hydrogen atom or a substituent. When R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ represent a substituent, they may further have a substituent, and R ₉ and R ₁₀ , R ₁₀ and R ₁₁ , R ₁₃ and R ₁₄ or R ₁₅ and R ₁₆ may be bonded to each other to form a ring.
(4) The organic electroluminescent element as described in (1), wherein the general formula (I) is the following general formula (V).

In the formula, R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ represent a hydrogen atom or a substituent. When R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ represent a substituent, they may further have a substituent, and R ₁₇ and R ₁₈ , R ₁₈ and R ₁₉ , R ₁₉ and R ₂₀ , R ₂₀ and R ₂₁ , R ₂₂ and R ₂₃ , R ₂₃ and R ₂₄ , R ₂₄ and R ₂₅ or R ₂₅ and R ₂₆ are bonded together to form a ring May be formed. _{R 8, R 9, R 10} , R 11, R 13, R 8 R 14, R 15 and R ₁₆ in the general formula _{(IV), R 9, R} 10, R 11, R 13, R 14, R 15 And R ₁₆ is synonymous.

(5) An organic electroluminescent device having an organic compound layer including a light emitting layer between a pair of electrodes, wherein at least one of the organic compound layers is composed of the compounds represented by the general formulas (I) to (IV) The organic electroluminescent element according to any one of (1) to (4), wherein the organic electroluminescent element comprises at least one kind and further contains at least one triplet light emitting material in the light emitting layer.
(6) The organic electroluminescent element according to any one of (1) to (5), wherein at least one triplet light-emitting material contained in the light-emitting layer is a platinum complex or an iridium complex.
(7) The organic electroluminescent element according to any one of (1) to (6), wherein at least one triplet light-emitting material contained in the light-emitting layer is a platinum complex.
(8) The lowest excited triplet energy level (hereinafter abbreviated as T ₁ ) of the compounds represented by the general formulas (I) to (V) is 65 kcal / mol (272.35 kJ / mol) or more and 95 kcal / mol ( (398.05 kJ / mol) or less, The organic electroluminescent element according to any one of (1) to (7),
(9) The glass transition temperature (hereinafter abbreviated as Tg) of the compounds represented by the general formulas (I) to (V) is 110 ° C. or higher and 400 ° C. or lower, (1) to (8) The organic electroluminescent element in any one.

  The light emitting element of the present invention has a low driving voltage and a low voltage rise. The light emitting device of the present invention can be suitably used in the fields of display devices, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like. In addition, the compounds represented by (I) to (V) of the present invention are used for medical use, fluorescent brighteners, photographic materials, UV absorbing materials, laser dyes, recording media materials, inkjet pigments, and color filters. It can also be applied to dyes, color conversion filters, analytical applications, and the like.

  In the present specification, the compounds represented by the general formulas (I), (II), (III), (IV) and (V) are used synonymously with “the compound of the present invention”. Moreover, the organic electroluminescent element which has the organic compound layer containing the compound of this invention is used synonymously with "the light emitting element of this invention." In this specification, the substituent group A is defined as follows.

(Substituent group A)
An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n- Decyl, n-hexadecyl), a cycloalkyl group (preferably having 3 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 3 to 10 carbon atoms, and examples thereof include cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, 3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 1 carbon atoms). , And the example propargyl and 3-pentynyl.),

An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl, anthranyl and the like), amino. Group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc. An alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc. An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably carbon 6 to 20, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, and the like, and heterocyclic oxy groups (preferably having 1 to 30 carbon atoms, more preferably ) Has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, and the like.

An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group ( Preferably it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and the like, and an aryloxycarbonyl group (preferably having a carbon number). 7 to 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl, and acyloxy groups (preferably 2 to 30 carbon atoms, more preferably carbon atoms). 2 to 20, particularly preferably 2 to 10 carbon atoms, for example, acetoxy, benzoyloxy An acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino). ,

An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino group ( Preferably it has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino, etc., and a sulfonylamino group (preferably 1 to 1 carbon atoms). 30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, methanesulfonylamino, benzenesulfonylamino, etc.), a sulfamoyl group (preferably C0-30, more preferably) Has 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms. Amoiru, methylsulfamoyl, dimethylsulfamoyl, and the like phenylsulfamoyl.),

A carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like), alkylthio. A group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), an arylthio group (preferably having 6 to 6 carbon atoms). 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and the like, and a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 carbon atom). -20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolyl Oh, 2-benzoxazolyl thio, and 2-benzthiazolylthio the like.),

A sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl), a sulfinyl group (preferably having 1 carbon atom). To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido groups (preferably 1 to 30 carbon atoms, more preferably C1-C20, Most preferably, it is C1-C12, for example, a ureido, methylureido, phenylureido etc. are mentioned), phosphoric acid amide groups (preferably C1-C30, more preferably carbon number) 1 to 20, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide That.), Hydroxy group, a mercapto group, a halogen atom (e.g. fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or more preferably fluorine atom),

A cyano group, a sulfo group, a carboxyl group, an oxo group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, a heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms). Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. Specifically, for example, an imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group , An azepinyl group, etc.), a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyl and triphenylsilyl). ), A silyloxy group (preferably having 3 to 40 carbon atoms, more preferably Properly 3 to 30 carbon atoms, particularly preferably from 3 to 24 carbon atoms, for example trimethylsilyloxy, etc. triphenylsilyl oxy and the like.) And the like. These substituents may be further substituted.

  The general formula (I) will be described.

In the general formula (I), R ₁ represents a substituent. The substituent is selected from the substituent group A. Q represents an atomic group consisting of carbon or nitrogen constituting a substituted or unsubstituted pyrazole ring together with a carbon atom. m represents an integer of 0 or more, and n represents an integer of 2 or more. However, the sum of m and n is 6 or less. The central benzene ring in the case where the sum of m and n is less than 6 means that a hydrogen atom is substituted except for a substituted or unsubstituted pyrazole ring composed of R ₁ or Q and a carbon atom. When the pyrazole ring composed of Q and a carbon atom has a substituent, specific examples thereof include the groups described in the substituent group A. Further, when having a plurality of substituents, they may be the same as or different from each other, and may be bonded to each other to form a condensed ring.

Next, the preferable range of general formula (I) is demonstrated.
R ₁ is preferably a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, amino group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkylthio group, arylthio group, hetero Ring thio group, sulfonyl group, hydroxy group, mercapto group, halogen atom, cyano group, nitro group, heterocyclic group, silyl group, more preferably hydrogen atom, alkyl group, cycloalkyl group, aryl group, aryloxy A group, a halogen atom, a cyano group, a heterocyclic group, and a silyl group, and more preferably a hydrogen atom, an alkyl group, an aryl group, a halogen atom, a cyano group, and a heterocyclic group. These substituents may be further substituted.
Q is preferably a case where it forms a substituted pyrazole ring together with a nitrogen atom and a carbon atom, and preferred substituents include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, Aryloxy group, heterocyclic oxy group, acyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, hydroxy group, mercapto group, halogen atom, cyano group, nitro group, heterocyclic group, silyl group, An alkyl group, a cycloalkyl group, an aryl group, an aryloxy group, a halogen atom, a cyano group, a heterocyclic group, and a silyl group are more preferable, and an alkyl group, a halogen atom, a cyano group, and a silyl group are more preferable. These substituents may be further substituted.
m represents an integer of 0 or more, and n is preferably 2 to 6, more preferably 2 to 5, further preferably 2 to 3, and particularly preferably n is 2. However, the sum of m and n is 6 or less.

  The relationship of the general formula in the present invention is as follows. The general formula (I) is preferably the general formula (II) or the general formula (III). Of the general formula (II) and the general formula (III), the general formula (II) is preferable. ) Is preferably general formula (IV), and general formula (IV) is preferably general formula (V).

The general formula (II) will be described. In the general formula (II), R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent.
R _1, m and n have the same meanings as R _1, m and n in the general formula (I). When R ₁ , R ₂ , R ₃ and R ₄ represent a substituent, they may further have a substituent, R ₁ and R ₃ , R ₁ and R ₂ , R ₁ and R ₄ or R ₃ and R ₄ may be bonded to each other to form a ring.
In the general formula (II), R ₂ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, Alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, hydroxy group, mercapto group, halogen atom, cyano group, nitro group, heterocyclic group, silyl group, more preferably hydrogen atom, alkyl group, cycloalkyl A group, an aryl group, an aryloxy group, a halogen atom, a cyano group, a heterocyclic group, and a silyl group, and more preferably an aryl group or a heterocyclic group. These substituents may be further substituted.

R ₃ and R ₄ are preferably hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, amino group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkylthio group, arylthio Group, heterocyclic thio group, sulfonyl group, hydroxy group, mercapto group, halogen atom, cyano group, nitro group, heterocyclic group, silyl group, more preferably hydrogen atom, alkyl group, cycloalkyl group, aryl group , An aryloxy group, a halogen atom, a cyano group, and a silyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, a halogen atom, and a cyano group, and particularly preferably an alkyl group or a cyano group. R _1, m and n have the same meanings as R _1, m and n in formula (I), a preferred range is also the same.
When R ₁ and R ₃ , R ₁ and R ₂ , R ₁ and R ₄ or R ₃ and R ₄ are bonded to each other to form a ring, a case where a 5- to 7-membered condensed ring is formed is preferable, More preferably, it is a 6-membered condensed ring, and more preferably, the condensed 6-membered ring forms a benzene condensed ring, a pyridine condensed ring, a pyrazine condensed ring, a pyrimidine condensed ring, or a pyridazine condensed ring.

The general formula (III) will be described. In the general formula (III), R ₅ , R ₆ and R ₇ represent a hydrogen atom or a substituent. R _1, m and n have the same meanings as R _1, m and n in the general formula (I). When R ₁ , R ₅ , R ₆ and R ₇ represent a substituent, they may further have a substituent, R ₁ and R ₅ , R ₁ and R ₆ , R ₁ and R ₇ , R ₅ and R ₆ or R ₆ and R ₇ may be bonded to each other to form a ring. In the general formula (III), R ₅ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, Alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, hydroxy group, mercapto group, halogen atom, cyano group, nitro group, heterocyclic group, silyl group, more preferably hydrogen atom, alkyl group, cycloalkyl A group, an aryl group, an aryloxy group, a halogen atom, a cyano group, a heterocyclic group, and a silyl group, and more preferably an aryl group or a heterocyclic group. These substituents may be further substituted.

R ₆ and R ₇ are preferably hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, amino group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkylthio group, arylthio Group, heterocyclic thio group, sulfonyl group, hydroxy group, mercapto group, halogen atom, cyano group, nitro group, heterocyclic group, silyl group, more preferably hydrogen atom, alkyl group, cycloalkyl group, aryl group , An aryloxy group, a halogen atom, a cyano group, and a silyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, a halogen atom, and a cyano group, and particularly preferably an alkyl group or a cyano group. R _1, m and n have the same meanings as R _1, m and n in formula (I), a preferred range is also the same.
When R ₁ and R ₅ , R ₁ and R ₆ , R ₁ and R ₇ , R ₅ and R ₆ or R ₆ and R ₇ are bonded to each other to form a ring, a 5- to 7-membered condensed ring is formed. Preferably, it is a 6-membered condensed ring, and more preferably a condensed 6-membered ring forms a benzene condensed ring, a pyridine condensed ring, a pyrazine condensed ring, a pyrimidine condensed ring, or a pyridazine condensed ring. is there.

The general formula (IV) will be described. In the general formula (IV), R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ represent a hydrogen atom or a substituent. When R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ represent a substituent, they may further have a substituent, and R ₉ and R ₁₀ , R ₁₀ and R ₁₁ , R ₁₃ and R ₁₄ or R ₁₅ and R ₁₆ may be bonded to each other to form a ring. In the general formula (IV), R ₈ , R ₉ , R ₁₀ and R ₁₁ are preferably hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, amino group, alkoxy group, aryloxy group , Heterocyclic oxy group, acyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, hydroxy group, mercapto group, halogen atom, cyano group, nitro group, heterocyclic group, silyl group, more preferably , Hydrogen atom, alkyl group, cycloalkyl group, aryl group, aryloxy group, halogen atom, cyano group, heterocyclic group, silyl group, more preferably hydrogen atom, alkyl group, aryl group, halogen atom, cyano Particularly preferably a hydrogen atom, an alkyl group or a cyano group.

R ₁₂ and R ₁₇ are preferably hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, amino group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkylthio group, arylthio group , Heterocyclic thio group, sulfonyl group, hydroxy group, mercapto group, halogen atom, cyano group, nitro group, heterocyclic group, silyl group, more preferably hydrogen atom, alkyl group, cycloalkyl group, aryl group, An aryloxy group, a halogen atom, a cyano group, a heterocyclic group, and a silyl group are preferable, and an aryl group or a heterocyclic group is more preferable. These substituents may be further substituted.

R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are preferably a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, amino group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl Group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, hydroxy group, mercapto group, halogen atom, cyano group, nitro group, heterocyclic group, silyl group, more preferably hydrogen atom, alkyl group, A cycloalkyl group, an aryl group, an aryloxy group, a halogen atom, a cyano group, a heterocyclic group, and a silyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, a halogen atom, and a cyano group, and particularly preferably an alkyl group. Group or cyano group.
When R ₉ and R ₁₀ , R ₁₀ and R ₁₁ , R ₁₃ and R ₁₄ or R ₁₅ and R ₁₆ are bonded to each other to form a ring, it is preferable to form a 5- to 7-membered condensed ring, More preferably, it is a 6-membered condensed ring, and more preferably, the condensed 6-membered ring forms a benzene condensed ring, a pyridine condensed ring, a pyrazine condensed ring, a pyrimidine condensed ring, or a pyridazine condensed ring.

The general formula (V) will be described. In the general formula (V), R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ (hereinafter referred to as R _{17 to} R ₂₆ in the present specification) Represents a hydrogen atom or a substituent. When adjacent groups (for example, R ₁₇ and R ₁₈ ) represent a substituent, they may further have a substituent and may be bonded to each other to form a ring. In the general formula (IV), R _{17 to} R ₂₆ are preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic ring. Oxy group, acyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, hydroxy group, mercapto group, halogen atom, cyano group, nitro group, heterocyclic group, silyl group, more preferably a hydrogen atom , An alkyl group, a cycloalkyl group, an aryl group, an aryloxy group, a halogen atom, a cyano group, a heterocyclic group, and a silyl group, and more preferably a hydrogen atom, an alkyl group, an aryl group, a halogen atom, and a cyano group. Particularly preferred are a hydrogen atom, an alkyl group, a halogen atom or a cyano group. _{R 8, R 9, R 10} , R 11, R 13, R 8 R 14, R 15 and R ₁₆ in the general formula _{(IV), R 9, R} 10, R 11, R 13, R 14, R 15 And R ₁₆ , and the preferred range is also the same.
When adjacent groups of R _{17 to} R ₂₆ (for example, R ₁₇ and R ₁₈ ) are bonded to each other to form a ring, it is preferable to form a 5- to 7-membered condensed ring, more preferably a 6-membered member. It is a condensed ring, and more preferably, a condensed 6-membered ring forms a benzene condensed ring, a pyridine condensed ring, a pyrazine condensed ring, a pyrimidine condensed ring, or a pyridazine condensed ring.

The lowest excited triplet energy level (hereinafter sometimes abbreviated as T ₁ ) of the compound of the present invention is preferably 65 kcal / mol (272.35 kJ / mol) or more and 95 kcal / mol (398.05 kJ / mol). Or less, more preferably 65 kcal / mol (272.35 kJ / mol) or more, 80 kcal / mol (335.2 kJ / mol) or less, more preferably 65 kcal / mol (272.35 kJ / mol) or more, It is 75 kcal / mol (314.3 kJ / mol) or less, and particularly preferably 65 kcal / mol (272.35 kJ / mol) or more and 70 kcal / mol (293.3 kJ / mol) or less.

  For the lowest excited triplet energy levels of compounds, see Haruo Inoue, Katsuhiko Takagi, Masako Sasaki, and Kogane Park “Photochemistry I”, pages 34-38, published by Maruzen Co., Ltd. in 1999 and Katsumi Tokumaru “The World of Photochemistry” 48-54, published by Dainippon Publishing Co., Ltd., 1993, etc., and can be calculated by the methods described therein.

  The compound of the present invention preferably has a glass transition temperature (hereinafter abbreviated as Tg) of 110 ° C. or higher and 400 ° C. or lower, more preferably 140 ° C., from the viewpoint of vapor deposition, thermal stability, film amorphousness, and crystallization suppression. The temperature is 350 ° C. or lower, more preferably 150 ° C. or higher and 300 ° C. or lower.

  The compound of the present invention may be a low molecular compound, and is an oligomer compound or a polymer compound (weight average molecular weight (polystyrene conversion) is preferably 1000 to 5000000, more preferably 2000 to 1000000, still more preferably 3000 to 100000. Yes.) In the case of a polymer compound, structures represented by the general formulas (I) to (V) may be included in the polymer main chain, or may be included in the polymer side chain. In the case of a polymer compound, it may be a homopolymer compound or a copolymer. The compound of the present invention is preferably a low molecular compound.

  Next, although the compound example of the compound of this invention is shown, this invention is not limited to this.

  The compound of the present invention can be synthesized by a method such as a condensation reaction between a dicarbonyl compound and a hydrazine derivative or a coupling reaction using a transition metal between an organic halide and an organic borate ester or organic borate compound as a catalyst. For example, it can be synthesized with reference to the method described in the European Journal of Organic Chemistry, 4, 747-755, (2003), but is not limited to the method mentioned here.

  The reaction time for synthesizing the compound of the present invention varies depending on the activity of the reaction and is not particularly limited, but is preferably 1 minute to 5 days, more preferably 5 minutes to 3 days, and more preferably 10 minutes to 24 hours. preferable.

  The reaction temperature for synthesizing the compound of the present invention varies depending on the activity of the reaction and is not particularly limited, but is preferably 0 ° C. or higher and 300 ° C. or lower, more preferably 5 ° C. or higher and 250 ° C. or lower, and more preferably 10 ° C. or higher and 200 ° C. or lower. preferable.

  Next, although the specific synthesis example of exemplary compound (1) and (11) is shown among the compounds of this invention, it is not limited to this method.

<Synthesis of Compound (1) of the Present Invention-1>
In a 300 ml three-necked flask, 4.21 g (18.0 mmol) of 1,3-dibromobenzene (A), 10.1 g (39.6 mmol) of bispinacolatodiboron, 200 ml of anhydrous N, N-dimethylformamide, 10.4 g of potassium acetate (106 Diphenylphosphinoferrocenepalladium dichloride 0.86 g (1.05 mmol) was added to the mixture while stirring under a nitrogen stream, and the mixture was stirred at 80 ° C. for 9 hours. Then, water was added and the aqueous layer was extracted with ethyl acetate. The collected organic layer was dried over anhydrous magnesium sulfate, the inorganic salt was filtered off, and the organic layer was concentrated on a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 3.86 g of compound (B) as a white solid in a yield of 65.0%.
¹ H-NMR (400 MHz, in CDCl ₃ ) δ = 7.37 (t, J = 7.6 Hz, 1 H), 7.90 (dd, J = 1.2, 7.6 Hz, 2H), 8.28 (br.s, 1H).

In a 300 mL three-necked flask, under a nitrogen stream, 25.0 g (183 mmol) of compound (C), 56.3 g (276 mmol) of iodobenzene, 1.31 g (9.16 mmol) of copper oxide, 120 g (368 mmol) of cesium carbonate. ), Salicylaldoxime 5.00 g (36.5 mmol) acetonitrile 195 ml was added, and the mixture was stirred with heating under reflux for 6 hours. Thereafter, water and ethyl acetate were added to the reaction mixture, and the mixture was filtered through Celite, and then the aqueous layer was extracted with ethyl acetate. The collected organic layer was dried over anhydrous magnesium sulfate, the inorganic salt was filtered off, and the filtrate was concentrated on a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 29.5 g of compound (D) as a pale yellow oily compound in a yield of 75.7%.
¹ H-NMR (300 MHz, in CDCl ₃ ): δ (ppm) = 6.72 (d, 1H, J = 2.7 Hz), 7.32 (m, 1H), 7.45-7.53 (m, 2H), 7.67-7.74 ( m, 2H), 7.93-7.97 (m, 1H).

Under a nitrogen stream, 9.61 g (45.3 mmol) of compound (D) and 96 ml of anhydrous tetrahydrofuran were added to a 500 mL three-necked flask, and the mixture was stirred at −78 ° C., where n-butyllithium hexane solution (1. 6M) 31.1 ml (49.8 mmol) was slowly added dropwise, and the mixture was further stirred at -78 ° C for 1 hour. Thereafter, 13.8 g (54.4 mmol) of iodine in anhydrous tetrahydrofuran (138 ml) was added to the reaction mixture, and the temperature was gradually raised from −78 ° C. to room temperature with stirring. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was stirred for 1 hour. The aqueous layer and the organic layer were separated, and the aqueous layer was extracted with ethyl acetate. The collected organic layer was dried over anhydrous magnesium sulfate, the inorganic salt was filtered off, and the filtrate was concentrated on a rotary evaporator. The obtained residue was purified by silica gel column chromatography to quantitatively obtain 15.8 g of compound (E) as a yellow oily compound.
¹ H-NMR (300 MHz, in CDCl ₃ ): δ (ppm) = 6.89 (br.s, 1H), 7.48-7.52 (m, 5H).

In a 200 mL three-necked flask, 0.33 g (1.00 mmol) of compound (B), 0.74 g (2.2 mmol) of compound (E), 0.022 g (0.098 mmol) of palladium acetate, 0.11 g (0.42 mmol) of phenylphosphine, 5 ml of 1,2-dimethoxyethane, and 5 ml of 1M aqueous sodium hydrogen carbonate solution were added, and the mixture was stirred for 6 hours while heating under reflux. Water was added to the reaction mixture, and the aqueous layer was extracted with ethyl acetate. The collected organic layer was dried over anhydrous magnesium sulfate, the inorganic salt was filtered off, and the filtrate was concentrated on a rotary evaporator. The obtained residue was purified by silica gel column chromatography. The obtained crystals were dispersed and washed with hexane to obtain 0.39 g of compound (1) in a yield of 78% as a white powder.
¹ H-NMR (400 MHz, in CDCl ₃ ): δ (ppm) = 6.57 (br.s, 2H), 7.13-7.18 (m, 3H), 7.23-7.30 (m, 5H), 7.36-7.44 (m , 6H).

<Synthesis of Compound (1) of the Present Invention-2>
To a 500 mL three-necked flask, 14.3 g (88.2 mmol) of 1,3-diacetylbenzene (F) and 143 ml of tetrahydrofuran were added under a nitrogen stream, and potassium t-butoxide 21. was added to the mixture while stirring with a mechanical stirrer. 8 g (194 mmol) was added, and 58 ml of an anhydrous tetrahydrofuran solution of 27.6 g (194 mmol) of ethyl trifluoroacetate was slowly added dropwise, and the mixture was stirred for 3 hours while heating under reflux. Dilute hydrochloric acid was added to the reaction mixture to adjust the pH in the system to 1-2, and then the aqueous layer was extracted with ethyl acetate. The collected organic layer was dried over anhydrous magnesium sulfate, the inorganic salt was filtered off, and the filtrate was concentrated on a rotary evaporator. The obtained crude crystals were dispersed and washed with hexane to obtain 24.5 g of compound (G) as a yellow powder in a yield of 78.5%.
¹ H-NMR (400 MHz, in CDCl ₃ ): δ (ppm) = 6.35 (br.s, 2H), 7.69 (t, 1H, J = 7.6 Hz), 8.17 (dd, 2H, J 1.6, 7.6 Hz ), 8.47-8.52 (m, 1H), 14.6-15.6 (br., 2H).

To a 500 mL three-necked flask, 14.0 g (39.5 mmol) of compound (G) and 140 ml of ethanol were added, and 9.4 g (86.9 mmol) of phenylhydrazine was added to the mixture while stirring at room temperature. For 6 hours. Water was added to the reaction mixture, and the aqueous layer was extracted with ethyl acetate. The collected organic layer was dried over anhydrous magnesium sulfate, the inorganic salt was filtered off, and the filtrate was concentrated on a rotary evaporator. The obtained residue was purified by silica gel column chromatography. The obtained crystals were dispersed and washed with hexane to obtain 11.0 g of compound (1) as a white powder in a yield of 55.8%. As a result of ¹ H-NMR analysis, it was in good agreement with the ¹ H-NMR result of (1) synthesized by the method described above. From the result of phosphorescence spectrum measurement of the compound (1) of the present invention in a dichloromethane solution at a low temperature, the lowest excited triplet energy level was estimated to be 68 kcal / mol (284.9 kJ / mol).

<Synthesis of Compound (11) of the Present Invention>
The compound (H) was synthesized with reference to the method described in Journal of the Medicinal Chemistry, 34 (9), 2892-2898, (1991). To a 100 mL three-necked flask were added 1.84 g (9.99 mmol) of compound (H), 2.23 g (9.98 mmol) of copper (II) bromide, and 18 ml of 45% aqueous hydrobromic acid solution, and the mixture was cooled with ice. While stirring at 0, 0.83 g (12 mmol) of sodium nitrite was carefully added. Thereafter, the reaction mixture was stirred at room temperature for 1 hour, water was added, and the mixture was further stirred for 1 hour. The resulting crude crystals were separated by filtration and purified by silica gel column chromatography to obtain 1.33 g of compound (I) as a powder in a yield of 53.6%.
¹ H-NMR (400 MHz, in CDCl ₃ ): δ (ppm) = 7.52-7.57 (m, 5H), 7.99 (s, 1H).

In a 200 mL three-necked flask, under nitrogen stream, 0.50 g (2.0 mmol) of compound (B), 0.33 g (1.0 mmol) of compound (I) 0.12 g (0.10 mmol) of tetrakistriphenylphosphine palladium 1,2-dimethoxyethane (10 ml) and 1M aqueous sodium hydrogen carbonate solution (10 ml) were added, and the mixture was stirred for 6 hours under reflux. Water was added to the reaction mixture, and the aqueous layer was extracted with ethyl acetate. The collected organic layer was dried over anhydrous magnesium sulfate, the inorganic salt was filtered off, and the filtrate was concentrated on a rotary evaporator. The obtained residue was purified by silica gel column chromatography. The obtained crystals were dispersed and washed with hexane to obtain 0.35 g of compound (11) in a yield of 85% as a white powder.
¹ H-NMR (300 MHz, in CDCl ₃ ): δ (ppm) = 7.18-7.54 (m, 14H), 8.03 (s, 2H).

Next, a light emitting device containing the compound of the present invention will be described.
The light-emitting device of the present invention can be used in ordinary light-emitting systems, driving methods, usage forms, and the like except that it is a device using the compound of the present invention. The compound of the present invention is preferably used as a light emitting material, host material, exciton blocking material, charge blocking material or charge transporting material, more preferably used as a host material, exciton blocking material or charge transporting material. Further preferred. When used as a light-emitting material, ultraviolet light emission or infrared light emission may be used, and fluorescent light emission or phosphorescence light emission may be used. When used as a charge transport material, it may be a hole transport property or an electron transport property. It is preferably used for an organic EL (electroluminescence) element as a typical light emitting element. By including the compound of the present invention in the organic compound layer, an organic EL device having a low driving voltage and a small voltage increase width can be obtained.
When using the compound of this invention as a luminescent material in a light emitting layer, it is preferable to be contained in 0.1-40 mass% in a light emitting layer, and it is preferable to be contained at 0.5-20 mass%.
When used as a host material in the light emitting layer, the light emitting layer preferably contains 60 to 99.9% by mass, and preferably 80 to 99.5% by mass.
When included in a layer other than the light emitting layer (for example, a charge blocking layer or a charge transport layer), it is preferably included in the layer at 0.1 to 100% by mass, and is included at 0.5 to 100% by mass. It is preferable.

[Organic electroluminescence device]
Hereinafter, the organic electroluminescence device of the present invention will be described in detail.
The light-emitting element of the present invention has a cathode and an anode on a substrate, and an organic compound layer including an organic light-emitting layer (hereinafter sometimes simply referred to as “light-emitting layer”) between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.

  As an aspect of lamination of the organic compound layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. Further, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Each layer may be divided into a plurality of secondary layers.

  Next, the elements constituting the light emitting material of the present invention will be described in detail.

<Board>
The substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic compound layer. Specific examples include zirconia-stabilized yttrium (YSZ), inorganic materials such as glass, polyesters such as polyethylene terephthalate, polybutylene phthalate, and polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, and polycycloolefin. , Organic materials such as norbornene resin and poly (chlorotrifluoroethylene).
For example, when glass is used as the substrate, alkali-free glass is preferably used as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. In the case of an organic material, it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.

  There is no restriction | limiting in particular about the shape of a board | substrate, a structure, a magnitude | size, It can select suitably according to the use, purpose, etc. of a light emitting element. In general, the shape of the substrate is preferably a plate shape. The structure of the substrate may be a single layer structure, a laminated structure, may be formed of a single member, or may be formed of two or more members.

  The substrate may be colorless and transparent or colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate light emitted from the organic light emitting layer.

The substrate can be provided with a moisture permeation preventing layer (gas barrier layer) on the front surface or the back surface.
As a material for the moisture permeation preventive layer (gas barrier layer), inorganic materials such as silicon nitride and silicon oxide are preferably used. The moisture permeation preventing layer (gas barrier layer) can be formed by, for example, a high frequency sputtering method.
When a thermoplastic substrate is used, a hard coat layer, an undercoat layer, or the like may be further provided as necessary.

<Anode>
The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials. As described above, the anode is usually provided as a transparent anode.

  Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof. Specific examples of the anode material include conductive metals such as tin oxide doped with antimony and fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metals such as oxides, gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene, polypyrrole, etc. Organic conductive materials, and a laminate of these and ITO. Among these, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

  The anode is composed of, for example, a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a chemical method such as a CVD and a plasma CVD method. It can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material to be processed. For example, when ITO is selected as the anode material, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.

  In the organic electroluminescent element of the present invention, the formation position of the anode is not particularly limited and can be appropriately selected according to the use and purpose of the light emitting element. Is preferably constructed on the substrate. In this case, the anode may be formed on the entire one surface of the substrate, or may be formed on a part thereof.

  The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching such as laser, or vacuum deposition or sputtering with a mask overlapped. It may be performed by a lift-off method or a printing method.

  The thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is usually about 10 nm to 50 μm, and preferably 50 nm to 20 μm.

The resistance value of the anode is preferably 10 ³ Ω / □ or less, and more preferably 10 ² Ω / □ or less. When the anode is transparent, it may be colorless and transparent or colored and transparent. In order to take out light emission from the transparent anode side, the transmittance is preferably 60% or more, and more preferably 70% or more.

  The transparent anode is described in detail in the book “New Development of Transparent Electrode Films” published by CMC (1999), supervised by Yutaka Sawada, and the matters described here can be applied to the present invention. In the case of using a plastic substrate having low heat resistance, a transparent anode formed using ITO or IZO at a low temperature of 150 ° C. or lower is preferable.

<Cathode>
The cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials.

  Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium. -Rare earth metals such as silver alloys, indium, ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, as a material constituting the cathode, an alkali metal or an alkaline earth metal is preferable from the viewpoint of electron injecting property, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01 to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.) Say.

  The materials for the cathode are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these public relations can also be applied in the present invention.

  There is no restriction | limiting in particular about the formation method of a cathode, According to a well-known method, it can carry out. For example, the cathode described above is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the cathode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like.

  Patterning when forming the cathode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or by vacuum deposition or sputtering with the mask overlaid. It may be performed by a lift-off method or a printing method.

In the present invention, the cathode formation position is not particularly limited, and may be formed on the entire organic compound layer or a part thereof.
Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the cathode and the organic compound layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 μm, and preferably 50 nm to 1 μm.
Further, the cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

<Organic compound layer>
The organic compound layer in the present invention will be described.
The organic electroluminescent element of the present invention has at least one organic compound layer. The organic compound layer includes at least a light emitting layer. Examples of the organic compound layer other than the light emitting layer include layers such as a hole transport layer, an electron transport layer, a charge blocking layer, a hole injection layer, and an electron injection layer as described above.

-Formation of organic compound layer-
In the organic electroluminescent element of the present invention, each layer constituting the organic compound layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a transfer method, and a printing method.

-Light emitting layer-
The light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines holes and electrons. It is a layer which has the function to provide and to emit light.
The light emitting layer in the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material. The light emitting material may be a fluorescent light emitting material or a triplet light emitting material (phosphorescent light emitting material), and the dopant may be one type or two or more types. The host material is preferably a charge transport material. The host material may be one type or two or more types, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Further, the light emitting layer may include a material that does not have charge transporting properties and does not emit light.
Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  Examples of fluorescent materials that can be used in combination with the compounds of the present invention include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimides. Derivatives, coumarin derivatives, condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styryl For metal complexes of amine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives and pyromethene derivatives. And various metal complexes represented by, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

Examples of the ligand of the complex include G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H. Yersin, “Photochemistry and Photophysics of Coordination Compounds,” Springer-Verlag, 1987, Akio Yamamoto. Examples of the ligands described in the book “Organic Metal Chemistry-Fundamentals and Applications-” published in 1982 by Hankabosha.
Specific ligands are preferably halogen ligands (preferably chlorine ligands), nitrogen-containing heterocyclic ligands (eg, phenylpyridine, benzoquinoline, quinolinol, bipyridyl, phenanthroline, etc.), diketones Ligand (for example, acetylacetone), carboxylic acid ligand (for example, acetic acid ligand), carbon monoxide ligand, isonitrile ligand, cyano ligand, more preferably nitrogen-containing Heterocyclic ligand. The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.

The phosphorescent material is preferably contained in the light emitting layer in an amount of 0.1 to 40% by mass, and more preferably 0.5 to 20% by mass.
As the phosphorescent material, a platinum complex or an iridium complex is preferable, and a platinum complex is more preferable.
Examples of the phosphorescent material include metal complexes described in WO04 / 099339 pamphlet, 04/006498 pamphlet, and 04/108857 pamphlet. The compound of the present invention is preferably applied in combination with these metal complexes.

  Examples of the host material contained in the light emitting layer in the present invention include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and aryl. Examples thereof include materials having a silane skeleton and materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later.

  Although the thickness of a light emitting layer is not specifically limited, Usually, it is preferable that they are 1 nm-500 nm, it is more preferable that they are 5 nm-200 nm, and it is still more preferable that they are 10 nm-100 nm.

-Hole injection layer, hole transport layer-
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon , Etc. are preferable.
The thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the hole injection layer is preferably 0.1 nm to 200 nm, more preferably 0.5 nm to 100 nm, and still more preferably 1 nm to 100 nm.
The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. .

-Electron injection layer, electron transport layer-
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various metal complexes typified by metal complexes, organosilane derivatives, and the like.

The thicknesses of the electron injection layer and the electron transport layer are each preferably 50 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the electron injection layer is preferably 0.1 nm to 200 nm, more preferably 0.2 nm to 100 nm, and still more preferably 0.5 nm to 50 nm.
The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

-Hole blocking layer-
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side.
Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like.
The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm.
The hole blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

-Exciton block layer-
The exciton blocking layer is a layer having a function of preventing a phenomenon in which the light emission efficiency is lowered due to energy transfer of excitation energy generated by charge recombination in the light emitting layer to an adjacent layer. In the present invention, an exciton blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the anode or cathode side.
Examples of the organic compound constituting the exciton blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like, and may be the same as the hole blocking layer described above.
The thickness of the exciton blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm.
The exciton blocking layer may have a single-layer structure composed of one or more of the materials described above, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

<Protective layer>
In the present invention, the entire organic EL element may be protected by a protective layer.
As a material contained in the protective layer, any material may be used as long as it has a function of preventing materials that promote device deterioration such as moisture and oxygen from entering the device.
As specific examples, In, Sn, Pb, Au , Cu, Ag, Al, Ti, a metal such as _{Ni, MgO, SiO, SiO 2,} Al 2 O 3, GeO, NiO, CaO, BaO, Fe 2 O ₃ , metal oxides such as Y ₂ O ₃ and TiO ₂ , metal nitrides such as SiN _x and SiN _x O _y , metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF ₂ , polyethylene, polypropylene, polymethyl Monomer mixture containing methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer Copolymer obtained by copolymerizing fluorinated copolymer having a cyclic structure in the copolymer main chain Water absorption of 1% by weight of the water absorbing material, the water absorption of 0.1% or less of moisture-proof material, and the like.

  The method for forming the protective layer is not particularly limited, and for example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency) Excited ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method can be applied.

<Sealing>
Furthermore, the organic electroluminescent element of this invention may seal the whole element using a sealing container.
Further, a moisture absorbent or an inert liquid may be sealed in a space between the sealing container and the light emitting element. Although it does not specifically limit as a moisture absorber, For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride Cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, magnesium oxide and the like. The inert liquid is not particularly limited, and examples thereof include fluorinated solvents such as paraffins, liquid paraffins, perfluoroalkanes, perfluoroamines, perfluoroethers, chlorinated solvents, and silicone oils. It is done.

The organic electroluminescent device of the present invention emits light by passing a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. Obtainable.
The driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-2441047. The driving method described in each publication, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429, 6023308, and the like can be applied.

  Hereinafter, the present invention will be described in detail based on examples, but the embodiment of the present invention is not limited thereto.

(Comparative example)
The cleaned ITO substrate is put in a vapor deposition apparatus, NPD is vapor-deposited by 50 nm, and CBP and Compound (83) (compound described in International Publication No. 2004/108857) are vapor-deposited by 40 nm at a mass ratio of 10: 1. Further, 3 nm of BAlq was deposited thereon, and 30 nm of Alq was further deposited thereon. A patterned mask (with a light emission area of 4 mm × 5 mm) was placed on the obtained organic thin film, and after 3 nm of lithium fluoride was deposited, 60 nm of aluminum was deposited to prepare an organic EL device of Comparative Example 1. When a DC constant current having a current density of 500 A / m ² was passed through the obtained organic EL element, light emission was observed. Light was emitted for 10 hours at a luminance of 300 cd / m ² .

Example 1
In Comparative Example 1, an organic EL device of Example 1 was prepared in the same manner as Comparative Example 1 except that the exemplified compound (1) of the present invention was used instead of BAlq. When a DC constant current having a current density of 500 A / m ² was passed through the obtained organic EL element, light emission was observed. When light was emitted for 10 hours at a luminance of 300 cd / m ² , the driving voltage was lower than that of Comparative Example 1, and the voltage increase was small.

  The organic electroluminescent element of the present invention can be suitably used in the fields of display elements, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like. The compounds of the present invention can also be applied to pharmaceuticals, fluorescent brighteners, photographic materials, UV absorbing materials, laser dyes, recording media materials, inkjet pigments, color filter dyes, color conversion filters, analytical applications, etc. It is.

Claims (6)

An organic electroluminescent device having an organic compound layer including a light emitting layer between a pair of electrodes, wherein the hole blocking layer contains at least one compound represented by the following general formula (IV) Organic electroluminescent device.

In the formula, R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ represent a hydrogen atom or a substituent. When R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ represent a substituent, they may further have a substituent, and R ₉ and R ₁₀ , R ₁₀ and R ₁₁ , R ₁₃ and R ₁₄ or R ₁₅ and R ₁₆ may be bonded to each other to form a ring.   In the general formula (IV), R ₈ , R ₉ , R _Ten And R ₁₁ Represents a hydrogen atom, an alkyl group or a cyano group, R ₁₂ And R ₁₇ Represents an aryl group or a heterocyclic group, R ₁₃ , R ₁₄ , R ₁₅ And R ₁₆ The organic electroluminescence device according to claim 1, wherein represents a hydrogen atom, an alkyl group, a cyano group, or a trifluoromethyl group. An organic electroluminescence device having an organic compound layer including a light emitting layer between a pair of electrodes, wherein the hole blocking layer contains at least one compound represented by the following general formula (V) Organic electroluminescent device.

In the formula, R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ represent a hydrogen atom or a substituent. _{R 8, R 9, R 10} , R 11, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25 And R ₂₆ represents a substituent, it may further have a substituent, R ₉ and R ₁₀ , R ₁₀ and R ₁₁ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ , R ₁₈ and R ₁₉ , R ₁₉ and R ₂₀ , R ₂₀ and R ₂₁ , R ₂₂ and R ₂₃ , R ₂₃ and R ₂₄ , R ₂₄ and R ₂₅ or R ₂₅ and R ₂₆ are bonded to each other to form a ring May be.   In the general formula (V), R ₈ , R ₉ , R _Ten And R ₁₁ Represents a hydrogen atom, an alkyl group or a cyano group, R ₁₃ , R ₁₄ , R ₁₅ And R ₁₆ Represents a hydrogen atom, an alkyl group, a cyano group or a trifluoromethyl group, and R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R _{twenty one} , R _{twenty two} , R _{twenty three} , R _{twenty four} , R _{twenty five} And R ₂₆ The organic electroluminescent element according to claim 3, wherein represents a hydrogen atom, an alkyl group, a halogen atom, or a cyano group. An organic electroluminescent device having an organic compound layer including a light emitting layer between a pair of electrodes, wherein the hole blocking layer contains at least one compound represented by formula (IV) or (V) , and further emits light The organic electroluminescent element according to claim 1, wherein the layer contains at least one triplet light emitting material. 6. The organic electroluminescent device according to claim 5 , wherein at least one triplet light-emitting material contained in the light-emitting layer is a platinum complex or an iridium complex.