JP2006032638A - Light emitting element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light emitting element which assures excellent light emitting characteristic and durability for drive. <P>SOLUTION: The light emitting element includes an organic compound including at least a light emitting layer between a pair of electrodes. At least one layer of the organic compound layer includes a compound expressed with a general expression (I), and a positive hole rejecting layer is also provided between the layer including the general expression (I) and the light emitting layer. In the expression, R<SP>1</SP>to R<SP>4</SP>respectively indicate independently hydrogen, halogen atom, alkyl group, aryl group, and heteroaryl group. Moreover, X<SP>1</SP>and X<SP>2</SP>respectively indicate independently alkyl group, aryl group, and heteroaryl group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an organic electroluminescent element (light emitting element or EL element) that can emit light by converting electric energy into light.

Today, research and development on various display elements are active. Among them, organic electroluminescence (EL) elements are attracting attention as promising display elements because they can emit light with high luminance at a low voltage.
However, this organic electroluminescent element has a very low luminous efficiency compared to inorganic LED elements and fluorescent tubes, which is a big problem. Most of the organic electroluminescent devices currently proposed utilize fluorescence emitted from singlet excitons of an organic compound luminescent material. In the mechanism of simple quantum chemistry, in the exciton state, the ratio of singlet excitons that give fluorescence emission and triplet excitons that give phosphorescence emission is 1: 3, as long as fluorescence emission is used. Only 25% of the excitons can be effectively used, resulting in low emission efficiency. On the other hand, if phosphorescence obtained from triplet excitons can be used, the luminous efficiency can be improved. The light emission efficiency (external quantum efficiency) is calculated by “external quantum efficiency φ = number of photons emitted from the device / number of electrons injected into the device”, and the larger this value, the more advantageous the device in terms of power consumption. . The external quantum efficiency of the organic electroluminescence device is determined by “external quantum efficiency φ = internal quantum efficiency × light extraction efficiency”.
Based on the above idea, a phosphorescent light emitting device using a phenylpyridine complex of iridium has recently been reported (Non-Patent Document 1). In these reports, the luminous efficiency of 2 to 3 times that of conventional organic light-emitting devices using fluorescence is reported. However, this is still low in terms of energy saving and durability improvement, and further improvement in luminous efficiency and luminance are strongly demanded.
In addition, organic compounds other than the light-emitting material used in the organic electroluminescent element, for example, an electron transport material, a hole transport material, and the like have been studied for improving luminance and driving durability. The silacyclopentadiene compound is disclosed to be used for a light-emitting material, an electron transport material, a hole blocking material, etc. (see, for example, Patent Documents 1 to 3, Non-Patent Documents 1 to 4, etc.), and particularly has an electron transport ability. Although it is known to be high and is expected in terms of luminous efficiency, it is still insufficient in terms of driving durability, and improvement is desired.
Japanese Patent No. 2918150 JP 2000-186094 A JP 2001-172284 A “Appl. Phys. Lett.”, 1999, Vol. 75, p. 4 “Chemical Physics Letters”, 2001, No. 339, p. 161-166 “Chemical Materials”, 2001, Vol. 13, p. 2680-2683 “Appl. Phys. Lett.”, 2002, 80, p. 89-191

  An object of the present invention is to provide a light emitting device having good light emission characteristics and driving durability.

This object has been achieved by the following means. That is,
<1> A light-emitting element having an organic compound layer including at least one light-emitting layer between a pair of electrodes, wherein at least one of the organic compound layers contains a compound represented by the following general formula (I) And a hole blocking layer between the layer containing the general formula (I) and the light emitting layer.

(In the general formula (I), R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heteroaryl group. X ¹ and X ² are each independently an alkyl group. Represents a group, an aryl group, or a heteroaryl group.)

<2> The light emitting device according to <1>, wherein the compound of the general formula (I) is the following general formula (II).

(In general formula (II), R ^{1 to} R ⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heteroaryl group.)

<3> In the hole blocking layer, at least any of a metal complex salt of an 8-quinolinol derivative and a compound selected from the following general formulas (III), (IV), (V), (VI), and (VII) The light-emitting element according to <1> or <2> above, comprising:

(In the general formula (III), Ar ¹¹ represents an aryl group or a heteroaryl group. Ar ¹² represents an orthophenylene group, a metaphenylene group, a paraphenylene group, a biphenylene group, or a group in which 3 to 6 rings of benzene rings are connected. , 2 or more rings 6 ring an arylene group fused ring aromatic rings are condensed, or .Ar ¹² representing the heteroarylene group may be those arylene group and heteroarylene group is linked together .R ^11, R ¹² and R ¹³ represent an alkyl group, an aryl group, or a heteroaryl group.)

In (formula (IV), Ar ²¹ is a one .Ar ²² representing an aryl group or a heteroaryl group .Ar ²² which represents an arylene group or a heteroarylene group linked the arylene group and heteroarylene group each other R ²¹ , R ²² , or R ²³ each independently represents an alkyl group, an aryl group, or a heteroaryl group, and m represents 1 or 2.

(In the general formula (V), Ar ³² represents an arylene group, a group containing an azole structure, a group containing an azine structure having two or more hetero atoms, a group containing a furan structure, or a group containing a thiophene structure. Ar ³² , the arylene group, a group containing an azole structure, groups heteroatom containing two or more azine structure, a group containing a furan structure, a group containing a thiophene structure may be one which is connected to one another .R ^31, R ³² or R ³³ each independently represents an alkyl group, an aryl group, or a heteroaryl group.)

(In the general formula ^{(VI), R 1, R} 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R ¹⁵ and R ¹⁶ represent a hydrogen atom or a substituent.)

(In General Formula (VII), L represents a single bond or a divalent or higher valent linking group, and T represents an atom such as a hydrogen atom from any ^one of R ^{1 to} R ^{16 in} the structure represented by General Formula (1). Or a group obtained by removing any one of R ^{1 to} R ¹⁶ , n represents an integer of 2 or more, and a plurality of T's are independent of each other.

  According to the present invention, it is possible to provide a light emitting device having high external quantum efficiency and maximum luminance, excellent light emitting characteristics, and excellent driving durability.

The light-emitting element of the present invention is a light-emitting element having an organic compound layer including at least one light-emitting layer between a pair of electrodes, and at least one of the organic compound layers is represented by the following general formula (I). And a hole blocking layer between the layer containing the general formula (I) and the light emitting layer.
The light-emitting element includes an organic compound layer including a light-emitting layer between a pair of electrodes, and at least one of the organic compound layers includes a compound represented by the following general formula (I), and the general formula (I) By having a hole blocking layer between the light emitting layer and the light emitting layer, the light emitting characteristics (external quantum efficiency and maximum luminance) are excellent, the low driving voltage is low, and the driving durability is excellent. it can.

(Compound represented by formula (I))
The compound represented by formula (I) will be described in detail.

In general formula (I), R < ¹ > -R < ⁴ > represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or heteroaryl group each independently. If a substituent can be introduced into R ^{1 to} R ⁴ , it may further have a substituent.
X ¹ and X ² each independently represents an alkyl group, an aryl group, or a heteroaryl group. If a substituent can be introduced into X ¹ and X ² , it may further have a substituent.

Examples of the halogen atom represented by R ^{1 to} R ⁴ include a chlorine atom, a bromine atom, and an iodine atom.
The alkyl group represented by R ^{1 to} R ⁴ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Preferred examples of the alkyl group represented by R ^{1 to} R ⁴ include a methyl group, an ethyl group, a propyl group, an iso-propyl group, an n-butyl group, and a t-butyl group.

The aryl group represented by R ^{1 to} R ⁴ is a condensed ring aryl group in which a single ring or two or more rings are condensed, preferably 6 to 30 carbon atoms, more preferably 6 to 6 carbon atoms. 20, particularly preferably an aryl group having 6 to 12 carbon atoms. Examples of the aryl group represented by R ^{1 to} R ⁴ include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group, a biphenyl group, and a terphenyl group. Among these, preferably A phenyl group, a triphenylenyl group, a biphenyl group, and a terphenyl group, more preferably a phenyl group, a biphenyl group, and a terphenyl group, and still more preferably a phenyl group.

The heteroaryl group represented by R ^{1 to} R ⁴ is a monocyclic ring or a condensed heteroaryl group in which two or more rings are condensed, preferably having 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Preferably it is 2-10 heteroaryl groups. Specific examples of the heteroaryl group represented by R ^{1 to} R ⁴ include, for example, a pyridyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a pteridinyl group, a pyrazinyl group, a quinoxalinyl group, a pyrimidinyl group, Quinazolyl, pyridazinyl, cinnolinyl, phthalazinyl, triazinyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, imidazolyl, benzoimidazolyl, pyrazolyl, indazolyl, isoxazolyl, benzoisoxazolyl Group, isothiazolyl group, benzoisothiazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, furyl group, benzofuryl group, thienyl group, benzothienyl group, pyrrolyl group, indolyl group, imine group Zopyridinyl group, carbazolyl group and the like, preferably pyridyl group, pyrazinyl group, pyrimidinyl group, triazinyl group, oxazolyl group, thiazolyl group, imidazolyl group, pyrazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, furyl group, thienyl group , A pyrrolyl group, an indolyl group, an imidazopyridinyl group, and a carbazolyl group, more preferably a pyridyl group, a triazinyl group, an imidazopyridinyl group, and a carbazolyl group, and still more preferably a pyridyl group.

The alkyl group, aryl group, or heteroaryl group represented by R ^{1 to} R ⁴ may have a substituent, and the substituent can be selected from the following substituent group A.

(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, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms). , For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms). Yes, such as propargyl, 3-pentynyl, etc.), aryl group (preferably having 6 to 30 carbon atoms, more preferred) Has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl, anthranyl, and the like, and an amino group (preferably having 0 to 30 carbon atoms, more preferably Has 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, and ditolylamino), alkoxy groups (preferably C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C10, for example, a methoxy, an ethoxy, butoxy, 2-ethylhexyloxy etc. are mentioned), an aryloxy group ( Preferably it has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms. For example, phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), heteroaryloxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably carbon number). 1 to 12, for example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to carbon atoms). 12 and examples thereof include acetyl, benzoyl, formyl, pivaloyl, and the like.

  An alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl and ethoxycarbonyl), aryloxycarbonyl group (Preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl), acyloxy group (preferably 2 to 2 carbon atoms). 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyloxy), acylamino group (preferably 2 to 30 carbon atoms, more preferably carbon atoms) 2 to 20, particularly preferably 2 to 10 carbon atoms, for example, acetylamino, benzoyl Mino and the like), an alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino and the like. ), An aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino). A sulfonylamino 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 methanesulfonylamino and benzenesulfonylamino), sulfamoyl group (Preferably 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably The number of carbon atoms is 0 to 12, and examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, and the like, and carbamoyl groups (preferably 1 to 30 carbon atoms, more preferably 1 carbon atoms). -20, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like.

  An alkylthio 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 carbon atoms). To 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), heteroarylthio groups (preferably 1 to 30 carbon atoms, more preferably carbon atoms). The number is 1 to 20, particularly preferably 1 to 12, and examples thereof include pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, and the like, and a sulfonyl group ( Preferably it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, And sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl and benzenesulfinyl). ), A ureido 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 ureido, methylureido, phenylureido and the like), phosphorus. An acid amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide), hydroxy Group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, Pho group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 12 carbon atoms, For example, nitrogen atom, oxygen atom, sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, 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, and examples thereof include trimethylsilyl and triphenylsilyl).

The substituent that the alkyl group, aryl group, or heteroaryl group represented by R ^{1 to} R ⁴ may have is an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms). Particularly preferably an aryl group or a heteroaryl group, more preferably an aryl group or a heteroaryl group, further preferably a phenyl group, a biphenyl group, a terphenyl group, or a pyridyl group, and a pyridyl group. The group is most preferred.

The alkyl group represented by X ¹ and X ² is preferably an alkyl group having 1 to 12 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, an iso-propyl group, an n-butyl group, Examples include t-butyl group.
The aryl group represented by X ¹ and X ² is a condensed ring aryl group obtained by condensing a single ring or two or more rings, preferably an aryl group having 6 to 30 carbon atoms. The aryl group represented by X ¹ and X ^2, for example, a phenyl group, a naphthyl group, an anthryl group, phenanthryl group, pyrenyl group, triphenylenyl group, a biphenyl group, a terphenyl group and the like wherein X ¹ and X ² Is a condensed heteroaryl group in which a single ring or two or more rings are condensed, and is preferably a C1-C20 heteroaryl group. Specific examples of the heteroaryl group represented by X ¹ and X ² include, for example, pyridyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthridinyl group, pteridinyl group, pyrazinyl group, quinoxalinyl group, pyrimidinyl group, Quinazolyl, pyridazinyl, cinnolinyl, phthalazinyl, triazinyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, imidazolyl, benzoimidazolyl, pyrazolyl, indazolyl, isoxazolyl, benzoisoxazolyl Group, isothiazolyl group, benzoisothiazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, furyl group, benzofuryl group, thienyl group, benzothienyl group, pyrrolyl group, indolyl group, imine group Examples thereof include a dazopyridinyl group and a carbazolyl group.

The alkyl group, aryl group and heteroaryl group represented by X ¹ and X ² may further have a substituent, and the substituent can be selected from the substituent group A described above.

(Compound represented by formula (II))
The compound represented by the general formula (I) in the present invention is preferably a compound represented by the following general formula (II).

In general formula (II), R < ¹ > -R < ⁸ > represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or heteroaryl group each independently. When a substituent can be introduced into R ^{1 to} R ^8, it may further have a substituent.

The halogen atom represented by R ^{1 to} R ⁸ has the same meaning as the halogen atom represented by R ^{1 to} R ⁴ in the general formula (I), and the preferred range is also the same.
The alkyl group represented by R ^{1 to} R ⁸ has the same meaning as the alkyl group represented by R ^{1 to} R ⁴ in the general formula (I), and the preferred range is also the same.
The aryl group represented by R ^{1 to} R ⁸ has the same meaning as the aryl group represented by R ^{1 to} R ⁴ in the general formula (I), and the preferred range is also the same.
The heteroaryl group represented by R ^{1 to} R ⁸ has the same meaning as the heteroaryl group represented by R ^{1 to} R ⁴ in the general formula (I), and the preferred range is also the same.

The alkyl group, aryl group, or heteroaryl group represented by R ^{1 to} R ⁸ may have a substituent, and the substituent can be selected from the substituent group A described above.

The compound represented by general formula (I) or general formula (II) may have a bis-type structure via R ¹ or R ² .

<Method for Synthesizing Compounds Represented by General Formula (I) and General Formula (II)>
The compounds represented by general formula (I) and general formula (II) can be synthesized, for example, according to the method described in Japanese Patent No. 2918150 (method described below).
That is, first, an alkali metal complex is reacted with the acetylene derivative represented by the general formula (A).

In general formula (A), X and Y are each independently a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a substituted or unsubstituted aryl group. Represents a substituted or unsubstituted heterocycle, or X and Y are combined to form a saturated or unsaturated ring, and R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a substituted Or an unsubstituted alkyl group having 1 to 6 carbon atoms, alkoxy group, aryloxy group, perfluoroalkyl group, perfluoroalkoxy group, amino group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, Azo group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyloxy group, arylo group Xoxycarbonyloxy group, sulfinyl group, sulfonyl group, sulfanyl group, silyl group, carbamoyl group, aryl group, heterocyclic group, alkenyl group, alkynyl group, nitro group, formyl group, nitroso group, formyloxy group, isocyano group, cyanate A group, an isocyanate group, a thiocyanate group, an isothiocyanate group, or a cyano group, or a substituted or unsubstituted ring may be condensed.
Subsequently, a silane derivative represented by the following general formula (B) is reacted.

  In general formula (B), X, Y and Z each independently represent a tertiary-butyl group or an aryl group.

  Furthermore, by reacting zinc chloride or a zinc chloride complex, a reactive silacyclopentadiene derivative represented by the following general formula (C) is obtained.

In general formula (C), A represents a zinc halide or a zinc halide complex, and X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group. Group, an alkynyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocycle, or X and Y are bonded to form a saturated or unsaturated ring, and R ¹ and R ² are Independently, a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an alkoxy group, an aryloxy group, a perfluoroalkyl group, a perfluoroalkoxy group, an amino group, an alkylcarbonyl group, an aryl A carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an azo group, an alkylcarbonyloxy group, an arylcarbonyloxy group, Alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfinyl group, sulfonyl group, sulfanyl group, silyl group, carbamoyl group, aryl group, heterocyclic group, alkenyl group, alkynyl group, nitro group, formyl group, nitroso group, formyl An oxy group, an isocyano group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, or a cyano group, or a substituted or unsubstituted ring may be condensed.

  As the substituent attached to the acetylene derivative used here, one that does not easily inhibit the reaction between the alkali metal complex and acetylene is preferable, and one that is inactive with respect to the alkali metal complex is particularly preferable. Examples of the alkali metal complex used include lithium naphthalenide, sodium naphthalenide, potassium naphthalenide, lithium 4,4′-ditertiarybutyl-2,2′-biphenylide or lithium (N, N-dimethylamino). ) Naphthalenide. The solvent to be used is not particularly limited as long as it is inactive to an alkali metal or an alkali metal complex, and usually an ether solvent such as ether or tetrahydrofuran is used. Subsequent substituents of the silane derivative used are preferably bulky, and specifically include tertiary-butyldiphenylchlorosilane or ditertiary-butylphenylchlorosilane. Further, as the zinc chloride or zinc chloride complex used subsequently, a zinc chloride solid is used directly, an ether solution of zinc chloride is used, or a tetramethylethylenediamine complex of zinc chloride is used. These zinc chlorides are preferably sufficiently dried. If the amount of water is large, it is difficult to obtain the target product. This series of reactions is preferably performed in an inert gas stream, and argon gas is used. A silacyclopentadiene derivative can be obtained by reacting the reactive silacyclopentadiene derivative thus obtained with a halide represented by the general formula (D) in the presence of a catalyst.

  In general formula (D), X represents a chlorine atom, a bromine atom or an iodine atom, and R represents a halogen, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group, an alkylcarbonyl group, an arylcarbonyl A group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfinyl group, a sulfonyl group, a sulfanyl group, a silyl group, an aryl group, a heterocyclic group, an alkenyl group, or an alkynyl group;

  Examples of the catalyst used here include palladium catalysts such as tetrakistriphenylphosphine palladium and dichlorobistriphenylphosphine palladium. In each stage of the first-speed reaction, the reaction temperature is not particularly limited. However, when an alkali metal complex, a silane derivative, zinc chloride, or the like is added and stirred, the temperature is preferably room temperature or lower, and is usually performed at 0 ° C. or lower. The reaction temperature after adding the halide is preferably room temperature or higher, and is usually carried out under reflux when tetrahydrofuran is used as a solvent. There is no restriction | limiting in particular also in reaction time, When adding an alkali metal complex, a silane derivative, zinc chloride, etc. and stirring, it is desirable for several minutes to several hours. The reaction after the halide is added may be traced by a general analytical means such as NMR or chromatography to determine the end point of the reaction.

  Specific examples of the compound represented by the general formula (I) and the compound represented by the general formula (II) [Exemplary compounds (S-1) to (S-12)] are shown below. The invention is not limited to these examples.

In the present invention, the content of the compound represented by the general formula (I) (or the compound represented by the general formula (II)) is preferably 5 to 95% by mass per one organic compound layer. The content is more preferably 10 to 90% by mass, and further preferably 20 to 80% by mass.
Moreover, the compound represented by general formula (I) (or the compound represented by general formula (II)) may be used individually by 1 type, and may use 2 or more together.

(Metal complexes of 8-quinolinol derivatives)
The metal complex salt of the 8-quinolinol derivative of the following general formula (1) will be described in detail.

In general formula (1), R ^{1 to} R ⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group, L is —OR ⁷ (R ⁷ is an alkyl group, a cycloalkyl group, or a nitrogen atom). An aromatic ring group that may be included, an aromatic ring group having a linking group consisting of a metal atom or an oxygen atom, or a ligand of an oxinoid compound having the linking group.), M represents a metal atom, and n represents It is an integer of 1 or 2.

In addition, in the compound represented by the general formula (1), when R ^{1 to} R ⁶ are an alkyl group or an alkoxy group in the general formula (I), the preferred carbon number is 1 to 6, particularly 1 to 4 preferable. Moreover, when R < ⁷ > is an alkyl group, the preferable carbon number is 1-6, and 1-4 are especially preferable.

  Examples of the compound represented by the general formula (1) include, for example, JP-A-5-214332, JP-A-5-258860, JP-A-5-258862, JP-A-5-198378, and JP-A-5 No. 331460, JP-A-9-95620, JP-A-9-13026, JP-A-9-31455, European Patent 765106, European Patent 777765, etc. And organometallic complexes containing the above.

  As a method for synthesizing the metal complex salt of the 8-quinolinol derivative of the general formula (1), for example, the synthesis methods described in the above-mentioned patent documents can be used, but the method is not limited thereto.

  Although the example of the specific compound of General formula (1) is shown in Table 1-Table 23, it is not limited to these.

(Compound represented by formula (III))
The following general formula (III) will be described in detail.

(In the general formula (III), Ar ¹¹ represents an aryl group or a heteroaryl group which may be the same or different. Ar ¹² represents an orthophenylene group, a metaphenylene group, a paraphenylene group, a biphenylene group, or a benzene ring. R ¹¹ , R ¹² , and R ¹³ are the same as or different from each other, and represent a condensed ring arylene group or a heteroarylene group formed by condensing two or more rings and six or less rings, or an aromatic ring condensed from two to six rings. Represents an alkyl group, an aryl group, or a heteroaryl group.

Ar ¹¹ represents an aryl group or a heteroaryl group which may be the same as or different from each other.

The aryl group represented by Ar ¹¹ is a monocyclic ring or a condensed ring aryl group in which two or more rings are condensed, preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably carbon atoms. It is an aryl group of formula 6-12. Examples of the aryl group represented by Ar ¹¹ include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group, a biphenyl group, and a terphenyl group. Among these, a phenyl group and a triphenylenyl group are preferable. Group, biphenyl group and terphenyl group, more preferably phenyl group, biphenyl group and terphenyl group, still more preferably phenyl group.

The heteroaryl group represented by Ar ¹¹ is a monocyclic ring or a condensed heteroaryl group in which two or more rings are condensed, preferably having 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 10 carbon atoms. Of the heteroaryl group. Specific examples of the heteroaryl group represented by Ar ¹¹ include, for example, a pyridyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a pteridinyl group, a pyrazinyl group, a quinoxalinyl group, a pyrimidinyl group, a quinazolyl group, and a pyridazinyl group. Cinnolinyl group, phthalazinyl group, triazinyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, indazolyl group, isoxazolyl group, benzoisoxazolyl group, isothiazolyl group, Benzoisothiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, furyl, benzofuryl, thienyl, benzothienyl, pyrrolyl, indolyl, imidazopyri Nyl group, carbazolyl group, etc., preferably pyridyl group, pyrazinyl group, pyrimidinyl group, triazinyl group, oxazolyl group, thiazolyl group, imidazolyl group, pyrazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, furyl group, thienyl group , A pyrrolyl group, an indolyl group, an imidazopyridinyl group, and a carbazolyl group, more preferably a pyridyl group, a triazinyl group, an imidazopyridinyl group, and a carbazolyl group, and still more preferably a pyridyl group.

The aryl group or heteroaryl group represented by Ar ¹¹ may have a substituent, and the substituent can be selected from the substituent group A described in the section of the general formula (I).

The substituent which the aryl group or heteroaryl group represented by Ar ¹¹ may have is an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms). ), An aryl group or a heteroaryl group is preferred, an aryl group or a heteroaryl group is more preferred, a phenyl group, a biphenyl group, a terphenyl group or a pyridyl group is further preferred, and a phenyl group or a pyridyl group is most preferred.

Ar ¹² is an orthophenylene group, a metaphenylene group, a paraphenylene group, a biphenylene group, a group in which 3 or more and 6 or less benzene rings are connected, an arylene group in a condensed ring in which 2 or more and 6 or less aromatic rings are condensed, Or represents a heteroarylene group.

The arylene group of the condensed ring in which 2 to 6 rings represented by Ar ¹² are condensed is preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 6 carbon atoms. 12 arylene groups such as naphthylene group, anthrylene group, phenanthrenylene group, pyrenylene group, peryleneylene group, fluorenylene group, rubrenylene group, chrysenylene group, triphenylenylene group, benzoanthrylene group, benzophenanthrenylene group Group, diphenylanthrylene group and the like.

The heteroarylene group represented by Ar ¹² is a monocyclic ring or a condensed heteroaryl group in which 2 to 6 rings are condensed, preferably 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Are 2 to 10 heteroaryl groups such as pyridylene, quinolylene, isoquinolylene, acridinylene, phenanthridinylene, pyrazinylene, quinoxalinylene, pyrimidinylene, triadylene, imidazolylene, pyrazolylene, oxadiazo Examples include a rylene group, a triazorylene group, a furylene group, a thienylene group, a pyrrolylene group, an indoylene group, and a carbazolylene group.

Ar ¹² may be an arylene group and a heteroarylene group linked to each other.

Preferably ortho-phenylene group as Ar ^12, metaphenylene group, a paraphenylene group, biphenylene group, terphenylene group, a naphthylene group, an anthrylene group, a pyridylene group, pyrimidylene group, Toriajiren group, oxadiazolylene group, triazolylene group, thienylene group, A pyrrolylene group, an indylene group, and a carbazolylene group, more preferably an orthophenylene group, a metaphenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a pyridylene group, a triadylene group, an oxadiazolylene group, a thienylene group, and a carbazolylene group. More preferred are a metaphenylene group, a biphenylene group, a pyridylene group, and an oxadiazolylene group, and most preferred are a metaphenylene group and a biphenylene group.

The arylene group or heteroarylene group represented by Ar ¹² may have a substituent, and the substituent can be selected from the substituent group A including an alkyl group. The substituent which the aryl group or heteroaryl group represented by Ar ¹² may have is an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms). ), An aryl group or a heteroaryl group is preferred, an aryl group or a heteroaryl group is more preferred, a phenyl group, a biphenyl group, a terphenyl group or a pyridyl group is further preferred, and a phenyl group or a pyridyl group is most preferred.

R ¹¹ , R ¹² and R ¹³ each represents an alkyl group, an aryl group or a heteroaryl group which may be the same or different.

The alkyl group represented by R ¹¹ , R ¹² and R ¹³ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 4 carbon atoms. R ¹¹ , R ¹² and R ¹³ are preferably a methyl group, an ethyl group, a propyl group, an n-butyl group and a t-butyl group, more preferably a methyl group, an ethyl group and a t-butyl group, and even more preferably. Is a methyl group.

Examples of the aryl group represented by R ¹¹ , R ¹² and R ¹³ include the examples given for Ar ¹¹ , and the preferred ranges are also the same.

Examples of the heteroaryl group represented by R ¹¹ , R ¹² and R ¹³ include the examples given for Ar ¹¹ , and the preferred ranges are also the same.

R ¹¹ , R ¹² and R ¹³ are most preferably a phenyl group.

The alkyl group, aryl group and heteroaryl group represented by R ¹¹ , R ¹² and R ¹³ may have a substituent, and the substituent can be selected from the above substituent group A.

(Compound Represented by General Formula (IV) Next, the following general formula (IV) will be described in detail.

In the general formula (IV), Ar ²¹ represents an aryl group or a heteroaryl group which may be the same or different from each other.

The aryl group or heteroaryl group represented by Ar ²¹ is synonymous with the aryl group or heteroaryl group described for Ar ¹¹ , and the preferred range is also the same.

The aryl group or heteroaryl group represented by Ar ²¹ may have a substituent, and can be selected from, for example, the substituent group A. The substituent that the aryl group or heteroaryl group represented by Ar ²¹ may have is preferably an alkyl group, an aryl group, or a heteroaryl group, more preferably an aryl group or a heteroaryl group, a phenyl group, or a biphenyl group. Terphenyl group and pyridyl group are more preferable, and phenyl group and pyridyl group are most preferable.

Ar ²² represents an arylene group or a heteroarylene group which may be the same or different from each other.

The arylene group represented by Ar ²² is an aryl group of a condensed ring in which a single ring or two or more rings are condensed, preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably. It is an arylene group having 6 to 12 carbon atoms. Specific examples of the arylene group represented by Ar ²² include a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthrylene group, a phenanthrenylene group, a pyrenylene group, a peryleneylene group, a fluorenylene group, a rubrenylene group, and a chrysenylene group. , Triphenylenylene group, benzoanthrylene group, benzophenanthrenylene group, diphenylanthrylene group and the like.

The heteroarylene group represented by Ar ²² is a heteroarylene group having a monocyclic ring or a condensed ring in which two or more rings are condensed, and preferably has 1 to 20 carbon atoms, more preferably 2 to 12 and even more preferably 2 to 10 A heteroarylene group. Specific examples of the heteroarylene group represented by Ar ²² include those listed as examples of the heteroarylene group exemplified for Ar ¹² .

Ar ²² may be one in which the arylene group and the heteroarylene group are linked to each other.

Ar ²² is preferably phenylene group, biphenylene group, terphenylene group, naphthylene group, anthrylene group, pyridylene group, pyrimidylene group, triadylene group, oxadiazolylene group, triazolylene group, thienylene group, pyrrolylene group, indoleylene group, carbazolylene group More preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a pyridylene group, a triadylene group, an oxadiazolylene group, a thienylene group, and a carbazolylene group, more preferably a phenylene group, a biphenylene group, and a pyridylene group. Most preferably, it is a paraphenylene group.

Arylene group, or represented by Ar ²² heteroarylene group may have a substituent, specific examples and preferred examples of the substituent that may be Ar ²² has may have said Ar ¹² It is the same as the substituent.

R ²¹ , R ²² and R ²³ represent an alkyl group, an aryl group or a heteroaryl group which may be the same or different from each other.

The alkyl group, aryl group, and heteroaryl group represented by R ²¹ , R ²² , and R ²³ are specific examples and preferred ranges, and the alkyl group, aryl group, and heteroaryl group represented by the aforementioned R ¹¹ , R ¹² , and R ¹³ together. Is the same.

  m represents 1 or 2, and 2 is more preferable.

(Compound represented by general formula (V))
Next, the following general formula (V) will be described in detail.

In the general formula (3), Ar ³² represents an arylene group, a group containing an azole structure, a group containing an azine structure having two or more heteroatoms, a group containing a furan structure, or a group containing a thiophene structure. R ³¹ , R ³² and R ³³ represent an alkyl group, an aryl group or a heteroaryl group which may be the same or different from each other.

Ar ³² represents an arylene group, a group containing an azole structure, a group containing an azine structure having two or more heteroatoms, a group containing a furan structure, or a group containing a thiophene structure.

The arylene group represented by Ar ³² has the same meaning as the arylene group represented by Ar ²² , and specific examples thereof are also the same.

Examples of the group containing an azole structure represented by Ar ³² include an oxazolylene group, a thiazolylene group, an imidazolylene group, a pyrazolylene group, an oxadiazolylene group, a thiadiazolylene group, a triazolylene group, a pyrrolylene group, an indylene group, an imidazolpyridylene group, and a carbazolylene group. Can be mentioned.

Examples of the group containing an azine structure having two or more heteroatoms represented by Ar ³² include a pyradylene group, a pyrimidylene group, and a triadylene group.

Examples of the group containing a furan structure represented by Ar ³² include a group containing a benzofuran structure and a group containing a dibenzofuran structure.

Examples of the group containing a thiophene structure represented by Ar ³² include a group containing a benzothiophene structure, a group containing a dibenzothiophene structure, and a group containing a bithiophene structure.

Ar ³² may be an arylene group, a group containing an azole structure, a group containing an azine structure having two or more heteroatoms, a group containing a furan structure, or a group containing a thiophene structure.

Ar ³² is preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthrylene group, a pyrimidylene group, a triadylene group, an oxadiazolylene group, a triazolylene group, a pyrrolylene group, an indylene group, or a carbazolylene group, more preferably a phenylene group. Group, biphenylene group, terphenylene group, naphthylene group, triadylene group, oxadiazolylene group and carbazolylene group, more preferably phenylene group and biphenylene group, and most preferably paraphenylene group.

Groups represented by Ar ³² may have a substituent, specific examples and preferred examples of the substituent that may be Ar ³² has are the same as the substituent that may be possessed by the Ar ^12.

R ³¹ , R ³² , and R ³³ represent an alkyl group, an aryl group, or a heteroaryl group, which may be the same as or different from each other.

The alkyl group, aryl group, or heteroaryl group represented by R ³¹ , R ³² , and R ³³ is an alkyl group represented by the above R ¹¹ , R ¹² , and R ¹³ together with specific examples and preferred ranges thereof, Same as aryl group or heteroaryl group.

  The compound represented by the general formula (III), the general formula (IV), or the general formula (V) may be a low molecular compound, and an oligomer compound or a polymer compound (weight average molecular weight (in terms of polystyrene) is preferably 1000 to 5000000, more preferably 2000 to 1000000, and still more preferably 3000 to 100,000. In the case of a polymer compound, the structure represented by general formula (III), general formula (IV), or general formula (V) may be included in the polymer main chain, or may be included in the polymer side chain. good. 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.

  Although the compound example of general formula (III), general formula (IV), and general formula (V) is shown below, this invention is not limited to these.

(Compound represented by formula (VI))
Below, the compound represented by the following general formula (VI) is demonstrated in detail.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , included in the general formula (VI) R ¹⁵ and R ¹⁶ represent a hydrogen atom or a substituent. Examples of the substituent include an alkyl 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 methyl, ethyl, iso-propyl, tert-butyl. , N-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably carbon atoms). 2 to 10 such as vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably carbon). 2-10, for example, propargyl, 3-pentynyl, etc.), aryl group (preferably carbon number) 30, more preferably 6 to 12 carbon 6 to 20 carbon atoms, and particularly preferably carbon, such as phenyl, p- methylphenyl, naphthyl, anthranyl.),

  An 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; And alkoxy groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy) An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2- Naphthyloxy, etc.), heteroaryloxy groups (preferably having 1 to 30 carbon atoms, more The number of carbon atoms is preferably 1 to 20, particularly preferably 1 to 12, and examples thereof include pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, and the like, and acyl groups (preferably having 1 to 30 carbon atoms, more preferably A carbon number of 1 to 20, particularly preferably a carbon number of 1 to 12, and examples thereof include acetyl, benzoyl, formyl, and pivaloyl).

  An alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl 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 phenyloxycarbonyl, etc.), an acyloxy group (preferably 2 to 30 carbon atoms, More preferably, it has 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy.), Acylamino group (preferably 2 to 30 carbon atoms, more preferably 2 to 2 carbon atoms). 20, particularly preferably 2 to 10 carbon atoms, such as acetylamino, 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 having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino), sulfonylamino group ( Preferably it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably carbon number). 0 to 30, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 1 carbon atoms For example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl etc.), carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably C1-C12, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl etc.).

  An alkylthio 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 carbon atoms). To 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), heteroarylthio groups (preferably 1 to 30 carbon atoms, more preferably carbon atoms). 1 to 20, particularly preferably 1 to 12 carbon atoms, and examples include pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, and the like, and sulfonyl groups (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl ), Sulfinyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.) A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid amide 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 diethyl phosphoric acid amide and phenyl phosphoric acid amide), a hydroxy group, Mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, A boxyl 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). Oxygen atoms, sulfur atoms, specifically, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl, and the like. (Preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl). These substituents may be further substituted and may combine with each other to form a ring.

Included in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ Examples of the substituent are preferably an alkyl group, an aryl group, and a heteroaryl group, and more preferably an aryl group and a heteroaryl group.

In the compound represented by the general formula (VI), two or more of them are bonded through R ^{1 to} R ¹⁶ on the skeleton or an atom such as a hydrogen atom of any of R ^{1 to} R ¹⁶ leaving. By doing so, a dimer or more multimer formed may be formed. Thus, the compound represented by the general formula (1) may be a low molecular compound, and an oligomer compound or a polymer compound (weight average molecular weight (polystyrene conversion) is preferably 1000 to 5000000, more preferably 2000 to 2000 1000000, more preferably 3000-100000). In the case of a polymer compound, a triphenylene structure may be included so as to constitute a polymer main chain, or may be included in a 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.

(Compound represented by formula (VII))
Next, the compound represented by the general formula (2) will be described.

L represents a single bond or a divalent or higher valent linking group. L is preferably a single bond, a linking group formed of C, N, O, S, Si, Ge, etc., more preferably a single bond, a divalent or higher aromatic ring, a divalent or higher aromatic heterocycle, A linking group formed of a carbon atom, a nitrogen atom, or a silicon atom. Most preferably, a single bond, divalent or higher benzene, divalent or higher naphthalene, divalent or higher biphenyl, divalent or higher terphenyl, divalent or higher triphenylene, divalent or higher phenanthrene, divalent or higher triazole, 2 A linking group formed of valent or higher pyridine, divalent or higher pyrimidine, carbon atom, nitrogen atom, or silicon atom. The compound represented by the general formula (VII) is bonded with a group obtained by removing an atom such as a hydrogen atom from any of R ^{1 to} R ¹⁶ of the compound represented by the general formula (VI). or corresponds to the formation of the dimer or more multimer bound except one of R ¹ to R ^16.

The linking group represented by L may have a substituent, and the substituent has the same meaning as the substituent described for R ^{1 to} R ¹⁶ . The substituent is preferably an alkyl group, an aryl group or a heteroaryl group, more preferably an aryl group or a heteroaryl group.

  Specific examples of the linking group represented by L include the following in addition to a single bond, but L in the present invention is not limited thereto. In the following linking groups, all of the free bonds may be bonded to a tetraphenylene group derived from the above general formula (VI), but the present invention is not limited to this, and at least two bonds are bonded. It only has to be joined to the hand. In this case, a hydrogen atom or a normal substituent may be bonded to a bond to which the tetraphenylene group is not bonded.

T represents a group obtained by removing an atom from any of R ^{1 to} R ^{16 having} a structure represented by the general formula (VI), or a group obtained by removing any one of R ^{1 to} R ^16. To express. n represents an integer greater than or equal to 2, and several T are mutually independent and may mutually be the same or different.

In the general formula (VII), n represents an integer of 2 or more, preferably an integer of 2 to 8, and more preferably an integer of 2 to 4.
The ratio of the compound represented by the general formula (VI) or (VII) to the triplet light-emitting material varies depending on the former structure, the latter T ₁ level, etc., but is preferably 50:50 to 99.9: by mass ratio. 0.1, more preferably 80:20 to 99: 1.

Next, although the compound example of general formula (VI) and general formula (VII) of this invention is shown, this invention is not limited to this.

  The compounds of the present invention are described in, for example, the non-patent document Just Liebigs Analder der Chemie, 704, 91 (1967). Tetrahedron Letters, 39, 5393 (1998), Journal of Chemical Society: Perkin Transactions 1, 159 (2001), Angewande Chemie, International Elig.

<Light emitting element>
Next, the light emitting device of the present invention will be described.
The light-emitting element of the present invention is a light-emitting element having an organic compound layer including at least one light-emitting layer, and at least one of the organic compound layers contains the compound of the general formula (I). As long as it is an element having a hole blocking layer between the layer containing I) and the light emitting layer, the system, the driving method, and the usage form are not particularly limited. An organic EL (electroluminescence) element can be mentioned as a typical light emitting element.

The external quantum efficiency of the light-emitting device of the present invention is preferably 5% or more. Among them, 10% or more is more preferable, and 13% or more is more preferable in terms of reducing power consumption and driving durability. The value of the external quantum efficiency should be the maximum value of the external quantum efficiency when the device is driven at 20 ° C. or the value of the external quantum efficiency near 100 to 300 cd / m ² when the device is driven at 20 ° C. Can do.
The external quantum efficiency of the device can be calculated from the result and the luminous efficiency curve obtained by measuring the emission luminance, emission spectrum, and current density. That is, the number of input electrons can be calculated using the current density value. The emission luminance can be converted into the number of photons emitted by integral calculation using the emission spectrum and the relative visibility curve (spectrum). From these, the external quantum efficiency (%) can be calculated by “(number of emitted photons / number of electrons input to the device) × 100”.
In the present invention, using a source measure unit type 2400 manufactured by Toyo Technica, a DC constant voltage is applied to the EL element to emit light, and the luminance is measured using a luminance meter BM-8 manufactured by Topcon Corporation, and is 100 cd / m ^2. The external quantum efficiency at can be calculated, and this value is used in the present invention.

The light-emitting element of the present invention is an element in which at least a light-emitting layer, the general formula (I) -containing layer, and a hole blocking layer are disposed between a pair of electrodes of an anode and a cathode. An element having other layers by forming a plurality of organic compound films including a blocking layer may be used.
As the other layers of the light emitting layer, the general formula (I) -containing layer, and the hole blocking layer, it is preferable to have a hole transport layer, and further, a hole injection layer, an electron injection layer, an electron transport layer, a protection layer. You may have a layer. Each of these layers may have other functions, or the same layer may be laminated. Various materials can be used for forming each layer.
The general formula (I) -containing layer is preferably an electron transport layer.

(anode)
The anode supplies holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like, and a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. The material preferably has a work function of 4 eV or more.
Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), metals such as gold, silver, chromium and nickel, and these metals and conductive metal oxides. A mixture or laminate thereof, inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene and polypyrrole, and laminates of these with ITO, preferably conductive It is a metal oxide, and ITO is particularly preferable in terms of productivity, high conductivity, transparency, and the like.
The thickness of the anode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 500 nm.

As the anode, a layer formed on a soda-lime glass, non-alkali glass, a transparent resin substrate or the like is usually used. When glass is used, it is preferable to use non-alkali glass 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. Transparent resin substrates include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polycarbonate, polyethersulfone, polyarylate, allyl diglycol carbonate, polyimide, polycycloolefin, norbornene resin, poly (chlorotrine). Fluoroethylene), Teflon (registered trademark), and polytetrafluoroethylene-polyethylene copolymer.
The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength, but when glass is used, a thickness of 0.2 mm or more, preferably 0.7 mm or more is usually used.
Various methods are used for producing the anode depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), and a dispersion of indium tin oxide are applied. A film is formed by such a method.
The anode can be driven to lower the drive voltage of the element or increase the light emission efficiency by washing or other processing. For example, in the case of ITO, UV-ozone treatment, plasma treatment, etc. are effective.

(cathode)
The cathode supplies electrons to the electron injection layer, the electron transport layer, the light emitting layer, etc., and the adhesion, ionization potential, and stability between the negative electrode and the adjacent layer such as the electron injection layer, the electron transport layer, and the light emitting layer. It is selected in consideration of etc.
As a material for the cathode, a metal, an alloy, a metal halide, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. As specific examples, an alkali metal (for example, Li, Na, K, etc.) and its Fluorides or oxides, alkaline earth metals (eg Mg, Ca, etc.) and their fluorides or oxides, gold, silver, lead, aluminum, sodium-potassium alloys or their mixed metals, lithium-aluminum alloys or their Examples thereof include mixed metals, magnesium-silver alloys or mixed metals thereof, rare earth metals such as indium and ytterbium, preferably materials having a work function of 4 eV or less, more preferably aluminum, lithium-aluminum alloys or mixtures thereof. A metal, a magnesium-silver alloy, or a mixed metal thereof.
The cathode can take not only a single layer structure of the above-mentioned compounds and a mixture thereof but also a laminated structure containing the above-mentioned compounds and a mixture thereof. For example, a laminated structure of aluminum / lithium fluoride and aluminum / lithium oxide is preferable.
The thickness of the cathode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 1 μm.
For production of the cathode, methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a coating method, and a transfer method are used, and a metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. Furthermore, a plurality of metals can be vapor-deposited simultaneously to form an alloy electrode, or a previously prepared alloy may be vapor-deposited.
The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less.

(Light emitting layer)
The material of the light emitting layer is a function that can inject holes from the anode or hole injection layer, hole transport layer and cathode or electron injection layer, electron transport layer when an electric field is applied, The material is not particularly limited as long as it is a material that can form a layer having a function of moving injected charges and a function of emitting light by providing a recombination field of holes and electrons, and a known light-emitting material can be used. . Among them, it is preferable to use a host material together with the known light emitting material. The known light emitting material may be a single substance or a combination of a plurality of substances. In order to obtain better performance by separating the charge transport function and the light emitting function, or to prevent the phenomenon that the excited state is non-radiatively deactivated (concentration quenching) in a high concentration light emitting material, the light emitting material is used as a dopant. It is preferable to dope into the charge transport material (host material).

-Luminescent material-
The light emitting layer of the present invention preferably contains both the light emitting material and the host material, and the light emitting material preferably contains 0.1% by mass or more and 20% by mass or less as the light emitting material. % To 15% by mass is more preferable, and 2% to 8% by mass is further preferable.
When the light emitting material is used at a concentration lower than the above range, sufficient light emission luminance cannot be obtained and the host material easily emits light at an undesired wavelength. In addition, when the light emitting material is used at a concentration higher than the above range, the light emission efficiency is likely to be reduced due to concentration quenching, and the driving of the light emitting element is deteriorated because the charge easily flows through the light emitting material and is decomposed. Tend to.
The light emission in the light emitting device of the present invention may be ultraviolet light emission, visible light light emission, or infrared light emission, and may be fluorescence light emission or phosphorescence light emission.
A preferable light-emitting material in the present invention may be a fluorescent compound that emits light from singlet excitons or a phosphorescent compound that emits light from triplet excitons.
Examples of light-emitting materials that can be used in the present invention include benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed fragrances. Group compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, Diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, metal complexes of 8-quinolinol derivatives and metal complexes of pyromethene derivatives, rare S complex, various metal complexes typified by transition metal complexes such as iridium trisphenylpyridine complexes and platinum porphyrin complexes, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

-Host material-
In addition to the light emitting material of the present invention, a host material is preferably used for the light emitting layer. For example, a carbazole derivative (for example, “Applied Physics Letters”, 1999, Vol. 74, No. 3, p. 442), tribenzoazepine derivatives (JP-A-10-59943, JP-A-10-219241, JP-A-10-316875, JP-A-10-324680, JP-A-10-330365, JP-A-2001-97953). ), A triazole derivative (US Pat. No. 3,121,197), an oxazole derivative (US Pat. No. 3,257,203), an imidazole derivative (Japanese Patent Publication No. 37-16096), a polyarylalkane derivative (US Pat. Nos. 3,615,402, 3,820,989, 354,254). 4, JP-B-45-555, JP-A-51-10983, JP-A-51-93224, JP-A-55-17105, JP-A-56-4148, JP-A-55-108667, JP-A-55-156953, JP-A-56. -36656), polyarylbenzenoid derivatives (JP-A-10-255985, JP-A-2002260861), arylamine derivatives (US Pat. Nos. 3,567,450, 3,180,703, 3,240,597, 3,658,520, 4,232,103) No. 4,175,961, No. 4012376, JP-B-49-35702, JP-A-39-27577, JP-A-55-144250, JP-A-56-119132, JP-A-56-22437, West German Patent No. 1105518), Styrylanthracene derivatives (Japanese Patent Laid-Open No. 56-46234), stil Derivatives (Japanese Patent Laid-Open Nos. 61-210363, 61-228451, 61-14642, 61-72255, 62-47646, 62-36674, 62-10652, 62- 30255, 60-93445, 60-94462, 60-174749, 60-175052), aromatic tertiary amine compounds and styrylamine compounds (JP-A 63-295695, 53- 27033, 54-58445, 54-149634, 54-64299, 55-79450, 55-144250, 56-119132, 61-295558, 61-98353 JP-A-8-239655, U.S. Pat. No. 4,127,412), aromatic dimethylidene compounds (Japanese Patent Laid-Open No. 30034), pyrazoline derivatives and pyrazolone derivatives (US Pat. Nos. 3,180,729, 4,278,746, JP-A-55-88064, 55-88065, 49-105537, 55-51086, 56-80051). No. 56-88141, No. 57-45545, No. 54-112537, No. 55-74546), Phenylenediamine derivatives (US Pat. No. 3,615,404, JP-B-51-10105, No. 46-3712, 47-25336, JP 54-53435, 54-11536, 54-1119925), amino-substituted chalcone derivative (US Pat. No. 3,526,501), fluorenone derivative (JP 54-110837) Hydrazone derivatives (US Pat. No. 3,717,462, JP 54-59143, 55-52063, 55-52064, 55-46760, 55-85495, 57-11350, 57-148799), silazane derivatives (US Pat. No. 4,950,950) ), Porphyrin compounds (JP-A 63-295695), anthraquinodimethane derivatives and anthrone derivatives (JP-A 57-149259, 58-55450, 63-104601, JP 61-225151). No. 61-233750), diphenoquinone derivatives, thiopyran dioxide derivatives and carbodiimide derivatives ("Polymer Preprints, Japan", 1988, Vol. 37, No. 3, p. 681), fluorenylidenemethane derivatives (JP-A-60-69657, JP-A-61-143764, JP-A-61-148159)), distyrylpyrazine derivatives ("Chemistry Letters", 1990, p.189). , JP-A-2-252793, JP-A-5-178842), heterocyclic tetracarboxylic acid anhydride derivatives ("Japanese Journal of Applied Physics", 1988, 27, L269), porphyrins and the like Phthalocyanine derivatives (Japanese Patent Laid-Open No. 63-295965), metal complexes of 8-quinolinol derivatives (Journal of the Institute of Electronics, Information and Communication Engineers, 1990, C-2, p.661), and benzoxazole as a ligand From the viewpoint of hole and electron transport properties, it is preferable to contain at least one host material selected from the group of metal complexes having a benzothiazole ligand and a metal complex having benzothiazole as a ligand. More preferred.

In order to efficiently transfer energy from the triplet excited state of the host material to the light emitting material, the energy level (T ₁ level) of the minimum triplet excited state of the host material is higher than the T ₁ level of the light emitting material. High is preferred. Since the T ₁ level of the luminescent material becomes higher as the emission wavelength is shorter, a high T ₁ host material is required in the light emitting layer for a short wave light emitting element, while T ₁ is the highest occupied orbit of the host material ( HOMO) and the lowest unoccupied orbit (LUMO), which are related to the ability to inject and transport charges (generally, the larger the energy difference between HOMO and LUMO, the less the charge is injected and the higher the electrical insulation) Therefore, it is important to select an optimal T ₁ level host material.
In particular, the T ₁ level of the light emitting layer host material for a blue light emitting element having an emission maximum wavelength of 500 nm or less is preferably 62 kcal / mol or more (259 kJ / mol or more), 85 kcal / mol or less (355 kJ / mol or less), More preferably, they are 65 kcal / mol or more (272 kJ / mol or more) and 80 kcal / mol or less (334 kJ / mol or less).

  As the host material in the light-emitting element of the present invention that satisfies the above physical property values, the host materials described in JP-A Nos. 2002-1000047 and 2002-338579 are preferable, and the host material described in JP-A No. 2002-1000047 is more preferable. A preferable range of the host material described in JP-A No. 2002-1000047 is as described in the specification.

For the light emitting layer in the present invention, a vacuum deposition method, an LB method, a method in which the hole injecting and transporting material is dissolved or dispersed in a solvent, a coating method, an ink jet method, a printing method, and a transfer method are used. Can form a thin film with a uniform film thickness and is preferable from the viewpoint of improving durability.
The vapor deposition method is a vacuum vapor deposition method in which a substance is heated and evaporated under high vacuum (10 ⁻² Pa or less), and a gaseous substance is deposited on a target to form a film. The substance is evaporated from an evaporation source. There are a resistance heating method, a high frequency heating method, an electron beam heating method, a laser heating method and the like as the heating method to be used, but the resistance heating method is the most common. Further, there are a sputtering method, an ion plating method, a molecular beam epitaxy method, and the like as a method for evaporating the material by a method other than heating, which can be properly used depending on the purpose. There is a CVD method in which a film is formed by a chemical reaction on the target surface as a vapor deposition method in a broader sense, and the vapor deposition method referred to in the present invention includes all these vapor deposition techniques. Details of the vapor deposition method are described in Chapter 8 of "New Format / Vacuum Handbook" (edited by ULVAC, Inc.) published by Ohm.
In the case of forming a film with a mixture of two or more substances, a mixture of a plurality of substances may be put into one evaporation source to evaporate, but in this method, the composition of the substance in the evaporated gas is kept constant. A difficult method is to fly molecules simultaneously from different evaporation sources. There is also known a method (Japanese Patent No. 3362504) in which a plurality of substances are sequentially stacked on a heated substrate to form a uniform film using diffusion by heat.

The light-emitting layer created by the vapor deposition method does not contain impurities, oxygen, and moisture derived from solvents, binders, etc., compared to the case where it is created by a wet film formation method typified by a spin coating method or an inkjet method. A light emitting layer thin film having a desired film thickness can be easily obtained without being concerned about driving durability and without worrying about dissolving an existing lower layer with a solvent.
Further, by performing masking during vapor deposition, different light emitting materials and host materials can be used for each pixel so that different light emission characteristics can be obtained, which is suitable for producing a full color display with high definition and high image quality.

When the light emitting layer of the present invention is formed by a vapor deposition method, a polymer material such as a polymer or an oligomer as the material of the light emitting layer has low volatility and is difficult to deposit, and the material itself has a molecular weight distribution. This is not preferable because it is difficult to obtain light emission with good reproducibility.
Moreover, it is preferable that the material of a light emitting layer is not an ionic compound but a neutral molecular compound from the ease of vapor deposition.
The light-emitting layer thin film formed by vapor deposition is preferably a uniform non-crystalline thin film (amorphous film) free from defects such as thinness and pinholes, and changes in the performance of the light-emitting element when recrystallization occurs due to aging or heat Therefore, it is preferable that the melting point and the glass transition temperature (Tg) are high. The melting point of the material of the light emitting layer is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, more preferably 250 ° C. or higher, and Tg is preferably 70 ° C. or higher, more preferably 100 ° C. or higher, more preferably 120 ° C. or higher. .
As a host material satisfying the above required performance, a carbazole derivative that has a high T ₁ level, is unlikely to cause crystallization, has a long excited state lifetime, and can be expected to have high emission efficiency is most preferable.

  Although the specific example of the said host material in this invention is given to the following, this invention is not limited to these.

  In addition to the above, for the light emitting layer, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide (JP-A-2-305886), coumarin, perylene (JP-A-2-189890), perinone, oxadiazole (JP-A-2). No. -216791, or the oxadiazole derivative disclosed by Hamada et al. At the 38th Applied Physics Relations Conference), aldazine (derivative JP-A-2-220393), pyrazirine (JP-A-2-220394), Metal complexes of cyclopentadiene (JP-A-2-289675), various metal complexes represented by rare earth complexes, transition metal complexes represented by organosilanes, iridium trisphenylpyridine complexes and platinum porphyrin complexes, and derivatives thereof Can be added.

Although the film thickness of a light emitting layer is not specifically limited, Usually, the thing of the range of 1 nm-5 micrometers is preferable, More preferably, it is 5 nm-1 micrometer, More preferably, it is 10 nm-500 nm.
There may be one or a plurality of light emitting layers, and each light emitting layer emits light in a different light emission color, for example, may emit white light as a whole, or may emit white light from a single light emitting layer. May be. When there are a plurality of light emitting layers, each light emitting layer may be formed of a single material or may be formed of a plurality of compounds.

(Hole injection layer, hole transport layer)
The material of the hole injection layer and the hole transport layer may be any one having a function of injecting holes from the anode, a function of transporting holes, or a function of blocking electrons injected from the cathode. Good.
Materials for the hole injection layer and hole transport layer are tribenzazepine derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, polyarylbenzene derivatives, arylamine derivatives, styrylanthracene derivatives. , Stilbene derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, metal complexes of 8-quinolinol derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, amino-substituted chalcone derivatives, fluorenone derivatives, hydrazone derivatives, It is preferable that it is 1 or more types selected from the group of a silazane derivative and a porphyrin-type compound. Preferable examples of these compounds are the same as those of the corresponding compounds described in the section of the host material.
Further, when the hole transport layer is a layer adjacent to the light emitting layer, the energy of the lowest triplet excited state of the hole transport material is prevented so that triplet excitons generated in the light emitting layer do not move to the hole transport layer. The level (T ₁ level) is preferably higher than the T ₁ level of the light emitting material or the light emitting layer host material. In particular, the T ₁ level of a hole transport material for a blue light emitting device having an emission maximum wavelength of 500 nm or less is preferably 62 kcal / mol or more (259 kJ / mol or more), 85 kcal / mol or less (355 kJ / mol or less), and 65 kcal. / Mol or more (272 kJ / mol or more) and 80 kcal / mol or less (334 kJ / mol or less).
As a hole transport material satisfying the above physical property values, a hole transport material described in JP-A No. 2002-1000047 is preferable, and a preferable range of the hole transport material described in JP-A No. 2002-1000047 is described in the same specification. As described.
Among the above compound groups, tribenzazepine derivatives can be expected to have high luminous efficiency at high T ₁ , and arylamine derivatives can be expected to improve durability due to high stability. More preferred.
In addition, carbazole, polysilane compounds, poly (N-vinylcarbazole), aniline copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, organic silanes, carbon films, and derivatives thereof as necessary Can be added.

The thickness of the hole injection layer is not particularly limited, but is usually preferably in the range of 0.2 nm to 1 μm, more preferably 1 nm to 0.2 μm, and further preferably 2 nm to 100 nm. .
The thickness of the hole transport layer is not particularly limited, but is usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and even more preferably 10 nm to 500 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.

As a method for forming the hole injection layer and the hole transport layer, a vacuum deposition method, an LB method, a method in which the hole injection transport material is dissolved or dispersed in a solvent, a coating method, an ink jet method, a printing method, or a transfer method is used. It is done.
In the case of the coating method, it can be dissolved or dispersed together with the resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly (N -Vinyl carbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, and the like.

Among the above-described layer forming methods, the hole transport layer is preferably installed by vapor deposition. By installing by the vapor deposition method, a thin film having a uniform and constant film thickness can be formed, and the durability tends to be improved.
When the hole transport layer is installed by vapor deposition, the material of the hole transport layer may be composed of a low molecular organic compound having a molecular weight of 3000 or less and / or a low molecular organic metal compound having a molecular weight of 3000 or less, like the light emitting layer material. preferable.

(Electron injection layer, electron transport layer)
The material for the electron injection layer and the electron transport layer may be any material having any one of a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode.
In the light-emitting device of the present invention, at least one of the organic compound layers between the pair of electrodes is a layer containing the general formula (I). Among them, the general formula (I) has a high electron transporting ability. From this point of view, the general formula (I) -containing layer is preferably a layer located between the light emitting layer and the cathode, and more preferably an electron injection layer or an electron transport layer, and particularly an electron transport layer. Is particularly preferred.
In the light-emitting element of the present invention, a layer containing a compound having an ionization potential of 5.9 eV or more (more preferably 6.0 eV or more) is preferably used between the cathode and the light-emitting layer, and an electron transport having an ionization potential of 5.9 eV or more is used. It is more preferable to use a material.

As materials for the electron injection layer and the electron transport layer of the present invention, specific examples other than the general formula (I) include triazole, oxazole, oxadiazole, imidazole, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiol. Pyrandoxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, naphthalene, perylene and other aromatic ring tetracarboxylic anhydrides, phthalocyanines, 8-quinolinol metal complexes, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands Examples thereof include various metal complexes typified by metal complexes, organosilanes, and derivatives thereof.
Preferable examples of these compounds are the same as those of the corresponding compounds described in the section of the host material.
The hole blocking layer is particularly preferably provided adjacent to the light emitting layer for the above purpose.
As an electron transport material other than the above, an electron transport material described in JP-A No. 2002-1000047 is preferable, and a preferable range of the electron transport material described in JP-A No. 2002-1000047 is as described in the specification. .
In addition, carbazole, polysilane compounds, poly (N-vinylcarbazole), aniline copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, organic silanes, carbon films, and derivatives thereof as necessary Can be added.
The thickness of the electron injection layer is not particularly limited, but is usually preferably in the range of 0.2 nm to 1 μm, more preferably 1 nm to 0.2 μm, and further preferably 2 nm to 100 nm.
Although the film thickness of an electron carrying layer is not specifically limited, Usually, the thing of the range of 1 nm-5 micrometers is preferable, More preferably, it is 5 nm-1 micrometer, More preferably, it is 10 nm-500 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.
As a method for forming the electron injection layer and the electron transport layer, a vacuum vapor deposition method, an LB method, a method in which the electron injection transport material is dissolved or dispersed in a solvent, a coating method, an ink jet method, a printing method, a transfer method, and the like are used.
In the case of the coating method, it can be dissolved or dispersed together with the resin component. As the resin component, for example, those exemplified in the case of the hole injection transport layer can be applied.
Among the layer forming methods described above, the electron transport layer is preferably installed by vapor deposition. By installing by the vapor deposition method, a thin film having a uniform and constant film thickness can be formed, and the durability tends to be improved.
Moreover, when installing an electron carrying layer by a vapor deposition method, it is preferable that the material of an electron carrying layer also consists of a low molecular organic compound with a molecular weight of 3000 or less and / or a low molecular organometallic compound with a molecular weight of 3000 or less like the light emitting layer material.

(Hole blocking layer)
The light emitting device of the present invention has a hole blocking layer between the layer containing the general formula (I) and the light emitting layer. By providing a hole blocking layer between the general formula (I) -containing layer and the light emitting layer, it is possible to prevent a decrease in light emission efficiency and deterioration in durability.
As the hole blocking layer, any compound can be used as long as it achieves the purpose of preventing holes from passing through the light emitting layer and flowing into a layer such as an electron transporting layer. A metal complex salt of a quinolinol derivative, any of compounds selected from the general formula (III), the general formula (IV), the general formula (V), the general formula (VI), and the general formula (VII) It is preferable to contain one of them. Preferred ranges and specific examples of each compound are as described above.
These compounds may be used alone or in combination of two or more.
In the present invention, the metal complex salt of the 8-quinolinol derivative, the general formula (III), the general formula (IV), the general formula (V), the general formula (VI), and the general formula (VII) are selected. Among the compounds to be formed, at least one of the compounds may constitute a layer alone or may be dispersed in a binder to form a layer.
As a method for forming the hole blocking layer, a vacuum deposition method, an LB method, a method in which the hole injecting and transporting material is dissolved or dispersed in a solvent, a coating method, an ink jet method, a printing method, and a transfer method are used. From the viewpoint of improving the durability, it is possible to form a thin film having a uniform film thickness with a uniform vacuum deposition method.
The thickness of the hole blocking layer is not particularly limited, but is usually preferably in the range of 5 nm to 50 μm, more preferably 5 nm to 30 μm, and further preferably 5 nm to 20 μm.
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.

(Protective layer)
The light emitting element of the present invention may have a protective layer in order to prevent moisture and oxygen from entering.
As a material for the protective layer, any material may be used as long as it has a function of suppressing the entry of elements that promote element deterioration such as moisture and oxygen into the element.
Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O. ₃ , metal oxides such as Y ₂ O ₃ and TiO ₂ , metal fluorides such as MgF ₂ , LiF, AlF ₃ , and CaF ₂ , SiN _x , SiO _x N _y Such as nitride, polyethylene, polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene And a copolymer obtained by copolymerizing a monomer mixture containing at least one comonomer, a fluorine-containing copolymer having a cyclic structure in the copolymer main chain, a water-absorbing substance having a water absorption of 1% or more, a water absorption of 0 .1% or less of moisture-proof substances and the like.
There is no particular limitation on the method for forming the protective layer. For example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency excitation ions) Plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, and transfer method can be applied.

<Method for producing organic electroluminescent element>
Although the manufacturing method of the organic electroluminescent element of this invention is demonstrated below below, this invention is not limited to this.
A glass substrate having an ITO thin film as a transparent electrode is subjected to solvent cleaning and then subjected to UV-ozone treatment. Furthermore, a hole injection layer and a hole transport layer are formed in this order on the transparent electrode by a vapor deposition method. A light emitting layer is formed thereon by co-evaporating the light emitting material and the host material in a vacuum. The light emitting material and the host material have the same meanings as described above, and the preferred ranges are also the same. The host material and the light emitting material used for the light emitting layer preferably have a molecular weight of 3000 or less, and the material constituting the light emitting layer preferably has a molecular weight of 3000 or less. Vapor deposition is facilitated by setting the molecular weight range to the above range.
As the deposition, a known deposition method can be used. Further, a hole blocking layer is formed thereon using a material such as a metal complex salt of an 8-quinolinol derivative. Subsequently, an electron transport layer and an electron injection layer containing the compound of the general formula (I) are provided in this order, a patterned mask is placed thereon, and a back electrode (cathode) is deposited by evaporation. . A lead wire is connected to each of the anode and the cathode to form a light emitting laminate. The light emitting laminate obtained here is sealed to prepare a light emitting element.

  The light emitting element can be evaluated by performing a durability test by applying a direct current voltage to emit light, performing a driving durability test at an initial luminance, and setting the time when the luminance is halved as a half time.

  The use of the light emitting device of the present invention is not particularly limited, but is suitable for the fields of display device, display, backlight, electrophotography, illumination light source, recording light source, exposure light source, reading light source, sign, signboard, interior, optical communication, etc. Can be used.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

[Comparative Example 1]
An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate with a thickness of 150 nm (manufactured by Geomat Corp .; electron beam film-formed product; sheet resistance 15 Ω) is 2 mm wide using ordinary photolithography and hydrochloric acid etching. The anode was formed by patterning into stripes. The patterned ITO substrate is 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 with ultraviolet ozone cleaning. installed. After the apparatus was roughly evacuated with an oil rotary pump, the apparatus was evacuated with a cryopump until the degree of vacuum in the apparatus was 2 × 10 ⁻⁶ Torr (about 2.7 × 10 ⁻⁴ Pa) or less.

Next, the following copper phthalocyanine (crystal form is β type) placed in a molybdenum boat arranged in the above apparatus is heated to a degree of vacuum of 1.4 × 10 ⁻⁶ Torr (about 1.9 × 10 ^−4). Pa), vapor deposition was performed at a vapor deposition rate of 0.1 nm / second to form a 10 nm-thick hole injection layer (anode buffer layer).

Next, α-NPD ((N, N′-di-α-naphthyl-N, N′-diphenyl) -benzidine) placed in a ceramic crucible disposed in the apparatus is heated to a tantalum wire around the crucible. The vapor deposition was carried out by heating. A degree of vacuum at the time of vapor deposition was 9.0 × 10 ⁻⁷ Torr (about 1.2 × 10 ⁻⁴ Pa), a vapor deposition rate was 0.2 nm / second, and a hole transport layer having a film thickness of 60 nm was formed.

Subsequently, CBP as the main component (host material) of the light emitting layer, and the iridium complex (Ir (ppy) ₃ ) as the phosphorescent organometallic complex as the secondary component (dopant) were placed in a ceramic crucible, and the two-way co-evaporation method was used. Film formation was performed. The deposition rate of CBP is controlled to 0.1 nm / second, and the deposition rate is controlled so that the iridium complex (Ir (ppy) ₃ ) is contained at 5% by weight with respect to the host. Laminated on the hole transport layer. The degree of vacuum at the time of vapor deposition was 1.3 × 10 ⁻⁶ Torr (about 1.7 × 10 ⁻⁴ Pa).

Further, BAlq ₂ was laminated as a hole blocking layer with a film thickness of 10 nm at a deposition rate of 0.1 nm / second. The degree of vacuum during the deposition was 7.0 × 10 ⁻⁷ Torr (about 0.9 × 10 ⁻⁴ Pa).

Next, the following comparative compound was deposited on the hole blocking layer in the same manner as an electron transport layer. The degree of vacuum during deposition was 6.0 × 10 ⁻⁷ Torr (about 0.8 × 10 ⁻⁴ Pa), the deposition rate was 0.2 nm / second, and the film thickness was 35 nm.

  The substrate temperature when vacuum-depositing the hole transport layer, the light emitting layer, the hole blocking layer, and the electron transport layer was maintained at room temperature.

Here, the element on which the electron transport layer has been deposited is once taken out from the vacuum deposition apparatus into the atmosphere, and a 2 mm wide striped shadow mask is orthogonal to the ITO stripe of the anode 2 as a mask for cathode deposition. In the same manner as in the formation of the organic layer, the vacuum degree in the device is 2 × 10 ⁻⁶ Torr (about 2.7 × 10 ⁻⁴ Pa). ) Exhaust until below.

Thereafter, as a cathode, first, magnesium fluoride (MgF ₂ ) was vapor deposited at a rate of 0.1 nm / second using a molybdenum boat, and the degree of vacuum was 7.0 × 10 ⁻⁶ Torr (about 9.3 × 10 ⁻⁴ Pa). The film was formed on the electron transport layer with a film thickness of 1.5 nm. Next, aluminum is similarly heated by a molybdenum boat to form an aluminum layer having a film thickness of 40 nm at a deposition rate of 0.5 nm / second and a degree of vacuum of 1 × 10 ⁻⁵ Torr (about 1.3 × 10 ⁻³ Pa). did. Furthermore, thereon silver to enhance conductivity of the cathode, as well as by heating of molybdenum boat, deposition rate 0.3 nm / sec, the degree of vacuum 1 × 10 ^-5 Torr (about 1.3 × 10 ^{- The} cathode 8 was completed by forming a silver layer with a thickness of 40 nm at ³ Pa). The substrate temperature during the deposition of the above three-layer cathode 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.
Evaluation was performed by the following method using the light-emitting element obtained above.

Using a source measure unit type 2400 manufactured by Toyo Technica, direct voltage was applied to the organic EL element to emit light, and the initial light emitting performance was measured.
The luminous efficiency (%) is the luminous efficiency at ₁₀₀ Cd / m ² as the external quantum efficiency (η ₁₀₀ ) (%), and the luminance / current (Cd / A) is the slope of the luminance-current density characteristic. Table 24 shows the values at 100 cd / m ² .
In addition, a driving durability test was performed at an initial luminance of 1000 Cd / m ² , and the test results are shown in Table 24, with the time when the luminance was reduced to half as the half time (T _1/2 ) (Hr).
The maximum wavelength of the emission spectrum of this device was 515 nm, and it was identified to be from an iridium complex (Ir (ppy) ₃ ).

[Comparative Examples 2-3, Examples 1-12]
A light emitting device was fabricated in the same manner as in Comparative Example 1 except that the compound of the electron transport layer and the compound of the hole blocking layer were changed as shown in the following table in Comparative Example 1. About the evaluation, it carries out similarly to the sample 1, and the result is shown in Table 24.
The maximum wavelength of the emission spectrum of these devices was 515 nm, and it was identified to be from an iridium complex (Ir (ppy) ₃ ).

  As is apparent from Table 24, it is understood that the example using the compound of the present invention for the electron transport layer and having the hole blocking layer is superior in external quantum efficiency, luminance / current, and driving voltage as compared with the comparative example. it can. Further, it can be understood that the driving durability is also good.

  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. The compounds of the present invention can also be applied to medical uses, fluorescent brighteners, photographic materials, UV absorbing materials, laser dyes, recording media materials, inkjet pigments, color filter dyes, color conversion filters, and the like. is there.

Claims (3)

A light-emitting element having an organic compound layer including at least one light-emitting layer between a pair of electrodes, wherein at least one of the organic compound layers contains a compound represented by the following general formula (I), and A light-emitting element having a hole blocking layer between a layer containing the general formula (I) and the light-emitting layer.

(In the general formula (I), R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heteroaryl group. X ¹ and X ² are each independently an alkyl group. Represents a group, an aryl group, or a heteroaryl group.) The light emitting device according to claim 1, wherein the compound of the general formula (I) is the following general formula (II).

(In general formula (II), R ^{1 to} R ⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heteroaryl group.) In the hole blocking layer, at least one of a metal complex salt of an 8-quinolinol derivative and a compound selected from the following general formulas (III), (IV), (V), (VI), and (VII): The light emitting device according to claim 1, comprising:

(In the general formula (III), Ar ¹¹ represents an aryl group or a heteroaryl group. Ar ¹² represents an orthophenylene group, a metaphenylene group, a paraphenylene group, a biphenylene group, or a group in which 3 to 6 rings of benzene rings are connected. , 2 or more rings 6 ring an arylene group fused ring aromatic rings are condensed, or .Ar ¹² representing the heteroarylene group may be those arylene group and heteroarylene group is linked together .R ^11, R ¹² and R ¹³ represent an alkyl group, an aryl group, or a heteroaryl group.)

In (formula (IV), Ar ²¹ is a one .Ar ²² representing an aryl group or a heteroaryl group .Ar ²² which represents an arylene group or a heteroarylene group linked the arylene group and heteroarylene group each other R ²¹ , R ²² , or R ²³ each independently represents an alkyl group, an aryl group, or a heteroaryl group, and m represents 1 or 2.

(In the general formula (V), Ar ³² represents an arylene group, a group containing an azole structure, a group containing an azine structure having two or more hetero atoms, a group containing a furan structure, or a group containing a thiophene structure. Ar ³² , the arylene group, a group containing an azole structure, groups heteroatom containing two or more azine structure, a group containing a furan structure, a group containing a thiophene structure may be one which is connected to one another .R ^31, R ³² or R ³³ each independently represents an alkyl group, an aryl group, or a heteroaryl group.)

(In the general formula ^{(VI), R 1, R} 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R ¹⁵ and R ¹⁶ represent a hydrogen atom or a substituent.)

(In General Formula (VII), L represents a single bond or a divalent or higher valent linking group, and T represents an atom such as a hydrogen atom from any ^one of R ^{1 to} R ^{16 in} the structure represented by General Formula (1). Or a group obtained by removing any one of R ^{1 to} R ¹⁶ , n represents an integer of 2 or more, and a plurality of T's are independent of each other.