KR20130043665A - Organic electroluminescent element - Google Patents

Abstract

It is to provide an organic electroluminescent element which has a small decrease in efficiency during high brightness driving and a small initial drop in driving durability. On a board | substrate, it has a pair of electrode which consists of an anode and a cathode, and has a light emitting layer between the electrodes, has at least 1 organic layer between this light emitting layer and this anode, and at least 1 organic layer between this light emitting layer and this cathode. An organic electroluminescent device having a compound comprising: at least one compound represented by, for example, (a-3) in at least one organic layer between the light emitting layer and the cathode, and at least one layer between the light emitting layer and the anode. An organic electroluminescent element containing at least one compound represented, for example, by (h-1) in an organic layer.

Description

Organic electroluminescent element {ORGANIC ELECTROLUMINESCENT ELEMENT}

The present invention relates to an organic electroluminescent device.

Organic electroluminescent elements (hereinafter, also referred to as "elements" and "organic EL elements") have been actively researched and developed because high luminance light emission is obtained by low voltage driving. An organic electroluminescent element has an organic layer between a pair of electrodes, and uses the energy of the excitons produced | generated when the electron injected from the cathode and the hole injected from the anode recombined in the organic layer.

In recent years, the use of phosphorescent light emitting materials has increased the efficiency of devices. Moreover, the dope type element which uses the light emitting layer which doped the light emitting material in the host material is employ | adopted widely.

For example, in Patent Literatures 1 and 2, an organic electroluminescent device using an iridium complex as a phosphorescent light emitting material and a compound containing a carbazole structure and a nitrogen-containing aromatic hetero 6-membered ring as a host material It is described.

Patent documents 4 and 5 also describe organic electroluminescent devices using a compound containing a carbazole structure and a nitrogen-containing aromatic hetero 6-membered ring.

Moreover, in order to improve the efficiency, durability, etc. of an organic electroluminescent element, the development of the compound which has electrical stability and high charge transport capability is also performed.

For example, Patent Documents 3 and 6 describe organic electroluminescent devices in which a layer made of a specific compound containing a phenylcarbazole structure is formed between a light emitting layer and an anode.

Japanese Unexamined Patent Publication No. 2009-88538 International Publication No. 05/085387 Japanese Laid-Open Patent Publication 2006-151979 International Publication No. 07/142083 Japanese Unexamined Patent Publication No. 2007-220721 Japanese Unexamined Patent Publication No. 2007-318101

The organic electroluminescent element can be considered to drive at a high brightness of about 10,000 cd / m 2, for example, in televisions and lighting applications. According to the inventors' review, in the conventional organic electroluminescent element, At the same time, it was found that the decrease in efficiency was observed as compared with the low luminance driving.

In addition, when the conventional organic electroluminescent element is driven with a constant current and the decrease in luminance is observed, the rate of decrease in luminance immediately after the start of the emission is large (the time until the luminance reaches 95% of the initial stage is short), and then the luminance is gradually decreased. Tends to be lowered. The fall of the luminance at this initial stage is called "initial fall". When the organic deterioration is applied to a display, this initial decrease is a so-called "ghosting", in which a decrease in luminance of a group of pixels exposed to continuous lighting by a fixed image pattern or the like is recognized by an observer as a luminance step with respect to surrounding pixels. Cause. Therefore, in order to put an organic electroluminescent element into a television etc., it is necessary to prevent this ghosting and it is important to suppress the initial fall of drive durability.

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide an organic electroluminescent device which has a low deterioration in efficiency during high luminance driving and a small initial deterioration in driving durability.

That is, this invention can be achieved by the following means.

[One]

On a board | substrate, it has a pair of electrode which consists of an anode and a cathode, and has a light emitting layer between the electrodes, has at least 1 organic layer between this light emitting layer and this anode, and at least 1 organic layer between this light emitting layer and this cathode. An organic electroluminescent device having

At least one compound represented by following General formula (1) is contained in the organic layer of at least 1 layer between this light emitting layer and this cathode,

An organic electroluminescent element comprising at least one compound represented by the following general formula (H-1) in at least one organic layer between the light emitting layer and the anode.

[Formula 1]

(In general formula (1), X <_3> , X <_4> and X <_5> are respectively independently the carbon atom which the nitrogen atom or the hydrogen atom couple | bonded, and the ring containing X <_3> , X <_4> and X <_5> is pyridine or pyrimidine. L 'represents a single bond or a benzene ring, R ¹ to R ⁵ each independently represent a fluorine atom, a methyl group, a phenyl group, a cyano group, a pyridyl group, a pyrimidyl group, a silyl group, a carbazolyl group, or tert-butyl N1 to n5 each independently represent 0 or 1, and p 'and q' each independently represent 1 or 2).

[Formula 2]

(In general formula (H-1), X represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted bivalent heterocyclic group.

R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted An aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a hydroxyl group, a cyano group, or a substituted or unsubstituted amino group is represented. At least two of R _H1 , R _H2 and R _{H3 may} be bonded to each other to form a ring. At least two of R _H1 ′, R _H2 ′ and R _H3 ′ may be bonded to each other to form a ring.

A _H1 and A _H1 'are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted aromatic heterocyclic group.)

[2]

The organic electroluminescent device according to the above [1], wherein A _H1 and A _H1 ′ are a substituted or unsubstituted aryl group in the general formula (H-1).

[3]

The organic electroluminescent device according to the above [1] or [2], wherein in the general formula (H-1), X is an unsubstituted arylene group.

[4]

In the general formula (H-1), the organic electroluminescence according to any one of the above [1] to [3], wherein A _H1 and A _H1 'are a substituted or unsubstituted phenyl group, biphenyl group, or anthryl group. device.

[5]

The organic electroluminescent device according to any one of the above [1] to [4], wherein in the general formula (H-1), X is a phenylene group, a naphthylene group, or a biphenylene group.

[6]

The organic electroluminescent device according to any one of the above [1] to [5], wherein the general formula (H-1) is represented by the following general formula (H-2).

(3)

(In General Formula (H-2), R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'each independently represent a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, substituted or unsubstituted. Substituted aryl group, substituted or unsubstituted heterocyclic group, cyano group, or substituted or unsubstituted amino group is shown.

R _H4 and R _H4 ′ each independently represent a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, or a substituted or unsubstituted amino group. Indicates)

[7]

The organic electroluminescent device according to any one of the above [1] to [6], wherein R _H1 , R _H1 ′, R _H2 , R _H2 ′, R _H3, and R _H3 ′ are hydrogen atoms.

[8]

The organic electroluminescent device according to the above [6] or [7], wherein R _H4 and R _H4 ′ are a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, or a cyano group.

[9]

The organic electroluminescent element as described in any one of said [1]-[8] which contains a phosphorescent light emitting material in the said light emitting layer.

[10]

The organic electroluminescent device according to the above [9], wherein the phosphorescent light emitting material is an iridium complex.

[11]

The light-emitting device using the organic electroluminescent element in any one of said [1]-[10].

[12]

The display apparatus using the organic electroluminescent element in any one of said [1]-[10].

[13]

The illuminating device using the organic electroluminescent element in any one of said [1]-[10].

[14]

On a board | substrate, it has a pair of electrode which consists of an anode and a cathode, and has a light emitting layer between the electrodes, has at least 1 organic layer between this light emitting layer and this anode, and at least 1 organic layer between this light emitting layer and this cathode. An organic electroluminescent device having

At least one compound represented by following General formula (1) is contained in the organic layer of at least 1 layer between this light emitting layer and this cathode,

An organic electroluminescent element comprising at least one compound represented by the following general formula (H-2) in at least one organic layer between the light emitting layer and the anode.

[Formula 4]

(In general formula (1), X <_3> , X <_4> and X <_5> are respectively independently the carbon atom which the nitrogen atom or the hydrogen atom couple | bonded, and the ring containing X <_3> , X <_4> and X <_5> is pyridine or pyrimidine. L 'represents a single bond or a benzene ring, R ¹ to R ⁵ each independently represent a fluorine atom, a methyl group, a phenyl group, a cyano group, a pyridyl group, a pyrimidyl group, a silyl group, a carbazolyl group, or tert-butyl N1 to n5 each independently represent 0 or 1, p 'represents 1 or 2, and q' represents 1)

[Chemical Formula 5]

(Formula (H2) of, R _{H1, H1} R ', R _H2 and R _H2' are each independently a hydrogen atom, a fluorine atom, an unsubstituted alkyl group, the unsubstituted aryl group, a group-unsubstituted pyrido, Or a cyano group.

R _H3 and R _H3 ′ represent a hydrogen atom.

R _H4 and R _H4 ′ each independently represent a hydrogen atom, a fluorine atom, an unsubstituted alkyl group, or an unsubstituted aryl group)

[15]

The organic electroluminescent device according to the above [14], wherein R _H1 , R _H1 ′, R _H2, and R _H2 ′ are hydrogen atoms.

[16]

The organic electroluminescent device according to the above [14] or [15], wherein R _H4 and R _H4 ′ are a hydrogen atom, a fluorine atom, or an unsubstituted alkyl group.

[17]

The organic electroluminescent element according to any one of the above [14] to [16], wherein the light emitting layer contains a phosphorescent light emitting material.

[18]

The organic electroluminescent device according to the above [17], wherein the phosphorescent light emitting material is an iridium complex.

[19]

The light-emitting device using the organic electroluminescent element in any one of said [14]-[18].

[20]

The display apparatus using the organic electroluminescent element in any one of said [14]-[18].

[21]

The illuminating device using the organic electroluminescent element in any one of said [14]-[18].

According to the present invention, it is possible to provide an organic electroluminescent device which is less deteriorated in efficiency at the time of high-brightness driving and has less initial reduction in driving durability.

1 is a schematic view showing an example of the configuration of an organic electroluminescence device according to the present invention.
2 is a schematic view showing an example of a light-emitting device related to the present invention.
3 is a schematic view showing an example of a lighting apparatus according to the present invention.

The hydrogen atom in description of general formula (1) and general formula (H-1) also contains an isotope (deuterium atom etc.), and the atom which comprises a substituent shows that the isotope also contains.

In the present invention, substituent group A and substituent group B are defined as follows.

(Substituent group A)

Alkyl group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, for example methyl, ethyl, isopropyl, t-butyl, n-octyl, n-decyl , n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, neopentyl and the like), alkenyl group (preferably C 2 to 30, more preferably C 2 to 20, particularly preferably C 2 -10, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc., an alkynyl group (preferably C2-C30, More preferably, it is C2-C20, Especially preferably, Has 2 to 10 carbon atoms, and for example, propargyl, 3-pentynyl and the like, an aryl group (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms), and particularly preferably 6-12, for example, phenyl, 4-methylphenyl, 2,6-dimethylphenyl, etc.), amino (Preferably 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, for example amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino , Ditrilamino, etc.), an alkoxy group (preferably C1-C30, More preferably, it is C1-C20, Especially preferably, it is C1-C10, For example, methoxy, ethoxy, Butoxy, 2-ethylhexyloxy, etc.) and an aryloxy group (preferably C6-C30, More preferably, it is C6-C20, Especially preferably, it is C6-C12, For example, Phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), heterocyclic oxy group (preferably C1-C30, More preferably, C1-C20, Especially preferably, C1-C20 12, for example pyridyloxy, pyrazyloxy, pyrimidyl jade Ci, quinolyloxy, etc.), an acyl group (preferably C2-C30, More preferably, it is C2-C20, Especially preferably, it is C2-C12, For example, acetyl, benzoyl, a fort Mill, pivaloyl, etc.), an alkoxycarbonyl group (preferably C2-C30, More preferably, it is C2-C20, Especially preferably, it is C2-C12, For example, methoxycarbonyl, Ethoxycarbonyl, etc.) and an aryloxycarbonyl group (preferably carbon number 7-30, More preferably, it is C7-20, Especially preferably, it is C7-12, For example, phenyloxycarbonyl etc. Acyloxy group (preferably C2-C30, More preferably, it is C2-C20, Especially preferably, it is C2-C10, For example, acetoxy, benzoyloxy, etc. are mentioned. ), Acylamino group (preferably carbon 2-30, More preferably, it is C2-C20, Especially preferably, it is C2-C10, For example, acetylamino, benzoylamino, etc. are mentioned, The alkoxycarbonylamino group (preferably C2-C30) More preferably, they are C2-C20, Especially preferably, it is C2-C12, For example, a methoxycarbonylamino etc. are mentioned, An aryloxycarbonylamino group (Preferably C7-C30, More Preferably it is C7-20, Especially preferably, it is C7-12, For example, a phenyloxycarbonylamino etc. are mentioned, A sulfonylamino group (Preferably C1-C30, More preferably, it is C1-C12) 1-20, Especially preferably, it is C1-C12, For example, methanesulfonylamino, benzenesulfonylamino, etc. are mentioned, A sulfamoyl group (preferably carbon number is 0-30, More preferably, it is carbon number) 0 to 2 0, Especially preferably, it is C12-C12, For example, a sulfamoyl, methyl sulfamoyl, dimethyl sulfamoyl, phenyl sulfamoyl, etc. are mentioned, Carbamoyl group (preferably C1-C30, more preferable) Preferably it is C1-C20, Especially preferably, it is C1-C12, For example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc. are mentioned, The alkylthio group ( Preferably it is C1-C30, More preferably, it is C1-C20, Especially preferably, it is C1-C12, For example, methylthio, ethylthio, etc. are mentioned, An arylthio group (preferably carbon number) 6-30, More preferably, it is C6-C20, Especially preferably, it is C6-C12, For example, a phenylthio etc. are mentioned, Heterocyclic thi group (Preferably C1-C30, More preferable Preferably 1 to 20 carbon atoms, particularly preferably 1-12, pyridylthio, 2-benzimizolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, etc. are mentioned, and a sulfonyl group (preferably C1-C30) More preferably, it is C1-C20, Especially preferably, it is C1-C12, For example, mesyl, tosyl, etc. are mentioned, A sulfinyl group (preferably C1-C30, More preferably, C1-C1) -20, Especially preferably, it is C1-C12, For example, methane sulfinyl, benzene sulfinyl, etc. are mentioned, A ureido group (preferably C1-C30, More preferably, it is C1-C20, Especially preferably, it is C1-C12, for example, ureido, methylureido, phenylureido, etc.), phosphate amide group (preferably C1-C30, More preferably, C1-C20 Especially preferably, it is C1-C12, For example, diethyl phosphate And phenyl phosphate amide), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, Hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (The aromatic heterocyclic group is included, Preferably it is C1-C30, More preferably, it is C1-C12, As a hetero atom, a For example, it is a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, a selenium atom, a tellurium atom, specifically, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, pyrrolyl, pyrazolyl, triazolyl, imido Dazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, quinolyl, furyl, thienyl, selenophenyl, tellurophenyl, piperidyl, piperidino, morpholino, pyrrolidyl, pipe Lolidino, Benzoxazolyl, Benzoimidazole Reels, benzothiazolyl, carbazolyl group, azepinyl group, silolyl group, etc.), silyl group (preferably C3-40, More preferably, C3-30, Especially preferably, C3 It is -24, For example, trimethylsilyl, a triphenylsilyl, etc. are mentioned, Silyloxy group (preferably C3-C40, More preferably, it is C3-C30, Especially preferably, it is C3-C24) For example, trimethylsilyloxy, a triphenylsilyloxy, etc. are mentioned, A phosphoryl group (For example, a diphenylphosphoryl group, a dimethylphosphoryl group, etc. are mentioned). These substituents may be further substituted, and examples of the additional substituent include groups selected from Substituent Group A described above.

(Substituent group B)

Alkyl group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, for example methyl, ethyl, isopropyl, t-butyl, n-octyl, n-decyl , n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like), alkenyl group (preferably carbon 2 to 30, more preferably carbon 2 to 20, particularly preferably carbon 2 to 10) For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc. are mentioned, Alkynyl group (preferably C2-C30, More preferably, C2-C20, Especially preferably, C2-C It is -10, For example, propargyl, 3-pentynyl, etc. are mentioned, Aryl group (preferably C6-C30, More preferably, C6-C20, Especially preferably, C6-C12 Phenyl, p-methylphenyl, naphthyl, anthranyl, etc.), cyano group, hete And a cyclic group (aromatic heterocyclic group is also included, preferably 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and as a hetero atom, for example, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom , Selenium atom, tellurium atom, and pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, pyrrolyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl , Quinolyl, furyl, thienyl, selenophenyl, tellurophenyl, piperidyl, piperidino, morpholino, pyrrolidyl, pyrrolidino, benzoxazolyl, benzoimidazolyl, benzothiazolyl, Carbazolyl group, azepinyl group, silolyl group, etc.); These substituents may be further substituted, and examples of the additional substituent include groups selected from Substituent Group B above. The substituent group substituted with a substituent may be further substituted, and examples of the additional substituent include groups selected from Substituent Group B described above. The substituent group substituted with a substituent may be further substituted, and examples of the additional substituent include groups selected from Substituent Group B described above.

The organic electroluminescent device of the present invention has a pair of electrodes consisting of an anode and a cathode on a substrate, a light emitting layer between the electrodes, at least one organic layer between the light emitting layer and the anode, the light emitting layer and An organic electroluminescent element having at least one organic layer between the cathodes,

At least one compound represented by following General formula (1) is contained in the organic layer of at least 1 layer between this light emitting layer and this cathode,

At least one compound represented by the following general formula (H-1) is contained in the at least 1 layer of organic layer between this light emitting layer and this anode.

[Compound represented by the general formula (1)

Hereinafter, the compound represented by General formula (1) is demonstrated.

[Formula 6]

(In general formula (1), X <_3> , X <_4> and X <_5> are respectively independently the carbon atom which the nitrogen atom or the hydrogen atom couple | bonded, and the ring containing X <_3> , X <_4> and X <_5> is pyridine or pyrimidine. L 'represents a single bond or a benzene ring, R ¹ to R ⁵ each independently represent a fluorine atom, a methyl group, a phenyl group, a cyano group, a pyridyl group, a pyrimidyl group, a silyl group, a carbazolyl group, or tert-butyl N1 to n5 each independently represent 0 or 1, and p 'and q' each independently represent 1 or 2).

General formula (1) is demonstrated.

X ₃ , X ₄ and X ₅ are each independently a carbon atom having a nitrogen atom or a hydrogen atom bonded thereto, and the ring containing X ₃ , X ₄ and X ₅ is pyridine or pyrimidine. Particularly preferably, the ring containing X ₄ and X ₅ is pyrimidine, X ₃ is preferably a nitrogen atom, X ₄ is preferably a carbon atom bonded to a hydrogen atom, and X ₅ is a nitrogen atom Do.

L 'represents a single bond or a benzene ring (for example, when p' + q 'is 2). L 'is connected with the benzene ring in the nitrogen-containing heteroaromatic structure in General formula (1).

R ¹ to R ⁵ each independently represent a fluorine atom, a methyl group, a phenyl group, a cyano group, a pyridyl group, a pyrimidyl group, a silyl group, a carbazolyl group, or a tert-butyl group. When R <^1> -R <^5> is multiple, some R <^1> -R <^5> may be same or different, respectively.

R ¹ to R ⁵ may further have a substituent if possible, and examples of the substituent include a fluorine atom, a chlorine atom, a methyl group, a phenyl group, a cyano group, a pyridyl group, a pyrimidyl group, a silyl group, a carbazolyl group, or tert-butyl group is mentioned. Moreover, the substituent may further have a substituent if possible, and the thing similar to the above is mentioned as this further substituent.

It is preferable that R <^1> and R <^2> is a tert- butyl group or a silyl group, and it is more preferable that the silyl group is a triphenyl silyl group.

R ³ is preferably a pyrimidyl group, and the pyrimidyl group preferably has a phenyl group as a substituent.

R ⁴ and R ⁵ are preferably a phenyl group.

It is preferable that q 'is 1.

Most preferably, the compound represented by General formula (1) consists only of a carbon atom, a hydrogen atom, and a nitrogen atom.

It is preferable that the molecular weight of the compound represented by General formula (1) is 400 or more and 1000 or less, It is more preferable that it is 450 or more and 800 or less, It is further more preferable that it is 500 or more and 700 or less.

The lowest triplet excitation (T ₁ ) energy in the film state of the compound represented by the general formula (1) is preferably 2.61 eV (62 dl / mol) or more and 3.51 eV (80 dl / mol), preferably 2.69 eV (63.5 GHz) / Mol) or more and 3.51 eV (80 dl / mol) or more, and more preferably 2.76 eV (65 dl / mol) or more and 3.51 eV (80 dl / mol).

It is preferable that the glass transition temperature (Tg) of the compound represented by General formula (1) is 80 degreeC or more and 400 degrees C or less, It is more preferable that they are 100 degreeC or more and 400 degrees C or less, It is further more preferable that they are 120 degreeC or more and 400 degrees C or less.

When General formula (1) has a hydrogen atom, an isotope (deuterium atom etc.) is also included. In this case, all the hydrogen atoms in the compound may be substituted with isotopes, or a mixture may be a compound in which a part contains isotopes.

Although the specific example of a compound represented by General formula (1) is illustrated below, this invention is not limited to these. In addition, Ph in the following specific example represents a phenyl group.

[Formula 7]

[Formula 8]

[Chemical Formula 9]

[Formula 10]

[Formula 11]

The compound illustrated as a compound represented by the said General formula (1) is a method as described in the international publication 03/080760 pamphlet, a method as described in the international publication 03/078541 pamphlet, and an international publication 05/085387 pamphlet It can synthesize | combine by various methods, such as a method.

For example, the said exemplary compound (a-3) uses m-bromobenzoaldehyde as a starting material, International Publication No. 05/085387 pamphlet paragraph [0074]-(page 45, line 11- Page 46, line 18). The said exemplary compound (a-17) uses 3, 5- dibromo benzoaldehyde as a starting material, and is the method of page 46, line 9-page 46, line 12 of the international publication 03/080760 pamphlet. Can be synthesized. Moreover, the said exemplary compound (a-39) is synthesize | combined by the method as described in page 137, line 10-page 139, line 9 of the international publication 05/022962 pamphlet using N-phenylcarbazole as a starting material. Can be.

After synthesis, purification by column chromatography, recrystallization or the like is preferably followed by purification by sublimation purification. By sublimation purification, not only an organic impurity can be separated but an inorganic salt, a residual solvent, etc. can be removed effectively.

In this invention, the compound represented by General formula (1) is not limited to the use, In addition to the organic layer between a light emitting layer and a cathode, you may contain in any other layer. As an introduction layer of the compound represented by General formula (1), it is preferable to contain either a light emitting layer, a hole injection layer, a hole transport layer, an electron carrying layer, an electron injection layer, an exciton block layer, and a charge block layer in multiple numbers, , A light emitting layer, an electron transport layer, or an electron injection layer is more preferable, and an electron transport layer is still more preferable.

When including the compound represented by General formula (1) in the organic layer between a cathode and a light emitting layer, it is preferable to contain 70-100 mass% with respect to the total mass of the organic layer, and it is more preferable to contain 85-100 mass%. . When including the compound represented by General formula (1) in a light emitting layer, it is preferable to contain 0.1-99 mass% with respect to the total mass of a light emitting layer, It is more preferable to contain 1-95 mass%, 10-95 mass% It is more preferable to make it contain.

[Compound represented by general formula (H-1)]

The compound represented by the following general formula (H-1) is demonstrated.

[Chemical Formula 12]

(In general formula (H-1), X represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted bivalent heterocyclic group.

R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted An aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a hydroxyl group, a cyano group, or a substituted or unsubstituted amino group is represented. At least two of R _H1 , R _H2 and R _{H3 may} be bonded to each other to form a ring. At least two of R _H1 ′, R _H2 ′ and R _H3 ′ may be bonded to each other to form a ring.

A _H1 and A _H1 'are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted aromatic heterocyclic group.)

In the organic electroluminescent device of the present invention, the compound represented by the general formula (H-1) is contained in at least one organic layer between the anode and the light emitting layer, but may be further contained in other layers.

In the element of this invention, it turned out that the efficiency fall at the time of high brightness drive is suppressed. This contains the compound represented by General formula (1) in a light emitting layer, and contains the compound represented by general formula (H-1) in the organic layer of at least 1 layer between a light emitting layer and an anode, and it is a high luminance area | region, ie, a high current area | region. The main factor in the amount of holes and electrons injected into the light emitting layer is a balance between the amount of holes injected by the compound represented by the general formula (H-1) and the amount of electrons injected by the compound represented by the general formula (1). .

Moreover, in the element of this invention, it turned out that the initial fall of drive durability is suppressed. The cause of the initial decrease in driving durability can be considered as the main factor that causes the deterioration of the interface due to the accumulation of electrons or holes at the interface between the light emitting layer and the adjacent layer. In the present invention, the hole injection amount and the electron injection amount for the light emitting layer When it is balanced, recombination of electrons and holes is promoted, and it is assumed that the accumulation of electrons or holes can be eliminated and the initial reduction can be suppressed.

In general formula (H-1), X represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted bivalent heterocyclic group.

When X represents a substituted or unsubstituted alkylene group, the alkylene group is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, for example, methylene group, ethylene group, and propylene. A group, a butylene group, an octylene group, a decylene group, a hexadecylene group, a cyclopropylene group, a cyclopentylene group, a cyclohexylene group, etc. are mentioned.

When this alkylene group has a substituent, the substituent selected from the said substituent group A is mentioned, Preferably it is an alkyl group (It is a C1-C8 alkyl group, More preferably, it is C1-C8) It is an alkyl group of 6, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, isobutyl group, t-butyl group, n-butyl group, cyclopropyl group, etc. are mentioned, A methyl group, an ethyl group, isobutyl Group or t-butyl group is preferable) and an aryl group (preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms), for example, a phenyl group, a biphenyl group, and fluorine. And a phenyl group or a biphenyl group are preferable, a halogen atom (preferably a fluorine atom), a cyano group, and an alkoxy group (preferably having 1 to 20 carbon atoms, in particular, a methoxy group and an ethoxy group) Time is preferred), or room Group is a heterocyclic ring group (preferably an aromatic heterocyclic group having 2 to 12, for example, there may be mentioned such as a pyridyl group, a furyl group, a thienyl group, more preferably group-pyridyl).

In the case where X represents a substituted or unsubstituted alkenylene group, the alkenylene group is preferably an alkenylene group having 2 to 30 carbon atoms, more preferably an alkyl group having 2 to 20 carbon atoms, for example, a vinyl group, an allyl group, 2-butenyl group, 3-pentenyl group, etc. are mentioned.

When this alkenylene group has a substituent, it is the same as the substituent in the case where the said alkylene group has a substituent.

When X represents a substituted or unsubstituted arylene group, as this arylene group, Preferably it is C6-C30, More preferably, it is C6-C20, Especially preferably, it is a C6-C12 arylene group. As this arylene group, a phenylene group, a naphthylene group, a biphenylene group, an anthylene group, a terphenylene group, a fluorenylene group, a phenanthryl group, a pyrenylene group, a triphenylenylene group, etc. are mentioned, for example. A phenylene group, a naphthylene group, a biphenylene group, or an anthylene group, and a phenylene group, a naphthylene group (preferably 1,5-naphthylene group), or a biphenylene group is more preferable. Phenylene group is more preferable.

When the arylene group has a substituent, the substituent is the same as the substituent in the case where the alkylene group has a substituent.

When X represents a substituted or unsubstituted divalent heterocyclic group, the divalent heterocyclic group preferably contains 1, 2 or 3 heteroatoms selected from a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom. Do. As a heterocyclic group, the group by which at least 1 carbon atom which forms the ring of a cycloalkyl group or an aryl group was substituted by the said hetero atom is mentioned. The divalent hetero ring group is a group formed by removing one hydrogen atom from a monovalent hetero ring group. Preferably it is C2-C30, More preferably, it is C2-C20, Especially preferably, it is a C2-C12 bivalent heterocyclic group. As the divalent heterocyclic group, a divalent aromatic heterocyclic group is preferable, and as the divalent aromatic heterocyclic group, for example, a divalent azole group, a divalent diazole group, a divalent triazole group, a divalent oxazole group, A divalent thiazole group, a bivalent pyridyl group, a bivalent furyl group, a bivalent thienyl group, etc. are mentioned, A bivalent azole group, a bivalent diazole group, a bivalent pyridyl group is preferable. In addition, the hetero ring may have a condensed ring structure, and examples thereof include a quinoline ring and the like.

When the divalent heterocyclic group has a substituent, the substituent is the same as the substituent in the case where the alkylene group has a substituent.

It is preferable that X represents a substituted or unsubstituted arylene group, and it is more preferable that an unsubstituted arylene group is represented. Specific examples and preferred ranges when X is an arylene group are as described above.

In General Formula (H-1), R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted compound. A substituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a hydroxyl group, a cyano group, or a substituted or unsubstituted amino group.

When _RH1 , _RH1 ', _RH2 , _RH2 ', _RH3 and _RH3 'represent a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are mentioned, and a fluorine atom is preferable.

When R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'represent a substituted or unsubstituted alkyl group, the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Preferred examples include methyl group, ethyl group, propyl group, isobutyl group, sec-butyl group, pentyl group, isoamyl group, hexyl group, and the like. One or more hydrogen atoms of the alkyl group may be a halogen atom or 1 carbon atom. Substituents, such as an alkyl group of 30, a C1-C30 alkoxy group, a lower alkyl amino group, a hydroxyl group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group You may substitute.

When R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'represent a substituted or unsubstituted alkoxy group, the alkoxy group is preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Preferred examples thereof include methoxy group, ethoxy group, propoxy group, isobutyloxy group, sec-butyloxy group, pentyloxy group, isoamyloxy group, hexyloxy group and the like. The hydrogen atom is a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a lower alkyl amino group, a hydroxyl group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxylic acid group You may substitute by substituents, such as a sulfonic acid group and a phosphoric acid group.

When R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'represent a substituted or unsubstituted aryl group, the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 carbon atoms. It is -20, Especially preferably, it is a C6-C12 aryl group. As this aryl group, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a terphenyl group, a fluorenyl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group, etc. are mentioned, for example, A phenyl group, a naphthyl group, Biphenyl group, anthryl group, or terphenyl group is preferable. At least one hydrogen atom of the aryl group may be a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a lower alkyl amino group, a hydroxyl group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine, You may substitute by substituents, such as a hydrazone, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

When R _H1 , R _H1 ′, R _H2 , R _H2 ′, R _H3 and R _H3 ′ represent a substituted or unsubstituted aryloxy group, the aryloxy group preferably has 6 to 30 carbon atoms, more preferably C6-C20, Especially preferably, it is a C6-C12 aryloxy group. As this aryloxy group, a phenyloxy group, a naphthyloxy group, a biphenyloxy group, etc. are mentioned, for example, A phenyloxy group and a naphthyloxy group are preferable. At least one hydrogen atom in the aryloxy group may be a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a lower alkyl amino group, a hydroxyl group, a nitro group, a cyano group, an amino group, an amidino group, or a hydrazine. You may substitute by substituents, such as a hydrazone, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

When R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'represent a substituted or unsubstituted heterocyclic group, the heterocyclic group may be a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom. Preference is given to containing 1, 2 or 3 hetero atoms selected from. As a heterocyclic group, the group by which at least 1 carbon atom which forms the ring of a cycloalkyl group or an aryl group was substituted by the said hetero atom is mentioned. Preferably it is a C2-C30, More preferably, it is a C2-C20, Especially preferably, it is a C2-C12 heterocyclic group. As this heterocyclic group, an aromatic heterocyclic group is preferable, As this aromatic heterocyclic group, an azole group, a diazole group, a triazole group, an oxazole group, a thiazole group, a pyridyl group, a furyl group, thienyl group, etc. are mentioned, for example. And an azole group, a diazole group, and a pyridyl group are preferable. In addition, the hetero ring may have a condensed ring structure, and examples thereof include a quinoline ring and the like.

When this heterocyclic group has a substituent, the substituent selected from the said substituent group A is mentioned, Specifically, a halogen atom, a C1-C30 alkyl group, a C1-C30 alkoxy group, lower Alkyl amino group, hydroxyl group, nitro group, cyano group, amino group, amidino group, hydrazine, hydrazone, carboxylic acid group, sulfonic acid group, phosphoric acid group, etc. are mentioned.

When R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'represent a substituted or unsubstituted amino group, the substituent is preferably an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms). More preferably, they are a C1-C6 alkyl group, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, isobutyl group, t-butyl group, n-butyl group, cyclopropyl group, etc. are mentioned. A methyl group, an ethyl group, an isobutyl group, or a t-butyl group is preferred, and an aryl group (preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms). A phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, etc. are mentioned, A phenyl group or a biphenyl group is preferable.

At least two of R _H1 , R _H2 and R _{H3 may} be bonded to each other to form a ring. For example, two R _H1 may be bonded to each other to form a ring. The same _{applies to} R _H1 ′, R _H2 ′ and R _H3 ′. As the ring, an aromatic ring is preferable, and a benzene ring is particularly preferable.

R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'are preferably a hydrogen atom, an alkyl group, a halogen atom, an aryl group, a cyano group or an aromatic heterocyclic group, and a hydrogen atom, a methyl group and a fluorine It is more preferable that they are an atom, a phenyl group, a cyano group, and a pyridyl group, and it is still more preferable that they are a hydrogen atom.

In General Formula (H-1), A _H1 and A _H1 'are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted aromatic heterocyclic group.

When _AH1 and _AH1 'represent a substituted or unsubstituted aryl group, the aryl group is preferably a C6-C30, particularly preferably a C6-C20 aryl group. As this aryl group, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a terphenyl group, a fluorenyl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group, etc. are mentioned, for example, A phenyl group, a naphthyl group, A biphenyl group and an anthryl group are preferable, and a phenyl group, a biphenyl group, or an anthryl group is more preferable.

When this aryl group has a substituent, the substituent selected from the said substituent group A is mentioned, Preferably it is an alkyl group (It is a C1-C8 alkyl group, More preferably, it is C1-C6) It is an alkyl group, and a methyl group, an ethyl group, n-propyl group, isopropyl group, isobutyl group, t-butyl group, n-butyl group, cyclopropyl group etc. are mentioned, for example, A methyl group, an ethyl group, and an isobutyl group Or a t-butyl group is preferable), an aryl group (preferably a C6-C18 aryl group, More preferably, it is a C6-C12 aryl group, For example, a phenyl group, a biphenyl group, a fluorenyl group) , A naphthyl group and the like, and a phenyl group or a biphenyl group is preferable), a halogen atom (preferably a fluorine atom), a cyano group and an alkoxy group (preferably having 1 to 20 carbon atoms, especially a methoxy group and an ethoxy group) Is preferred), or direction Heterocyclic group (It is a C2-C12 aromatic heterocyclic group, For example, a pyridyl group, a furyl group, thienyl group, etc. are mentioned, A pyridyl group is more preferable.), Especially preferably, a cyano group , An alkyl group, a halogen atom and an alkoxy group.

When A _H1 and A _H1 'represent a substituted or unsubstituted aromatic heterocyclic group, the aromatic heterocyclic group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 2 carbon atoms. It is an aromatic heterocyclic group of 12. As this aromatic heterocyclic group, an azole group, a diazole group, a triazole group, an oxazole group, a thiazole group, a pyridyl group, a furyl group, thienyl group, carbazolyl group etc. are mentioned, for example.

When the heterocyclic group has a substituent, the substituent is the same as the substituent which may be used when A _H1 and A _H1 ′ are an aryl group.

A _H1 and A _H1 ′ are preferably a substituted or unsubstituted aryl group. Specific examples and preferred ranges when A _H1 and A _H1 'are an aryl group are as described above.

Specific examples of A _H1 and A _H1 ′ include a phenyl group, ethylphenyl group, ethylbiphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group, trifluoromethoxyphenyl group, o-, m Or p-tolyl group, o-, m- or p-cumenyl group, mesityl group, phenoxyphenyl group, (α, α-dimethylbenzene) phenyl group, (N, N'-dimethyl) aminophenyl group, (N, N '-Diphenyl) aminophenyl group, pentarenyl group, indenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, azulenyl group, heptarenyl group, acetaphthylenyl group, phenanthrenyl group, fluorenyl group, anthraquinolyl Group, methyl anthryl group, phenanthryl group, triphenylene group, pyrenyl group, chrysenyl group, ethyl-crisenyl group, pisenyl group, perylenyl group, chloroperylenyl group, pentaphenyl group, pentaxenyl group, tetraphenyl Renyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl group, heptasenyl group, pyrantrenyl group, obare Group, and the like carbazolyl group.

A _H1 and A _H1 'are preferably a phenyl group, a lower alkylphenyl group, a lower alkoxyphenyl group, a cyanophenyl group, a phenoxyphenyl group, a halophenyl group, a naphthyl group, a lower alkylnaphthyl group, a lower alkoxynaphthyl group, a cyanonaphthyl group, a halo Naphthyl group, fluorenyl group, carbazolyl group, lower alkylcarbazolyl group, biphenyl group, lower alkylbiphenyl group, lower alkoxybiphenyl group, thiophenyl group, indolyl group or pyridyl group. As for carbon number of the lower alkyl and lower alkoxy mentioned above, the range of 1-5 is preferable.

More preferably, A _H1 and A _H1 'are C1-C3 to a monocyclic, bicyclic, tricyclic aryl group selected from fluorenyl group, carbazolyl group, phenyl group, naphthyl group, phenanthrenyl group, or these aromatic rings. Lower alkyl of C1-C3 lower alkoxy, cyano, phenoxy, phenyl, or an aryl group in which 1-3 halogens are substituted, Preferably 1 halogen is mentioned.

It is preferable that the compound represented by general formula (H-1) is represented with the following general formula (H-2).

[Chemical Formula 13]

(In General Formula (H-2), R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'each independently represent a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, substituted or unsubstituted. Substituted aryl group, substituted or unsubstituted heterocyclic group, cyano group, or substituted or unsubstituted amino group is shown.

R _H4 and R _H4 ′ each independently represent a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, or a substituted or unsubstituted amino group. Indicates)

In the general formula (H2), R _{H1, H1} R ', R _H2, R _H2', R _H3, and the preferable range of R _H3 ', respectively in the formula (H1) R _H1, R _H1 It is the same as the preferable range of ', R _H2 , R _H2 ', R _H3 and R _H3 '.

Preferable ranges for R _H4 and R _H4 ′ are also the same as those for R _H1 , R _H1 ′, R _H2 , R _H2 ′, R _H3 and R _H3 ′, but are hydrogen, fluorine, substituted or unsubstituted alkyl groups. (Preferably an alkyl group having 1 to 30 carbon atoms, a methyl group, an ethyl group and the like are particularly preferable) or a cyano group is particularly preferable.

Although the specific example of a compound represented by general formula (H-1) is shown below, it is not limited to these.

[Formula 14]

[Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

The compound represented by general formula (H-1) can be synthesize | combined by the method of Unexamined-Japanese-Patent No. 2006-151979.

After synthesis, purification by column chromatography, recrystallization or the like is preferably followed by purification by sublimation purification. By sublimation purification, not only an organic impurity can be separated but an inorganic salt, a residual solvent, etc. can be removed effectively.

In the light emitting device of the present invention, the compound represented by the general formula (H-1) is contained in at least one organic layer between the light emitting layer and the anode, but its use is not limited, and is further contained in any other layer. You may be. As an introduction layer of the compound represented by general formula (H-1) which concerns on this invention, any of a light emitting layer, a hole injection layer, a hole transport layer, an electron carrying layer, an electron injection layer, an exciton block layer, a charge block layer, or a plurality It may contain.

As for the organic layer between the light emitting layer and anode which the compound represented by general formula (H-1) contains, it is more preferable that it is a hole injection layer and a hole transport layer, It is still more preferable that it is a hole injection layer.

[Organic electroluminescent device]

The element of this invention is demonstrated in detail.

An organic electroluminescent device of the present invention is an organic electroluminescent device having a pair of electrodes consisting of an anode and a cathode on a substrate, and a light emitting layer between the electrodes, and having at least one organic layer between the light emitting layer and the anode, The light emitting layer contains at least one compound represented by the general formula (1), and at least one compound represented by the general formula (H-1) is contained in at least one layer of the organic layer between the light emitting layer and the anode.

In the organic electroluminescent device of the present invention, the light emitting layer is an organic layer and further includes at least one organic layer between the light emitting layer and the anode, and may further have an organic layer.

It is preferable that at least one electrode of an anode and a cathode is transparent or translucent on the property of a light emitting element.

1 shows an example of the configuration of an organic electroluminescent element according to the present invention.

In the organic electroluminescent element 10 according to the present invention shown in FIG. 1, the light emitting layer 6 is sandwiched between the anode 3 and the cathode 9 on the support substrate 2. Specifically, the hole injection layer 4, the hole transport layer 5, the light emitting layer 6, the hole block layer 7 and the electron transport layer 8 are laminated in this order between the anode 3 and the cathode 9. It is.

<Configuration of Organic Layer>

There is no restriction | limiting in particular as a layer structure of the said organic layer, Although it can select suitably according to the use and the objective of an organic electroluminescent element, It is preferable to form on the said transparent electrode or the said back electrode. In this case, the organic layer is formed on the front surface or one surface on the transparent electrode or the back electrode.

There is no restriction | limiting in particular depending on the shape, size, thickness, etc. of an organic layer, According to the objective, it can select suitably.

Although the following is mentioned as a specific laminated constitution, This invention is not limited to these constitutions.

· Anode / hole transporting layer / light emitting layer / electron transporting layer / cathode

· Anode / hole transporting layer / light emitting layer / block layer / electron transporting layer / cathode

Anode / hole transporting layer / light emitting layer / block layer / electron transporting layer / electron injection layer / cathode

Anode / hole injecting layer / hole transporting layer / light emitting layer / electron transporting layer / electron injecting layer / cathode

· Anode / hole injecting layer / hole transporting layer / light emitting layer / block layer / electron transporting layer / cathode

Anode / hole injection layer / hole transporting layer / light emitting layer / block layer / electron transporting layer / electron injection layer / cathode

About the element structure of a organic electroluminescent element, a board | substrate, a cathode, and an anode, it is described in detail in Unexamined-Japanese-Patent No. 2008-270736, for example, and the matter of the publication can be applied to this invention.

<Substrate>

The substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic layer. In the case of an organic material, it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.

<Anode>

The shape of the anode is not particularly limited as long as it has a function as an electrode for supplying holes to the organic layer, and the shape, structure, and size of the anode are suitably selected from known electrode materials according to the purpose and purpose of the light- . As described above, the anode is usually formed as a transparent anode.

<Cathode>

The cathode may have a function as an electrode which injects electrons into an organic layer normally, and there is no restriction | limiting in particular about the shape, structure, size, etc. According to the use and the objective of a light emitting element, it can select suitably from well-known electrode materials. .

About the board | substrate, an anode, and a cathode, the matter described in Paragraph No. 0070-Unexamined-Japanese-Patent No. 2008-270736 can be applied to this invention.

<Organic layer>

The organic layer in this invention is demonstrated.

[Formation of Organic Layer]

In the organic electroluminescent device of the present invention, each organic layer is preferably formed by any of a solution coating process such as a dry film forming method such as a vapor deposition method or a sputtering method, a transfer method, a printing method, a spin coat method, a bar coat method, or the like. Can be.

[Light Emitting Layer]

The light emitting layer receives a hole from an anode, a hole injection layer, or a hole transport layer when an electric field is applied, receives electrons from a cathode, an electron injection layer, or an electron transport layer, and provides a place for recombination of holes and electrons to emit light. It is a layer having.

About a board | substrate, an anode, a cathode, an organic layer, and a light emitting layer, it is described in detail in Unexamined-Japanese-Patent No. 2008-270736, Unexamined-Japanese-Patent No. 2007-266458, and the matter of these publications can be applied to this invention. . Moreover, the light emitting layer may contain a material which does not have charge transportability and which does not emit light.

(Luminescent material)

As the light emitting material in the present invention, any of a phosphorescent light emitting material and a fluorescent light emitting material can be used.

The light emitting layer in this invention can contain two or more types of light emitting materials in order to improve color purity and to widen a light emission wavelength range. It is preferable that at least one of the light emitting materials is a phosphorescent light emitting material.

It is preferable from the viewpoint of driving durability that the light emitting material in the present invention further satisfies the relationship of 1.2 eV> ΔIp> 0.2 eV and / or 1.2 eV> ΔEa> 0.2 eV with the host material. Here, ΔIp means the difference between the Ip values of the host material and the light emitting material, and ΔEa means the difference between the Ea values of the host material and the light emitting material.

It is preferable that it is at least 1 type of a platinum complex material or an iridium complex material of the said luminescent material, and it is more preferable that it is an iridium complex material.

For the fluorescent light emitting material and the phosphorescent light emitting material, for example, paragraphs [0100] to [0164] of JP 2008-270736 and paragraphs [0088] to [0090] of JP 2007-266458 The matters described in detail and described in these publications can be applied to the present invention.

From a viewpoint of luminous efficiency etc., a phosphorescent light emitting material is preferable. Phosphorescent light emitting materials that can be used in the present invention include, for example, US6303238B1, US6097147, WO00 / 57676, WO00 / 70655, WO01 / 08230, WO01 / 39234A2, WO01 / 41512A1, WO02 / 02714A2, WO02 / 15645A1, WO02 / 44189A1, WO05 / 19373A2, JP 2001-247859, JP 2002-302671, JP 2002-117978, JP 2003-133074, JP 2002-235076, JP 2002-235076, JP 2003-123982, Japanese Laid-Open Patent Publication 2002-170684, EP1211257, Japanese Laid-Open Patent Publication 2002-226495, Japanese Laid-Open Patent Publication 2002-234894, Japanese Laid-Open Patent Publication 2001-247859, Japanese Laid-Open Patent Publication 2001-298470, Japanese Laid-Open Patent Publication 2002-173674, Japanese Laid-Open Patent Publication 2002-203678, Japanese Laid-Open Patent Publication 2002-203679, Japanese Laid-Open Patent Publication 2004-357791, Japanese Laid-Open Patent Publication 2006-256999, Japanese Laid-Open Patent Publication 2007-19462, Japanese Laid-Open Patent Publication 2007- It describes in patent documents, such as 84635 and Unexamined-Japanese-Patent No. 2007-96259. A phosphorescent compound etc. are mentioned, Especially, a more preferable luminescent dopant is Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex, Eu complex, Tb. Complexes, Gd complexes, Dy complexes, and Ce complexes. Particularly preferred are Ir complexes, Pt complexes or Re complexes, and among them, Ir complexes containing at least one coordination mode of metal-carbon bond, metal-nitrogen bond, metal-oxygen bond and metal- , Or a Re complex is preferable. Moreover, Ir complex and Pt complex are especially preferable from a viewpoint of luminous efficiency, drive durability, chromaticity, etc., and Ir complex is the most preferable.

As a platinum complex, it is preferably a platinum complex represented with the following general formula (C-1).

[Chemical Formula 19]

(Wherein Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a ligand coordinated to Pt. L ¹ , L ² and L ³ each independently represent a single bond or a divalent linking group)

General formula (C-1) is demonstrated. Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a ligand that is coordinated to Pt. At this time, any one of Q ¹ , Q ² , Q ^3, and Q ⁴ and Pt may be a covalent bond, an ionic bond, a coordination bond, or the like. As an atom couple | bonded with Pt in Q <^1> , Q <^2> , Q <^3> and Q <^4> , a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom are preferable, and Pt in Q <^1> , Q <^2> , Q <^3> and Q <^4> is preferable. It is preferable that at least 1 of the atoms couple | bonded is a carbon atom, It is more preferable that 2 is a carbon atom, It is especially preferable that 2 is a carbon atom and 2 is a nitrogen atom.

Q ¹ , Q ² , Q ^3, and Q ⁴ bonded to the carbon atom Pt may be an anionic ligand or a neutral ligand, and an anionic ligand may be a vinyl ligand, an aromatic hydrocarbon ring ligand (for example, a benzene ligand, Naphthalene ligands, anthracene ligands, phenanthrene ligands, etc., heterocyclic ligands (e.g. furan ligands, thiophene ligands, pyridine ligands, pyrazine ligands, pyrimidine ligands, pyridazine ligands, triazine ligands, thiazole ligands, oxazoles Ligands, pyrrole ligands, imidazole ligands, pyrazole ligands, triazole ligands and condensates containing them (for example, quinoline ligands, benzothiazole ligands, etc.). Neutral ligands include carbene ligands.

Q ¹ , Q ² , Q ³ and Q ⁴ bonded to the nitrogen atom Pt may be a neutral ligand or an anionic ligand, and the neutral ligand may be a nitrogen-containing aromatic heterocyclic ligand (pyridine ligand, pyrazine ligand, pyrimidine ligand). , Pyridazine ligands, triazine ligands, imidazole ligands, pyrazole ligands, triazole ligands, oxazole ligands, thiazole ligands and condensers containing them (e.g. quinoline ligands, benzimidazole ligands, etc.), Amine ligands, nitrile ligands, and imine ligands. Anionic ligands include amino ligands, imino ligands, nitrogen-containing aromatic heterocyclic ligands (pyrrole ligands, imidazole ligands, triazole ligands and condensers containing them (e.g. indole ligands, benzimidazole ligands, etc.) ).

Q ¹ , Q ² , Q ^3, and Q ⁴ bonded to the oxygen reactor Pt may be a neutral ligand or an anionic ligand, and the neutral ligand may be an ether ligand, a ketone ligand, an ester ligand, an amide ligand, or an oxygen group. Heterocyclic ligands (furan ligand, oxazole ligand, and the condensate containing them (benzoxazole ligand etc.)) are mentioned. Examples of the anionic ligands include alkoxy ligands, aryloxy ligands, heteroaryloxy ligands, acyloxy ligands, silyloxy ligands, and the like.

Q ¹ , Q ² , Q ³ and Q ⁴ bonded to the sulfur reactor Pt may be a neutral ligand or an anionic ligand, and the neutral ligand may be a thioether ligand, a thioketone ligand, a thioester ligand or a thioamide. Ligands, sulfur-containing heterocyclic ligands (thiophene ligands, thiazole ligands and condensates containing them (benzothiazole ligands, etc.)). Examples of the anionic ligands include alkyl mercapto ligands, aryl mercapto ligands, heteroaryl mercapto ligands, and the like.

Q ¹ , Q ² , Q ³ and Q ⁴ bonded to the phosphorus reactor Pt may be a neutral ligand or an anionic ligand, and the neutral ligand may be a phosphine ligand, a phosphate ester ligand, a phosphite ester ligand, or a phosphorus hetero Ring ligands (phosphinine ligands, etc.), and anionic ligands include phosphino ligands, phosphinyl ligands, phosphoryl ligands, and the like.

The group represented by Q <^1> , Q <^2> , Q <^3> and Q <^4> may have a substituent and the thing illustrated as said substituent group A can be suitably applied as a substituent. Moreover, substituents may be connected (when Q <^3> and Q <^4> are connected, it will become a Pt complex of a cyclic 4 left ligand).

A group represented by Q ¹ , Q ² , Q ³ and Q ⁴ is preferably an aromatic hydrocarbon ring ligand bonded to Pt by a carbon atom, an aromatic hetero ring ligand bonded to Pt by a carbon atom, and a nitrogen-containing aromatic hetero bond bound to Pt by a nitrogen atom Aromatic hydrocarbon ring ligands, which are ring ligands, acyloxy ligands, alkyloxy ligands, aryloxy ligands, heteroaryloxy ligands, silyloxy ligands, more preferably bonded to carbon atoms Pt, aromatic heterocyclic ligands bonded to carbon atoms Pt , A nitrogen-containing aromatic heterocyclic ligand bonded to Pt with a nitrogen atom, an acyloxy ligand, an aryloxy ligand, more preferably an aromatic hydrocarbon ring ligand bonded to Pt with a carbon atom, an aromatic heterocyclic ligand bonded to Pt with a carbon atom, nitrogen Nitrogen containing aromatic heads bonded to the reactor Pt Terrocyclic ligands, acyloxy ligands.

L ¹ , L ² and L ³ represent a single bond or a divalent linking group. Examples of the divalent linking groups represented by L ¹ , L ^2, and L ³ include an alkylene group (methylene, ethylene, propylene, and the like), an arylene group (phenylene, naphthalenediyl), a heteroarylene group (pyridindiyl, thiophendiyl, and the like), Imino group (-NR-) (phenylimino group, etc.), oxy group (-O-), thio group (-S-), phosphinidene group (-PR-) (phenylphosphinidene group, etc.), silylene group (- SiRR'-) (dimethylsilylene group, diphenylsilylene group, etc.), or what combined these is mentioned. Here, as R and R ', an alkyl group, an aryl group, etc. are respectively independently mentioned. These coupling groups may further have a substituent.

In view of the stability of the complex and the luminescence quantum yield, L ¹ , L ² and L ³ are preferably a single bond, an alkylene group, an arylene group, a heteroarylene group, an imino group, an oxy group, a thio group, a silylene group, and more. Preferably they are a single bond, an alkylene group, an arylene group, and an imino group, More preferably, they are a single bond, an alkylene group, an arylene group, More preferably, they are a single bond, a methylene group, a phenylene group, More preferably, a single bond And a di-substituted methylene group, more preferably a single bond, a dimethyl methylene group, a diethyl methylene group, a diisobutyl methylene group, a dibenzyl methylene group, an ethyl methylene methylene group, a methyl propyl methylene group, an isobutyl methylene methylene group , Diphenylmethylene group, methylphenylmethylene group, cyclohexanediyl group, cyclopentanediyl group, fluorenediyl group, and fluoromethylene methylene group.

L ¹ is particularly preferably a dimethylmethylene group, a diphenylmethylene group or a cyclohexanediyl group, and most preferably a dimethylmethylene group.

Most preferably, it is a single bond as L <^2> and L <^3> .

Among the platinum complexes represented by General Formula (C-1), more preferably, they are platinum complexes represented by the following General Formula (C-2).

[Chemical Formula 20]

In the formula, L ²¹ represents a single bond or a divalent linking group. A ²¹ and A ²² each independently represent a carbon atom or a nitrogen atom. Z ²¹ and Z ²² each independently represent a nitrogen-containing aromatic hetero ring. Z ²³ and Z ²⁴ each independently represent a benzene ring or an aromatic hetero ring)

General formula (C-2) is demonstrated. L <^21> is synonymous with L <^1> in the said general formula (C-1), and its preferable range is also the same.

A ²¹ and A ²² each independently represent a carbon atom or a nitrogen atom. At least one of A ²¹ and A ²² is preferably a carbon atom, and both A ²¹ and A ²² are preferably carbon atoms from the viewpoint of the stability of the complex and the light emission quantum yield of the complex.

Z ²¹ and Z ²² each independently represent a nitrogen-containing aromatic hetero ring. Examples of the nitrogen-containing aromatic hetero rings represented by Z ²¹ and Z ²² include pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, triazole ring and oxa A diazole ring, a thiadiazole ring, and the like. In view of stability of the complex, emission wavelength control and emission quantum yield, the ring represented by Z ²¹ , Z ²² is preferably a pyridine ring, a pyrazine ring, an imidazole ring, a pyrazole ring, and more preferably a pyridine ring, It is a diazole ring, a pyrazole ring, More preferably, it is a pyridine ring and a pyrazole ring, Especially preferably, it is a pyridine ring.

The nitrogen-containing aromatic heterocycle represented by Z ²¹ and Z ²² may have a substituent, and the above substituent group B may be used as the substituent on the carbon atom and the above substituent group B as the substituent on the nitrogen atom. As a substituent on a carbon atom, Preferably, they are an alkyl group, a perfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, an alkoxy group, a cyano group, and a fluorine atom. Substituents are appropriately selected for the control of the emission wavelength or potential, but in the case of shortening, electron donating groups, fluorine atoms, and aromatic ring groups are preferable. For example, alkyl groups, dialkylamino groups, alkoxy groups, fluorine atoms, aryl groups, aromatics Hetero ring groups and the like are selected. Moreover, when making it long-wavelength, an electron withdrawing group is preferable, for example, a cyano group, a perfluoroalkyl group, etc. are selected. As a substituent on a nitrogen atom, Preferably, they are an alkyl group, an aryl group, an aromatic heterocyclic group, and an alkyl group and an aryl group are preferable from a viewpoint of stability of a complex. The substituents may be linked to each other to form a condensed ring. Examples of the ring formed include a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring and a pyrazole. A ring, a thiophene ring, a furan ring, etc. are mentioned.

Z ²³ and Z ²⁴ each independently represent a benzene ring or an aromatic hetero ring. Examples of the nitrogen-containing aromatic hetero rings represented by Z ²³ and Z ²⁴ include pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring and tria A sol ring, an oxadiazole ring, a thiadiazole ring, a thiophene ring, a furan ring, etc. are mentioned. As a ring represented by Z ²³ , Z ²⁴ from the viewpoint of stability of the complex, emission wavelength control, and emission quantum yield, a benzene ring, a pyridine ring, a pyrazine ring, an imidazole ring, a pyrazole ring, a thiophene ring, and more preferably Preferably it is a benzene ring, a pyridine ring, a pyrazole ring, More preferably, they are a benzene ring and a pyridine ring.

The benzene ring and nitrogen-containing aromatic heterocyclic ring represented by Z ²³ and Z ²⁴ may have a substituent, and the substituent group B may be applied to the substituent group A as a substituent on a carbon atom and the substituent group B as a substituent on a nitrogen atom. . The substituent on the carbon is preferably an alkyl group, a perfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, an alkoxy group, a cyano group, or a fluorine atom. The substituent is appropriately selected for the control of the emission wavelength or potential, but in the case of making the wavelength longer, an electron donating group and an aromatic ring group are preferable, and an alkyl group, a dialkylamino group, an alkoxy group, an aryl group, an aromatic heterocyclic group, etc. are selected. do. Moreover, when shortening, an electron withdrawing group is preferable, for example, a fluorine atom, a cyano group, a perfluoroalkyl group, etc. are selected. As a substituent on a nitrogen atom, Preferably, they are an alkyl group, an aryl group, an aromatic heterocyclic group, and an alkyl group and an aryl group are preferable from a viewpoint of stability of a complex. The substituents may be linked to each other to form a condensed ring. Examples of the ring formed include a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring and a pyrazole. A ring, a thiophene ring, a furan ring, etc. are mentioned.

Among the platinum complexes represented by General Formula (C-2), one of more preferred embodiments is a platinum complex represented by the following General Formula (C-4).

[Chemical Formula 21]

(In General Formula (C-4), A ⁴⁰¹ to A ⁴¹⁴ each independently represent CR or a nitrogen atom. R represents a hydrogen atom or a substituent. L ⁴¹ represents a single bond or a divalent linking group.)

General formula (C-4) is demonstrated.

A ⁴⁰¹ to A ⁴¹⁴ each independently represent CR or a nitrogen atom. R represents a hydrogen atom or a substituent.

As a substituent represented by R, the thing illustrated as said substituent group A is applicable.

It is preferably CR as A ⁴⁰¹ to A ⁴⁰⁶ , and R may be connected to each other to form a ring. In the case where A ⁴⁰¹ to A ⁴⁰⁶ are CR, R ⁴⁰² and A ⁴⁰⁵ are preferably hydrogen atoms, alkyl groups, aryl groups, amino groups, alkoxy groups, aryloxy groups, fluorine atoms, and cyano groups, and more preferably. It is a hydrogen atom, an amino group, an alkoxy group, an aryloxy group, and a fluorine atom, Especially preferably, they are a hydrogen atom and a fluorine atom. R of A ⁴⁰¹ , A ⁴⁰³ , A ⁴⁰⁴ , A ⁴⁰⁶ is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine atom, a cyano group, more preferably a hydrogen atom, an amino group, It is an alkoxy group, an aryloxy group, and a fluorine atom, Especially preferably, it is a hydrogen atom.

L ⁴¹ has the same meaning as L ¹ in General Formula (C-1), and the preferred range thereof is also the same.

As A ⁴⁰⁷ -A ⁴¹⁴ , in each of A ⁴⁰⁷ -A ⁴¹⁰ and A ⁴¹¹ -A ⁴¹⁴ , the number of N (nitrogen atoms) is preferably 0 to 2 and more preferably 0 to 1. When shifting the emission wavelength of the short wavelength side, A ⁴⁰⁸ and A ⁴¹² of which is preferably a nitrogen atom, the A ⁴⁰⁸ and A ⁴¹² are both more preferably a nitrogen atom.

When A ⁴⁰⁷ to A ⁴¹⁴ represent CR, R ⁴⁰⁸ and R ⁴¹² are preferably hydrogen atoms, alkyl groups, perfluoroalkyl groups, aryl groups, amino groups, alkoxy groups, aryloxy groups, fluorine atoms, and cyano groups. More preferably, they are a hydrogen atom, a perfluoroalkyl group, an alkyl group, an aryl group, a fluorine atom, and a cyano group, Especially preferably, they are a hydrogen atom, a phenyl group, a perfluoroalkyl group, and a cyano group. R of A ⁴⁰⁷ , A ⁴⁰⁹ , A ⁴¹¹ , A ⁴¹³ is preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine atom or a cyano group, and more preferably It is a hydrogen atom, a perfluoroalkyl group, a fluorine atom, and a cyano group, Especially preferably, they are a hydrogen atom, a phenyl group, and a fluorine atom. R of A ⁴¹⁰ and A ⁴¹⁴ is preferably a hydrogen atom or a fluorine atom, and more preferably a hydrogen atom. When any of A ⁴⁰⁷ to A ⁴⁰⁹ and A ⁴¹¹ to A ⁴¹³ represents CR, Rs may be connected to each other to form a ring.

Among the platinum complexes represented by General Formula (C-2), one of more preferred embodiments is a platinum complex represented by the following General Formula (C-5).

[Formula 22]

(In General Formula (C-5), A ⁵⁰¹ to A ⁵¹² each independently represent CR or a nitrogen atom. R represents a hydrogen atom or a substituent. L ⁵¹ represents a single bond or a divalent linking group.)

General formula (C-5) is demonstrated. A ⁵⁰¹ to A ⁵⁰⁶ and L ⁵¹ have the same meanings as A ⁴⁰¹ to A ⁴⁰⁶ and L ^{41 in} the general formula (C-4), and the preferred range thereof is also the same.

A ⁵⁰⁷ , A ⁵⁰⁸ and A ⁵⁰⁹ and A ⁵¹⁰ , A ⁵¹¹ and A ⁵¹² each independently represent a CR or nitrogen atom. R represents a hydrogen atom or a substituent. As a substituent represented by R, the thing illustrated as said substituent group A is applicable. When A ⁵⁰⁷ , A ⁵⁰⁸ and A ⁵⁰⁹ and A ⁵¹⁰ , A ⁵¹¹ and A ⁵¹² are CR, R is preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, It is a diarylamino group, an alkyloxy group, a cyano group, and a fluorine atom, More preferably, a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, a dialkylamino group, a cyano group, a fluorine atom, More preferably, a hydrogen atom and an alkyl group , Trifluoromethyl group and fluorine atom. If possible, substituents may be linked to each other to form a condensed structure. At least one of A ⁵⁰⁷ , A ⁵⁰⁸ and A ⁵⁰⁹ and A ⁵¹⁰ , A ⁵¹¹ and A ⁵¹² is preferably a nitrogen atom, particularly preferably A ⁵¹⁰ or A ⁵⁰⁷ is a nitrogen atom.

Among the platinum complexes represented by General Formula (C-1), another more preferred embodiment is a platinum complex represented by the following General Formula (C-6).

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In the formula, L ⁶¹ represents a single bond or a divalent linking group. A ⁶¹ each independently represents a carbon atom or a nitrogen atom. Z ⁶¹ and Z ⁶² each independently represent a nitrogen-containing aromatic hetero ring. Z ⁶³ represents Each independently represents a benzene ring or an aromatic hetero ring, Y being an anionic acyclic ligand bonded to Pt)

General formula (C-6) is demonstrated. L ⁶¹ has the same meaning as L ¹ in General Formula (C-1), and the preferred range thereof is also the same.

A ⁶¹ represents a carbon atom or a nitrogen atom. It is preferable that A ⁶¹ is a carbon atom from a viewpoint of the stability of a complex, and the light emission quantum yield of a complex.

Z ⁶¹ and Z ⁶² have the same meanings as Z ²¹ and Z ^{22 in} the general formula (C-2), and the preferred ranges are also the same. Z ⁶³ has the same meaning as Z ²³ in General Formula (C-2), and the preferred range thereof is also the same.

Y is an anionic acyclic ligand that is bound to Pt. Acyclic ligands are those in which the atoms bonded to Pt do not form a ring in the ligand state. As an atom couple | bonded with Pt in Y, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom are preferable, a nitrogen atom and an oxygen atom are more preferable, and an oxygen atom is the most preferable.

Examples of Y bonded to Pt as a carbon atom include vinyl ligands. Examples of Y bonded to Pt with a nitrogen atom include amino ligands and imino ligands. Examples of Y bonded to Pt by an oxygen atom include alkoxy ligands, aryloxy ligands, heteroaryloxy ligands, acyloxy ligands, silyloxy ligands, carboxyl ligands, phosphoric acid ligands, sulfonic acid ligands and the like. Examples of Y bonded to Pt with a sulfur atom include alkyl mercapto ligands, aryl mercapto ligands, heteroaryl mercapto ligands, and thiocarboxylic acid ligands.

The ligand represented by Y may have a substituent and the thing illustrated as said substituent group A can be suitably applied as a substituent. Moreover, substituents may be connected.

The ligand represented by Y is preferably a ligand bound to Pt with an oxygen atom, more preferably an acyloxy ligand, an alkyloxy ligand, an aryloxy ligand, a heteroaryloxy ligand and a silyloxy ligand, still more preferably an acyloxy ligand. to be.

Among the platinum complexes represented by General Formula (C-6), one of more preferred embodiments is a platinum complex represented by the following General Formula (C-7).

&Lt; EMI ID =

(Wherein, A ⁷⁰¹ to A ⁷¹⁰ each independently represent CR or a nitrogen atom. R represents a hydrogen atom or a substituent. L ⁷¹ represents a single bond or a divalent linking group. Y represents an anionic bond to Pt. Acyclic ligand)

General formula (C-7) is demonstrated. L ⁷¹ has the same meaning as L ⁶¹ in General Formula (C-6), and the preferred range thereof is also the same. A ⁷⁰¹ to A ⁷¹⁰ have the same meanings as A ⁴⁰¹ to A ⁴¹⁰ in General Formula (C-4), and the preferred ranges are also the same. Y is synonymous with Y in General formula (C-6), and its preferable range is also the same.

Specifically as a platinum complex represented by general formula (C-1), the compound of Unexamined-Japanese-Patent No. 2005-310733, [0143]-[0152], [0157]-[0158], [0162]-[0168] , The compounds described in [0065] to [0083] of JP 2006-256999 A, the compounds described in [0065] to [0090] of JP 2006-93542 A, and the compounds of JP 2007-73891 A The compound described in [0071], The compound described in [0079]-[0083] of Unexamined-Japanese-Patent No. 2007-324309, The compound of [0065]-[0090] of Unexamined-Japanese-Patent No. 2006-93542, Unexamined-Japanese-Patent No. The compound described in 2007-96255 [0055]-[0071], and [0043]-[0046] of Unexamined-Japanese-Patent No. 2006-313796 are mentioned, In addition, the platinum complex illustrated below is mentioned.

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Platinum complex compounds represented by the general formula (C-1) are described, for example, in page 789, left paragraph 53 to right paragraph 7 in Journal of Organic Chemistry 53, 786, (1988), GRNewkome et al. 2752 of the method described, page 790, left paragraph 18-38, the method of page 790, right paragraph 19-30 and combinations thereof, Chemische Berichte 113, 2749 (1980), H. Lexy et al.) It can synthesize | combine by various techniques, such as the method described on pages 26-35.

For example, a ligand or a dissociation agent thereof and a metal compound may be a solvent (for example, a halogen solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a nitrile solvent, an amide solvent, and a sulfone solvent). In the presence of a base (inorganic, various organic bases, for example, sodium methoxide, t-butoxy potassium, tri) Ethylamine, potassium carbonate and the like) or in the absence of a base, can be obtained at room temperature or under heating (a method of heating by microwave in addition to normal heating is also effective).

It is preferable that content of the compound represented by general formula (C-1) in the light emitting layer of this invention is 1-30 mass% in a light emitting layer, It is more preferable that it is 3-25 mass%, It is 5-20 mass% More preferred.

As the iridium complex, it is preferably an iridium complex represented by the following general formula (T-1).

[Compound represented by general formula (T-1)]

The compound represented by general formula (T-1) is demonstrated.

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(In General Formula (T-1), R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyano group, a perfluoroalkyl group, and a tri Fluorovinyl group, -CO ₂ R _T , -C (O) R _T , -N (R _T ) ₂ , -NO ₂ , -OR _T , a halogen atom, an aryl group or a heteroaryl group, and further a substituent T You may have

E represents a carbon atom or a nitrogen atom.

Q is a 5 or 6 membered aromatic heterocyclic ring or a condensed aromatic heterocyclic ring containing at least one nitrogen.

In the ring Q, although the line which connects E and N is shown by one line, a single bond or a double bond may be sufficient, respectively, regardless of a bond type.

R _T3 , R _T4 , R _T5 and R _T6 may be bonded to any two adjacent to each other to form a condensed 4 to 7 membered ring, and the condensed 4 to 7 membered ring is cycloalkyl, aryl or heteroaryl, The condensed 4 to 7 membered ring may further have a substituent T.

R _T3 'and R _T6 are -C (R _T ) ₂ -C (R _T ) _2- , -CR _T = CR _T- , -C (R _T ) _2- , -O-, -NR _T- , May be linked by a linking group selected from -OC (R _T ) _2- , -NR _T -C (R _T ) ₂ -and -N = CR _T- , and each R _T is independently a hydrogen atom; , An alkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group, or a heteroaryl group, and may further have a substituent T. In addition, two R _T may be bonded to each other to form a ring.

Substituents T are each independently a fluorine atom, -R ', -OR', -N (R ') ₂ , -SR', -C (O) R ', -C (O) OR', -C (O ) N (R ′) ₂ , —CN, —NO ₂ , —SO ₂ , —SOR ′, —SO ₂ R ′, or —SO ₃ R ′, and R ′ are each independently a hydrogen atom, an alkyl group, A perfluoroalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.

(X-Y) represents a ligand. m is an integer of 1-3, n represents the integer of 0-2. m + n is 3)

The alkyl group may have a substituent and the above-mentioned substituent T is mentioned as group which may be substituted. The alkyl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , R _T6 is preferably an alkyl group having 1 to 8 carbon atoms in total, and more preferably an alkyl group having 1 to 6 carbon atoms in total. For example, a methyl group, an ethyl group, i-propyl group, a cyclohexyl group, t-butyl group etc. are mentioned.

The cycloalkyl group may have a substituent and the above-mentioned substituent T is mentioned as group which may be substituted. The cycloalkyl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , R _T6 is preferably a cycloalkyl group having 4 to 7 ring atoms, and more preferably a cycloalkyl group having 5 to 6 carbon atoms in total. For example, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

The alkenyl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. Vinyl, allyl, 1-propenyl, 1-isopropenyl, 1-butenyl, 2-butenyl, 3-pentenyl, and the like. The alkynyl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , and R _T6 is preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. For example, ethynyl, propargyl, 1-propynyl, 3-pentynyl, etc. are mentioned.

Examples of the heteroalkyl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 include groups in which at least one carbon of the alkyl group is substituted with O, NR _T , or S.

_Examples of the halogen atoms represented by R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and are preferably fluorine atoms.

As the aryl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , or R _T6 , it is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms. . Examples of the aryl group include a phenyl group, naphthyl group, biphenyl group, anthryl group, terphenyl group, fluorenyl group, phenanthryl group, pyrenyl group, triphenylenyl group, tolyl group, and the like. A fluorenyl group, a naphthyl group, a biphenyl group, an anthryl group, or a terphenyl group is preferable, and a phenyl group, a fluorenyl group, and a naphthyl group are more preferable.

The heteroaryl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , or R _T6 is preferably a heteroaryl group having 5 to 8 carbon atoms, more preferably a substituted or unsubstituted hetero of 5 or 6 atoms. It is an aryl group, For example, a pyridyl group, a pyrazinyl group, a pyridazinyl group, a pyrimidinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a quinazolinyl group, a cinnaolinyl group, a phthalazinyl group, Quinoxalinyl group, pyrrolyl group, indolyl group, furyl group, benzofuryl group, thienyl group, benzothienyl group, pyrazolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, oxazolyl group, benzoxazolyl Group, thiazolyl group, benzothiazolyl group, isothiazolyl group, benzisothiazolyl group, thiadiazolyl group, isoxazolyl group, benzisooxazolyl group, pyrrolidinyl group, piperidinyl group, piperazinyl Group, imidazolidinyl group, thiazolinyl group, sulfolanyl group, carbazolyl group, dibenzo A furyl group, a dibenzothienyl group, a pyridindolyl group, etc. are mentioned. Preferable examples are pyridyl group, pyrimidinyl group, imidazolyl group and thienyl group, and more preferably pyridyl group and pyrimidinyl group.

R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 are preferably hydrogen atom, alkyl group, cyano group, trifluoromethyl group, perfluoroalkyl group, dialkylamino group, fluorine atom, aryl group, heteroaryl group More preferably, they are a hydrogen atom, an alkyl group, a cyano group, a trifluoromethyl group, a fluorine atom, and an aryl group, More preferably, they are a hydrogen atom, an alkyl group, and an aryl group. As a substituent T, an alkyl group, an alkoxy group, a fluorine atom, a cyano group, and a dialkylamino group are preferable, and a hydrogen atom is more preferable.

R _T3 , R _T4 , R _T5 and R _T6 may be bonded to any two adjacent to each other to form a condensed 4 to 7 membered ring, and the condensed 4 to 7 membered ring is cycloalkyl, aryl or heteroaryl, The condensed 4 to 7 membered ring may further have a substituent T. In addition, the condensed 4 to 7 membered ring may be further condensed by a 4 to 7 membered ring. The definitions and preferred ranges of the cycloalkyl, aryl, heteroaryl formed are the same as the cycloalkyl, aryl, and heteroaryl groups defined in R _T3 ′, R _T3 , R _T4 , R _T5 , R _T6 .

Examples of the aromatic hetero ring represented by ring Q include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrazole ring, a pyrrole ring, an imidazole ring, a triazole ring, an oxazole ring, an oxadiazole ring, a thiazole ring and a thiadia A sol ring etc. are mentioned. Preferably they are a pyridine ring, a pyrazine ring, a pyrazole ring, More preferably, they are a pyridine ring or a pyrazole ring.

As a condensed aromatic heterocyclic ring which ring Q represents, a quinoline ring, an isoquinoline ring, a quinoxaline ring, etc. are mentioned. Preferably it is a quinoline ring and an isoquinoline ring, More preferably, it is a quinoline ring.

It is preferable that it is 1-3, and, as for m, it is more preferable that it is 2 or 3. In other words, n is preferably 0 or 1. It is preferable that the kind of ligand in a complex consists of one or two types, More preferably, it is one type. When introducing a reactive group into a complex molecule, it is also preferable that a ligand consists of two types from a viewpoint of the ease of synthesis.

The metal complex represented by general formula (T-1) is a ligand represented by the following general formula (T-1-A) in general formula (T-1), its tautomer, and the ligand represented by (XY), or its It is comprised including the combination of tautomers, or all the ligands of the metal complex may be comprised only by the ligand represented by the following general formula (T-1-A), or its tautomer.

[Formula 29]

(In the general formula (T-1-A), R _T3 ', R _T3, R _T4, R _T5, R _T6, E and Q, in formula _{(T-1), R T3} ', R T3 , R _T4 , R _T5 , R _T6 , E and Q. * indicates the coordination position with respect to iridium)

Moreover, as a so-called ligand used for conventionally known metal complex formation, the said supplier may have a known ligand (also called a coordination compound) as a ligand represented by (X-Y) as needed.

There are several known ligands for ligands used in conventionally known metal complexes. For example, `` Photochemistry and Photophysics of Coordination Compounds '' by Springer-Verlag H.Yersin, published in 1987, "Organic Metal Chemistry-Based" Ligands (eg, halogen ligands (preferably chlorine ligands), nitrogen-containing heteroaryl ligands (eg, bipyridyl, phenanthroline, etc.) described in 1982, published by Shokabosa Yamamoto Akio The diketone ligand (for example, acetylacetone etc.) is mentioned As a ligand represented by (XY), Preferably it is a diketone or a picolinic acid derivative, and is shown below from the viewpoint of obtaining the stability of a complex and high luminous efficiency. Most preferred is acetylacetonate (acac).

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* Indicates a coordination position relative to iridium.

Although the example of the ligand represented by (X-Y) is given concretely below, this invention is not limited to these.

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In the example of the ligand represented by the above-mentioned (X-Y), * represents the coordination position with respect to iridium in general formula (T-1). Rx, Ry and Rz each independently represent a hydrogen atom or a substituent. Examples of the substituent include a substituent selected from the substituent group A. Preferably, Rx and Rz are each independently an alkyl group, a perfluoroalkyl group, a fluorine atom or an aryl group, more preferably an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, a fluorine atom, It is a phenyl group which may be substituted, Most preferably, they are a methyl group, an ethyl group, a trifluoromethyl group, a fluorine atom, and a phenyl group. Ry is preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, a fluorine atom, or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted, and most preferably hydrogen It is either an atom or a methyl group. Since these ligands are not considered to be sites where electrons are concentrated by the charge transport or excitation in the device, Rx, Ry, and Rz may be chemically stable substituents, and do not affect the effect of the present invention. Since complex synthesis | combination is easy, Preferably it is (I-1), (I-4), (I-5), Most preferably, it is (I-1). Complexes having these ligands can be synthesized in the same manner as known synthesis examples by using the corresponding ligand precursor. For example, it can synthesize | combine by the method shown below using commercially available difluoroacetylacetone similarly to the method of international publication 2009-073245.

(32)

Moreover, the monoanionic ligand shown by General formula (I-15) can also be used as a ligand.

(33)

In the formula _{(I-15) R T ~} R T10 is the same meaning as R _T3 ~ _T6 R in formula (T-1), are also the same preferable range. _T7 R 'is as defined, a preferred range is also R _T3' '~ R _T10' R is the same as _T3. * Indicates a coordination position relative to iridium.

The compound represented by general formula (T-1) is preferably a compound represented by the following general formula (T-2).

[Formula 34]

(In General Formula (T-2), R _T3 'to R _T6 ' and R _T3 to R _T6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyano group, a perfluoroalkyl group, and a trifluoro group. A vinyl group, -CO ₂ R _T , -C (O) R _T , -N (R _T ) ₂ , -NO ₂ , -OR _T , a halogen atom, an aryl group or a heteroaryl group, and further has a substituent T You may be.

R <_T3> , R <_T4> , R <_T5> and R <_T6> may couple | bond two arbitrary arbitrary mutually, and may form the condensed 4-7 membered ring, and the condensed 4-7 membered ring may have a substituent T further.

R _T3 'and R _T6 are -C (R _T ) ₂ -C (R _T ) _2- , -CR _T = CR _T- , -C (R _T ) _2- , -O-, -NR _T- , It may be connected by a linking group selected from -OC (R _T ) _2- , -NR _T -C (R _T ) ₂ -and -N = CR _T -to form a ring.

Each R _T independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group, or a heteroaryl group, and may further have a substituent T.

Substituents T are each independently a fluorine atom, -R ', -OR', -N (R ') ₂ , -SR', -C (O) R ', -C (O) OR', -C (O ) N (R ′) ₂ , —CN, —NO ₂ , —SO ₂ , —SOR ′, —SO ₂ R ′, or —SO ₃ R ′, and R ′ are each independently a hydrogen atom, an alkyl group, A perfluoroalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.

(X-Y) represents a ligand. m is an integer of 1-3, n represents the integer of 0-2. m + n is 3)

R _T3 ′, R _T3 to R _T6 , (XY), m and n in the general formula (T-2) are preferably in the range of R _T3 ′, R _T3 to R in the general formula (T-1). _{It is the} same as the preferable range of _T6 , (XY), m, and n.

R _T4 ′ is preferably a hydrogen atom, an alkyl group, an aryl group, or a fluorine atom, and more preferably a hydrogen atom.

R _T5 ′ and R _T6 ′ represent a hydrogen atom or are bonded to each other to form a condensed 4 to 7 membered cyclic group, and the condensed 4 to 7 membered cyclic group is cycloalkyl, cycloheteroalkyl, aryl Or heteroaryl, more preferably aryl.

R _T4 '~ R _T6' is the substituent T roneun alkyl group, an alkoxy group, a fluorine atom, a cyano group, an alkylamino group, a diarylamino group are preferable, and an alkyl group is more preferable. Fig.

One preferred form of the represented by the above-mentioned formula (T-2) compound, R _T3 ', R _T4' in the general formula _{(T-2), R T5} ', R T6', R T3, R T4, R _{It is} a case where any two neighboring of _T5 and _RT6 combine with each other and do not form a condensed ring.

One of the preferable forms of the compound represented by said general formula (T-2) is a case represented by the following general formula (T-3).

(35)

In the formula (T3) _T3 R '~ R _T6', R ~ R _{T3 T6} is, in the general formula _{(T-2) R T3 '} ~ R T6', R T3 ~ _T6 is the same as R It is meaning, and a preferable range is also the same.

R _T7 to R _T10 have the same meaning as R _T3 to R _T6, and the preferred range is also the same.

R _T7 '-R _T10 ' has the same meaning as R _T3 '-R _T6 ', and the preferred range is also the same.

Another preferable form of the compound represented by said general formula (T-2) is a compound represented with the following general formula (T-4).

(36)

R _T3 'to R _T6 ', R _T3 to R _T6 , (XY), m and n in General Formula (T-4) are R _T3 'to R _T6 ' in General Formula (T-2). , R _T3 to R _T6 , (XY), m and n have the same meanings, and preferred ranges are also the same. Particularly preferred is 0 to 2 of R _T3 'to R _T6 ' and R _T3 to R _{T6, each} of which is an alkyl group or a phenyl group, and the rest are all hydrogen atoms, and among R _T3 'to R _T6 ' and R _T3 to R _T6 , More preferably, one or two are alkyl groups and all others are hydrogen atoms.

Another preferable form of the compound represented by said general formula (T-2) is a compound represented with the following general formula (T-5).

[Formula 37]

R _T3 'to R _T7 ', R _T3 to R _T6 , (XY), m and n in General Formula (T-5) are R _T3 'to R _T7 ' in General Formula (T-2). , R _T3 to R _T6 , (XY), m and n have the same meanings, and preferred ones are also the same.

Another preferable form of a compound represented by general formula (T-1) is a case represented by the following general formula (T-6).

(38)

In general formula (T-6), the definition and preferable range of R <_1a> -R <_1i> are the same as that of R <_T3> -R <_T6> in general formula (T-1). Moreover, especially when 0-2 are an alkyl group or an aryl group, and all remainder are hydrogen atoms in R <_1a> -R <_1i> . Definition and preferable range of (XY), m, and n are the same as that of (XY), m, and n in general formula (T-1).

Another preferable form of a compound represented by general formula (T-1) is a case represented by the following general formula (TC-1).

[Chemical Formula 39]

(In General Formula (TC-1), R _T3 'to R _T5 ' and R _T3 to R _T6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyano group, a perfluoroalkyl group, and a trifluoro group. A vinyl group, -CO ₂ R _T , -C (O) R _T , -N (R _T ) ₂ , -NO ₂ , -OR _T , a halogen atom, an aryl group or a heteroaryl group, and further has a substituent T You may be.

R <_T3> , R <_T4> , R <_T5> and R <_T6> may couple | bond two arbitrary arbitrary mutually, and may form the condensed 4-7 membered ring, and the condensed 4-7 membered ring may have a substituent T further.

R _T3 ′, R _T4 ′ and R _T5 ′ may be bonded to any two adjacent to each other to form a condensed 4 to 7 membered ring, and the condensed 4 to 7 membered ring may further have a substituent T.

R _T3 'and R _T6 are -C (R _T ) ₂ -C (R _T ) _2- , -CR _T = CR _T- , -C (R _T ) _2- , -O-, -NR _T- , It may be connected by a linking group selected from -OC (R _T ) _2- , -NR _T -C (R _T ) ₂ -and -N = CR _T -to form a ring.

Each R _T independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group, or a heteroaryl group, and may further have a substituent T.

Substituents T are each independently a fluorine atom, -R ', -OR', -N (R ') ₂ , -SR', -C (O) R ', -C (O) OR', -C (O ) N (R ′) ₂ , —CN, —NO ₂ , —SO ₂ , —SOR ′, —SO ₂ R ′, or —SO ₃ R ′, and R ′ are each independently a hydrogen atom, an alkyl group, A perfluoroalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.

(X-Y) represents a ligand. m is an integer of 1-3, n represents the integer of 0-2. m + n is 3)

R _T3 ′, R _T3 to R _T6 , (XY), m and n in the general formula (TC-1) are preferably in the range of R _T3 ′, R _T3 to R in the general formula (T-1). _{It is the} same as the preferable range of _T6 , (XY), m, and n.

R _T4 ′ is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an aryl group. As this aryl group, Preferably it is a C6-C30 substituted or unsubstituted aryl group, More preferably, it is a C6-C20 aryl group. As this aryl group, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a terphenyl group, a fluorenyl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group, a tolyl group, etc. are mentioned, for example, A phenyl group, A fluorenyl group, a naphthyl group, a biphenyl group, a triphenylenyl group, an anthryl group, or a terphenyl group is preferable, and a phenyl group, a biphenyl group, a naphthyl group, and a triphenylenyl group are more preferable.

R _T5 ′ is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group. As this alkyl group, Preferably it is C1-C10, For example, a methyl group, an ethyl group, isopropyl group, t-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclo A pentyl group, a cyclohexyl group, a neopentyl group, etc. are mentioned, Preferably it is a methyl group, an ethyl group, isopropyl group, t-butyl group, More preferably, it is a methyl group.

One of the preferable forms of the said general formula (TC-1) is a case where any two neighboring R <_T4> , R <_T5> and R <_T6> combine with each other, and form a condensed ring. The ring is more preferably cycloalkyl, cycloheteroalkyl, aryl or heteroaryl. In particular, it is preferable that R _T4 and R _T5 combine with each other to form a heteroaryl ring.

In General Formula (TC-1), m is preferably 3, and n is preferably 0.

 General formula (TC-1), Preferably it is the following general formula (TC-2).

[Formula 40]

(In General Formula (TC-2), R _T3 'to R _T5 ', R _T3 , R _T6 and R _TC1 to R _TC4 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyano group, and a perfluorine. Fluoroalkyl group, trifluorovinyl group, -CO ₂ R _T , -C (O) R _T , -N (R _T ) ₂ , -NO ₂ , -OR _T , a halogen atom, an aryl group or a heteroaryl group, Furthermore, you may have substituent T.

R _T3 ′, R _T4 ′ and R _T5 ′ may be bonded to any two adjacent to each other to form a condensed 4 to 7 membered ring, and the condensed 4 to 7 membered ring may further have a substituent T.

R _T3 'and R _T6 are -C (R _T ) ₂ -C (R _T ) _2- , -CR _T = CR _T- , -C (R _T ) _2- , -O-, -NR _T- , It may be connected by a linking group selected from -OC (R _T ) _2- , -NR _T -C (R _T ) ₂ -and -N = CR _T -to form a ring.

Each R _T independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group, or a heteroaryl group, and may further have a substituent T.

Substituents T are each independently a fluorine atom, -R ', -OR', -N (R ') ₂ , -SR', -C (O) R ', -C (O) OR', -C (O ) N (R ′) ₂ , —CN, —NO ₂ , —SO ₂ , —SOR ′, —SO ₂ R ′, or —SO ₃ R ′, and R ′ are each independently a hydrogen atom, an alkyl group, A perfluoroalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.

W represents the carbon atom, oxygen atom, or sulfur atom which the hydrogen atom or the substituent T couple | bonded.

(X-Y) represents a ligand. m is an integer of 1-3, n represents the integer of 0-2. m + n is 3)

The preferred ranges of R _T3 'to R _T5 ', R _T3 and R _T6 , (XY), m and n in General Formula (TC-2) are R _T3 'to General Formula (TC-1). It is equal to the preferred ranges of R _T5 ′, R _T3 and R _T6 , (XY), m and n.

The preferred range of R _TC1 to R _TC4 is the _{same as} the preferred range of R _T3 , preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom.

It is preferable that W is a carbon atom which has a substituent T, As the substituent T, an alkyl group is preferable, As this alkyl group, Preferably it is a methyl group, an ethyl group, isopropyl group, t-butyl group, More preferably, it is a methyl group. .

Moreover, about general formula (TC-1), it is described also in Unexamined-Japanese-Patent No. 2008-147353.

Although the preferable specific example of a compound represented by general formula (T-1) is listed below, it is not limited to the following.

(41)

(42)

(43)

(44)

The compound illustrated as a compound represented by the said general formula (T-1) can be synthesize | combined by the method of Unexamined-Japanese-Patent No. 2009-99783, and the various methods of US Pat. After synthesis, purification by column chromatography, recrystallization or the like is preferably followed by purification by sublimation purification. By sublimation purification, not only an organic impurity can be separated but an inorganic salt, a residual solvent, etc. can be removed effectively.

Although the compound represented by general formula (T-1) is contained in a light emitting layer, the use is not limited and may be contained further in any layer in an organic layer.

As the iridium complex, in addition to the compound represented by the general formula (T-1), a compound represented by the following general formula (T-7) and one having carbene as a ligand can be preferably used.

[Chemical Formula 45]

In General Formula (T-7), R _T11 to R _T17 have the same meanings as R _T3 to R _{T6 in} General Formula (T-2), and the preferred range thereof is also the same. In addition, (XY), n, and m are synonymous with (XY), n, and m in general formula (T-2), and its preferable range is also the same.

Although these preferable specific examples are listed below, it is not limited to the following.

(46)

Although the light emitting material in a light emitting layer contains 0.1 mass%-50 mass% with respect to the mass of all the compounds which form a light emitting layer generally in a light emitting layer, it is preferable to contain 1 mass%-50 mass% from a viewpoint of durability and external quantum efficiency, It is more preferable to contain 2 mass%-40 mass%.

Although the thickness of a light emitting layer is not specifically limited, Usually, it is preferable that it is 2 nm-500 nm, Especially, it is more preferable that it is 3 nm-200 nm from a viewpoint of an external quantum efficiency, It is 5 nm-100 nm More preferred.

The light emitting layer in the device of the present invention may have a configuration of a mixed layer of a host material and a light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and one type or two or more types of dopants may be used. The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, and for example, a structure in which a host material having electron transporting property and a host material having hole transporting property are mixed. Moreover, the light emitting layer may contain a material which does not have charge transportability and which does not emit light.

The light emitting layer may be one layer or a multilayer of two or more layers. Moreover, each light emitting layer may emit light in a different light emission color.

<Host material>

It is preferable that the host material used for this invention is a compound represented by General formula (1).

As a host material used for this invention, in addition to the compound represented by General formula (1), you may contain the following compounds.

The host material includes an electron transporting material and a hole transporting material, and is preferably a charge transporting material. The host material may be one kind or two or more kinds, and for example, a structure in which a host material having electron transporting property and a host material having hole transporting property are mixed.

For example, pyrrole, indole, carbazole (eg CBP (4,4'-di (9-carbazolyl) biphenyl), 3,3'-di (9-carbazolyl) biphenyl)) , Azaindole, azacarbazole, triazole, oxazole, oxadiazole, pyrazole, imidazole, thiophene, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino substituted calcon, styryl Anthracene, fluorenone, hydrazone, stilbene, silazane, aromatic tertiary amine compound, styrylamine compound, porphyrin compound, polysilane compound, poly (N-vinylcarbazole), aniline copolymer, tee Conductive polymer oligomers such as offenol oligomer and polythiophene, organosilane, carbon film, pyridine, pyrimidine, triazine, imidazole, pyrazole, triazole, oxazole, oxadiazole, fluorenone, anthraquinodimethane, Antron, diphenylquinone, thiopyrandioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, Various metals represented by metal complexes of heterocyclic tetracarboxylic anhydrides such as fluorine-substituted aromatic compounds and naphthalene perylene, phthalocyanine and 8-quinolinol derivatives, and metal complexes having metal phthalocyanine, benzoxazole or benzothiazole as ligands Complexes and derivatives thereof (which may have a substituent or an axial ring);

In the light emitting layer of the present invention, the host material triplet minimum excitation energy (T ₁ energy) is preferably higher than the T ₁ energy of the phosphorescent light emitting material in view of color purity, luminous efficiency and driving durability.

Moreover, although content of the host compound in this invention is not specifically limited, It is preferable that it is 15 mass% or more and 95 mass% or less with respect to the mass of all the compounds which form a light emitting layer from a light emitting efficiency and a driving voltage.

(Charge transport layer)

The charge transport layer refers to a layer in which charge transfer occurs when a voltage is applied to the organic electroluminescent element. Specifically, a hole injecting layer, a hole transporting layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, or an electron injecting layer can be given. Preferably it is a hole injection layer, a hole transport layer, an electron block layer, or a light emitting layer. If the charge transport layer formed by the coating method is a hole injection layer, a hole transport layer, an electron blocking layer or a light emitting layer, it is possible to manufacture a low cost and high efficiency organic electroluminescent device. The charge transport layer is more preferably a hole injection layer, a hole transport layer or an electron block layer.

(Hole injection layer, hole transport layer)

The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side.

The hole injection layer and the hole transport layer are described in detail in, for example, Japanese Patent Application Laid-Open No. 2008-270736 and Japanese Patent Application Laid-Open No. 2007-266458, and the matters described in these publications can be applied to the present invention.

As thickness of a positive hole transport layer, it is preferable that it is 1 nm-500 nm, It is more preferable that it is 5 nm-200 nm, It is further more preferable that it is 10 nm-100 nm.

As thickness of a positive hole injection layer, it is preferable that it is 0.1 nm-200 nm, It is more preferable that it is 0.5 nm-100 nm, It is further more preferable that it is 1 nm-100 nm.

Moreover, in this invention, it is preferable to contain the compound represented by the said general formula (H-1) in a hole injection layer or a hole transport layer, and it is more preferable to contain in a hole injection layer.

Moreover, the following compound can also be used as a hole injection material and a transport material.

[Formula 47]

The hole injection layer preferably contains an electron accepting dopant. By incorporating the electron-accepting dopant in the hole injection layer, the hole injection property is improved, the driving voltage is lowered, or the efficiency is improved. The electron-accepting dopant may be any of an organic material and an inorganic material as long as it is a material capable of drawing electrons from a material to be doped to generate radical cations. For example, tetracyanoquinomimethane (TCNQ), tetra Fluorotetracyanoquinomethane (F ₄ -TCNQ), molybdenum oxide, and the like.

It is preferable to contain 0.1 mass%-50 mass% with respect to the mass of all the compounds which form a hole injection layer, and, as for the electron accepting dopant in a hole injection layer, it is more preferable that 0.1 mass%-40 mass% are contained, and it is 0.5 mass It is more preferable that% -30 mass% is contained.

(Electron injection layer, electron transport layer)

The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or cathode side and transporting them to the anode side. The electron injecting material and electron transporting material used in these layers may be a low molecular compound or a high molecular compound.

About an electron injection layer and an electron carrying layer, it describes in detail in Unexamined-Japanese-Patent No. 2008-270736 and Unexamined-Japanese-Patent No. 2007-266458, for example, and the matter described in these publications can be applied to this invention.

As thickness of an electron carrying layer, it is preferable that it is 1 nm-500 nm, It is more preferable that it is 5 nm-200 nm, It is further more preferable that it is 10 nm-100 nm.

As thickness of an electron injection layer, it is preferable that it is 0.1 nm-200 nm, It is more preferable that it is 0.2 nm-100 nm, It is still more preferable that it is 0.5 nm-50 nm.

Moreover, in this invention, it is preferable to contain the compound represented by the said General formula (1) in an electron injection layer or an electron carrying layer, and it is more preferable to contain in an electron carrying layer.

The electron injecting layer preferably contains an electron donating dopant. By including the electron donating dopant in the electron injection layer, there is an effect that the electron injection property is improved, the driving voltage is lowered, or the efficiency is improved. The electron donating dopant may be any of an organic material and an inorganic material as long as it is capable of imparting electrons to the doped material to generate radical anions. For example, tetrathiaflubarene (TTF) and tetrathia Naphthacene (TTT), lithium, cesium and the like.

It is preferable to contain 0.1 mass%-50 mass% with respect to the mass of the whole compound which forms an electron injection layer, and, as for the electron donating dopant in an electron injection layer, it is more preferable that 0.1 mass%-40 mass% are contained, 0.5 It is more preferable to contain mass%-30 mass%.

(Hole blocking layer)

The hole block layer is a layer having a function of preventing the holes transported from the anode side to the light emitting layer from escaping to the cathode side. In the present invention, the hole block layer can be formed as an organic layer adjacent to the light emitting layer and the cathode side.

Examples of the organic compound constituting the hole block layer include aluminum (III) bis (2-methyl-8-quinolinato) 4-phenylphenolate (Aluminum) in addition to the compound represented by the general formula (1) in the present invention. (III) aluminum complexes such as bis (2-methyl-8-quinolinato) 4-phenylphenolate (abbreviated as BAlq), triazole derivatives, 2,9-dimethyl-4,7-diphenyl-1,10-phenan Phenanthroline derivatives such as trolline (2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (abbreviated as BCP)), triphenylene derivatives, carbazole derivatives, and the like.

As thickness of a hole block layer, it is preferable that it is 1 nm-500 nm, It is more preferable that it is 5 nm-200 nm, It is further more preferable that it is 10 nm-100 nm.

The hole block layer may be a single layer structure composed of one or two or more kinds of the above-described materials, or may be a multilayer structure composed of a plurality of layers of the same composition or different compositions.

(Electronic block layer)

The electron block layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from escaping to the anode side. In the present invention, the electron blocking layer can be formed as the organic layer adjacent to the light emitting layer and the anode side.

As an example of the organic compound which comprises an electron block layer, what was illustrated as the above-mentioned hole transport material is applicable, for example.

As thickness of an electron blocking layer, it is preferable that it is 1 nm-500 nm, It is more preferable that it is 5 nm-200 nm, It is further more preferable that it is 10 nm-100 nm.

The electron blocking layer may be a single layer structure composed of one or two or more kinds of the above-described materials, or may be a multilayer structure composed of a plurality of layers of the same composition or different compositions.

(Protective layer)

In the present invention, the entire organic EL device may be protected by a protective layer.

The material contained in the protective layer may be one having a function of suppressing entry into the device by accelerating device degradation such as moisture and oxygen.

About a protective layer, the matter of Paragraph No. [0169]-[0170] of Unexamined-Japanese-Patent No. 2008-270736 can be applied to this invention.

(Bag container)

In the device of the present invention, the entire device may be sealed using an encapsulating container.

About the sealing container, the matter described in Paragraph No. [0171] of Unexamined-Japanese-Patent No. 2008-270736 can be applied to this invention.

Moreover, you may enclose a water absorbent or an inert liquid in the space between a sealing container and a light emitting element. Although it does not specifically limit as a water absorbent, For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride, cesium fluoride, niobium fluoride , Calcium bromide, vanadium bromide, molecular sieves, zeolites, magnesium oxide and the like. Although it does not specifically limit as an inert liquid, For example, paraffins, a liquid paraffin, fluoro solvents, such as a perfluoro alkane, a perfluoroamine, and a perfluoro ether, a chlorine solvent, and silicone oil are mentioned.

(Driving)

In the organic electroluminescent element of the present invention, light emission can be obtained by applying a direct current (may include an alternating current component) voltage (usually 2 volts to 15 volts) or a direct current between the anode and the cathode.

As for the driving method of the organic electroluminescent element of the present invention, JP-A-2-148687, JP-A-6-301355, JP-A 5-29080, JP-A-7- 134558, Japanese Patent Application Laid-Open No. Hei 8-234685, Japanese Patent Application Laid-Open No. Hei 8-241047, the driving method described in each specification of Japanese Patent No. 2784615, US Patent 5828429, US Patent 6023308, etc. can be applied. have.

As external quantum efficiency of the organic electroluminescent element of this invention, 5% or more is preferable and 7% or more is more preferable. The value of the external quantum efficiency may 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 at around 100 to 300 cd / m 2 when the device is driven at 20 ° C. .

It is preferable that the internal quantum efficiency of the organic electroluminescent element of this invention is 30% or more, 50% or more is more preferable, and 70% or more is more preferable. The internal quantum efficiency of the device is calculated by dividing the external quantum efficiency by the light extraction efficiency. Although the light extraction efficiency is about 20% in a conventional organic EL device, the light extraction efficiency is studied by studying the shape of the substrate, the shape of the electrode, the film thickness of the organic layer, the film thickness of the inorganic layer, the refractive index of the organic layer, the refractive index of the inorganic layer, and the like. It is possible to make 20% or more.

It is preferable that the organic electroluminescent element of this invention has maximum emission wavelength (maximum intensity wavelength of a light emission spectrum) in 350 nm or more and 700 nm or less, More preferably, it is 350 nm or more and 600 nm or less, More preferably, 400 nm 520 nm or less, Especially preferably, they are 400 nm or more and 465 nm or less.

(Use of the light emitting element of the present invention)

The light emitting element of the present invention can be preferably used for a light emitting device, a pixel, a display element, a display, a backlight, an electrophotographic light, an illumination light source, a recording light source, an exposure light source, a reading light source, a sign, a sign, an interior, or an optical communication. In particular, it is used suitably for the device driven in the area | region where light emission brightness is high, such as an illumination device and a display device.

(Light emitting device)

Next, the light emitting device of the present invention will be described with reference to FIG.

The light-emitting device of this invention uses the said organic electroluminescent element.

2 is a cross-sectional view schematically showing an example of the light emitting device of the present invention.

The light emitting device 20 of FIG. 2 is comprised by the board | substrate (support substrate) 2, the organic electroluminescent element 10, the sealing container 16, etc. As shown in FIG.

The organic electroluminescent device 10 is constituted by sequentially stacking a positive electrode (first electrode) 3, an organic layer 11, and a negative electrode (second electrode) 9 on a substrate 2. Moreover, the protective layer 12 is laminated | stacked on the cathode 9, and the sealing container 16 is formed on the protective layer 12 via the contact bonding layer 14. Moreover, as shown in FIG. Further, a part of each of the electrodes 3 and 9, a partition wall, an insulating layer, and the like are omitted.

Here, as the adhesive layer 14, photocurable adhesives, such as an epoxy resin, and a thermosetting adhesive can be used, for example, a thermosetting adhesive sheet can also be used.

The use of the light emitting device of the present invention is not particularly limited, and for example, it can be used as a display device such as a television, a personal computer, a mobile phone, an electronic paper, etc. in addition to the lighting device.

(Lighting device)

Next, with reference to FIG. 3, the illuminating device which concerns on embodiment of this invention is demonstrated.

3 is a cross-sectional view schematically showing an example of the lighting apparatus according to the embodiment of the present invention.

The illuminating device 40 which concerns on embodiment of this invention is equipped with the above-mentioned organic electroluminescent element 10 and the light scattering member 30. As shown in FIG. More specifically, the illumination device 40 is configured such that the substrate 2 of the organic EL element 10 and the light-scattering member 30 are in contact with each other.

The light scattering member 30 is not particularly limited as long as it can scatter light, but in FIG. 3, the light scattering member 30 is a member in which the fine particles 32 are dispersed in the transparent substrate 31. As the transparent substrate 31, a glass substrate is mentioned preferably, for example. As the microparticles | fine-particles 32, transparent resin microparticles | fine-particles are mentioned preferably. As a glass substrate and transparent resin microparticles | fine-particles, a well-known thing can all be used. When the light emission from the organic electroluminescent element 10 is incident on the light incident surface 30A of the light scattering member 30, the lighting device 40 scatters the incident light by the light scattering member 30, and the scattered light. Is emitted as the illumination light from the light exit surface 30B.

Example

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these.

The compound represented by General formula (1) used by the Example is international publication 03/080760 pamphlet, international publication 03/078541 pamphlet, international publication 05/085387 pamphlet, international publication 05/022962 pamphlet, etc. Was synthesized for reference. For example, compound (a-3) uses m-bromobenzoaldehyde as a starting material, and is published in International Publication No. 05/085387 pamphlet (page 45, line 11 to page 46, Synthesizing by the method described in line 18).

The compound represented by general formula (H-1) was synthesize | combined with reference to Unexamined-Japanese-Patent No. 2006-151979.

In addition, all the organic materials used for the present Example used the sublimation refine | purified, and analyzed by the high performance liquid chromatography (TOSO TSKgel ODS-100Z), and used the thing of 99.9% or more by the absorption intensity area ratio of 254 nm.

[Examples 1-30, Comparative Examples 1-20]

<Production of Organic Electroluminescent Device>

A glass substrate (ITO film thickness of 120 nm) having an indium tin oxide (ITO) film having a thickness of 0.7 mm and a width of 2.5 cm was placed in a washing container, ultrasonically cleaned in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. It was. The following organic compound layers were sequentially deposited on this transparent anode (ITO film) by the vacuum evaporation method using a vacuum evaporation apparatus (Toki Co., Small-ELVESS).

First layer (hole injection layer): Material shown in Table 1: Film thickness 60 nm

Second layer: NPD: film thickness 30nm

Third layer: CBP and Ir (ppy) ₃ (mass ratio 95: 5): film thickness 30 nm

Fourth layer (electron transport layer): Materials shown in Table 1: Film thickness 30 nm

On this fourth layer, BCP 1 nm, lithium fluoride 1 nm and metal aluminum 100 nm were deposited in this order to form a cathode.

This laminated body was put in the glove box substituted with nitrogen gas, without contacting air | atmosphere, and it sealed using the glass sealing can and the ultraviolet curable adhesive (XNR5516HV, Nagase Chiba Co., Ltd. make), and an organic electroluminescent element Got.

(evaluation)

The light emission efficiency at the time of low brightness, high brightness drive, and the initial fall time of drive durability of the manufactured organic electroluminescent element were evaluated as follows.

<Measurement of Luminescence Efficiency>

DC source voltage was applied to each element to emit light using a source major unit 2400 manufactured by KEITHLEY Co., Ltd., and its luminance and emission spectrum were measured by using a luminance meter SR-3 manufactured by Topcon Corporation. Based on these, the external quantum efficiency at luminance of 100 cd / m 2 and the external quantum efficiency at luminance of 15000 cd / m 2 were calculated by the luminance conversion method.

<Measurement of initial deterioration time of driving durability>

The device was driven with a constant current at an initial luminance of 15000 cd / m 2, and the time when the luminance became 95% of the initial stage (that is, the time when the luminance fell 5% from the initial stage) was measured.

The result was represented by the relative value which made the initial stage fall time of the comparative example 1 100.

Example 31, Comparative Examples 21 to 23

Device configuration is glass substrate / ITO (120 nm) / HIL-1 (10 nm) / hole transport layer (80 nm) / BAlq + Ir-B (mass ratio 95: 5) (30 nm) / electron transport layer (30 nm) / BCP (1 nm) / LiF (1 nm) / Al (100 nm), except that the material of the hole transport layer and the material of the electron transport layer were changed as shown in Table 2 below. An electroluminescent device was manufactured.

DC source voltage was applied to each element to emit light using a source major unit 2400 manufactured by KEITHLEY Co., Ltd., and its luminance and emission spectrum were measured by using a luminance meter SR-3 manufactured by Topcon Corporation. Based on these, the external quantum efficiency with luminance of 100 cd / m 2 and the external quantum efficiency with luminance of 3000 cd / m 2 were calculated by the luminance conversion method.

"Initial decay time" is a relative current drive of the device at an initial luminance of 3000 cd / m 2, and the time at which the luminance becomes the initial 95% (that is, the time when the luminance falls 5% from the initial stage) is made relative to Comparative Example 21 as 100. Represented by value.

The results are shown in Table 2.

Example 32, Comparative Examples 24-26

Device configuration is glass substrate / ITO (120 nm) / hole injection layer (60 nm) / HIL-1 (10 nm) / NPD (20 nm) / Zn-1 + Ir-B (mass ratio 95: 5) (30 nm) / Electron transport layer (30 nm) / Alq (1 nm) / LiF (1 nm) / Al (100 nm), the material of the hole injection layer and the material of the electron transport layer was changed as shown in Table 3 below In the same manner as in Example 1 except for the above, an organic EL device was manufactured.

DC source voltage was applied to each element to emit light using a source major unit 2400 manufactured by KEITHLEY Co., Ltd., and its luminance and emission spectrum were measured by using a luminance meter SR-3 manufactured by Topcon Corporation. Based on these, the external quantum efficiency with luminance of 100 cd / m 2 and the external quantum efficiency with luminance of 3000 cd / m 2 were calculated by the luminance conversion method.

"Initial decay time" is a relative current drive of the device at a constant luminance of 3000 cd / m 2, and the time when the luminance becomes 95% of the initial stage (that is, the time when the luminance falls by 5% from the initial stage) is set relative to 100 as Comparative Example 24. Represented by value.

The results are shown in Table 3.

Example 33, Comparative Examples 27 to 29

Device configuration is glass substrate / ITO (120 nm) / hole injection layer (60 nm) / HTL-A (30 nm) / a-3 + Ir-A (mass ratio 95: 5) (30 nm) / electron transport layer (30 nm ) / Alq (1 nm) / LiF (1 nm) / Al (100 nm), except that the material of the hole injection layer and the material of the electron transport layer were changed as shown in Table 4 below. In the same manner, an organic electroluminescent device was manufactured.

DC source voltage was applied to each element to emit light using a source major unit 2400 manufactured by KEITHLEY Co., Ltd., and its luminance and emission spectrum were measured by using a luminance meter SR-3 manufactured by Topcon Corporation. Based on these, the external quantum efficiency at luminance of 100 cd / m 2 and the external quantum efficiency at luminance of 15000 cd / m 2 were calculated by the luminance conversion method.

"Initial decay time" is a relative current drive of the element at a constant luminance of 15000 cd / m 2, and the time at which the luminance becomes the initial 95% (that is, the time when the luminance falls by 5% from the initial stage) is made relative to Comparative Example 27 as 100. Represented by value.

The results are shown in Table 4.

Example 34, Comparative Examples 30 to 32

The device configuration is glass substrate / ITO (120 nm) / hole injection layer (60 nm) / NPD (30 nm) / mCP + Ir-C (mass ratio 85:15) (30 nm) / electron transport layer (30 nm) / Liq ( An organic electroluminescent device was manufactured in the same manner as in Example 1, except that 1 nm) / Al (100 nm) was changed, and the material of the hole injection layer and the material of the electron transport layer were changed as shown in Table 5 below. .

DC source voltage was applied to each element to emit light using a source major unit 2400 manufactured by KEITHLEY Co., Ltd., and its luminance and emission spectrum were measured by using a luminance meter SR-3 manufactured by Topcon Corporation. Based on these, the external quantum efficiency with luminance of 100 cd / m 2 and the external quantum efficiency with luminance of 2000 cd / m 2 were calculated by the luminance conversion method.

"Initial fall time" is a relative current drive of the device at an initial luminance of 2000 cd / m 2, and the time at which the luminance becomes 95% of the initial stage (that is, the time when the luminance falls 5% from the initial stage) is set relative to 100. Represented by value.

The results are shown in Table 5.

Example 35, Comparative Example 33

The organic electroluminescent element of the following element structure was manufactured using the material shown in following Table 6 for the positive hole injection layer and the electron carrying layer.

Element structure: glass substrate / ITO (70 nm) / hole injection layer (95 nm) / B-2 + complex K-1 (mass ratio 93: 7) (40 nm) / a-3 (electron transport layer) (25 nm) / Alq (5 nm) / LiF (1 nm) / Al (150 nm)

The obtained device was evaluated as follows.

DC source voltage was applied to each element to emit light using a source major unit 2400 manufactured by KEITHLEY Co., Ltd., and its luminance and emission spectrum were measured by using a luminance meter SR-3 manufactured by Topcon Corporation. Based on these, the external quantum efficiency at luminance of 100 cd / m 2 and the external quantum efficiency at luminance of 15000 cd / m 2 were calculated by the luminance conversion method.

"Initial fall time" refers to the time when the device is driven at a constant luminance of 2,000 cd / m 2 at an initial luminance, when the luminance becomes 95% of the initial stage (that is, when the luminance falls 5% from the initial stage), and the result of Comparative Example 33 is 100. The relative values are shown.

The results are shown in Table 6.

From the results of Table 6, it can be seen that the device of Example 35 is suppressed from the decrease in efficiency at the time of high brightness driving and the initial decrease time is longer with respect to the device of Comparative Example 33.

Example 36, Comparative Example 34

The organic electroluminescent element of the following element structure was manufactured using the material shown in following Table 7 for the positive hole injection layer and the electron carrying layer.

Element structure: glass substrate / ITO (70 nm) / hole injection layer (80 nm) / mCP (10 nm) / Compound A + Compound D (mass ratio 92.5: 7.5) (40 nm) / a-3 (electron transport layer) (30 Nm) / Alq (5 nm) / LiF (0.1 nm) / Al (150 nm)

The obtained device was evaluated as follows.

DC source voltage was applied to each element to emit light using a source major unit 2400 manufactured by KEITHLEY Co., Ltd., and its luminance and emission spectrum were measured by using a luminance meter SR-3 manufactured by Topcon Corporation. Based on these, the external quantum efficiency at luminance of 100 cd / m 2 and the external quantum efficiency at luminance of 15000 cd / m 2 were calculated by the luminance conversion method.

"Initial fall time" is the time when the element is driven at a constant luminance of 2,000 cd / m 2 at an initial luminance, the time when the luminance becomes 95% of the initial stage (that is, the time when the luminance falls 5% from the initial stage), and the result of Comparative Example 34 is 100. The relative values are shown.

From the result of Table 7, it can be seen that, in the device of Example 36, the decrease in efficiency at the time of high luminance driving is suppressed and the initial decrease time is long with respect to the device of Comparative Example 34.

Example 37, Comparative Example 35

The organic electroluminescent element of the following element structure was created using the material shown in following Table 8 for the positive hole injection layer and the electron carrying layer.

Element structure: glass substrate / ITO (130 nm) / h-3 (hole injection layer) (160 nm) / NPD (30 nm) / CBP + Ir (ppy) ₃ (mass ratio 92: 8) (30 nm) / electron transport layer ( 5 nm) / Alq (25 nm) / LiF (0.3 nm) / Al (150 nm)

The obtained device was evaluated as follows.

DC source voltage was applied to each element to emit light using a source major unit 2400 manufactured by KEITHLEY Co., Ltd., and its luminance and emission spectrum were measured by using a luminance meter SR-3 manufactured by Topcon Corporation. Based on these, the external quantum efficiency at luminance of 100 cd / m 2 and the external quantum efficiency at luminance of 15000 cd / m 2 were calculated by the luminance conversion method.

"Initial fall time" is the time when the device is driven at a constant current of 15,000 cd / m 2 at initial luminance, the time when the luminance becomes 95% of the initial stage (the luminance falls 5% from the initial stage), and the result of Comparative Example 36 is 100. By the relative value.

From the results of Table 8, it can be seen that, in the device of Example 37, the decrease in efficiency at the time of high brightness driving is suppressed and the initial decrease time is long with respect to the device of Comparative Example 35.

From the result of Tables 1-8, it turns out that the element of an Example is suppressed from the fall of the efficiency at the time of high brightness drive with respect to the element of a comparative example, and also the initial fall time is long. Moreover, when the material of the electron carrying layer and the material of a hole injection layer in this invention are used separately, for example by the contrast of the comparative example 1 and the comparative example 2, and the contrast of the comparative example 1 and the comparative example 11. It turns out that the characteristic improvement width at the time of combining the material of the electron carrying layer and the material of a positive hole injection layer in this invention rather than the characteristic improvement width of is high.

The compound used by the Example and the comparative example below is shown.

(48)

(49)

(50)

(51)

(52)

(53)

[Formula 54]

(55)

Industrial availability

According to the present invention, it is possible to provide an organic electroluminescent device which is less deteriorated in efficiency at the time of high-brightness driving and has less initial reduction in driving durability.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

This application is based on the JP Patent application (Japanese Patent Application 2010-157352) of an application on July 9, 2010, The content is taken in here as a reference.

2… Board
3 ... anode
4… Hole injection layer
5 ... Hole transport layer
6 ... The light-
7 ... Hole block layer
8… Electron transport layer
9 ... cathode
10... Organic electroluminescent device
11 ... Organic layer
12... Protective layer
14 ... Adhesive layer
16 ... Sealing container
20... Light emitting device
30 ... Light scattering member
31 ... Transparent substrate
30A... Light incident surface
30B... Light emitting surface
32 ... Particulate
40 ... Lighting device

Claims (13)

On a board | substrate, it has a pair of electrode which consists of an anode and a cathode, and has a light emitting layer between the electrodes, has at least 1 organic layer between this light emitting layer and this anode, and at least 1 organic layer between this light emitting layer and this cathode. An organic electroluminescent device having
At least one compound represented by following General formula (1) is contained in the organic layer of at least 1 layer between this light emitting layer and this cathode,
An organic electroluminescent element comprising at least one compound represented by the following general formula (H-1) in at least one organic layer between the light emitting layer and the anode.
[Formula 1]

(In general formula (1), X <_3> , X <_4> and X <_5> are respectively independently the carbon atom which the nitrogen atom or the hydrogen atom couple | bonded, and the ring containing X <_3> , X <_4> and X <_5> is pyridine or pyrimidine. L 'represents a single bond or a benzene ring, R ¹ to R ⁵ each independently represent a fluorine atom, a methyl group, a phenyl group, a cyano group, a pyridyl group, a pyrimidyl group, a silyl group, a carbazolyl group, or tert-butyl N1 to n5 each independently represent 0 or 1, and p 'and q' each independently represent 1 or 2).
(2)

(In general formula (H-1), X represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted bivalent heterocyclic group.
R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted An aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a hydroxyl group, a cyano group, or a substituted or unsubstituted amino group is represented. At least two of R _H1 , R _H2 and R _{H3 may} be bonded to each other to form a ring. At least two of R _H1 ′, R _H2 ′ and R _H3 ′ may be bonded to each other to form a ring.
A _H1 and A _H1 'are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted aromatic heterocyclic group.) The method of claim 1,
In the general formula (H-1), A _H1 and A _H1 ′ are an substituted or unsubstituted aryl group. 3. The method according to claim 1 or 2,
The organic electroluminescent device according to the general formula (H-1), wherein X is an unsubstituted arylene group. The method according to any one of claims 1 to 3,
In said general formula (H-1), _AH1 and _AH1 'are a substituted or unsubstituted phenyl group, a biphenyl group, or an anthryl group. The method according to any one of claims 1 to 4,
In said general formula (H-1), X is a phenylene group, a naphthylene group, or a biphenylene group, The organic electroluminescent element. 6. The method according to any one of claims 1 to 5,
The organic electroluminescent element in which said general formula (H-1) is represented with the following general formula (H-2).
(3)

(In General Formula (H-2), R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'each independently represent a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, substituted or unsubstituted. Substituted aryl group, substituted or unsubstituted heterocyclic group, cyano group, or substituted or unsubstituted amino group is shown.
R _H4 and R _H4 ′ each independently represent a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, or a substituted or unsubstituted amino group. Indicates) 7. The method according to any one of claims 1 to 6,
The organic electroluminescent device of which R _H1 , R _H1 ', R _H2 , R _H2 ', R _H3 and R _H3 'are hydrogen atoms. The method according to claim 6 or 7,
The organic electroluminescent device wherein R _H4 and R _H4 ′ are a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, or a cyano group. The method according to any one of claims 1 to 8,
An organic electroluminescent element comprising a phosphorescent light emitting material in the light emitting layer. The method of claim 9,
An organic electroluminescent device, wherein the phosphorescent light emitting material is an iridium complex. A light emitting device using the organic electroluminescent device according to any one of claims 1 to 10. A display device using the organic electroluminescent device according to any one of claims 1 to 10. An illumination device using the organic electroluminescent device according to any one of claims 1 to 10.

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