JP6109797B2 - Organic electroluminescence device - Google Patents

Description

  The present invention relates to an organic electroluminescent device.

  Organic electroluminescent elements (hereinafter also referred to as “elements” and “organic EL elements”) are actively researched and developed because they emit light with high luminance when driven at a low voltage. An organic electroluminescent element has an organic layer between a pair of electrodes, and electrons injected from the cathode and holes injected from the anode recombine in the organic layer, and the generated exciton energy is used for light emission. To do.

In recent years, the use of phosphorescent light emitting materials has led to higher efficiency of devices. In addition, a doped element using a light emitting layer in which a light emitting material is doped in a host material is widely used.
For example, in Patent Documents 1 to 3, iridium complex or platinum complex is used as a phosphorescent material, and a compound having a specific structure including a nitrogen-containing heterocyclic group and a carbazole structure is used as a host material. An organic electroluminescent device with improved resistance has been proposed.

Patent Document 4 describes an organic electroluminescent device using a compound in which a benzene ring is substituted with a cyano group and two or more carbazole groups as a host material in a light emitting layer. Patent Document 5 discloses CBP (4,4′-di (9-carbazoyl) biphenyl), mCBP (meta-4,4′-di (9-carbazoyl) biphenyl) and an organic electroluminescent device using the same. Is described.
However, there is a need for an organic electroluminescent device that is compatible with luminous efficiency and durability at a higher level than the devices described in these patent documents and has a small chromaticity shift.

International Publication No. 05/085387 International Publication No. 03/080760 International Publication No. 03/078541 JP 2009-94486 A International Publication No. 01/041512

  For lighting applications and the like, it is necessary to drive with high luminance exceeding 10,000 candela. However, according to the study by the present inventors, the light emission position (thickness direction) in the low-luminance driving and in the light emitting layer during high luminance driving. The change in chromaticity due to the change in the brightness, the change in the light emission position during high-intensity driving, as well as the generation of heat, higher density of excitons, etc. It was found that there was a problem that the chromaticity change and the voltage increase with time were large.

An object of the present invention is to provide an organic electroluminescent device having excellent luminous efficiency and durability. It is another object of the present invention to obtain an organic electroluminescence device having a low driving voltage and a small chromaticity shift due to a difference in driving voltage.
Another object of the present invention is to provide a charge transporting material useful for an organic electroluminescence device having excellent luminous efficiency and durability, low driving voltage, and small chromaticity deviation due to a difference in driving voltage. It is. Another object of the present invention is to provide a light emitting device and an illumination device including an organic electroluminescent element.

According to the study by the present inventors, excellent light emission is achieved by containing a specific compound containing a carbazole structure in the light emitting layer, and a hydrocarbon compound having a specific condensed polycyclic skeleton in the cathode side layer from the light emitting layer. It has been found that an organic electroluminescence device having efficiency and durability, having a low driving voltage, and having a small chromaticity shift due to a difference in driving voltage can be provided.
That is, the present invention can be achieved by the following means.
[1]
An organic electroluminescence device having a pair of electrodes composed of an anode and a cathode and an organic layer including a light emitting layer between the electrodes on a substrate, wherein at least one layer of the organic layer is represented by the following general formula (1). An organic electroluminescent device containing at least one compound to be produced.
(In the general formula (1), R _{11 to} R ₁₄ each independently represents an aryl group, a heteroaryl group or a cyano group. R ₁₅ represents an electron-withdrawing group. N represents 1 or 2. n ₁ independently represents an integer of 0 to 4. n ₂ represents an integer of 1 to 4, and when there are a plurality of n, they may be the same as or different from each other. .)
[2]
The organic electroluminescence device according to [1], wherein R ₁₅ represents a cyano group, a fluorine atom, or a halogenated alkyl group.
[3]
The organic electroluminescent element according to [1], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).
(In General Formula (2), R _{11 to} R ₁₄ each independently represents an aryl group, a heteroaryl group or a cyano group. N represents 1 or 2. n ₁ represents an integer of 0 to 4 independently. .)
[4]
The organic electroluminescent element according to any one of [1] to [3], wherein n ₁ represents 0.
[5]
[1] to [4], wherein the light emitting layer contains at least one of the compound represented by the general formula (1) and the compound represented by the general formula (2). Organic electroluminescent device.
[6]
The organic electroluminescence device according to [5], wherein the light emitting layer further contains at least one phosphorescent metal complex.
[7]
The organic electroluminescent element as described in [6], wherein the metal complex is an iridium complex.
[8]
The organic electroluminescence according to any one of [1] to [7], which has at least one organic layer between the light emitting layer and the cathode and contains an aromatic hydrocarbon compound in the organic layer. element.
[9]
[1] to [7] having at least one organic layer between the light emitting layer and the cathode, wherein the organic layer contains at least one compound represented by the following general formula (O-1). The organic electroluminescent element of any one.
(Wherein R ⁰¹ represents an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ⁰¹ may be the same or different. A ^{01 to} A ⁰⁴ are each independently C—R ^A or a nitrogen atom. R ^A represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and when there are a plurality thereof, they may be the same or different from each other L ⁰¹ represents at least one of an aryl ring and a heteroaryl ring (Represents a divalent to hexavalent linking group comprising a seed, and n ⁰¹ represents an integer of 2 to 6.)
[10]
The organic electroluminescent element according to any one of [1] to [9], wherein at least one of the organic layers is formed by a solution coating process.
[11]
A charge transport material represented by the following general formula (1).
(In the general formula (1), R _{11 to} R ₁₄ each independently represents an aryl group, a heteroaryl group or a cyano group. R ₁₅ represents an electron-withdrawing group. N represents 1 or 2. n ₁ independently represents an integer of 0 to 4. n ₂ represents an integer of 1 to 4, and when there are a plurality of n, they may be the same as or different from each other. .)
[12]
[11] A light emitting layer containing the charge transport material according to [11].
[13]
The display apparatus using the organic electroluminescent element of any one of [1]-[10].
[14]
[1] A lighting device using the organic electroluminescent element according to any one of [10].

  According to the present invention, it is possible to provide an organic electroluminescent device having excellent luminous efficiency and durability, low driving voltage, and small chromaticity deviation due to the difference in driving voltage.

It is the schematic which shows an example of a structure of the organic electroluminescent element which concerns on this invention. It is the schematic which shows an example of the light-emitting device which concerns on this invention. It is the schematic which shows an example of the illuminating device which concerns on this invention.

In the present invention, the substituent group A, the substituent group B, and the substituent Z are defined as follows.
(Substituent group A)
An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, for example vinyl , Allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as propargyl , 3-pentynyl, etc.), an aryl group (preferably having 6 to 30 carbon atoms, more preferably carbon 6 to 20, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc.), amino group (preferably 0 to 30 carbon atoms, more preferably 0 carbon atoms). -20, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc.), an alkoxy group (preferably having 1 to 30 carbon atoms). More preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), an aryloxy group (preferably 6 to 6 carbon atoms). 30 and more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms. Nyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), a heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), an acyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, acetyl , Benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms such as methoxycarbonyl, ethoxy Carbonyl, etc.), an aryloxycarbonyl group (preferably It has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyloxy), an acylamino group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino, benzoylamino, and the like, and an alkoxycarbonylamino group (preferably having 2-2 carbon atoms). 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.), aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino). ), A sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenyl Sulfamoyl, etc.), a carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, Phenylcarbamoyl etc.), alkylthio group ( Preferably, it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio, ethylthio and the like, and an arylthio group (preferably 6 to 30 carbon atoms). , More preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 to carbon atoms). 20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, and a sulfonyl group (preferably having a carbon number). 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl). Rufinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl. ), A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid. An amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenylphosphoric acid amide), a hydroxy group , Mercapto group, halogen atom (eg 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 ( An aromatic heterocyclic group is also included, preferably 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, Is, for example, a nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom, selenium atom, tellurium atom, specifically pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, pyrrolyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, thiazolyl, And isoxazolyl, isothiazolyl, quinolyl, furyl, thienyl, selenophenyl, tellurophenyl, piperidyl, piperidino, morpholino, pyrrolidyl, pyrrolidino, benzoxazolyl, benzoimidazolyl, benzothiazolyl, carbazolyl group, azepinyl group, silolyl group and the like. A silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl). Ryloxy group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyloxy, triphenylsilyloxy, etc.), phosphoryl group (for example, A diphenylphosphoryl group, a dimethylphosphoryl group, etc.). These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group A described above.
(Substituent group B)
An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, for example vinyl , Allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as propargyl , 3-pentynyl, etc.), an aryl group (preferably having 6 to 30 carbon atoms, more preferably carbon 6 to 20, particularly preferably 6 to 12 carbon atoms, including, for example, phenyl, p-methylphenyl, naphthyl, anthranyl, etc.), cyano group, heterocyclic group (including aromatic heterocyclic group, Has 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, a selenium atom, and a tellurium atom. Is pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, pyrrolyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, quinolyl, furyl, thienyl, selenophenyl, tellurophenyl, piperidyl, piperidino, morpholino, pyrrolidyl, pyrrolidino, benzoxazolid Le, benzimidazo , Benzothiazolyl, carbazolyl group, azepinyl group, silylyl group, etc.) These substituents may be further substituted, and examples of further substituents include groups selected from the above substituent group A. Can do.
(Substituent Z)
C1-C6 alkyl group, C2-C6 alkenyl group, phenyl group, C5-C10 aromatic heterocyclic group, C1-C4 alkoxy group, phenoxy group, fluoro group, silyl group , An amino group, a cyano group, or a group formed by combining these. A plurality of substituents Z may be connected to each other to form an aromatic hydrocarbon ring.

In the following description of the general formula (1) and general formula (2), the hydrogen atom includes isotopes (deuterium atoms, etc.), and the atoms constituting the substituent further include the isotopes. .
In the present invention, when referred to as “substituent”, the substituent may be substituted. For example, the term “alkyl group” in the present invention includes an alkyl group substituted with a fluorine atom (for example, trifluoromethyl group) and an alkyl group substituted with an aryl group (for example, triphenylmethyl group). When the term “alkyl group having 1 to 6 carbon atoms” is used, it means that the number of carbon atoms is 1 to 6 as all groups including those substituted.

  The organic electroluminescent element of the present invention is an organic electroluminescent element having a pair of electrodes consisting of an anode and a cathode and an organic layer including a luminescent layer between the electrodes on a substrate, and at least one layer of the organic layer. Contains at least one compound represented by the following general formula (1).

According to the study by the present inventors, when driving at a high luminance exceeding 10,000 candela, the conventional element has a problem such as a large change in chromaticity when driving at a low luminance.
The difference in chromaticity between high luminance and low luminance is mainly due to the difference in the light emission position (film thickness direction) inside the light emitting layer, which is the charge injection barrier at each layer interface from the electrode to the light emitting layer, This is considered to be due to the electric field strength dependence of the charge mobility of each layer. In the element of the present invention, the charge injection barrier is reduced by using the compound represented by the general formula (1), and the dependence of the charge mobility on the electric field strength is reduced. It is estimated to be small.

[Compound represented by the general formula (1)]
Hereinafter, the compound represented by Formula (1) will be described.

(In the general formula (1), R _{11 to} R ₁₄ each independently represents an aryl group, a heteroaryl or a cyano group. R ₁₅ represents an electron-withdrawing group. N represents 1 or 2. n ₁ independently represents an integer of 0 to 4. n ₂ represents an integer of 1 to 4, and when a plurality of n ₂ exist, they may be the same as or different from each other. )

The aryl group represented by R _{11 to} R ₁₄ may be condensed or may have a substituent. In the case of having a substituent, examples of the substituent include the above-described substituent Z. The substituent Z is preferably an alkyl group or a phenyl group, and more preferably an alkyl group. The aryl group represented by R _{11 to} R ₁₄ is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 18 carbon atoms. The aryl group having 6 to 18 carbon atoms is preferably an aryl group having 6 to 18 carbon atoms which may have an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. It is a C6-C18 aryl group which may have. For example, a phenyl group, a dimethylphenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a methylnaphthyl group, a t-butylnaphthyl group, an anthranyl group, a phenanthryl group, a chrysenyl group, and the like. Group, biphenyl group and terphenyl group are preferable, phenyl group, dimethylphenyl group and biphenyl group are more preferable, and phenyl group is still more preferable.

The heteroaryl group represented by R _{11 to} R ₁₄ may be condensed or may have a substituent. In the case of having a substituent, examples of the substituent include the above-described substituent Z. The substituent Z is preferably an alkyl group or a phenyl group, and more preferably an alkyl group. The heteroaryl group represented by R _{11 to} R ₁₄ is preferably a C 4-12 heteroaryl group, more preferably a 5- or 6-membered substituted or unsubstituted heteroaryl group. , Pyridyl group, pyrazinyl group, pyridazinyl group, pyrimidinyl group, triazinyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, cinnolinyl group, phthalazinyl group, quinoxalinyl group, pyrrolyl group, indolyl group, furyl group, benzofuryl group, thienyl group, benzo Thienyl, pyrazolyl, imidazolyl, benzimidazolyl, triazolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, thiadiazolyl, isoxazolyl, benzisooxy Zoriru group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, imidazolidinyl group, carbazolyl group, thiazolinyl group, and a sulfolanyl group.

R _{11 to} R ₁₄ are preferably each independently a phenyl group, a pyridyl group or a cyano group, and more preferably a phenyl group.
In addition, when a substituent is introduced into the carbazole skeleton, the 3rd and 6th positions of the carbazole skeleton are reactive positions, and the substituent is located at the 3rd or 6th position from the viewpoint of ease of synthesis and improvement of chemical stability. Is preferably introduced.

The electron-withdrawing group represented by R ₁₅ is preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.2 or more, and an σp value of 0.3 or more. It is preferably a group. For example, acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group , Alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, fluorine atom, halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group, halogenated alkylamino group And a halogenated alkylthio group, preferably a fluorine atom, a halogenated alkyl group or a cyano group, more preferably a fluorine atom, a trifluoromethyl group or a cyano group. Fluorine atom, it is more preferably from the viewpoint of stability of a cyano group and more preferably Hammett's substituent constant σp value and a compound or a cyano group.
When a plurality of electron withdrawing groups represented by R ₁₅ are present, they may be the same as or different from each other.

n ₁ preferably independently represents 0 to 3, more preferably 0 or 1, and still more preferably 0. When n ₁ represents 0, the carbazole group in the general formula (1) has no substituent and is unsubstituted.
n ₂ preferably represents 1 to 3, more preferably 1 or 2, and still more preferably 1.

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

(In General Formula (2), R _{11 to} R ₁₄ each independently represents an aryl group, a heteroaryl group or a cyano group. N represents 1 or 2. n ₁ represents an integer of 0 to 4 independently. .)

R _{11 to} R ₁₄ , n, and n ₁ have the same meanings as those given in the general formula (1), and preferred ones are also the same.

  The compound represented by the general formula (1) or (2) is most preferably composed of only carbon atoms, hydrogen atoms and nitrogen atoms.

The present invention also relates to a charge transport material represented by the general formula (1). R _{11 to} R ₁₄ , n and n ₁ in the general formula (1) have the same meanings as described above, and preferable ones are also the same.

  The molecular weight of the compound represented by the general formula (1) or (2) is preferably 400 or more and 1000 or less, more preferably 450 or more and 800 or less, and further preferably 500 or more and 700 or less.

The lowest excited triplet (T ₁ ) energy in the film state of the compound represented by the general formula (1) or (2) is 2.42 eV (56 kcal / mol) or more and 3.51 eV (80 kcal / mol) or less. Is preferably 2.51 eV (58 kcal / mol) or more and 3.51 eV (80 kcal / mol) or less, more preferably 2.60 eV (60 kcal / mol) or more and 3.51 eV (80 kcal / mol). preferable.
The T ₁ energy can be obtained from the short wavelength end of a phosphorescence emission spectrum of a thin film of material. For example, a material is deposited on a cleaned quartz glass substrate to a film thickness of about 50 nm by vacuum deposition, and the phosphorescence emission spectrum of the thin film is measured at F-7000 Hitachi Spectrofluorimeter (Hitachi High-Technologies) at liquid nitrogen temperature. Use to measure. The T ₁ energy can be obtained by converting the rising wavelength on the short wavelength side of the obtained emission spectrum into energy units.

  The glass transition temperature (Tg) of the compound represented by the general formula (1) or (2) is preferably 80 ° C. or higher and 400 ° C. or lower, more preferably 100 ° C. or higher and 400 ° C. or lower, more preferably 110 ° C. or higher. More preferably, it is 400 degrees C or less.

When the general formula (1) or (2) has a hydrogen atom, an isotope (such as a deuterium atom) is also included. In this case, all hydrogen atoms in the compound may be replaced with isotopes, or a mixture in which a part is a compound containing isotopes may be used.
Although the specific example of a compound represented by general formula (1) or (2) below is illustrated below, this invention is not limited to these. The following compounds a-1 to a-36 are to be read as compounds a-1 to a-36 of Reference Examples, respectively.

  The compound exemplified as the compound represented by the general formula (1) or (2) can be synthesized by Suzuki coupling of a corresponding 3-halogenophenylcarbazole derivative and a 3- (9-carbazolyl) phenylboric acid derivative. I can do it. (Synth. Commun. 11, 513 (1981)).

In said general formula, R < ₁ > -R < ₄ > is synonymous with R < ₁₁ > -R < ₁₄ > in the said General formula (1), respectively. R ₅ and R ₅ ′ have the same meaning as R ₁₅ in the general formula (1). R ′ and R ″ each independently represents a hydrogen atom or an alkyl group. X represents a halogen atom.

In the present invention, the compound represented by the general formula (1) or (2) is preferably contained in the light emitting layer, but its use is not limited, and any compound in the organic layer may be further added. It may be contained. As the introduction layer of the compound represented by the general formula (1) or (2), a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an exciton block layer, a charge block layer Either can be mentioned.
The compound represented by the general formula (1) or (2) is preferably included in an amount of 0.1 to 99% by mass, more preferably 1 to 95% by mass, based on the total mass of the light emitting layer. It is more preferable to include 95% by mass. When the compound represented by the general formula (1) or (2) is further contained in a layer other than the light emitting layer, it is preferably contained in an amount of 70 to 100% by mass, more preferably 85 to 100% by mass.

[Organic electroluminescence device]
The device of the present invention will be described in detail.
The organic electroluminescent element of the present invention is an organic electroluminescent element having a pair of electrodes consisting of an anode and a cathode and an organic layer including a luminescent layer between the electrodes on a substrate, and at least one layer of the organic layer. Contains at least one compound represented by the following general formula (1).

In the organic electroluminescent element of the present invention, the light emitting layer is an organic layer, and includes at least one organic layer between the light emitting layer and the cathode, and has an organic layer adjacent to the light emitting layer between the light emitting layer and the cathode, Furthermore, you may have a some organic layer.
In view of the properties of the light-emitting element, at least one of the anode and the cathode is preferably transparent or translucent.
FIG. 1 shows an example of the configuration of an organic electroluminescent device according to the present invention. In the organic electroluminescent element 10 according to the present invention shown in FIG. 1, a light emitting layer 6 is sandwiched between an anode 3 and a cathode 9 on a support substrate 2. Specifically, a hole injection layer 4, a hole transport layer 5, a light emitting layer 6, a hole block layer 7, and an electron transport layer 8 are laminated in this order between the anode 3 and the cathode 9.

<Structure 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 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 of the transparent electrode or the back electrode.
There is no restriction | limiting in particular about the shape of a organic layer, a magnitude | size, thickness, etc., According to the objective, it can select suitably.

Specific examples of the layer configuration include the following, but the present invention is not limited to these configurations.
Anode / hole transport layer / light emitting layer / electron transport layer / cathode,
Anode / hole transport layer / light emitting layer / block layer / electron transport layer / cathode,
Anode / hole transport layer / light emitting layer / block layer / electron transport layer / electron injection layer / cathode,
Anode / hole injection layer / hole transport layer / light emitting layer / block layer / electron transport layer / cathode,
Anode / hole injection layer / hole transport layer / light emitting layer // electron transport layer / electron injection layer / cathode,
Anode / hole injection layer / hole transport layer / light emitting layer / block layer / electron transport layer / electron injection layer / cathode.
The element configuration, the substrate, the cathode, and the anode of the organic electroluminescence element are described in detail in, for example, Japanese Patent Application Laid-Open No. 2008-270736, and the matters described in the publication can be applied to the present invention.

<Board>
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 anode usually only needs to have a function as an electrode for supplying holes to the organic layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials. As described above, the anode is usually provided as a transparent anode.
<Cathode>
The cathode usually has a function as an electrode for injecting electrons into the organic layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the use and purpose of the light-emitting element. The electrode material can be selected as appropriate.

  Regarding the substrate, anode, and cathode, the matters described in paragraphs [0070] to [0089] of JP-A-2008-270736 can be applied to the present invention.

<Organic layer>
The organic layer in the present invention will be described.

[Formation of organic layer]
In the organic electroluminescence device of the present invention, each organic layer is preferably formed by any of dry deposition methods such as vapor deposition and sputtering, and solution coating processes such as transfer, printing, spin coating, and bar coating. Can be formed. It is preferable that at least one of the organic layers is formed by a solution coating process.

[Light emitting layer]
The light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines holes and electrons. It is a layer which has the function to provide and to emit light.
The present invention also relates to a light emitting layer containing the charge transport material represented by the general formula (1). The light emitting layer of this invention can be used for an organic electroluminescent element. The light emitting layer of the present invention preferably further contains the phosphorescent organometallic complex in addition to the charge transport material represented by the general formula (1). Further, a host material may be further included. The host material may be a hole transporting host material or an electron transporting host material, but a both-charge transporting host material is preferable.

  The substrate, anode, cathode, organic layer, and light emitting 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 documents can be applied to the present invention. . May be. Furthermore, the light emitting layer may include a material that does not have charge transporting properties and does not emit light.

(Luminescent material)
As the light emitting material in the present invention, any of phosphorescent light emitting materials, fluorescent light emitting materials and the like can be used.
The light emitting layer in the present invention can contain two or more kinds of light emitting materials in order to improve the color purity and widen the light emission wavelength region. The element of the present invention preferably further contains at least one phosphorescent metal complex in the light emitting layer.
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. It is preferable from the viewpoint. Here, ΔIp means the difference in Ip value between the host material and the light emitting material, and ΔEa means the difference in Ea value between the host material and the light emitting material.
It is preferable that at least one of the light emitting materials is a platinum complex material or an iridium complex material.
In the present invention, the light emitting layer preferably contains a platinum complex material or iridium complex material, more preferably contains a platinum complex material or iridium complex material having a tetradentate ligand, and further contains an iridium complex material. preferable.
The fluorescent light-emitting material and the phosphorescent light-emitting material are described in detail, for example, in paragraph numbers [0100] to [0164] of JP-A-2008-270736 and paragraph numbers [0088] to [0090] of JP-A-2007-266458, The matters described in these publications can be applied to the present invention.

  The platinum complex is preferably a platinum complex represented by the following general formula (C-1).

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

General formula (C-1) is demonstrated. Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a ligand coordinated to Pt. At this time, the bond between Q ¹ , Q ² , Q ³ and Q ⁴ and Pt may be any of a covalent bond, an ionic bond, a coordinate bond, and 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 in Q < ¹ >, Q < ² >, Q < ³ > and Q < ⁴ > Of the atoms bonded to Pt, at least one is preferably a carbon atom, more preferably two are carbon atoms, particularly preferably two are carbon atoms and two are nitrogen atoms.
Q ¹ , Q ² , Q ³ and Q ⁴ bonded to Pt by a carbon atom may be an anionic ligand or a neutral ligand, and the anionic ligand is a vinyl ligand, Aromatic hydrocarbon ring ligand (eg benzene ligand, naphthalene ligand, anthracene ligand, phenanthrene ligand), heterocyclic ligand (eg furan ligand, thiophene ligand, pyridine) Ligand, pyrazine ligand, pyrimidine ligand, pyridazine ligand, triazine ligand, thiazole ligand, oxazole ligand, pyrrole ligand, imidazole ligand, pyrazole ligand, triazole And a condensed ring containing them (for example, quinoline ligand, benzothiazole ligand, etc.). A carbene ligand is mentioned as a neutral ligand.
Q ¹ , Q ² , Q ³ and Q ⁴ bonded to Pt with a nitrogen atom may be neutral ligands or anionic ligands, and as neutral ligands, nitrogen-containing aromatic hetero Ring ligand (pyridine ligand, pyrazine ligand, pyrimidine ligand, pyridazine ligand, triazine ligand, imidazole ligand, pyrazole ligand, triazole ligand, oxazole ligand, Examples include thiazole ligands and condensed rings containing them (for example, quinoline ligands, benzimidazole ligands), amine ligands, nitrile ligands, and imine ligands. Examples of anionic ligands include amino ligands, imino ligands, nitrogen-containing aromatic heterocyclic ligands (pyrrole ligands, imidazole ligands, triazole ligands and condensed rings containing them) (For example, indole ligand, benzimidazole ligand, etc.)).
Q ¹ , Q ² , Q ³ and Q ⁴ bonded to Pt with an oxygen atom may be neutral ligands or anionic ligands, and neutral ligands are ether ligands, Examples include ketone ligands, ester ligands, amide ligands, oxygen-containing heterocyclic ligands (furan ligands, oxazole ligands and condensed rings containing them (benzoxazole ligands, etc.)). It is done. Examples of the anionic ligand include an alkoxy ligand, an aryloxy ligand, a heteroaryloxy ligand, an acyloxy ligand, a silyloxy ligand, and the like.
Q ¹ , Q ² , Q ³ and Q ⁴ bonded to Pt with a sulfur atom may be neutral ligands or anionic ligands, and neutral ligands include thioether ligands, Examples include thioketone ligands, thioester ligands, thioamide ligands, sulfur-containing heterocyclic ligands (thiophene ligands, thiazole ligands and condensed rings containing them (such as benzothiazole ligands)). It is done. Examples of the anionic ligand include an alkyl mercapto ligand, an aryl mercapto ligand, and a heteroaryl mercapto ligand.
Q ¹ , Q ² , Q ³ and Q ⁴ bonded to Pt with a phosphorus atom may be neutral ligands or anionic ligands, and neutral ligands include phosphine ligands, Examples include phosphate ester ligands, phosphite ester ligands, and phosphorus-containing heterocyclic ligands (phosphinin ligands, etc.). Anionic ligands include phosphino ligands and phosphinyl ligands. And phosphoryl ligands.
The groups represented by Q ¹ , Q ² , Q ^3, and Q ⁴ may have a substituent, and those listed as the substituent group A can be appropriately applied as the substituent. Moreover, substituents may be connected to each other (when Q ³ and Q ⁴ are connected, a Pt complex of a cyclic tetradentate ligand is formed).

The group represented by Q ¹ , Q ² , Q ³ and Q ⁴ is preferably an aromatic hydrocarbon ring ligand bonded to Pt with a carbon atom, and an aromatic heterocyclic ligand bonded to Pt with a carbon atom. A nitrogen-containing aromatic heterocyclic ligand that binds to Pt with a nitrogen atom, an acyloxy ligand, an alkyloxy ligand, an aryloxy ligand, a heteroaryloxy ligand, a silyloxy ligand, and more Preferably, an aromatic hydrocarbon ring ligand bonded to Pt by a carbon atom, an aromatic heterocyclic ligand bonded to Pt by a carbon atom, a nitrogen-containing aromatic heterocyclic ligand bonded to Pt by 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, a nitrogen atom Containing Pt Containing aromatic heterocyclic ligand, an acyloxy ligand.

L ¹ , L ² and L ³ represent a single bond or a divalent linking group. Examples of the divalent linking group represented by L ¹ , L ² and L ³ include alkylene groups (methylene, ethylene, propylene, etc.), arylene groups (phenylene, naphthalenediyl), heteroarylene groups (pyridinediyl, thiophenediyl, etc.) ), Imino group (—NR—) (such as phenylimino group), oxy group (—O—), thio group (—S—), phosphinidene group (—PR—) (such as phenylphosphinidene group), silylene group (-SiRR'-) (dimethylsilylene group, diphenylsilylene group, etc.), or a combination of these. These linking groups may further have a substituent.
From the viewpoint of the stability of the complex and the emission 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 or a silylene group. More preferably a single bond, an alkylene group, an arylene group or an imino group, still more preferably a single bond, an alkylene group or an arylene group, still more preferably a single bond, a methylene group or a phenylene group, still more preferably. Single bond, disubstituted methylene group, more preferably single bond, dimethylmethylene group, diethylmethylene group, diisobutylmethylene group, dibenzylmethylene group, ethylmethylmethylene group, methylpropylmethylene group, isobutylmethylmethylene group, diphenyl Methylene group, methylphenylmethylene group, cyclohexanediyl group, A lopentanediyl group, a fluorenediyl group, and a fluoromethylmethylene group, particularly preferably a single bond, a dimethylmethylene group, a diphenylmethylene group, and a cyclohexanediyl group.

  Of the platinum complexes represented by the general formula (C-1), a platinum complex represented by the following general formula (C-2) is more preferable.

(In the formula, L ²¹ represents a single bond or a divalent linking group. A ²¹ and A ²² each independently represent C or N. Z ²¹ and Z ²² each independently represent a nitrogen-containing aromatic heterocyclic ring. Z ²³ and Z ²⁴ each independently represent a benzene ring or an aromatic heterocycle.

General formula (C-2) is demonstrated. L ²¹ has the same meaning as L ^{1 in} formula (C-1), and the preferred range is also the same.

A ²¹ and A ²² each independently represent a carbon atom or a nitrogen atom. Of A ^21, A ^22, Preferably, at least one is a carbon atom, it A ^21, A ²² are both carbon atoms are preferred from the standpoint of emission quantum yield stability aspects and complexes of the complex .

Z ²¹ and Z ²² each independently represent a nitrogen-containing aromatic heterocycle. Examples of the nitrogen-containing aromatic heterocycle represented by Z ²¹ and Z ²² include a pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, triazole ring, oxadiazole ring, Examples include thiadiazole rings. From the viewpoint of the stability of the complex, emission wavelength control and emission quantum yield, the ring represented by Z ²¹ and Z ²² is preferably a pyridine ring, a pyrazine ring, an imidazole ring or a pyrazole ring, more preferably a pyridine ring. , An imidazole ring and a pyrazole ring, more preferably a pyridine ring and a pyrazole ring, and particularly preferably a pyridine ring.

The nitrogen-containing aromatic heterocycle represented by Z ²¹ and Z ²² may have a substituent, the substituent group A as a substituent on a carbon atom, and the substituent on a nitrogen atom as The substituent group B can be applied. The substituent on the carbon atom is preferably an alkyl group, a polyfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, an alkoxy group, a cyano group, or a halogen atom. The substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of shortening the wavelength, an electron donating group, a fluorine atom, and an aromatic ring group are preferable. For example, an alkyl group, a dialkylamino group, an alkoxy group, A fluorine atom, an aryl group, an aromatic heterocyclic group and the like are selected. Moreover, when making it long wavelength, an electron withdrawing group is preferable, for example, a cyano group, a polyfluoroalkyl group, etc. are selected. The substituent on N is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex. The substituents may be linked to form a condensed ring, and the formed ring includes 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. Ring, thiophene ring, furan ring and the like.

Z ²³ and Z ²⁴ each independently represent a benzene ring or an aromatic heterocycle. Examples of the nitrogen-containing aromatic heterocycle represented by Z ²³ and Z ²⁴ include a pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, triazole ring, oxadi Examples include an azole ring, a thiadiazole ring, a thiophene ring, and a furan ring. From the viewpoint of stability of the complex, emission wavelength control and emission quantum yield, the ring represented by Z ²³ and Z ²⁴ is preferably a benzene ring, a pyridine ring, a pyrazine ring, an imidazole ring, a pyrazole ring, or a thiophene ring, More preferred are a benzene ring, a pyridine ring and a pyrazole ring, and still more preferred are a benzene ring and a pyridine ring.

The benzene ring and nitrogen-containing aromatic heterocycle represented by Z ²³ and Z ²⁴ may have a substituent. As the substituent on the carbon atom, the substituent group A is substituted on the nitrogen atom. The substituent group B can be applied as the group. Preferred substituents on carbon are alkyl groups, polyfluoroalkyl groups, aryl groups, aromatic heterocyclic groups, dialkylamino groups, diarylamino groups, alkoxy groups, cyano groups, and halogen atoms. The substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of increasing the wavelength, an electron donating group and an aromatic ring group are preferable, for example, an alkyl group, a dialkylamino group, an alkoxy group, an aryl group, An aromatic heterocyclic group or the like is selected. In order to shorten the wavelength, an electron withdrawing group is preferable. For example, a fluorine group, a cyano group, a polyfluoroalkyl group, or the like is selected. The substituent on N is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex. The substituents may be linked to form a condensed ring, and the formed ring includes 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. Ring, thiophene ring, furan ring and the like.

  Among the platinum complexes represented by the general formula (C-2), one of more preferable embodiments is a platinum complex represented by the following general formula (C-4).

(In General Formula (C-4), A ^{401 to} A ⁴¹⁴ each independently represents C—R or N. 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 C—R or N. R represents a hydrogen atom or a substituent.
Or as a substituent represented by R, what was mentioned as the said substituent group A is applicable.
A ^{401 to} A ⁴⁰⁶ are preferably C—R, and Rs may be connected to each other to form a ring. When A ^{401 to} A ⁴⁰⁶ are C—R, R in A ⁴⁰² and A ⁴⁰⁵ is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group, or a cyano group. More preferably a hydrogen atom, an amino group, an alkoxy group, an aryloxy group or a fluorine group, and particularly preferably a hydrogen atom or a fluorine group. R in A ⁴⁰¹ , A ⁴⁰³ , A ⁴⁰⁴ and A ⁴⁰⁶ is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group or a cyano group, more preferably a hydrogen atom or an amino group. Group, alkoxy group, aryloxy group and fluorine group, particularly preferably a hydrogen atom.
L ⁴¹ has the same meaning as L ^{1 in} formula (C-1), and the preferred range is also the same.

As A ^{407 to} A ⁴¹⁴ , in each of A ^{407 to} A ⁴¹⁰ and A ^{411 to} A ⁴¹⁴ , the number of N (nitrogen atoms) is preferably 0 to 2, and more preferably 0 to 1. When shifting the emission wavelength to the short wavelength side, either A ⁴⁰⁸ or A ⁴¹² is preferably an N atom, and both A ⁴⁰⁸ and A ⁴¹² are more preferably N atoms.
In the case where A ^{407 to} A ⁴¹⁴ represent C—R, R in A ⁴⁰⁸ and A ⁴¹² is preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group. A cyano group, more preferably a hydrogen atom, a polyfluoroalkyl group, an alkyl group, an aryl group, a fluorine group or a cyano group, and particularly preferably a hydrogen atom, a phenyl group, a polyfluoroalkyl group or a cyano group. . R of A ⁴⁰⁷ , A ⁴⁰⁹ , A ⁴¹¹ , and A ⁴¹³ is preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group, or a cyano group, and more preferably Is a hydrogen atom, a polyfluoroalkyl group, a fluorine group or a cyano group, particularly preferably a hydrogen atom, a phenyl group or a fluorine group. R in A ⁴¹⁰ and A ⁴¹⁴ is preferably a hydrogen atom or a fluorine group, 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.

  Of the platinum complexes represented by the general formula (C-2), one of more preferable embodiments is a platinum complex represented by the following general formula (C-5).

(In General Formula (C-5), A ^{501 to} A ⁵¹² each independently represents C—R or N. R represents a hydrogen atom or a substituent. L ⁵¹ represents a single bond or a divalent linking group. Represents.)

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 preferred ranges thereof are also the same.

A ⁵⁰⁷ , A ⁵⁰⁸ and A ⁵⁰⁹ and A ⁵¹⁰ , A ⁵¹¹ and A ⁵¹² and each independently represent C—R or N. R represents a hydrogen atom or a substituent. As the substituent represented by R, those exemplified as the substituent group A can be applied. When A ⁵⁰⁷ , A ⁵⁰⁸ and A ⁵⁰⁹ and A ⁵¹⁰ , A ⁵¹¹ and A ⁵¹² are C—R, R is preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, or an aromatic heterocyclic group. , Dialkylamino group, diarylamino group, alkyloxy group, cyano group, halogen atom, more preferably hydrogen atom, alkyl group, polyfluoroalkyl group, aryl group, dialkylamino group, cyano group, fluorine atom, Preferably, they are a hydrogen atom, an alkyl group, a trifluoromethyl group, or a fluorine atom. If possible, the substituents may be linked to form a condensed ring structure. At least one of A ⁵⁰⁷ , A ⁵⁰⁸ and A ⁵⁰⁹ and A ⁵¹⁰ , A ⁵¹¹ and A ⁵¹² is preferably N, and particularly preferably A ⁵¹⁰ or A ⁵⁰⁷ is N.

  Among the platinum complexes represented by the general formula (C-1), another more preferable embodiment is a platinum complex represented by the following general formula (C-6).

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

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

A ⁶¹ represents C or N. A ⁶¹ is preferably C from the viewpoint of the stability of the complex and the light emission quantum yield of the complex.

Z ⁶¹ and Z ⁶² are synonymous with Z ²¹ and Z ²² in the general formula (C-2), respectively, and preferred ranges thereof are also the same. Z ⁶³ has the same meaning as Z ²³ in formula (C-2), and the preferred range is also the same.

Y is an anionic acyclic ligand that binds to Pt. An acyclic ligand is one in which atoms bonded to Pt do not form a ring in the form of a ligand. 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.
A vinyl ligand is mentioned as Y couple | bonded with Pt by a carbon atom. Examples of Y bonded to Pt with a nitrogen atom include an amino ligand and an imino ligand. Examples of Y bonded to Pt with an oxygen atom include an alkoxy ligand, an aryloxy ligand, a heteroaryloxy ligand, an acyloxy ligand, a silyloxy ligand, a carboxyl ligand, a phosphate ligand, Examples thereof include sulfonic acid ligands. Examples of Y bonded to Pt with a sulfur atom include alkyl mercapto ligands, aryl mercapto ligands, heteroaryl mercapto ligands, thiocarboxylic acid ligands, and the like.
The ligand represented by Y may have a substituent, and those exemplified as the substituent group A can be appropriately applied as the substituent. Moreover, substituents may be connected to each other.

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

  Of the platinum complexes represented by the general formula (C-6), one of more preferred embodiments is a platinum complex represented by the following general formula (C-7).

(In the formula, A ^{701 to} A ⁷¹⁰ each independently represents C—R or N. R represents a hydrogen atom or a substituent. L ⁷¹ represents a single bond or a divalent linking group. Y represents Pt. Anionic acyclic ligand that binds to

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

  Specific examples of the platinum complex represented by the general formula (C-1) include [0143] to [0152], [0157] to [0158], and [0162] to [0168] of JP-A-2005-310733. The compounds described in JP-A-2006-256999, [0065] to [0083], the compounds described in JP-A-2006-93542, [0065] to [0090], JP-A-2007-73891 Nos. [0063] to [0071], No. 2007-324309, No. 0079 to [0083], No. 2006-93542 No. [0065] to [0090] The compounds described in JP-A-2007-96255, [0055] to [0071], JP-A-2006-313796 0043] include - [0046], platinum complexes exemplified other following can be mentioned.

Examples of the platinum complex compound represented by the general formula (C-1) include Journal of Organic Chemistry 53,786, (1988), G.S. R. Newkome et al. ), Page 789, method described in left line 53 to right line 7, line 790, method described in left line 18 to line 38, method 790, method described in right line 19 line to line 30 and The combination, Chemische Berichte 113, 2749 (1980), H.C. Lexy et al.), Page 2752, lines 26-35, and the like.
For example, a ligand or a dissociated product thereof and a metal compound are mixed with 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, a sulfone solvent, In the presence of a sulfoxide solvent, water, etc., or in the absence of a solvent, in the presence of a base (inorganic and organic bases such as sodium methoxide, t-butoxypotassium, triethylamine, potassium carbonate, etc.) Or in the absence of a base, at room temperature or below, or by heating (in addition to normal heating, a method of heating with a microwave is also effective).

  The content of the compound represented by the general formula (C-1) in the light emitting layer of the present invention is preferably 1 to 30% by mass, more preferably 3 to 25% by mass in the light emitting layer, More preferably, it is 20 mass%.

The iridium complex is preferably an iridium complex represented by the following general formula (T-1). [Compound represented by formula (T-1)]
The compound represented by formula (T-1) will be described.

(In the general formula (T-1), R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, —CN, a perfluoroalkyl group, a trifluorovinyl group. , —CO ₂ R, —C (O) R, —NR ₂ , —NO ₂ , —OR, a halogen atom, an aryl group, or a heteroaryl group, and may further have a substituent Z.
Q is a 5-membered or 6-membered aromatic heterocyclic ring or condensed aromatic heterocyclic ring containing one or more nitrogen atoms.
R _T3 , R _T4 , R _T5 and R _T6 may be 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 hetero It is aryl, and the condensed 4- to 7-membered ring may further have a substituent Z.
R _T3 'and _{R T6 are, -CR 2 -CR 2 -, -} CR = CR -, - CR 2 -, - O -, - NR -, - O-CR 2 -, - NR-CR 2 - and - They may be linked by a linking group selected from N = CR- to form a ring.
Each R 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 Z.
Z is independently a halogen 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' represents, R 'are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
(X—Y) represents an auxiliary ligand. m _T represents an integer of 1 to 3, and n _T represents an integer of 0 to 2. m _T + n _T is 3. )

  The general formula (T-1) is a complex having iridium (Ir) as a metal, and can be combined with the charge transport material of the present invention to reduce the voltage, increase the efficiency, and increase the durability of the device.

The alkyl group may have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the above-described substituent Z. 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, more preferably an alkyl group having 1 to 6 carbon atoms. Group, for example, methyl group, ethyl group, i-propyl group, cyclohexyl group, t-butyl group and the like.
The cycloalkyl group may have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the above-described substituent Z. The cycloalkyl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , and R _T6 is preferably a cycloalkyl group having 4 to 7 ring members, and more preferably a cycloalkyl group having 5 to 6 total carbon atoms. Examples of the alkyl group include a cyclopentyl group and a cyclohexyl group.
The alkenyl 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, particularly preferably 2 to 10 carbon atoms. And 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 , R _T6 is preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms. Yes, for example, ethynyl, propargyl, 1-propynyl, 3-pentynyl and the like.

_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 replaced with O, NR, or S.

The aryl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , and R _T6 is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group. Groups and the like.

The heteroaryl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , R _T6 is preferably a heteroaryl group having 5 to 8 carbon atoms, more preferably a 5- or 6-membered substitution. Or an unsubstituted heteroaryl group, for example, pyridyl group, pyrazinyl group, pyridazinyl group, pyrimidinyl group, triazinyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, cinnolinyl group, 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, a Examples include a soxazolyl group, a benzisoxazolyl group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, an imidazolidinyl group, a thiazolinyl group, a sulfolanyl group, a carbazolyl group, a dibenzothryl group, a dibenzothienyl group, and a 7 pyridoindolyl group. Preferred examples include pyridyl group, pyrimidinyl group, imidazolyl group, and thienyl group, and more preferred are pyridyl group and pyrimidinyl group.

R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 are preferably a hydrogen atom, alkyl group, cyano group, trifluoromethyl group, perfluoroalkyl group, dialkylamino group, fluoro group, aryl group, heteroaryl group Or a halogen atom, more preferably a hydrogen atom, an alkyl group, a cyano group, a trifluoromethyl group, a fluoro group, an aryl group, or a halogen atom, and still more preferably a hydrogen atom, an alkyl group, an aryl group, or A halogen atom, particularly preferably a hydrogen atom, a methyl group, an isobutyl group, a phenyl group, or a fluorine atom. As the substituent Z, an alkyl group, an alkoxy group, a fluoro group, 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 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 hetero It is aryl, and the condensed 4- to 7-membered ring may further have a substituent Z. The definition and preferred range of the cycloalkyl, aryl and heteroaryl formed are the same as the cycloalkyl group, aryl group and heteroaryl group defined by R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 .

  Examples of the aromatic heterocyclic ring represented by ring Q include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, an oxadiazole ring, a thiazole ring, and a thiadiazole ring. Preferred are a pyridine ring, a pyrazine ring, a pyrazole ring and an imidazole ring, more preferred are a pyridine ring, a pyrazole ring and an imidazole ring, and further preferred are a pyridine ring and an imidazole ring.

  Examples of the condensed aromatic heterocyclic ring represented by ring Q include a quinoline ring, an isoquinoline ring, and a quinoxaline ring. Preferred are a quinoline ring and an isoquinoline ring, and more preferred is a quinoline ring.

m _T is preferably from 1 to 3, and more preferably 2-3. That, _{n T} is preferably 0-1. The type of ligand in the complex is preferably composed of 1 to 2 types, and more preferably 1 type. When introducing a reactive group into the complex molecule, it is also preferred that the ligand consists of two types from the viewpoint of ease of synthesis.

  The metal complex represented by the general formula (T-1) is composed of a combination of a main ligand or a tautomer thereof and a subligand or a tautomer thereof, or the coordination of the metal complex All of the children may be composed of only a partial structure represented by the main ligand or a tautomer thereof.

  Further, as a so-called ligand used for forming a conventionally known metal complex, the trader may have a known ligand (also referred to as a coordination compound) as a sub-ligand as necessary.

  There are various known ligands used in conventionally known metal complexes. For example, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag H. Published by Yersin, 1987, “Organometallic Chemistry-Fundamentals and Applications-” Liu Huabosha, Akio Yamamoto, published by 1982, etc. (for example, halogen ligands (preferably chlorine ligands), Nitrogen heteroaryl ligands (for example, bipyridyl, phenanthroline, etc.), diketone ligands (for example, acetylacetone, etc.) Preferred secondary ligands are diketones or picolinic acid derivatives, and the stability of the complex From the viewpoint of obtaining high luminous efficiency, acetylacetonate (acac) is most preferable, and M represents a metal atom in the following general formula.

  Although the example of a subligand is specifically mentioned below, this invention is not limited to these.

In the example of the sub-ligand, M ₁ represents an Ir atom. Rx, Ry and Rz each independently represents a hydrogen atom or a substituent. Since the complex synthesis method is generally known and easy, it is preferably I-1, I-4, or I-5, and most preferably I-1. Complexes having these subligands can be synthesized in the same manner as in known synthesis examples by using corresponding ligand precursors. For example, it can synthesize | combine by the method shown below using commercially available difluoro acetylacetone similarly to the method as described in international publication 2009-073245 public information pamphlet 46 page.

  Moreover, the monoanionic ligand shown to general formula (I-15) can also be used as a subligand.

R _T7 ′ and R _{T7 to} R _T10 in General Formula (I-15) have the same _{meanings as} R _T3 ′ and R _{T3 to} R _T6 in General Formula (T-1), and preferred ones are also the same. R _T8 ′ to R _T10 ′ are synonymous with R _T3 ′.
R _T8 ′ is preferably a hydrogen atom, an alkyl group, an aryl group, or a fluoro group, and more preferably a hydrogen atom.
R _T9 ′ and R _T10 ′ represent a hydrogen atom or preferably bonded to each other to form a condensed 4- to 7-membered cyclic group, and the condensed 4- to 7-membered cyclic group includes a cycloalkyl group, a cyclo A heteroalkyl group, an aryl group, or a heteroaryl group is more preferable, and an aryl group is still more preferable.
R _T9 ′ to R _T10 ′ may further have a substituent Z, and the substituent Z is preferably an alkyl group, an alkoxy group, a fluoro group, a cyano group, an alkylamino group, or a diarylamino group, and an alkyl group is More preferred.

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

R _T3 ′, R _{T3 to} R _T6 , (XY), m _T and n _T in the general formula (T-2) are R _T3 ′, R _{T3 to} R _T6 , ( X-Y), has the same meaning as _{m T} and _{n T,} preferable ones are also same.
R _T4 ′ to R _T6 ′ are synonymous with R _T3 ′.
R _T4 ′ is preferably a hydrogen atom, an alkyl group, an aryl group, or a fluoro group, and more preferably a hydrogen atom.
R _T5 ′ and R _T6 ′ represent a hydrogen atom or are preferably bonded to each other to form a condensed 4- to 7-membered cyclic group, and the condensed 4- to 7-membered cyclic group includes a cycloalkyl group, a cyclo A heteroalkyl group, an aryl group, or a heteroaryl group is more preferable, and an aryl group is still more preferable.
R _T4 ′ to R _T6 ′ may further have a substituent Z, and the substituent Z is preferably an alkyl group, an alkoxy group, a fluoro group, a cyano group, an alkylamino group, or a diarylamino group, and an alkyl group is More preferred.

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

(In the general formula (T-3), R _T3 ′, R _T4 ′, R _T5 ′, R _T6 ′, R _T3 , R _T4 , R _T5, and R _T6 are a hydrogen atom, an alkyl group, an alkenyl group, and an alkynyl group. , —CN, a perfluoroalkyl group, —NR ₂ , a halogen atom, an aryl group, or a heteroaryl group, and may further have a substituent Z.
R _T3 ′, R _T4 ′, R _T5 ′, R _T6 ′, R _T3 , R _T4 , R _T5 and R _T6 are not bonded to each other to form a condensed ring.
Z represents each independently a halogen atom, -R ', -OR', -N (R ') ₂ , -SR', or -CN, and R 'independently represents a hydrogen atom, an alkyl group, or a perhaloalkyl group. Represents an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
(X-Y), _{m T} and _{n T} is in the general formula (T-2) (X- Y), has the same meaning as _{m T} and _{n T,} preferable ones are also same.

  The compound represented by the general formula (T-3) is preferably a compound represented by the following general formula (T-3-1).

_{R T3} in the general formula _{(T-3-1) '~R T6} ', R T3 ~R T6, and _{m T} is, _{R T3} in the general formula _{(T3) '~R T6',} R T3 ~R T6 , And m _T , and preferable examples are also the same.
R _{T7 to} R _T10 have the same _meanings as R _{T3 to} R _T6 . R _T7 ′ to R _T10 ′ are synonymous with R _T3 ′ to R _T6 ′.

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

_{R T3 '~R 6'} in the general formula _{(T-4), R T3} ~R T6, (X-Y), m T and _{n T} is, _{R T3} in the general formula _{(T-2) '~R T6} ' , R _{T3 to} R _T6 , (X—Y), m _T, and n _T , and preferable examples are also the same. R _T7 ′ has the same meaning as R _T3 ′, and preferred ones are also the same.

  Another preferred embodiment of the compound represented by the general formula (T-2) is a compound represented by the following general formula (T-5).

Formula (T-5) in the _{R T3 '~R T7', R} T3 ~R T6, (X-Y), m T and _{n T} is Formula (T-2) in _{R T3 '~R T6'} , R _{T3 to} R _T6 , (X—Y), m _T, and n _T , and preferable examples are also the same.

  One of the preferable forms of the compound represented by the general formula (T-1) is a compound represented by the following general formula (A9).

In general formula (A9), the definitions and preferred ranges of R _{1a to} R _1i are the same as those in R _{3 to} R ₆ in general formula (T-1). The definitions and preferred ranges of X and Y are the same as those in X and Y in the general formula (T-1). n represents an integer of 0 to 3.

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

  The compound illustrated as a compound represented by the said general formula (T-1) is compoundable by the method of Unexamined-Japanese-Patent No. 2009-99783, the various method as described in US Patent 7279232, etc. For example, TR-1 can be synthesized by the method described in US Pat. No. 7,279,232, column 24, line 1 to column 27, line 33 using 2-chloromethylquinoline as a starting material. TG-1 can be synthesized by the method described in US Pat. No. 7,279,232, column 29, line 1 to column 31, line 29 using 2-bromo-3-methylpyridine as a starting material. After synthesis, it is preferable to purify by sublimation purification after purification by column chromatography, recrystallization or the like. By sublimation purification, not only can organic impurities be separated, but inorganic salts and residual solvents can be effectively removed.

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

  The light emitting material in the light emitting layer is contained in an amount of 0.1% by mass to 50% by mass with respect to the total mass of the compound generally forming the light emitting layer in the light emitting layer, but from the viewpoint of durability and external quantum efficiency. The content is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 40% by mass.

  Although the thickness of the light emitting layer is not particularly limited, it is usually preferably 2 nm to 500 nm, more preferably 3 nm to 200 nm, and more preferably 5 nm to 100 nm from the viewpoint of external quantum efficiency. More preferably.

The light emitting layer in the element of the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one kind or two or more kinds. The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Furthermore, the light emitting layer may include a material that does not have charge transporting properties and does not emit light.
The light emitting layer may be a single layer or a multilayer of two or more layers. In addition, each light emitting layer may emit light with different emission colors.

<Host material>
The host material used in the present invention is preferably a compound represented by the general formula (1).
The compound represented by the general formula (1) is a compound capable of transporting both charges of holes and electrons.

As a host material used in the present invention, in addition to the compound represented by the general formula (1), the following compounds may be contained.
Examples of the host material include an electron transport material and a hole transport material, and a charge transport material is preferable. The host material may be one type or two or more types, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed.
For example, pyrrole, indole, carbazole (eg, CBP (4,4′-di (9-carbazoyl) biphenyl)), azaindole, azacarbazole, triazole, oxazole, oxadiazole, pyrazole, imidazole, thiophene, polyarylalkane, Pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone, stilbene, silazane, aromatic tertiary amine compound, styrylamine compound, porphyrin compound, polysilane compound, poly (N-vinyl) Carbazole), aniline copolymer, thiophene oligomer, conductive polymer oligomer such as polythiophene, organic silane, carbon film, pyridine, pyrimidine, triazine, imidazo , Pyrazole, triazole, oxazole, oxadiazol, fluorenone, triphenylene, etc., condensed hydrocarbon aromatic compounds, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide, fluorenylidene Ligands such as methane, distyrylpyrazine, fluorine-substituted aromatic compounds, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, metal complexes of phthalocyanine and 8-quinolinol derivatives, metal phthalocyanine, benzoxazole and benzothiazol And various metal complexes typified by metal complexes and derivatives thereof (which may have a substituent or a condensed ring).

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

  Further, the content of the host compound in the present invention is not particularly limited, but from the viewpoint of light emission efficiency and driving voltage, it is 15% by mass to 95% by mass with respect to the total compound mass forming the light emitting layer. Preferably there is.

[Aromatic hydrocarbon compounds]
The organic electroluminescent element of the present invention preferably has at least one organic layer between the light emitting layer and the cathode, and the organic layer preferably contains an aromatic hydrocarbon compound.
The aromatic hydrocarbon compound is more preferably contained in the organic layer adjacent to the light emitting layer between the light emitting layer and the cathode, but its use is not limited and further contained in any layer in the organic layer. May be. As the introduction layer of the aromatic hydrocarbon compound according to the present invention, any one or more of a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an exciton block layer, and a charge block layer are used. It can contain.
The organic layer adjacent to the light emitting layer between the light emitting layer and the cathode containing the aromatic hydrocarbon compound is preferably a charge blocking layer or an electron transport layer, and more preferably an electron transport layer.

The aromatic hydrocarbon compound is preferably composed of only carbon atoms and hydrogen atoms from the viewpoint of ease of synthesis.
When the aromatic hydrocarbon compound is contained in a layer other than the light emitting layer, it is preferably contained in an amount of 70 to 100% by mass, and more preferably 85 to 100% by mass. When the aromatic hydrocarbon compound is contained in the light emitting layer, it is preferably included in an amount of 0.1 to 99% by mass, more preferably 1 to 95% by mass, and more preferably 10 to 95%, based on the total mass of the light emitting layer. It is more preferable to include the mass%.

As the aromatic hydrocarbon compound, a hydrocarbon compound represented by the following general formula (Tp-1) (hereinafter sometimes simply referred to as “hydrocarbon compound”) is preferable.
The hydrocarbon compound represented by the general formula (Tp-1) is composed of only carbon atoms and hydrogen atoms and is excellent in terms of chemical stability. Therefore, the driving durability is high, and various changes are difficult to occur during high luminance driving. There is an effect.

  The hydrocarbon compound represented by the general formula (Tp-1) preferably has a molecular weight in the range of 400 to 1200, more preferably 400 to 1000, and still more preferably 400 to 800. If the molecular weight is 400 or more, a high-quality amorphous thin film can be formed, and if the molecular weight is 1200 or less, it is preferable in terms of solubility in a solvent, sublimation, and appropriate deposition.

  The use of the hydrocarbon compound represented by the general formula (Tp-1) is not limited, and it may be further contained not only in the organic layer adjacent to the light emitting layer but also in any layer within the organic layer. .

(In General Formula (Tp-1), R ^{12 to} R ²³ are each independently a hydrogen atom, an alkyl group or an alkyl group, a phenyl group which may be substituted with a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, Represents a fluorenyl group, a naphthyl group, or a triphenylenyl group, provided that R ^{12 to} R ²³ are not all hydrogen atoms.)

Examples of the alkyl group represented by R ^{12 to} R ²³ include a substituted or unsubstituted, for example, methyl group, ethyl group, isopropyl group, n-butyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like can be mentioned, preferably methyl group, ethyl group, isopropyl group, tert-butyl group, cyclohexyl group, more preferably methyl group, ethyl group, or A tert-butyl group.

R ^{12 to} R ²³ are preferably an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (these are further an alkyl group, a phenyl group, and a fluorenyl group). More preferably a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, which may be substituted with a group, a naphthyl group, or a triphenylenyl group.
A benzene ring that may be substituted with a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (which may be further substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group); It is particularly preferred.

  The total number of aryl rings in the general formula (Tp-1) is preferably 2 to 8, and preferably 3 to 5. By setting it as this range, a high-quality amorphous thin film can be formed, and solubility in a solvent, sublimation, and deposition suitability are improved.

R ^{12 to} R ²³ each independently preferably has a total carbon number of 20 to 50, and more preferably a total carbon number of 20 to 36. By setting it as this range, a high-quality amorphous thin film can be formed, and solubility in a solvent, sublimation, and deposition suitability are improved.

  In one embodiment of the present invention, the hydrocarbon compound represented by the general formula (Tp-1) is preferably a hydrocarbon compound represented by the following general formula (Tp-2).

(In General Formula (Tp-2), a plurality of Ar ¹ are the same, and a phenyl group, a fluorenyl group, a naphthyl group, which may be substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, Or represents a triphenylenyl group.)

As the alkyl group and alkyl group represented by Ar ¹ , a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group that may be substituted with a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, R ^{12 to} R ²³ It is synonymous with what was mentioned, and a preferable thing is also the same.

  In another aspect of the present invention, the hydrocarbon compound represented by the general formula (Tp-1) is preferably a hydrocarbon compound represented by the following general formula (Tp-3).

(In General Formula (Tp-3), L represents an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a phenyl group optionally substituted with a triphenylenyl group, a fluorenyl group, a naphthyl group, a triphenylenyl group, or a combination thereof. And n represents an integer of 1 to 6.)

The alkyl group, phenyl group, fluorenyl group, naphthyl group, or triphenylenyl group that forms the n-valent linking group represented by L has the same meaning as that described for R ^{12 to} R ²³ .
L is preferably an alkyl group or an n-valent linking group formed by combining a benzene ring, a fluorene ring, or a combination thereof, which may be substituted with a benzene ring.
Although the preferable specific example of L is given to the following, it is not limited to these. In the specific examples, it is bonded to the triphenylene ring by *.

  n is preferably 1 to 5, and more preferably 1 to 4.

  In another embodiment of the present invention, the hydrocarbon compound represented by the general formula (Tp-1) is preferably a hydrocarbon compound represented by the following general formula (Tp-4).

(In General Formula (Tp-4), Ar ² in the case where a plurality thereof is present is the same, and Ar ² represents a group formed by substitution with an alkyl group, phenyl group, naphthyl group, or triphenylenyl group, or a combination thereof. , And q each independently represent 0 or 1, but p and q are not simultaneously 0. When p and q represent 0, Ar ² represents a hydrogen atom.)

Ar ² is preferably a group formed by combining an alkyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, or a triphenylenyl group, and more preferably a combination of a methyl group, a t-butyl group, a phenyl group, or a triphenylenyl group. It is a group consisting of Ar ² is particularly preferably a benzene ring substituted at the meta position with an alkyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, a triphenylenyl group, or a combination thereof.

When the hydrocarbon compound according to the present invention is used as a host material of a light emitting layer of an organic electroluminescent device or a charge transport material of a layer adjacent to the light emitting layer, the energy gap in a thin film state than the light emitting material (the light emitting material is a phosphorescent light emitting material) In the case of ( ₂ ), when the lowest excited triplet (T ₁ ) energy in the thin film state is large, the emission is prevented from being quenched, which is advantageous for improving the efficiency. On the other hand, from the viewpoint of chemical stability of the compound, it is preferable that the energy gap and T ₁ energy are not too large. The T ₁ energy in the film state of the hydrocarbon compound represented by the general formula (Tp-1) is preferably 2.61 eV (62 kcal / mol) or more and 3.51 eV (80 kcal / mol) or less. It is more preferably 69 eV (63.5 kcal / mol) or more and 3.51 eV (75 kcal / mol) or less, and further preferably 2.76 eV (65 kcal / mol) or more and 3.51 eV (70 kcal / mol) or less. In particular, when a phosphorescent light emitting material is used as the light emitting material, the T ₁ energy is preferably in the above range.

  The glass transition temperature (Tg) of the hydrocarbon compound according to the present invention is 80 ° C. or more and 400 ° C. or less from the viewpoint of stably operating the organic electroluminescence device against heat generation during high temperature driving or during device driving. The temperature is preferably 100 ° C. or higher and 400 ° C. or lower, more preferably 120 ° C. or higher and 400 ° C. or lower.

  Although the specific example of the hydrocarbon compound concerning this invention is illustrated below, this invention is not limited to these.

The compounds exemplified as the hydrocarbon compounds according to the present invention include those described in International Publication No. 05/013388, International Publication No. 06/130598, International Publication No. 09/021107, US2009 / 0009065, International Publication No. 09 / It can be synthesized by the methods described in the 008311 pamphlet and the international publication 04/018587 pamphlet.
After synthesis, it is preferable to purify by sublimation purification after purification by column chromatography, recrystallization or the like. By sublimation purification, not only can organic impurities be separated, but inorganic salts and residual solvents can be effectively removed.

In the light-emitting device of the present invention, the hydrocarbon compound is contained in an organic layer adjacent to the light-emitting layer between the light-emitting layer and the cathode, but the use thereof is not limited, and the hydrocarbon compound is further added to any layer in the organic layer. It may be contained. As the introduction layer of the hydrocarbon compound according to the present invention, contained in one or more of the light emitting layer, the hole injection layer, the hole transport layer, the electron transport layer, the electron injection layer, the exciton block layer, the charge block layer can do.
The organic layer adjacent to the light emitting layer between the light emitting layer containing the hydrocarbon compound and the cathode is preferably a charge blocking layer or an electron transport layer, and more preferably an electron transport layer.

The light emitting device of the present invention preferably contains at least one organic layer between the light emitting layer and the cathode, and the organic layer contains at least one compound represented by the following general formula (O-1). preferable.
General formula (O-1) is demonstrated.

(In the formula, R ^O1 represents an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ^O1 may be the same or different. A ^{O1 to} A ^O4 each independently represent C—R ^A or N. R ^A represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ^A may be the same or different, and L ^O1 includes at least one of an aryl ring and a heteroaryl ring. The divalent to hexavalent linking group is represented by n ^O1 represents an integer of 2 to 6.)

R ^O1 represents an alkyl group, an aryl group, or a heteroaryl group.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. For example, methyl, ethyl, isopropyl, tert-butyl, n-octyl, n -Decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.
The aryl group may be condensed or may have a substituent. Preferably it is a C6-C30 aryl group, More preferably, it is a C6-C18 aryl group. For example, a phenyl group, a biphenyl group, a naphthyl group, etc. are mentioned. Examples of the substituent in the case of having a substituent include the above-described substituent group A, and the substituent group A includes an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and 6 to 14 carbon atoms. An aryl group having 4 to 13 carbon atoms, an amino group having 0 to 12 carbon atoms, a cyano group, and a fluoro group, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and carbon. A heteroaryl group having 5 to 9 carbon atoms, an amino group having 2 to 12 carbon atoms, and a cyano group are more preferable. A methyl group, a t-butyl group, a phenyl group, a methylphenyl group, a dimethylphenyl group, a pyridyl group, a dimethylamino group, A diphenylamino group and a cyano group are more preferable, a methyl group, a phenyl group, and a cyano group are particularly preferable, and a methyl group and a phenyl group are most preferable.
The heteroaryl group may be condensed and may have a substituent. Preferably, it is a heteroaryl group having 4 to 12 carbon atoms, more preferably a 5- or 6-membered heteroaryl group, for example, pyridyl group, pyrazinyl group, pyridazinyl group, pyrimidinyl group, triazinyl group, quinolinyl group, Isoquinolinyl group, quinazolinyl group, cinnolinyl group, 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, thiazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, thiadiazolyl, isoxazolyl, benzisoxazolyl, pyrrolidinyl, piperidinyl, piperazinyl, imida Lysinyl group, carbazolyl group, thiazolinyl group, and a sulfolanyl group. Examples of the substituent in the case of having a substituent include the above-described substituent group A, and the substituent group A includes an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and 6 to 14 carbon atoms. An aryl group having 4 to 13 carbon atoms, an amino group having 0 to 12 carbon atoms, a cyano group, and a fluoro group, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and carbon. A heteroaryl group having 5 to 9 carbon atoms, an amino group having 2 to 12 carbon atoms, and a cyano group are more preferable. A methyl group, a t-butyl group, a phenyl group, a methylphenyl group, a dimethylphenyl group, a pyridyl group, a dimethylamino group, A diphenylamino group and a cyano group are more preferable, a methyl group, a phenyl group, and a cyano group are particularly preferable, and a methyl group and a phenyl group are most preferable.

From the viewpoint of device durability, R ^O1 is preferably an aryl group or a heteroaryl group, more preferably an aryl group. Among the aryl groups, a substituted or unsubstituted phenyl group or a naphthyl group is preferable, a substituted or unsubstituted phenyl group is more preferable, and a phenyl group substituted with an alkyl group or an aryl group is more preferable. Among the phenyl groups substituted with an alkyl group or an aryl group, a methyl group, a t-butyl group, a phenyl group, or a phenyl group substituted with a methylphenyl group is preferred, and a methyl group or a phenyl group substituted with a phenyl group is more preferred. More preferred are 2-methylphenyl group and 2-phenylphenyl group, and most preferred is 2-phenylphenyl group.

A ^{O1 to} A ^O4 each independently represent C—R ^A or a nitrogen atom. Of A ^{O1 to} A ^O4 , 0 to 2 are preferably nitrogen atoms, and 0 or 1 is more preferably a nitrogen atom. Or A ^O1 to A ^O4 all are ^{C-R A,} or ^{A O1} be a nitrogen atom, and is preferably ^A O2 ^{to A O4} is ^{C-R A, A O1} be a nitrogen atom, and ^{A O2} It is more preferable that ^{˜A O4} is C—R ^A , A ^O1 is a nitrogen atom, A ^{O2 to} A ^O4 are C—R ^A , and R ^A is all preferably a hydrogen atom.

L ^O1 represents a divalent to hexavalent linking group comprising an aryl ring and a heteroaryl ring. L ^O1 is preferably an arylene group, heteroarylene group, aryltriyl group, heteroaryltriyl group, more preferably a phenylene group, a biphenylene group, a benzenetriyl group, a pyridinediyl group, a fluorenediyl group, a dibenzofuran. Diyl group and carbazolediyl, more preferably phenylene group, biphenylene group and benzenetriyl group, particularly preferably biphenylene group and benzenetriyl group, most preferably 3,3′-biphenylene group, benzene- 1,3,5-triyl group. L ^O1 may have a substituent, and the substituent is preferably an alkyl group, an aryl group, or a cyano group, more preferably a methyl group, a phenyl group, or a cyano group, and a phenyl group or a cyano group is preferable. Specific examples of L ^O1 include the following.

n ^O1 is an integer of 2 to 6, preferably 2 to 4, more preferably 2 to 3, most preferably from the viewpoint of device efficiency, and most preferably 3 from the viewpoint of device durability. It is.
The compound represented by the general formula (O-1) is more preferably a compound represented by the general formula (O-2).

(Wherein R ^O1 represents an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ^O1 may be the same or different. R ^{O2 to} R ^O4 are a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. A ^{O1 to} A ^O4 each independently represent C—R ^A or N. R ^A represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ^A may be the same or different. good.)

R ^O1 and A ^{O1 to} A ^O4 have the same ^meanings as those in General Formula (O-1), and preferred ranges thereof are also the same. R ^{02 to} R ⁰⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a heteroaryl group having 4 to 13 carbon atoms, preferably a hydrogen atom or 1 carbon atom. Is an alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, more preferably a hydrogen atom or an aryl group having 6 to 14 carbon atoms, still more preferably a hydrogen atom or a phenyl group, most preferably a hydrogen atom. It is.

  The compound represented by the general formula (O-1) has a glass transition temperature (Tg) of 80 ° C. from the viewpoint of stable operation at high temperature storage, stable operation against high temperature driving, and heat generation during driving. It is preferably ˜300 ° C., more preferably 100 ° C. to 300 ° C., further preferably 120 ° C. to 300 ° C., and further preferably 130 ° C. to 300 ° C.

  The compound represented by the general formula (O-1) can be synthesized by the method described in JP-A No. 2001-335776. After synthesis, purification by column chromatography, recrystallization, reprecipitation, etc., followed by purification by sublimation is preferred. Not only can organic impurities be separated by sublimation purification, but inorganic salts, residual solvents, moisture, and the like can be effectively removed.

  In the light emitting device of the present invention, the compound represented by the general formula (O-1) is preferably contained in an organic layer between the light emitting layer and the cathode, but may be contained in a layer adjacent to the light emitting layer. More preferred. When the compound represented by the general formula (O-1) is contained in the organic layer between the light emitting layer and the cathode, it is preferably contained in an amount of 70 to 100% by mass, more preferably 85 to 100% by mass. .

  Specific examples of the compound represented by the general formula (O-1) are shown below, but the present invention is not limited thereto.

  The compound represented by the general formula (O-1) can be synthesized by the method described in JP-A No. 2001-335776. After synthesis, purification by column chromatography, recrystallization, reprecipitation, etc., followed by purification by sublimation is preferred. Not only can organic impurities be separated by sublimation purification, but inorganic salts, residual solvents, moisture, and the like can be effectively removed.

  In the light emitting device of the present invention, the compound represented by the general formula (O-1) is preferably contained in an organic layer between the light emitting layer and the cathode, but may be contained in a layer adjacent to the light emitting layer. More preferred.

(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. Specific examples include a hole injection layer, a hole transport layer, an electron block layer, a light emitting layer, a hole block layer, an electron transport layer, and an electron injection layer. A hole injection layer, a hole transport layer, an electron blocking layer, or a light emitting layer is preferable. If the charge transport layer formed by the coating method is a hole injection layer, a hole transport layer, an electron block layer, or a light emitting layer, it is possible to produce an organic electroluminescent element with low cost and high efficiency. 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.
In the present invention, the organic layer preferably includes a hole injection layer or a hole transport layer containing an electron-accepting dopant.

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

The hole injection layer, the hole transport layer, the electron injection layer, and the electron 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. Can be applied to.
The hole injection layer, the hole transport layer, the electron injection layer, and the electron transport layer are described in detail in paragraphs [0165] to [0167] of Japanese Patent Application Laid-Open No. 2008-270736. The matter can be applied to the present invention.

(Hole blocking layer)
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic layer adjacent to the light emitting layer on the cathode side.
As an example of the organic compound constituting the hole blocking layer, in addition to the compound represented by the general formula (1) in the present invention, aluminum (III) bis (2-methyl-8-quinolinato) 4-phenylphenolate ( Aluminum complexes such as Aluminum (III) bis (2-methyl-8-quinolinato) 4-phenylphenolate (abbreviated as BAlq)), triazole derivatives, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline ( Phenanthroline derivatives such as 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (abbreviated as BCP)) and the like.
The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm.
The hole blocking layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.

(Electronic block layer)
The electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side. In the present invention, an electron blocking layer can be provided as an organic layer adjacent to the light emitting layer on the anode side.
As an example of the organic compound constituting the electron blocking layer, for example, those mentioned as the hole transport material described above can be applied.
The thickness of the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
The electron blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

(Protective layer)
In the present invention, the entire organic EL element may be protected by a protective layer.
As a material contained in the protective layer, any material may be used as long as it has a function of preventing materials that promote device deterioration such as moisture and oxygen from entering the device.
Regarding the protective layer, the matters described in paragraph numbers [0169] to [0170] of JP-A-2008-270736 can be applied to the present invention.

(Sealing container)
The element of this invention may seal the whole element using a sealing container.
Regarding the sealing container, the matters described in paragraph No. [0171] of JP-A-2008-270736 can be applied to the present invention.
Further, a moisture absorbent or an inert liquid may be sealed in a space between the sealing container and the light emitting element. Although it does not specifically limit as a moisture absorber, For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride Cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, magnesium oxide and the like. The inert liquid is not particularly limited, and examples thereof include fluorinated solvents such as paraffins, liquid paraffins, perfluoroalkanes, perfluoroamines, perfluoroethers, chlorinated solvents, and silicone oils. It is done.

(Drive)
The organic electroluminescence device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. Can be obtained.
The driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-2441047. The driving methods described in each publication, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6,023,308 can be applied.

The external quantum efficiency of the organic electroluminescent element of the present invention is preferably 5% or more, more preferably 7% or more. The value of the external quantum efficiency should be the maximum value of the external quantum efficiency when the device is driven at 20 ° C., or the value of the external quantum efficiency near 100 to 300 cd / m ² when the device is driven at 20 ° C. Can do.

  The internal quantum efficiency of the organic electroluminescence device of the present invention is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more. The internal quantum efficiency of the device is calculated by dividing the external quantum efficiency by the light extraction efficiency. In a normal organic EL element, the light extraction efficiency is about 20%. However, the shape of the substrate, the shape of the electrode, the thickness of the organic layer, the thickness of the inorganic layer, the refractive index of the organic layer, the refractive index of the inorganic layer, etc. By devising it, it is possible to increase the light extraction efficiency to 20% or more.

The organic electroluminescent element of the present invention preferably has a maximum emission wavelength (maximum intensity wavelength of emission spectrum) of 350 nm to 700 nm, more preferably 450 nm to 600 nm, still more preferably 470 nm to 580 nm, particularly preferably. It is 490 nm or more and 550 nm or less _.

(Use of light-emitting element of the present invention)
The light-emitting element of the present invention can be suitably used for light-emitting devices, pixels, display elements, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like. . In particular, it is preferably used for a device driven in a region having a high light emission luminance such as a lighting 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 the present invention uses the organic electroluminescent element.
FIG. 2 is a cross-sectional view schematically showing an example of the light emitting device of the present invention.
The light emitting device 20 in FIG. 2 includes a transparent substrate (supporting substrate) 2, an organic electroluminescent element 10, a sealing container 11, and the like.

The organic electroluminescent device 10 is configured by sequentially laminating an anode (first electrode) 3, an organic layer 11, and a cathode (second electrode) 9 on a substrate 2. A protective layer 12 is laminated on the cathode 9, and a sealing container 16 is provided on the protective layer 12 with an adhesive layer 14 interposed therebetween. In addition, a part of each electrode 3 and 9, a partition, an insulating layer, etc. are abbreviate | omitted.
Here, as the adhesive layer 14, a photocurable adhesive such as an epoxy resin or a thermosetting adhesive can be used, and 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, in addition to a lighting device, a display device such as a television, a personal computer, a mobile phone, and electronic paper can be used.

(Lighting device)
Next, an illumination device according to an embodiment of the present invention will be described with reference to FIG.
FIG. 3 is a cross-sectional view schematically showing an example of a lighting device according to an embodiment of the present invention.
As shown in FIG. 3, the illumination device 40 according to the embodiment of the present invention includes the organic EL element 10 and the light scattering member 30 described above. More specifically, the lighting 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. In FIG. 3, the light scattering member 30 is a member in which fine particles 32 are dispersed on a transparent substrate 31. As the transparent substrate 31, for example, a glass substrate can be preferably cited. As the fine particles 32, transparent resin fine particles can be preferably exemplified. As the glass substrate and the transparent resin fine particles, known ones can be used. In such an illuminating device 40, when light emitted from the organic electroluminescent element 10 is incident on the light incident surface 30A of the scattering member 30, the incident light is scattered by the light scattering member 30, and the scattered light is emitted from the light emitting surface 30B. It is emitted as illumination light.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In particular, the presence or absence of a substituent hardly affects the effect of the present invention, and the same effect can be obtained even if the compound used in the following examples has a substituent.
[Synthesis Example 1]
[Synthesis of Compound (a-01) of Reference Example ]

Synthesis of Compound (1) Under nitrogen, 61.45 g of carbazole and 200 ml of 1,3-dimethyl-2-imidazolidinone (hereinafter abbreviated as DMI) were placed in a three-necked flask, and 20 g of sodium hydride (60% oily) was added. Gradually added. The mixture was stirred for 30 minutes, 61.25 g of 3-bromofluorobenzene was added dropwise, and the mixture was stirred at 110 ° C. for 6 hours. Water was added to the reaction solution, and extraction was performed with ethyl acetate. The obtained oil layer was concentrated with an evaporator, and the residue was purified with a silica gel column. 57.5 g (yield 50.8%) of the target compound (1) was obtained. ¹ H-NMR (300 MHz, in CDCl ₃ ): δ (ppm) = 7.28-7.33 (m, 2H), 7.39-7.62 (m, 7H), 7.75 (s, 1H ), 8.14 (d, J = 3.9 Hz, 2H)

Synthesis of Compound (2) Under nitrogen, 57.5 g of Compound (1) and 500 ml of tetrahydrofuran (THF) were placed in a three-necked flask and cooled to −60 ° C. or lower using a dry ice-acetone bath. After 117 ml of 1.6M n-butyllithium hexane solution was added dropwise, the mixture was stirred for 30 minutes, and further 39.8 g of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added and stirred. While returning to room temperature. Water was added to the reaction solution, and extraction was performed with ethyl acetate. The obtained oil layer was concentrated with an evaporator, and the residue was purified with a silica gel column. 33.5 g (yield 51%) of the target compound (2) was obtained. ¹ H-NMR (300 MHz, in CDCl ₃ ): δ (ppm) = 1.35 (s, 12H), 7.27 (t, J = 8.1 Hz, 2H), 7.35-7.43 (m , 4H), 7.60-7.63 (m, 1H), 7.89 (d, J = 6.6 Hz, 1H), 7.98 (s, 1H), 8.14 (d, J = 7 .2Hz, 1H)

Synthesis of Compound (3) Under nitrogen, 9.2 g of carbazole and 30 ml of DMI were placed in a three-necked flask, and 2.4 g of sodium hydride (60% oily) was gradually added. The mixture was stirred for 30 minutes, 10 g of 3-bromofluorobenzonitrile was added dropwise, and the mixture was stirred at 80 ° C. for 6 hours. Water was added to the reaction solution, and extraction was performed with ethyl acetate. The obtained oil layer was concentrated with an evaporator, and the residue was purified with a silica gel column. 9.8 g (yield 56%) of the target compound (3) was obtained. ¹ H-NMR (300 MHz, in DMSO-d ₆ ): δ (ppm) = 7.31-7.35 (m, 2H), 7.45 (d, J = 3 Hz, 1H), 8.25-8 .27 (m, 4H), 8.33 (d, J = 2.1 Hz, 1H)

Synthesis of Reference Example Compound (a-01) In a three-necked flask under nitrogen, 7.4 g of Compound (2), 7.0 g of Compound (3), 0.12 g of palladium acetate, 0.52 g of triphenylphosphine, sodium carbonate 10.6 g, 1,2-dimethyloxyethane 200 ml, and water 200 ml were added and stirred at 80 ° C. for 3 hours. Water was added to the reaction solution, and the precipitate was filtered off. The precipitate was purified with a silica gel column. 8.2 g (yield 81%) of the compound (a-01) of the target reference example was obtained. 1H-NMR (300 MHz, in DMSO-d6): δ (ppm) = 7.31 (dt, J = 9.3, 5.4 Hz, 4H), 7.41-7.49 (m, 3H), 7 .53 (d, J = 6.3 Hz, 1H), 7.71 (d, J = 6.0 Hz, 1H), 7.81 (t, J = 5.8 Hz, 1H), 8.05 (d, J = 6.0 Hz, 1H), 8.21-8.22 (m, 2H), 8.25 (d, J = 6.0 Hz, 2H), 8.45 (s, 1H), 8.50 ( s, 1H)

[Synthesis Example 2]
[Synthesis of Compound (a-02) of Reference Example ]

Synthesis of Reference Example Compound (a-02) 2.78 g of compound (3), bis (pinacolato) diboron 1.
02 g, 27 mg of palladium acetate, 1.18 g of potassium acetate and 20 ml of N, N-dimethylformamide (DMF) were added, and the mixture was stirred at 80 ° C. for 2 hours. Thereafter, 1.96 g of cesium carbonate, 27 mg of palladium acetate and 0.22 g of triphenylphosphine were added, and the mixture was stirred at 80 ° C. for 3 hours. Water was added to the reaction solution, and the precipitate was filtered off. 1.51 g (yield 70%) of the target compound (a-02) was obtained. 1H-NMR (400 MHz, in DMSO-d6): δ (ppm) = 7.32 (t, J = 7.2 Hz, 4H), 7.45 (t, J = 7.6 Hz, 4H), 7.56 (D, J = 9.6 Hz, 4H), 8.26 (d, J = 7.6 Hz, 4H), 8.61 (s, 4H)

[Synthesis of Compound (a-20) of Reference Example ]

Synthesis of Reference Example Compound (a-20) In a three-necked flask under nitrogen, 3.52 g of compound (4), bis (pinacolato) diboron 1.
27 g, 33 mg of palladium acetate, 1.47 g of potassium acetate, and 25 ml of DMF were added, and the mixture was stirred at 80 ° C. for 2 hours. Thereafter, 2.44 g of cesium carbonate, 33 mg of palladium acetate, and 0.27 g of triphenylphosphine were added, and the mixture was stirred at 80 ° C. for 3 hours. Water was added to the reaction solution, and the precipitate was filtered off. 2.05 g (yield 74%) of the target compound (a-20) was obtained. 1H-NMR (400 MHz, in DMSO-d6): δ (ppm) = 7.32 (t, J = 7.2 Hz, 4H), 7.45 (t, J = 7.6 Hz, 4H), 7.50 (D, J = 8.4 Hz, 4H), 8.07 (s, 2H), 8.27 (d, J = 8.0 Hz, 4H), 8.46 (s, 2H), 8.58 (s , 2H)

[Synthesis of Compound (a-38)]

Synthesis of Compound (a-38) Under nitrogen, 3.40 g of compound (5), 1.27 g of bis (pinacolato) diboron, 33 mg of palladium acetate, 1.47 g of potassium acetate, and 25 ml of DMF were added to 80 ° C. Stir for 2 hours. Thereafter, 2.44 g of cesium carbonate, 33 mg of palladium acetate, and 0.27 g of triphenylphosphine were added, and the mixture was stirred at 80 ° C. for 3 hours. Water was added to the reaction solution, and the precipitate was filtered off. 1.63 g (yield 63%) of the target compound (a-38) was obtained. ¹ H-NMR (400 MHz, in DMSO-d ₆ ): δ (ppm) = 7.30 (t, J = 7.2 Hz, 4H), 7.40-7.51 (m, 10H), 7. 57 (d, J = 8.4 Hz, 4H), 7.92 (d, J = 6.8 Hz, 4H), 8.22 (s, 2H), 8.26 (d, J = 7.6 Hz, 4H) ), 8.30 (s, 2H)

[Example 1]
[Production of element]
A glass substrate having a thickness of 0.5 mm and a 2.5 cm square ITO film (manufactured by Geomat Co., Ltd., surface resistance 10 Ω / □) is placed in a cleaning container, ultrasonically cleaned in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. Went. The following organic compound layers were sequentially deposited on the transparent anode (ITO film) by vacuum deposition.
First layer: CuPc: film thickness 10 nm
Second layer: NPD: film thickness 30 nm
Third layer: compounds a-01 and GD-1 (mass ratio 85:15) of reference example : film thickness 30 nm
Fourth layer: Materials shown in the table: Film thickness 5 nm
Fifth layer: ET-1: Film thickness 45 nm
On this, 1 nm of lithium fluoride and 100 nm of metal aluminum were vapor-deposited in this order, and it was set as the cathode.

This laminated body is put in a glove box substituted with nitrogen gas without being exposed to the atmosphere, and sealed with a glass sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.). Then, an organic electroluminescent element was obtained.
As a result of light emission of these elements, light emission derived from the light emitting material was obtained for each element.

(Performance evaluation of organic electroluminescence device)
Each element obtained was evaluated from the viewpoint of drive voltage, external quantum efficiency, durability, and chromaticity change at the time of increase from DC current density of 0.25 mA / cm ² to 25 mA / cm ² . Various measurements were performed as follows. The results are shown in Table 1. In Tables 3 to 6 and 9 to 17 below, a-01 to a-03, a-05, a-07, a-10 and a-20 are the compounds of Reference Examples a-01 to a-, respectively. It shall be read as 03, a-05, a-07, a-10, a-20.

(A) Drive voltage The applied voltage of each element at a DC current density of ^2.5 mA / cm ² is used as an index for evaluating the drive voltage. In Table 1, the value of the element 1-1 is shown, and in Table 2, the value of the element 2-1 is shown. In Table 3, the value of the comparison element 3-1, in Table 4, the value of the comparison element 4-1, in Table 5, the value of the comparison element 5-1, and in Table 6, the comparison element 6- The value of 1 in Table 7, the value of element 7-1 in Table 8, the value of element 8-1 in Table 8, the value of comparison element 9-1 in Table 9, the element 10-1 in Table 10 Of Table 11, the value of the comparison element 11-1, the value of the comparison element 12-1 in Table 12, the value of the comparison element 13-1 in Table 13, and the comparison element 14 in Table 14. −1, the value of the comparison element 15-1 in Table 15, and the comparison element 16-in Table 16 The values were respectively based on the value of the comparison element 17-1 in Table 17, and evaluated by the following criteria and expressed as a relative value in each table. The drive voltage is most preferably ◎.
◎: When the voltage drops by 1V or more ○: When the voltage drops by 0.5V or more and less than 1V △: When the voltage drops by 0V or more and less than 0.5V ×: When the drive voltage increases

(B) External quantum efficiency Using a source measure unit 2400 manufactured by Toyo Technica, a DC voltage was applied to each element to emit light, and the luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation. The emission spectrum and emission wavelength were measured using a spectrum analyzer PMA-11 manufactured by Hamamatsu Photonics. Based on these, the external quantum efficiency with a luminance near 1500 cd / m ² is calculated by the luminance conversion method. In Table 1, the value of the element 1-1 is shown, in Table 2, the value of the element 2-1 is shown in Table 3. Represents the value of the comparison element 3-1, the value of the comparison element 4-1 in Table 4, the value of the comparison element 5-1 in Table 5, the value of the comparison element 6-1 in Table 6, 7 shows the value of the element 7-1, Table 8 shows the value of the element 8-1, Table 9 shows the value of the comparison element 9-1, Table 10 shows the value of the element 10-1, In Table 12, the value of the comparison element 12-1 in Table 12, the value of the comparison element 13-1 in Table 13, the value of the comparison element 14-1 in Table 14, In Table 15, the value of the comparison element 15-1, and in Table 16, the value of the comparison element 16-1, 17, the value of the comparison element 17-1 was used as a standard, and the evaluation was performed according to the following standard. The external quantum efficiency is most preferably ◎.
◎: When increased by 3% or more ○: When increased by 1% or more and less than 3% △: When increased by 0% or more and less than 1% ×: When external quantum efficiency decreases

(C) Durability Each element was continuously caused to emit light by applying a DC voltage so that the luminance was 2000 cd / m ² , and the time required until the luminance became 1500 cd / m ² was used as an index of durability. In Table 2, the value of element 2-1 in Table 2, the value of comparison element 3-1 in Table 3, the value of comparison element 4-1 in Table 4, and the value of Table 5 In Table 6, the value of Comparative Element 6-1 in Table 6, the value of Element 7-1 in Table 7, the value of Element 8-1 in Table 8, and the value of Table 9 In Table 10, the value of the comparison element 9-1, in Table 10, the value of the element 10-1, in Table 11, the value of the comparison element 11-1, in Table 12, the value of the comparison element 12-1, 13 shows the value of the comparison element 13-1, Table 14 shows the value of the comparison element 14-1, and Table 15 shows the value. In Table 16, the value of the comparison element 15-1, the value of the comparison element 16-1 in Table 16, and the value of the comparison element 17-1 in Table 17 are evaluated based on the following criteria, respectively. Shown as a relative value. The durability is most preferably ◎.
◎: When it is 2 times or more ○: When it is 1.5 times or more and less than 2 times △: When it is 1.2 times or more and less than 1.5 times ×: When it is less than 1.2 times

(D) Change in chromaticity when the DC current density is increased from 0.25 mA / cm ² to 25 mA / cm ^{2 When} each element is caused to emit light by applying a DC voltage so that the DC current density is 0.25 mA / cm ^2. Chromaticity (x, y) and chromaticity (x, y) when a direct current voltage was applied to emit light such that the direct current density was 25 mA / cm ² were measured. The absolute value of the difference between the x value and the y value of the two was expressed in the form of (Δx, Δy) and used as an index of chromaticity change. Evaluation was performed according to the following criteria, and the relative values are shown in Tables 3-17. Smaller values of Δx and Δy are preferable.
◎: Less than 0.003 ○: 0.003 or more and less than 0.006 △: 0.006 or more and less than 0.010 ×: 0.010 or more

[Example 2]
The compound a-01 of the reference example of the third layer in Example 1 was changed to the compound a-02 of the reference example , ET-1 of the fifth layer was changed to ET-2, and the material of the fourth layer is shown in Table 2. Elements 2-1 to 2-5 were produced in the same manner as in Example 1 except that the material was changed to the described fourth layer material.

Example 3
The compound a-01 of the reference example of the third layer in Example 1 was changed to the host material described in Table 3, GD-1 was changed to GD-2, and the fourth layer material was changed to ET-4. Were produced in the same manner as in Example 1, and Comparative Elements 3-1, 3-2 and Elements 3-1 to 3-8 were produced.

Example 4
Comparative element in the same manner as in Example 1 except that the compound a-01 of the reference example of the third layer in Example 1 was changed to the host material shown in Table 4 and the material of the fourth layer was changed to ET-6. 4-1 and elements 4-1 to 4-5 were produced.

Example 5
Compound a-01 of the reference example of the third layer in Example 1 was changed to the host material shown in Table 5, the fourth layer material was changed to ET-7, and ET-1 of the fifth layer was changed to ET-2 Comparative element 5-1 and elements 5-1 to 5-3 were produced in the same manner as in Example 1 except that the above was changed.

Example 6
The compound a-01 of the reference example of the third layer in Example 1 was changed to the host material described in Table 6, GD-1 was changed to BD-1, and the fourth layer material was changed to ET-5. Comparative element 6-1 and elements 6-1, 6-2, and 6-3 were fabricated in the same manner as in Example 1 except that ET-1 of the fifth layer was changed to ET-2.

Example 7
Except for changing GD-1 of the third layer in Example 1 to the dopant materials described in Table 7, changing the fourth layer material to ET-4, and changing ET-1 of the fifth layer to ET-2 In the same manner as in Example 1, the device 7-1 and the device 7-2 were manufactured.

Example 8
The GD-1 of the third layer in Example 1 is changed to the dopant material described in Table 7, the compound a-01 of the reference example is changed to a-38, the fourth layer material is changed to ET-4, Element 8-1 and element 8-2 were produced in the same manner as in Example 1 except that ET-1 of the fifth layer was changed to ET-2.

Example 9
The CuPc of the first layer in Example 1 was changed to GD-2, the compound a-01 of the reference example of the third layer was changed to the host material shown in Table 9, and GD-1 was changed to GD-2. Comparative element 9-1, element 9-1 and element 9-2 were produced in the same manner as in Example 1 except that the fourth layer material was changed to the fourth layer material shown in Table 9.

Example 10
The CuPc of the first layer in Example 1 was changed to GD-2, the compound a-01 of the reference example of the third layer was changed to the host material shown in Table 10, and GD-1 was changed to GD-2. Comparative element 10-1, element 10-1, and element 10-2 were produced in the same manner as in Example 1 except that the fourth layer material was changed to the fourth layer material shown in Table 10.

Example 11
The CuPc of the first layer in Example 1 was changed to GD-2, the compound a-01 of the reference example of the third layer was changed to the host material described in Table 11, and GD-1 was changed to GD-4. Comparative element 11-1 and element 11-1 were produced in the same manner as in Example 1 except that the fourth layer material was changed to OM-8.

Example 12
The CuPc of the first layer in Example 1 was changed to GD-2, the compound a-01 of the reference example of the third layer was changed to the host material shown in Table 12, and GD-1 was changed to BD-2. Comparative element 12-1 and element 12-1 were produced in the same manner as in Example 1 except that the fourth layer material was changed to OM-8.

Example 13
The CuPc of the first layer in Example 1 was changed to GD-2, the compound a-01 of the reference example of the third layer was changed to the host material shown in Table 13, and GD-1 was changed to RD-1. Comparative element 13-1 and element 13-1 were produced in the same manner as in Example 1 except that the fourth layer material was changed to OM-8.

Example 14
The CuPc of the first layer in Example 1 was changed to GD-2, the compound a-01 of the reference example of the third layer was changed to the host material described in Table 14, and GD-1 was changed to GD-4. Comparative element 14-1 and element 14-1 were produced in the same manner as in Example 1 except that the fourth layer material was changed to OM-5.

Example 15
The CuPc of the first layer in Example 1 was changed to GD-2, the compound a-01 of the reference example of the third layer was changed to the host material shown in Table 15, and GD-1 was changed to BD-2. Comparative element 15-1 and element 15-1 were produced in the same manner as in Example 1 except that the fourth layer material was changed to OM-5.

Example 16
The CuPc of the first layer in Example 1 was changed to GD-2, the compound a-01 of the reference example of the third layer was changed to the host material described in Table 16, and GD-1 was changed to RD-1. Comparative element 16-1 and element 16-1 were produced in the same manner as in Example 1 except that the fourth layer material was changed to OM-5.

Example 17
In Example 1, the first layer CuPc was changed to GD-2, the third layer reference example compound a-01 was changed to the host material shown in Table 17, and GD-1 was changed to RD-1. The fourth layer material was changed to the fourth layer material described in Table 17, and ET-1 was changed to OM-5, and in the same manner as in Example 1, the comparison element 17-1, the element 17-1, and Element 17-2 was produced.

DESCRIPTION OF SYMBOLS 2 ... Substrate 3 ... Anode 4 ... Hole injection layer 5 ... Hole transport layer 6 ... Light emitting layer 7 ... Hole block layer 8 ... Electron transport layer 9 ... -Cathode 10-Organic electroluminescent element 11-Organic layer 12-Protective layer 14-Adhesive layer 16-Sealing container 20-Light-emitting device 30-Light scattering member 30A- ..Light incident surface 30B ... Light emitting surface 31 ... Transparent substrate 32 ... Particulate 40 ... Lighting device

Claims (12)

An organic electroluminescence device having a pair of electrodes composed of an anode and a cathode and an organic layer including a light emitting layer between the electrodes on a substrate, wherein at least one layer of the organic layer is represented by the following general formula (1). An organic electroluminescent device containing at least one compound to be produced.
(In the general formula (1), R _{11 to} R ₁₄ each independently represents an aryl group, a heteroaryl group or a cyano group. R ₁₅ represents an electron-withdrawing group. However, not all R ₁₅ have Hammett's substituent constant σp value of 0.2 or more, and all R ₁₅ are phenyl groups , pyridyl-substituted phenyl groups. Or a carbazolyl-substituted phenyl group , n represents 1 or 2, n ₁ independently represents an integer of 0 to 4, n ₂ represents an integer of 1 to 4, and when there are a plurality, (It may be the same integer or different integers.) The organic electroluminescent element according to claim 1, wherein n ₁ represents 0.   The organic electroluminescent element of Claim 1 or 2 which contains at least 1 of the compound represented by the said General formula (1) in the said light emitting layer.   The organic electroluminescent element according to claim 3, wherein the light emitting layer further contains at least one phosphorescent metal complex.   The organic electroluminescent element according to claim 4, wherein the metal complex is an iridium complex.   The organic electroluminescent element according to any one of claims 1 to 5, further comprising at least one organic layer between the light emitting layer and the cathode, wherein the organic layer contains an aromatic hydrocarbon compound. The organic light-emitting device according to claim 1, further comprising at least one organic layer between the light emitting layer and the cathode, wherein the organic layer contains at least one compound represented by the following general formula (O-1). 2. The organic electroluminescent element according to item 1.
(In the formula, R ⁰¹ represents an alkyl group, an aryl group, or a heteroaryl group, and the plurality of R ^O1 may be the same or different. A ^{01 to} A ⁰⁴ are each independently C—R ^A or a nitrogen atom. R ^A represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and when there are a plurality of them, they may be the same or different from each other L ⁰¹ is at least one of an aryl ring and a heteroaryl ring (Represents a divalent to hexavalent linking group comprising a seed, and n ⁰¹ represents an integer of 2 to 6.)   The organic electroluminescent element according to claim 1, wherein at least one of the organic layers is formed by a solution coating process. A charge transport material represented by the following general formula (1).
(In the general formula (1), R _{11 to} R ₁₄ each independently represents an aryl group, a heteroaryl group or a cyano group. R ₁₅ represents an electron-withdrawing group. However, not all R ₁₅ have Hammett's substituent constant σp value of 0.2 or more, and all R ₁₅ are phenyl groups , pyridyl-substituted phenyl groups. Or a carbazolyl-substituted phenyl group , n represents 1 or 2, n ₁ independently represents an integer of 0 to 4, n ₂ represents an integer of 1 to 4, and when there are a plurality, (It may be the same integer or different integers.)   A light emitting layer containing the charge transport material according to claim 9.   The display apparatus using the organic electroluminescent element of any one of Claims 1-8.   The illuminating device using the organic electroluminescent element of any one of Claims 1-8.