JP5619395B2 - Organic electroluminescent device and carbazole compound - Google Patents

Description

  The present invention relates to an organic electroluminescent device containing a carbazole compound having a specific structure, and particularly relates to an organic electroluminescent device in which the material is formed by wet film formation.

  As a device using an organic material, an organic electroluminescent element (hereinafter also referred to as OLED) has been actively researched. In particular, the organic electroluminescence device is expected to be developed as a lighting application as a solid light-emitting large-area full-color display device or an inexpensive large-area surface light source. In general, an organic electroluminescent element is composed of an organic compound layer including a light emitting layer and a pair of counter electrodes sandwiching the organic compound layer. When a voltage is applied to such an organic electroluminescent device, electrons are injected from the cathode and holes are injected from the anode into the organic compound layer. The electrons and holes recombine in the light emitting layer, and light is emitted by releasing energy as light when the energy level returns from the conduction band to the valence band.

A device using such an organic material is conventionally formed by a vacuum deposition process. It has been pointed out that the vacuum deposition process is difficult to produce a large area device, has a low material utilization efficiency, and uses a lot of energy in the manufacturing process. On the other hand, the wet film-forming process has the characteristics that a large-area device can be easily manufactured, the material utilization efficiency is high, and it can be formed at normal pressure, so that not much energy is used in the manufacturing process. Therefore, many studies have been made on the creation of an organic device using a wet film-forming process, but there are problems such as failure to obtain an organic device with higher efficiency and stability than vacuum deposition. . .
In particular, regarding organic electroluminescent elements, two types of methods using high molecular materials and low molecular materials have been proposed. Polymeric materials are likely to form good films by a wet film-forming process, but are susceptible to impurities. Some low molecular weight materials are easy to obtain high purity and exhibit high performance, but it is generally difficult to form a good film in a wet film forming process. So far, there has been a report on the creation of an organic device by a wet film-forming process using a low-molecular material, but sufficient performance may not be obtained (Patent Documents 1 to 3, Non-Patent Documents). 1-3).
Carbazole compounds are widely known as skeletons that give relatively high performance as organic electroluminescent devices, and examples of application to wet film forming processes have been reported so far, but sufficient performance cannot be obtained. (Patent Document 4). In particular, compounds with specific substituents introduced at the 3- and 6-positions have been reported for the purpose of improving solubility with respect to the carbazole skeleton, but sufficient performance may not be obtained. (Non-patent document 4, Patent document 5). Moreover, although the compound which introduce | transduced the trityl group with respect to the carbazole skeleton has been reported, in this case, sufficient performance may not be obtained (Patent Document 6).

JP 2006-176699 A JP 2007-284408 A US Pat. No. 7,285,432 JP 2007-67383 A JP 2004-311410 A JP 2008-1621 A

Organic Electronics, Vol. 10, p. 189, 2009 Organic Electronics, Vol. 10, p. 581, 2009 Journal of Material Chemistry, Vol. 18, p. 1799, 2008 Macromolecules, 33, 801, 2000

An object of the present invention is to provide an organic electroluminescent device which exhibits high efficiency even after aging in a high temperature and high humidity environment and has a small decrease in light emission luminance at the initial stage of driving. In particular, it is possible to provide an organic electroluminescence device that exhibits high efficiency even after a lapse of time in a high temperature and high humidity environment by wet film formation, and can provide an organic electroluminescence device having a small decrease in light emission luminance in the initial stage of driving. It is providing the composition for organic electroluminescent elements.
In addition, a method for producing a compound, which can provide an organic electroluminescence device capable of providing a high efficiency even after aging in a high temperature and high humidity environment and having a small decrease in light emission luminance at the initial stage of driving, and its It is to provide a production intermediate.

  In view of the above situation, the present inventor has conducted intensive research and found that organic compounds that give very high efficiency even after aging in a high temperature and high humidity environment by using a carbazole compound having a specific substituent. The device can be realized. Further, the present inventors have found that the carbazole compound of the present invention is suitable for a wet film-forming process, and by using a composition for an organic electroluminescent device containing the carbazole compound, under a high temperature and high humidity environment. It has been found that it is possible to provide an organic electroluminescent device exhibiting high efficiency even after the elapse of time. Furthermore, an organic device that gives a very high efficiency even after aging in a high temperature and high humidity environment, especially an organic device that has a small decrease in light emission luminance in the initial stage of driving, is manufactured through wet film formation. The knowledge that it can be realized was obtained, and further studies were made based on this knowledge, and the present invention was completed.

Means for solving the above-mentioned problems are as follows.
[1]
A composition used for an organic electroluminescent device having a pair of electrodes and at least one organic layer including a light emitting layer between the electrodes on a substrate, comprising a compound represented by the following general formula (1) A composition characterized by comprising:
General formula (1)
(In General Formula (1), Ar ₁ represents an aryl group or a heteroaryl group. R _{1 to} R ₈ each independently represents a hydrogen atom or a substituent, and at least one of R _{1 to} R ₈ is the following substituent. Represents a group (2), and when R ₃ and R ₆ both represent a substituent (2), R ₃ and R ₆ represent different substituents.)
Substituent (2)
(In General Formula (2), R ₉ , R ₁₀ , and R ₁₁ each independently represents an alkyl group, an aryl group, or a heteroaryl group, and at least one of R ₉ , R ₁₀ , and R ₁₁ is an alkyl group. And R ₉ , R ₁₀ and R ₁₁ do not all represent the same substituent at the same time (the wavy line represents the bonding position).
[2]
In the general formula (1), R ₃ is the substituent (2). The composition according to [1].
[3]
[1] or [2], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).
(In General Formula (3), Ar ₂ represents an aryl group or a heteroaryl group. R _{16 to} R ₂₃ each independently represents a hydrogen atom or a substituent, and at least one of R _{16 to} R ₂₃ is substituted as described above. Represents a group (2), wherein when R ₁₈ and R ₂₁ both represent a substituent (2), R ₃ and R ₆ represent different substituents, and n represents an integer of 2 or more.)
[4]
In the general formula (3), Ar ₂ represents phenylene or biphenylene, [3].
[5]
[3] or [4], wherein n is 2 in the general formula (3).
[6]
An organic electroluminescent element having a pair of electrodes and at least one organic layer including a light emitting layer between the electrodes on a substrate, wherein any one of the organic layers is described in [1] to [5] An organic electroluminescent device comprising a compound represented by any one of the general formulas (1) to (3).
[7]
[6] The organic material according to [6], wherein the light-emitting layer contains a compound represented by any one of the general formulas (1) to (3) according to [1] to [5] and a phosphorescent material. Electroluminescent device.
[8]
[7] The organic electroluminescent element as described in [7], wherein the phosphorescent material is Ir or Pt complex.
[9]
Any one of the organic layers is formed using the composition according to any one of [1] to [5], and the organic electroluminescent element according to any one of [6] to [8] .
[10]
Any one of the organic layers is formed by wet film formation using the composition according to any one of [1] to [5], according to any one of [6] to [9] Organic electroluminescent device.
[11]
[10] The organic electroluminescence device as set forth in [10], wherein the wet film formation is selected from a coating method, an inkjet method, and a spray coating method.
[12]
The manufacturing method characterized by manufacturing the compound represented by following General formula (3) using following General formula (4).
(In General Formula (3), Ar ₂ represents an aryl group or a heteroaryl group. R _{16 to} R ₂₃ each independently represents a hydrogen atom or a substituent, and at least one of R _{16 to} R ₂₃ is substituted as described above. Represents a group (2), wherein when R ₁₈ and R ₂₁ both represent a substituent (2), R ₃ and R ₆ represent different substituents, and n represents an integer of 2 or more.)
(In General Formula (4), R _{1 to} R ₈ represent a hydrogen atom or a substituent, but at least one of R _{1 to} R ₈ represents the substituent (2). In addition, R ₃ and R ₆ When both represent the substituent (2), R ₃ and R ₆ represent different substituents.)
[13]
A carbazole compound represented by the following structural formula.

  According to the present invention, there is provided a composition and a compound that can provide an organic electroluminescence device that exhibits high efficiency even after aging in a high-temperature and high-humidity environment and that has a small decrease in light emission luminance at the initial stage of driving. A production method and a production intermediate thereof can be provided. Moreover, the organic electroluminescent element using them can be provided.

  Hereinafter, the present invention will be described in detail. In the present specification, “to” indicates a range including the numerical values described before and after the minimum and maximum values, respectively.

[Composition for organic electroluminescence device]
The composition for an organic electroluminescent element of the present invention is a composition used for an organic electroluminescent element having a pair of electrodes and at least one organic layer between the electrodes on a substrate, and the following general formula (1 The compound represented by this is contained.
The compound represented by the general formula (1) has a high amorphous property and can form a film with few defects in a short time due to the structural feature that the carbazole group has a specific substituent. As described above, the high efficiency is exhibited even after the elapse of time in a high-temperature and high-humidity environment, and the effect of reducing the decrease in light emission luminance particularly in the initial stage of driving is achieved.
(Compound represented by the general formula (1))

(In General Formula (1), Ar ₁ represents an aryl group or a heteroaryl group. R _{1 to} R ₈ each independently represents a hydrogen atom or a substituent, and at least one of R _{1 to} R ₈ is the following substituent. Represents a group (2), and when R ₃ and R ₆ both represent a substituent (2), R ₃ and R ₆ represent different substituents.)
Substituent (2)

(In General Formula (2), R ₉ , R ₁₀ , and R ₁₁ each independently represents an alkyl group, an aryl group, or a heteroaryl group, and at least one of R ₉ , R ₁₀ , and R ₁₁ is an alkyl group. And R ₉ , R ₁₀ and R ₁₁ do not all represent the same substituent at the same time (the wavy line represents the bonding position).

  The hydrogen atom may be a deuterium atom.

Examples of the substituent represented by R _{1 to} R ₈ include the following substituent group V.
<Substituent group V>
An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (for example, methyl group, ethyl group, n-propyl group, n-butyl group, t-butyl group) Pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group), substituted alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms {for example, triphenyl A methyl group, a trifluoromethyl group, a benzyl group, a carboxyethyl group, an ethoxycarbonylmethyl group, an acetylaminomethyl group, or a carbon number of 2-18, preferably a carbon number of 3-10, more preferably a carbon number of 3-5. Of the substituted hydrocarbon group (eg, vinyl group, ethynyl group 1-cyclohexenyl group, benzylidine group, benzylidene group). A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms (for example, a phenyl group, a naphthyl group, a p-carboxyphenyl group, p -Nitrophenyl group, 3,5-dichlorophenyl group, p-cyanophenyl group, m-fluorophenyl group, p-tolyl group, 4-propylcyclohexyl-4'-biphenyl, 4-butylcyclohexyl-4'-biphenyl, 4 -Pentylcyclohexyl-4′-biphenyl, 4-propylphenyl-2-ethynyl-4′-biphenyl); substituted or non-substituted having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms. Substituted heteroaryl groups (eg N-carbazoyl, 3-carbazoyl, 2-pyridyl, 5-methyl-3-pyridyl) , 2-thienyl group, 2-furyl group, morpholino group, tetrahydrofurfuryl group, pyridimidyl group); halogen atom (for example, chlorine, bromine, iodine, fluorine); cyano group; carboxyl group; phosphate group; sulfo group; A carbamoyl group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms (for example, methylcarbamoyl group, ethylcarbamoyl group, morpholinocarbamoyl group); 0 to 10 carbon atoms, preferably A sulfamoyl group having 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms (for example, methylsulfamoyl group, ethylsulfamoyl group, piperidinosulfamoyl group); nitro group; 1 to 20 carbon atoms, preferably An alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, 2-methoxy group) Ethoxy group, 2-phenylethoxy group); aryloxy group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (for example, phenoxy group, p-methylphenoxy group, p-chloro) A phenoxy group, a naphthoxy group); an acyl group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (for example, an acetyl group, a benzoyl group, a trichloroacetyl group); An acyloxy group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (for example, an acetyloxy group or a benzoyloxy group); 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably a carbon number. An acylamino group having 2 to 8 carbon atoms (for example, an acetylamino group); a sulfo group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms Phonyl group (for example, methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group); sulfinyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 8 carbon atoms (for example, methanesulfinyl group, ethanesulfinyl group) Group, a benzenesulfinyl group); a sulfonylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (for example, methanesulfonylamino group, ethanesulfonylamino group, benzenesulfonylamino group). ;

  A substituted or unsubstituted amino group having 0 to 20 carbon atoms, preferably 0 to 12 carbon atoms, more preferably 0 to 8 carbon atoms (for example, an unsubstituted amino group, a methylamino group, a dimethylamino group, a benzylamino group) Anilino group, diphenylamino group); an ammonium group having 0 to 15 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (for example, trimethylammonium group or triethylammonium group); A hydrazino group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (for example, trimethylhydrazino group); 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Ureido group (for example, ureido group, N, N-dimethylureido group); carbon number 1-15, preferably carbon number 1-10, more preferably carbon number -6 imide group (for example, succinimide group); C1-C20, preferably C1-C12, more preferably C1-C8 alkylthio group (for example, methylthio group, ethylthio group, propylthio group); An arylthio group having 6 to 80, preferably 6 to 40, more preferably 6 to 30 carbon atoms (for example, phenylthio group, p-methylphenylthio group, p-chlorophenylthio group, 2-pyridylthio group, 1-naphthylthio group) 2-naphthylthio group, 4-propylcyclohexyl-4′-biphenylthio group, 4-butylcyclohexyl-4′-biphenylthio group, 4-pentylcyclohexyl-4′-biphenylthio group, 4-propylphenyl-2-ethynyl -4'-biphenylthio group); 1 to 80 carbon atoms, preferably 1 to 40 carbon atoms, The Mashiku heteroarylthio group having 1 to 30 carbon atoms (e.g., 2-pyridylthio group, 3-pyridylthio group, 4-pyridylthio group, 2-Kinoriruchio group, 2-furylthio group, 2-Piroriruchio group);

An alkoxycarbonyl group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonyl group, or a 2-benzyloxycarbonyl group); An aryloxycarbonyl group having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (for example, a phenoxycarbonyl group) is preferable. These substituent groups V can have a structure in which a benzene ring or a naphthalene ring is condensed. Furthermore, any substituent selected from the substituent group V may be further substituted on these substituents.

R _{1 to} R ₈ are preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a fluorine atom. Particularly preferred are a hydrogen atom, an alkyl group, an aryl group, and a carbazolyl group. The substituent may be substituted with deuterium.

Ar ₁ represents an aryl group or a heteroaryl group.
The aryl group represented by Ar ₁ is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms (for example, a phenyl group, a biphenyl group, a naphthyl group, p-carboxyphenyl group, p-nitrophenyl group, 3,5-dichlorophenyl group, p-cyanophenyl group, m-fluorophenyl group, p-tolyl group, 4-propylcyclohexyl-4'-biphenyl, 4-butylcyclohexyl -4′-biphenyl, 4-pentylcyclohexyl-4′-biphenyl, 4-propylphenyl-2-ethynyl-4′-biphenyl, a phenyl group substituted with a carbazolyl group, a biphenyl group substituted with a carbazolyl group) Preferably a phenyl group or a biphenyl group, and particularly preferably a carbazolyl group. Phenyl group, a substituted biphenyl group carbazolyl group.

The heteroaryl group represented by Ar ₁ is a substituted or unsubstituted heteroaryl group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms (for example, an N-carbazoyl group, 3- Carbazoyl group, 2-pyridyl group, 5-methyl-3-pyridyl group, 2-thienyl group, 2-furyl group, morpholino group, tetrahydrofurfuryl group, pyridimidyl group).
Ar ₁ is preferably an aryl group, a phenyl group or a biphenyl group, and may further have a substituent.
Examples of the further substituent include the above-mentioned substituent group V, preferably an alkyl group, an aryl group, and a heteroaryl group, and particularly preferably a carbazolyl group.

  In general formula (2), a wavy line represents a coupling position.

Examples of the alkyl group represented by R ₉ , R ₁₀ , and R ₁₁ include those described in the above substituent group V, preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a t-butyl group. , A pentyl group, a hexyl group and a cyclohexyl group, more preferably a methyl group, an ethyl group and a propyl group.

Examples of the aryl group represented by R ₉ , R ₁₀ and R ₁₁ include those described in the above-mentioned Substituent group V, preferably a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-methylphenyl group, 3 -A methylphenyl group and a 2-methoxyphenyl group, more preferably a phenyl group.

Examples of the heteroaryl group represented by R ₉ , R ₁₀ , and R ₁₁ include those described in Substituent Group V, preferably a 2-pyridyl group, a 3-pyridyl group, a 2-thienyl group, and a 2-quinolyl group. , 2-furyl group, more preferably 2-pyridyl group.

R ₉ , R ₁₀ and R ₁₁ may further have a substituent. Examples of the substituent in this case include the above-mentioned substituent group V, preferably alkyl, aryl, alkoxy, aryloxy, and halogen atoms, and more preferably alkoxy and halogen atoms.
At least one of R ₉ , R ₁₀ and R ₁₁ is an alkyl group, and R ₉ , R ₁₀ and R ₁₁ do not all represent the same substituent at the same time.
Examples of the combination of R ₉ , R ₁₀ and R ₁₁ include the following.
R ₉ = R ₁₀ = R ₁₁ = alkyl group R ₉ = R ₁₀ = alkyl group, R ₁₁ = aryl group R ₉ = R ₁₀ = alkyl group, R ₁₁ = heteroaryl group R ₉ = alkyl group, R ₁₀ = R ₁₁ = aryl group R ₉ = alkyl group, R ₁₀ = R ₁₁ = heteroaryl group

Among the above, it is more preferable that R ₉ and R ₁₀ are methyl groups, and R ₁₁ is ethyl.

In the general formula (1), R ₃ is preferably the substituent (2).

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

(In General Formula (3), Ar ₂ represents an aryl group or a heteroaryl group. R _{16 to} R ₂₃ each independently represents a hydrogen atom or a substituent, and at least one of R _{16 to} R ₂₃ is substituted as described above. Represents a group (2), wherein when R ₁₈ and R ₂₁ both represent a substituent (2), R ₃ and R ₆ represent different substituents, and n represents an integer of 2 or more.)
Substituent (2)

(In General Formula (2), R ₉ , R ₁₀ , and R ₁₁ each independently represents an alkyl group, an aryl group, or a heteroaryl group, and at least one of R ₉ , R ₁₀ , and R ₁₁ is an alkyl group. And R ₉ , R ₁₀ and R ₁₁ do not all represent the same substituent at the same time (the wavy line represents the bonding position).

Ar ₂ represents an aryl group or a heteroaryl group.
The aryl group represented by Ar ₂ is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms (for example, a phenyl group, a biphenyl group, a naphthyl group, p-carboxyphenyl group, p-nitrophenyl group, 3,5-dichlorophenyl group, p-cyanophenyl group, m-fluorophenyl group, p-tolyl group, 4-propylcyclohexyl-4'-biphenyl, 4-butylcyclohexyl -4′-biphenyl, 4-pentylcyclohexyl-4′-biphenyl, 4-propylphenyl-2-ethynyl-4′-biphenyl).

The heteroaryl group represented by Ar ₂ is a substituted or unsubstituted heteroaryl group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms (for example, an N-carbazoyl group, 3- Carbazoyl group, 2-pyridyl group, 5-methyl-3-pyridyl group, 2-thienyl group, 2-furyl group, morpholino group, tetrahydrofurfuryl group, pyridimidyl group).

Ar ₂ is preferably an aryl group, a phenyl group or a biphenyl group, and may further have a substituent.
Examples of the further substituent include the above-mentioned substituent group V, preferably an alkyl group, an aryl group, and a heteroaryl group, and particularly preferably a carbazolyl group.

R _{16 to} R ₂₃ represent a hydrogen atom or a substituent, and at least one of R _{16 to} R ₂₃ represents the following substituent (2). In addition, when R ₁₆ and R ₂₃ both represent the substituent (2), R ₁₆ and R ₂₃ represent different substituents. Examples of the substituent include the substituent group V.

  n is an integer of 2 or more, preferably n = 2, 3, and 4 and particularly preferably n = 2.

The T ₁ level (energy level in the lowest triplet excited state) of the compound represented by the general formula (1) is 45 Kcal / mol or more (188.3 KJ / mol or more) and 85 Kcal / mol or less (355. 6 KJ / mol or less), preferably 55 Kcal / mol or more (251.0 KJ / mol or more), 85 Kcal / mol or less (355.6 KJ / mol or less), more preferably 60 Kcal / mol or more (272.0 KJ / mol or more), 85 Kcal / mol or less (355.6 KJ / mol or less) is more preferable.

The T ₁ level can be obtained from the wavelength of the short wavelength end of the spectrum by measuring the phosphorescence spectrum of the compound in the film state.

  The glass transition temperature (Tg) of the compound represented by the general formula (1) is preferably 80 ° C. or higher and 400 ° C. or lower, more preferably 100 ° C. or higher and 400 ° C. or lower, and 120 ° C. or higher and 400 ° C. or lower. More preferably it is.

  Specific examples of the compound represented by formula (1) that can be used in the present invention are shown below, but the present invention is not limited to the following specific examples.

  The compound represented by the general formula (1) can be synthesized by combining various known synthesis methods. For example, the method described in Chemical Review, 46, 359-380, 1947 can be used.

In addition to the compound represented by the general formula (1), the composition of the present invention includes a host compound, a light emitting material, a polymer, and a compound having a function of improving device performance (for example, an antioxidant, a water supplement, oxygen Supplemental agents, etc.), coating solvents, surfactants, and the like.
The content of the compound represented by the general formula (1) is preferably 0.1 to 99% by mass, more preferably 1 to 95% by mass with respect to the total mass of the composition, It is more preferable to include 95% by mass.

Moreover, this invention relates also to the manufacturing method of the compound represented by General formula (3).
Hereinafter, the production method of the present invention will be described.

[Production Method of Compound Represented by General Formula (3)]
The manufacturing method of this invention is a manufacturing method characterized by manufacturing the compound represented by General formula (3) using following General formula (4).
By using this method, it is possible to obtain a compound having high purity and high device performance.

(In General Formula (3), Ar ₂ represents an aryl group or a heteroaryl group. R _{16 to} R ₂₃ each independently represents a hydrogen atom or a substituent, and at least one of R _{16 to} R ₂₃ is substituted as described below. Represents a group (2), wherein when R ₁₈ and R ₂₁ both represent a substituent (2), R ₃ and R ₆ represent different substituents, and n represents an integer of 2 or more.)
Substituent (2)

(In General Formula (2), R ₉ , R ₁₀ , and R ₁₁ each independently represents an alkyl group, an aryl group, or a heteroaryl group, and at least one of R ₉ , R ₁₀ , and R ₁₁ is an alkyl group. And R ₉ , R ₁₀ and R ₁₁ do not all represent the same substituent at the same time (the wavy line represents the bonding position).

(In General Formula (4), R _{1 to} R ₈ represent a hydrogen atom or a substituent, but at least one of R _{1 to} R ₈ represents the substituent (2). In addition, R ₃ and R ₆ When both represent the substituent (2), R ₃ and R ₆ represent different substituents.)

Examples of the method for producing the compound represented by the general formula (3) using the general formula (4) include a method utilizing a coupling reaction, and among them, the compound represented by the general formula (4) and It is preferable to synthesize by a method in which a halogen compound is linked by a coupling reaction.
Preferable ranges and specific examples of the compound represented by the general formula (3) and the compound represented by the general formula (4) are the same as those described above.
According to the method of the present invention, the compound represented by the general formula (4) can be obtained in high yield.
As the coupling reaction, a method using a transition metal catalyst, particularly a copper, nickel, or palladium catalyst, is preferable. C. Mignani, G.M. A. Aldrichichima Acta, 39, 17, p. 2006, Schlummer, B .; Scholz, U., et al. Author Advanced. Synthetic. Catalyst. 346, 1599, 2004, Anderson, K. et al. W. Author. Angew. Chem. Int. Ed. 45, 6523, 2006, Altman, R .; A. Buchwald, S .; L. Organic Letters, Vol. 8, 2779, 2006, Kiyomori, A. et al. Tetrahedron Letters 40, 2657, 1999, Shafir, A. et al. Buchwald, S .; L. The method described in the book Journal of the American Chemical Society vol. 128, page 8742, 2006 is mentioned.

  The method for producing the compound represented by the general formula (3) using the general formula (4) is preferably performed in the presence of a solvent. As the solvent, ether type, amide type, halogenated hydrocarbon, aromatic hydrocarbon and ester type are appropriately used. Examples of the catalyst include palladium, copper, nickel and the like, and palladium and copper are preferable. The reaction temperature is preferably in the range of 50 ° C to 300 ° C, more preferably in the range of 60 ° C to 200 ° C. The reaction time is preferably in the range of 10 minutes to 10 days, more preferably in the range of 1 hour to 24 hours.

[Carbazole compound]
The present invention also relates to the following carbazole compounds. The carbazole compound of the present invention is a novel compound, and can provide an organic electroluminescence device that exhibits high efficiency even after aging in a high temperature and high humidity environment and has a small decrease in light emission luminance at the initial stage of driving. It is useful as an intermediate for the production of compounds.

[Organic electroluminescence device]
The organic electroluminescent element of the present invention is an organic electroluminescent element having a pair of electrodes and at least one organic layer including a luminescent layer between the electrodes on a substrate, wherein any one of the organic layers is A compound represented by any one of the general formulas (1) to (3) is included.
In the present invention, the compound represented by the general formula (1) may be contained in any layer of the organic layer. As the introduction layer of the compound represented by the general formula (1), any 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, a charge block layer, or It is preferably contained in a plurality, preferably contained in a hole transport layer, an electron transport layer or a light emitting layer, and more preferably contained in a light emitting layer.
When the compound represented by the general formula (1) is contained in the light emitting layer, it is preferably contained in an amount of 1 to 99% by mass, more preferably 5 to 95% by mass with respect to the total mass of the light emitting layer. It is more preferable to contain -95 mass%. When the compound represented by the general formula (1) is further contained in a layer other than the light emitting layer, it is preferably contained in an amount of 50 to 100% by mass, and more preferably 60 to 100% by mass.
The organic electroluminescence device of the present invention usually emits light when a DC voltage (which may include an AC component) or a DC current of about 2 to 40 volts is applied between the transparent electrode and the back electrode. In driving the light emitting device of the present invention, JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234585, and JP-A-8-2441047. , US Pat. Nos. 5,828,429, 6,022,308, and Japanese Patent No. 2,784,615 can be used. Hereinafter, although each layer which comprises the light emitting laminated body used by this invention is explained in full detail, this invention is not limited by them.

(A) Substrate The substrate used in the present invention is preferably made of a material that does not allow moisture to permeate or a material that has a very low moisture permeability. The material preferably does not scatter or attenuate light emitted from the organic compound layer. Specific examples thereof include zirconia stabilized yttrium (YSZ), inorganic materials such as glass, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, allyl diglycol carbonate, Examples thereof include organic materials such as polyimide, polycycloolefin, norbornene resin, and poly (chlorotrifluoroethylene). Among these, organic materials that are excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation and workability, and have low air permeability and low moisture absorption can be particularly preferably used. The substrate may be formed of a single material or two or more materials. The material for the substrate may be appropriately selected according to the transparent electrode material. For example, when the transparent electrode is indium tin oxide (ITO), it is preferable to use a material having a small difference in lattice constant from ITO.

  The shape, structure, size, and the like of the substrate can be appropriately selected according to the use and purpose of the light emitting element. The shape is generally plate-like. The structure may be a single layer structure or a laminated structure. The substrate may be colorless and transparent or colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate light emitted from the light emitting layer.

  A moisture permeation preventing layer (gas barrier layer) may be provided on the electrode-side surface of the substrate, the surface opposite to the electrode, or both. As a material constituting the moisture permeation preventing layer, it is preferable to use an inorganic material such as silicon nitride or silicon oxide. The moisture permeation preventing layer can be formed by a high frequency sputtering method or the like. Moreover, you may provide a hard-coat layer and an undercoat layer in a base material as needed.

(B) Transparent electrode Normally, the transparent electrode functions as an anode for supplying holes to the organic compound layer, but it can also function as a cathode. In this case, the back electrode functions as an anode. Hereinafter, the case where a transparent electrode is used as an anode will be described.

  The shape, structure, size, and the like of the transparent electrode are not particularly limited, and can be appropriately selected according to the use and purpose of the light emitting element. As a material for forming the transparent electrode, a metal, an alloy, a metal oxide, an electrically conductive compound, a mixture thereof, or the like can be used, and a material having a work function of 4 eV or more is preferably used. Specific examples include tin oxide doped with antimony (ATO), tin oxide doped with fluorine (FTO), semiconductive metal oxides (tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), zinc oxide). Indium (IZO, etc.), metals (gold, silver, chromium, nickel, etc.), mixtures or laminates of these metals and conductive metal oxides, inorganic conductive substances (copper iodide, copper sulfide, etc.), organic conductivity Materials (polyaniline, polythiophene, polypyrrole, etc.) and laminates of this and ITO.

  The transparent electrode may be formed on the substrate by a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method or an ion plating method, or a chemical method such as CVD or plasma CVD method. it can. The formation method may be appropriately selected in consideration of suitability with the transparent electrode material. For example, when ITO is used as the material for the transparent electrode, a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like may be used. Further, when an organic conductive material is used as the material for the transparent electrode, a wet film forming method may be used.

  The patterning of the transparent electrode can be performed by chemical etching using photolithography, physical etching using a laser, or the like. Alternatively, patterning may be performed by vacuum deposition using a mask, sputtering, a lift-off method, a printing method, or the like.

  The formation position of the transparent electrode may be appropriately selected according to the use and purpose of the light-emitting element, but is preferably formed on the substrate. At this time, the transparent electrode may be formed on the entire surface of the substrate or only on a part thereof.

The thickness of the transparent electrode may be appropriately selected according to the material, but is usually 10 nm to 50 μm, preferably 50 nm to 20 μm. The resistance value of the transparent electrode is preferably 10 ³ Ω / □ or less, and more preferably 10 ² Ω / □ or less. The transparent electrode may be colorless and transparent or colored and transparent. In order to extract emitted light from the transparent electrode side, the transmittance is preferably 60% or more, and more preferably 70% or more. The transmittance can be measured according to a known method using a spectrophotometer.

  Further, electrodes described in detail in “New development of transparent conductive film” (supervised by Yutaka Sawada, published by CMC, 1999) and the like can also be applied to the present invention. In particular, when using a plastic substrate having low heat resistance, it is preferable to use ITO or IZO as the transparent electrode material and to form a film at a low temperature of 150 ° C. or lower.

(C) Back electrode Normally, the back electrode has a function as a cathode for injecting electrons into the organic compound layer, but can also function as an anode. In this case, the transparent electrode functions as a cathode. Hereinafter, a case where the back electrode is a cathode will be described.

  The shape, structure, size, and the like of the back electrode are not particularly limited, and can be appropriately selected according to the use and purpose of the light emitting element. As a material for forming the back electrode, a metal, an alloy, a metal oxide, an electrically conductive compound, a mixture thereof, or the like can be used, and a material having a work function of 4.5 eV or less is preferably used. Specific examples include alkali metals (Li, Na, K, Cs, etc.), alkaline earth metals (Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloy, lithium-aluminum alloy, magnesium-silver. Examples include alloys, indium, rare earth metals (ytterbium, etc.). These may be used alone, but in order to achieve both stability and electron injection properties, it is preferable to use two or more in combination. Among these materials, alkali metals and alkaline earth metals are preferable from the viewpoint of electron injecting property, and materials mainly composed of aluminum are preferable from the viewpoint of storage stability. Here, the material mainly composed of aluminum refers to aluminum alone, an alloy or a mixture of aluminum and 0.01 to 10% by mass of an alkali metal or alkaline earth metal (lithium-aluminum alloy, magnesium-aluminum alloy, etc.). . As materials for the back electrode, those described in detail in JP-A-2-15595, JP-A-5-121172 and the like can be used.

  The back electrode can be formed by a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method or an ion plating method, or a chemical method such as CVD or plasma CVD method. The formation method may be appropriately selected in consideration of suitability with the back electrode material. For example, when two or more metals are used as the back electrode material, the materials can be formed by sputtering simultaneously or sequentially.

  The back electrode can be patterned by chemical etching using photolithography or the like, physical etching using a laser, or the like. Alternatively, patterning may be performed by vacuum deposition using a mask, sputtering, a lift-off method, a printing method, or the like.

  The formation position of the back electrode may be appropriately selected according to the use and purpose of the light emitting element, but is preferably formed on the organic compound layer. At this time, the back electrode may be formed on the entire surface of the organic compound layer or only on a part thereof. Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or the like may be provided between the back electrode and the organic compound layer with a thickness of 0.1 to 5 nm. The dielectric layer can be formed by a vacuum deposition method, a sputtering method, an ion plating method, or the like.

  The thickness of the back electrode may be appropriately selected depending on the material, but is usually 10 nm to 5 μm, preferably 50 nm to 1 μm. The back electrode may be transparent or opaque. The transparent back electrode may be formed by thinly forming the above-described material layer to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

(D) Light emitting layer In the light emitting device of the present invention, the light emitting layer contains a fluorescent compound (fluorescent material) or a phosphorescent compound (phosphorescent material). A phosphorescent compound is preferred. The phosphorescent compound is not particularly limited as long as it is a compound that can emit light from triplet excitons. As the phosphorescent compound, an orthometalated complex or a porphyrin complex is preferably used, and an orthometalated complex is more preferably used. Of the porphyrin complexes, a porphyrin platinum complex is preferred. In the present invention, the phosphorescent material is preferably an Ir or Pt complex. The phosphorescent compounds may be used alone or in combination of two or more.

  Orthometalated complexes are described by Akio Yamamoto, “Organic Metal Chemistry Fundamentals and Applications,” pages 150 and 232, Hankabo (1982), H.C. Yersin's “Photochemistry and Photophysics of Coordination Compounds”, pages 71-77 and pages 135-146, Springer-Verlag (1987), etc. The ligand forming the ortho-metalated complex is not particularly limited, but a 2-phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2- (2-thienyl) pyridine derivative, a 2- (1-naphthyl) pyridine derivative or A 2-phenylquinoline derivative is preferred. These derivatives may have a substituent. Moreover, you may have another ligand other than these essential ligands for ortho metalation complex formation. As the central metal forming the orthometalated complex, any transition metal can be used. In the present invention, rhodium, platinum, gold, iridium, ruthenium, palladium and the like can be preferably used. Of these, iridium is particularly preferable. An organic compound layer containing such an orthometalated complex is excellent in light emission luminance and light emission efficiency. Specific examples of the orthometalated complex are also described in paragraphs 0152 to 0180 of Japanese Patent Application No. 2000-254171.

  The orthometalated complex used in the present invention can be obtained from Inorg. Chem. , 30, 1685, 1991, Inorg. Chem. 27, 3464, 1988, Inorg. Chem. 33, 545, 1994, Inorg. Chim. Acta, 181, 245, 1991; Organomet. Chem. , 335, 293, 1987; Am. Chem. Soc. , 107, 1431, 1985 and the like.

  Although content in particular of the luminescent compound in a light emitting layer is not restrict | limited, For example, it is 0.1-70 mass%, and it is preferable that it is 1-20 mass%. If the content of the phosphorescent compound is less than 0.1% by mass or exceeds 70% by mass, the effect may not be sufficiently exhibited.

The external quantum efficiency of the light emitting device of the present invention is preferably 5% or more, more preferably 10% or more, and further preferably 13% or more. The maximum value of the external quantum efficiency when numeric external quantum efficiency of the device is driven at 20 ° C., or around 100~300cd / ^{m 2} when the device is driven at 20 ° C. (preferably 200~300cd ^{/ m} 2) The value of external quantum efficiency at can be used.

  The internal quantum efficiency of the light emitting 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 as follows: internal quantum efficiency = external quantum efficiency / 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 glass transition point of the host material, electron transport layer, and hole transport material contained in the light emitting layer of the present invention is preferably 90 ° C. or higher and 400 ° C. or lower, more preferably 100 ° C. or higher and 380 ° C. or lower, The temperature is more preferably 120 ° C. or higher and 370 ° C. or lower, and particularly preferably 140 ° C. or higher and 360 ° C. or lower.

  In the present invention, the light emitting layer may contain a host compound, a hole transport material, an electron transport material, an electrically inactive polymer binder, and the like, if necessary.

  The host compound is preferably a compound represented by the general formula (1) of the present invention, but may further contain another host compound. Such host materials include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styryl. Anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran Dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthaleneperylene, etc. Ring tetracarboxylic anhydride, phthalocyanine derivative, metal complex of 8-quinolinol derivative, metal phthalocyanine, metal complex having benzoxazole or benzothiazole as a ligand, polysilane compound, poly (N-vinylcarbazole) derivative, aniline Examples thereof include conductive polymers such as polymers, thiophene oligomers, and polythiophenes, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, and polyfluorene derivatives. A host compound may be used individually by 1 type, or may use 2 or more types together.

The method for forming the organic layer of the light-emitting element containing the compound of the present invention is not particularly limited, but various coating methods (sprays) can be used as resistance heating vapor deposition, electron beam, sputtering, molecular lamination, and wet film formation. Coating method, dip coating method, impregnation method, roll coating method, gravure coating method, reverse coating method, roll brush method, air knife coating method, curtain coating method, spin coating method, flow coating method, bar coating method, micro gravure coating Method, air doctor coating, blade coating method, squeeze coating method, transfer roll coating method, kiss coating method, cast coating method, extrusion coating method, wire bar coating method, screen coating method, etc.), inkjet method, printing method, transfer method , Spray coating, etc. Surface, wet casting method in terms of production, it is preferred resistance heating evaporation, the wet casting method, a coating method, spray coating, ink jet method is preferable.
When the wet film-forming method is used, the organic compound layer can be easily increased in area, and a light-emitting element having high luminance and excellent light emission efficiency can be obtained efficiently at low cost, which is preferable. The wet film forming method can be appropriately selected depending on the material of the organic compound layer. When the film is formed by a wet film forming method, the film may be dried after film formation. Drying is performed by selecting conditions such as temperature and pressure so that the wet film-forming layer is not damaged.

The coating solution used in the wet film-forming method usually comprises a material for the organic compound layer and a solvent for dissolving or dispersing it. A solvent is not specifically limited, What is necessary is just to select according to the material used for an organic compound layer. Specific examples of the solvent include halogen solvents (chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, diethyl ketone, n-propyl methyl ketone, cyclohexanone, isophorone, Mentone, etc.), aromatic solvents (benzene, toluene, xylene, decalin, naphthalene, biphenyl, alkyl-substituted biphenyl, etc.), ester solvents (ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, propionic acid) Ethyl, γ-butyrolactone, diethyl carbonate, etc.), ether solvents (tetrahydrofuran, dioxane, etc.), amide solvents (dimethylformamide, dimethylacetamide, etc.), dimethyl sulfoxide, water and the like. The solid content with respect to the solvent in the coating solution is not particularly limited, and the viscosity of the coating solution can be arbitrarily selected according to the film forming method.
The reaction solvent to be used is not particularly limited. Preferable examples of these solvents include water, alcohols, aromatic hydrocarbons, ethers, ketones and esters.

  Examples of alcohols include monohydric alcohols and dihydric alcohols. Among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

  Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.

Preferred organic solvents have a boiling point of 100 ° C. or higher, more preferably a boiling point of 120 ° C. or higher. A boiling point within this range is preferable for forming a uniform film.
Further, two or more organic solvents may be mixed and used. When two or more kinds are mixed, the light-emitting material and host material contained in the light-emitting layer are dissolved as the first solvent, and contain at least one kind selected from solvents having a boiling point of 200 ° C. or higher. The boiling point of the first solvent is 200 It is preferable that it is -300 degreeC, and it is more preferable that it is 200-250 degreeC.
Thereby, the improvement of the smoothness of a light emitting layer coating film and the adhesiveness with an adjacent layer can be improved, and the luminous efficiency of an organic EL element and element durability can be improved.
Examples of the first solvent include amide solvents, aprotic polar solvents excluding amide solvents, and high-boiling hydrophobic solvents.
Examples of amide solvents include N-methyl-2-pyrrolidone (boiling point 202 ° C.), 2-pyrrolidone (boiling point 245 ° C.), 1-acetyl-2-pyrrolidone (boiling point 231 ° C.), N-ethyl-2-pyrrolidone (boiling point). 218 ° C), 1,3-dimethyl-2-imidazolidinone (boiling point 220 ° C), formamide (boiling point 210.5 ° C), N, N-dibutylformamide (boiling point 243 ° C), m-xylylenediamine (boiling point 245) ° C), etc., or derivatives thereof.
Examples of aprotic polar solvents excluding amides include propylene carbonate (boiling point 243 ° C), γ-butyrolactone (boiling point 204 ° C), γ-valerolactone (boiling point 207 ° C), α-acetyl-γ-butyrolactone (boiling point 235 ° C). Etc.) or their derivatives.
Examples of high-boiling hydrophobic solvents include cyclohexylbenzene (boiling point 240 ° C.), 1,2,3,4-tetramethylbenzene (boiling point 203 ° C.), 3-methylbiphenyl (boiling point 272 ° C.), 4-methylbiphenyl (boiling point 262). ° C), 1-methylnaphthalene (boiling point 244.8 ° C) and the like, or derivatives thereof.
From the viewpoint of the solubility of the light emitting material, an amide solvent is preferable. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone are preferable, and N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone. Is more preferable.
The first solvent may further be a mixture of two or more.

The second solvent is preferably at least one selected from solvents having an azeotropic temperature with water of 99 ° C. or lower. In this case, the azeotropic temperature with water is preferably 98 to 50 ° C, and preferably 80 to 50 ° C.
Thereby, the water | moisture content in the organic layer formed into a film can be removed, and lifetime improvement of an organic electroluminescent element can be enabled.
As the second solvent, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-n-butoxyethanol, propylene glycol monomethyl ether acetate, methyl ethyl ketone, hexane, toluene, cumene, ethyl acetate, butyl acetate , Isobutyl acetate, propyl acetate, isopropyl acetate and the like.
Two or more kinds of the second solvent may be further mixed.

  As a preferable combination of the first solvent and the second solvent, it is preferable to use a solvent selected from an amide solvent as the first solvent and a solvent selected from an alcohol solvent as the second solvent. . In addition, a solvent selected from N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone as the first solvent, and 2-n-butoxyethanol, propylene glycol monomethyl ether as the second solvent It is more preferable to use a solvent selected from acetate.

  The amount of the first solvent and the second solvent used is preferably 50:50 to 95: 5, more preferably 60:40 to 90:10, by mass ratio. Within this range, the solubility of the luminescent material and the host material can be maintained, and an organic film in which the luminescent material is uniformly dispersed in the host material of the present invention can be formed without precipitation and phase separation. Because.

Furthermore, it is preferable that the coating solution further contains a polyhydric alcohol as a third solvent. Thereby, the dissolved oxygen concentration in a coating liquid can be reduced. Examples of the third solvent include polyhydric alcohols such as glycerin, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol, and a mixture of two or more of these may be used. The polyhydric alcohol is preferably at least one selected from ethylene glycol, diethylene glycol, and glycerin, more preferably ethylene glycol or diethylene glycol. The amount of the third solvent added is preferably 2 to 20% by mass and more preferably 5 to 10% by mass with respect to the total amount of the coating solution.
The first solvent, the second solvent, and the third solvent are preferably purified. Specifically, (1) column purification treatment of silica gel, alumina, cationic ion exchange resin, anionic ion exchange resin, etc., (2) anhydrous sodium sulfate, anhydrous calcium sulfate, magnesium sulfate, strontium sulfate, barium sulfate, oxidation Dehydration treatment of barium, calcium oxide, magnesium oxide, molecular sieve, zeolite, etc. (3) Distillation treatment, (4) Bubbling treatment with inert gas (nitrogen, argon), etc. (4) Impurities caused by filtration, centrifugal sedimentation, etc. Any method such as a removal process can be used. More preferred is a purification method by column purification treatment and dehydration treatment.

  The viscosity of the coating solution for organic EL elements of the present invention is preferably 1 mPa · s to 50 mPa · s, and more preferably 2 mPa · s to 10 mPa · s.

  Moreover, the coating liquid for organic EL elements of the present invention has a surface tension of 20 mN / m to 70 mN / m, preferably 25 mN / m to 40 mN / m. By setting the surface tension within this range, it is possible to form a smooth coating film free from repelling or unevenness.

  Moreover, it is preferable that the coating liquid for organic EL elements of the present invention satisfies the numerical range for at least one of the above-described viscosity and surface tension, but satisfies the conditions for the characteristics of any combination of two or more. Furthermore, it may satisfy all the characteristics. Thereby, it can be set as the composition suitable for application | coating.

  The hole transport material is not particularly limited as long as it has any of the function of injecting holes from the anode, the function of transporting holes, and the function of blocking electrons injected from the cathode. It may be a molecular material or a polymer material. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives. Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline copolymers, Conductive polymer such as thiophene oligomer, polythiophene, polythiophene derivative, polyphenylene derivative, polyphenylene vinylene derivative, polyfluor Ren derivatives and the like. These may be used alone or in combination of two or more.

  The electron transport material is not particularly limited as long as it has any of the function of injecting electrons from the cathode, the function of transporting electrons, and the function of blocking holes injected from the anode. For example, a triazole derivative , Oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, Ring tetracarboxylic anhydride, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal complexes with metallophthalocyanine, benzoxazole, benzothiazole, etc., aniline copolymers, thiophene oligomers, polythiophenes, etc. Conductive polymer, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives and the like can be used.

  As polymer binder, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, Polyurethane, melamine resin, unsaturated polyester, alkyd resin, epoxy resin, silicone resin, polyvinyl butyral, polyvinyl acetal, etc. can be used. The light-emitting layer containing the polymer binder can be easily applied and formed in a large area by a wet film forming method.

  The thickness of the light emitting layer is preferably 10 to 200 nm, and more preferably 20 to 80 nm. When the thickness exceeds 200 nm, the driving voltage may increase. When the thickness is less than 10 nm, the light emitting element may be short-circuited.

(E) Electron transport layer The light emitting device of the present invention may have an electron transport layer made of the above-described electron transport material, if necessary. The electron transport layer may contain the polymer binder described above. The thickness of the electron transport layer is preferably 10 to 200 nm, and more preferably 20 to 80 nm. When the thickness exceeds 200 nm, the driving voltage may increase. When the thickness is less than 10 nm, the light emitting element may be short-circuited.

(F) Hole transport layer The light emitting element of this invention may have a hole transport layer which consists of a hole transport material mentioned above as needed. The hole transport layer may contain the polymer binder described above. The thickness of the hole transport layer is preferably 10 to 200 nm, more preferably 20 to 80 nm. When the thickness exceeds 200 nm, the driving voltage may increase. When the thickness is less than 10 nm, the light emitting element may be short-circuited.

(G) Others The light-emitting device of the present invention has a protective layer described in JP-A-7-85974, 7-192866, 8-22891, 10-275682, 10-106746, and the like. It may be. The protective layer is formed on the uppermost surface of the light emitting element. Here, the top surface refers to the outer surface of the back electrode when the base material, the transparent electrode, the organic compound layer, and the back electrode are laminated in this order, and the base material, the back electrode, the organic compound layer, and the transparent electrode in this order. When laminating, it refers to the outer surface of the transparent electrode. The shape, size, thickness and the like of the protective layer are not particularly limited. The material for forming the protective layer is not particularly limited as long as it has a function of suppressing intrusion or permeation of a light-emitting element such as moisture or oxygen into the element. Silicon, germanium oxide, germanium dioxide or the like can be used.

  The method for forming the protective layer is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular sensing epitaxy, cluster ion beam, ion plating, plasma polymerization, plasma CVD, laser CVD Thermal CVD method, coating method, etc. can be applied.

In addition, the light-emitting element is preferably provided with a sealing layer for preventing moisture and oxygen from entering. As a material for forming the sealing layer, a copolymer of tetrafluoroethylene and at least one comonomer, a fluorinated copolymer having a cyclic structure in the copolymer main chain, polyethylene, polypropylene, polymethyl methacrylate, polyimide, Polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, chlorotrifluoroethylene or a copolymer of dichlorodifluoroethylene and another comonomer, a water-absorbing substance having a water absorption of 1% or more, a water absorption of 0. 1% or less moisture-proof material, metal (In, Sn, Pb, Au, Cu, Ag, Al, Tl, Ni, etc.), metal oxide (MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, _{CaO, BaO, Fe 2 O 3} , Y 2 O 3, TiO 2 , etc.), metal fluorides (M _{F 2, LiF, AlF 3,} CaF 2 , etc.), liquid fluorinated carbon (perfluoroalkane, perfluoro amines, perfluoroether, etc.), the liquid fluorinated carbon as dispersed adsorbent moisture or oxygen, etc. Can be used.

The present invention will be described more specifically with reference to the following examples. The materials, reagents, substance amounts and ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. In addition, the following Examples 5-7 shall be read as Reference Examples 5-7, respectively.

[Synthesis Example 1] (Synthesis of 3-t-amylcarbazole)

Concentrated hydrochloric acid (equivalent to 0.2 mol) was added dropwise to an ethanol solution of 4-t-amylcyclohexanone 20 g (0.12 mol) (Tokyo Chemicals) and phenylhydrazine 12.85 g (0.12 mol) (Tokyo Chemicals). After heating and refluxing for 6 hours, after cooling, the precipitated solid was separated. The resulting crude crystals were purified by a silica gel column (eluent, hexane / ethyl acetate) to obtain 18.5 g (yield 65%) of Compound M-1 as a white solid.
¹ H NMR (CDCl ₃ ): δ 7.6 (s, 1H), 7.45 (d, 1H, J = 10 Hz), 7.26 (d, 1H, J = 10 Hz), 7.1-7.0 (M, 2H), 2.8-2.7 (m, 3H), 2.4 (t, 1H, J = 15 Hz), 2.05 (d, 1H, J = 15 Hz), 1.7-1. .55 (m, 1H), 1.51.3 (m, 3H), 0.95 (s, 6H), 0.85 (t, 3H, J = 10 Hz)

After dissolving 5.0 g (21 mmol) of Compound M-1 in xylene and adding 0.1 g of a palladium / carbon catalyst (Tokyo Kasei), heating under reflux was performed for 80 hours in a nitrogen atmosphere. After cooling, the catalyst was filtered off, the filtrate was distilled off under reduced pressure, and the resulting residue was purified by a silica gel column (eluent, hexane / ethyl acetate) to give 3-t-amylcarbazole (Cz-1). As a white solid, 4.0 g (yield 82%) was obtained.
¹ H NMR (CDCl ₃ ): δ 8.05 (d, 1H, J = 10 Hz), 8.0 (s, 1H), 7.95 (s, 1H), 7.5-7.4 (m, 4H) ), 7.2-7.15 (m, 1H), 1.75 (q, 2H, J = 10 Hz), 1.4 (s, 6H, J = 15 Hz), 0.7 (t, 3H, J = 10Hz)

[Synthesis Example 2] (Synthesis of Compound No. 35 of the present invention)

Cz-1 2.0 g (8.4 mmol), 4,4′-dibromobenzene 1.1 g (3.4 mmol), palladium acetate 61 mg and rubidium carbonate 3.1 g were added to xylene, and then P- (t-Bu ₃ ) 218 mg was added and heated to reflux for 4 hours under a nitrogen atmosphere. The reaction mixture was cooled, 1N hydrochloric acid was added, the organic matter was extracted with ethyl acetate, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The resulting residue was purified by a silica gel column (eluent, hexane / ethyl acetate) to obtain 1.7 g (yield 81%) of the target compound (No. 35) as a white solid.
¹ H NMR (CDCl ₃ ): δ 8.18 (d, 2H, J = 10 Hz), 8.10 (s, 2H), 7.92 (d, 4H, J = 12 Hz), 7.70 (d, 4H) , J = 12 Hz), 7.5-7.3 (m, 8H), 7.3 (t, 2H, J = 10 Hz), 1.8 (q, 4H, J = 12 Hz), 1.42 (s) , 6H), 0.74 (t, 3H, J = 12 Hz)

[Example 1] (Green vapor deposition type OLED element)
The cleaned ITO substrate was put into a vapor deposition apparatus, and α-NPD was deposited to 100 nm. On top of this, Ir (ppy) ₃ and compound no. 35 was deposited at a ratio of 5:95 (mass ratio) by 50 nm, and Balq was deposited thereon by 6 nm, and Alq was deposited thereon by 20 nm. On top of this, magnesium and silver were co-evaporated at a ratio of 10: 1 (molar ratio) to 100 nm to produce an EL device. The produced laminate was sealed with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.) in a glove box substituted with argon gas.
When a source measure unit 2400 type manufactured by Toyo Technica was used to emit light by applying a DC constant voltage to the EL element, light emission having a maximum emission wavelength in the vicinity of 520 nm was obtained.
(Performance evaluation)
(1) Damp heat aging durability The element was allowed to stand for 1 week in an environment of 95% humidity and 80 ° C. The efficiency after being allowed to stand was evaluated. The results are shown in Table 1.
The evaluation criteria are as follows.

◎: Less than 5% of decrease in efficiency compared to external quantum efficiency before wet heat aging ○: Within a range of less than 5% to 10% decrease in efficiency compared to external quantum efficiency before wet heat aging △: Humid heat aging Compared to the previous external quantum efficiency, the range of decrease in efficiency is within a range of 10% to less than 20%. X: The decrease in efficiency is 20% or more compared to the external quantum efficiency before wet heat aging

(2) Light emission luminance change at the initial stage of driving
The light emission luminance driven at a drive current density of ^2.5 mA / cm ² was measured, and the ratio of the decrease in light emission luminance after driving for 1 hour with respect to the light emission luminance at the start of driving was determined. The measurement measured the spectral radiance in the front of an organic EL element using the spectral radiance meter (CS-1000 by Konica Minolta Co., Ltd.). The results are shown in Table 1. The evaluation criteria are as follows.

A: Less than 1% decrease in emission luminance compared to the emission luminance at the start of driving O: Within a range of decrease in emission luminance from 1% to less than 2% compared to the emission luminance at the start of driving Δ: Start of driving In the range where the decrease in emission brightness is 2% to less than 5% compared to the emission brightness at the time ×: The decrease in emission brightness is 5% or more compared to the emission brightness at the start of driving

[Comparative Example 1]
In preparing the light emitting device of Example 1, the compound No. 1 of the present invention was used. A light emitting device was produced in the same manner as in Example 1 except that the following comparative compound 1 was used instead of 35.

  Evaluation similar to Example 1 was performed. The results are shown in Table 1.

[Example 2] (Blue vapor deposition type OLED element)
A light emitting device was produced in the same manner as in Example 1 except that in the production of the light emitting device of Example 1, Firpic was used instead of Ir (ppy) ₃ . When the device was made to emit light in the same manner as in Example 1, light emission having a maximum emission wavelength near 485 nm was obtained.
Evaluation similar to Example 1 was performed.

[Comparative Example 2]
In preparing the light emitting device of Example 2, the compound No. 1 of the present invention was used. A light emitting device was produced in the same manner as in Example 1 except that Comparative Compound 1 was used instead of 35.

  Evaluation similar to Example 1 was performed. The results are shown in Table 2.

Example 3
(Coating solution adjustment)
Iridium complex (Ir (ppy) ₃ ) 0.15 mass%, host compound No. shown in the table below. 35 1.85 mass% and methyl ethyl ketone 98 mass% were mixed, and the coating liquid for organic electroluminescent elements (coating liquid A) was obtained.

(Production of organic EL element)
A transparent support substrate was obtained by depositing ITO to a thickness of 150 nm on a 25 mm × 25 mm × 0.7 mm glass substrate. This transparent support substrate was etched and washed.
A hole injection layer (PEDOT-PSS solution (polyethylenedioxythiophene-polystyrene sulfonic acid dope) / manufactured by Bayer) was spin-coated on this ITO glass substrate, and then dried in vacuo at 150 ° C. for 1 hour. An injection layer was formed (film thickness of about 40 nm).
The coating liquid A was spin-coated on this in a glove box (dew point -68 degrees, oxygen concentration 10 ppm) to form a light emitting layer (film thickness of about 40 nm).
Subsequently, Balq was vapor-deposited to a film thickness of 40 nm by a vacuum vapor deposition method to form an electron injection layer. And 1 nm of lithium fluoride was vapor-deposited on this, and also metal aluminum was vapor-deposited 70 nm, and it was set as the cathode.
The produced laminate was put in a glove box substituted with argon gas, and sealed with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by CHIBA NAGASE Co., Ltd.). Evaluation similar to Example 1 was performed. The results are shown in Table 3.

[Comparative Example 3]
In preparing the light-emitting device of Example 3, the compound No. 1 of the present invention was used. A light emitting device was produced in the same manner as in Example 3 except that Comparative Compound 1 was used instead of 35. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.

Example 4
(Adjustment of coating solution B)
Iridium complex (Ir (ppy) ₃ ) 0.23% by mass, host compound No. 35 1.77% by mass, solvent (N-methyl-2-pyrrolidone, 2-n-butoxyethanol, and ethylene glycol in mass Solvent mixed at a mass ratio of 55/35/10) and 98% by mass of a solvent mixed at a mass ratio of 55/35/10 were mixed to obtain a coating liquid for organic electroluminescent elements (coating liquid B).

(Production of organic EL element)
A transparent support substrate was obtained by depositing ITO to a thickness of 150 nm on a 25 mm × 25 mm × 0.7 mm glass substrate. This transparent support substrate was etched and washed.
A hole injection layer (PEDOT-PSS solution (polyethylenedioxythiophene-polystyrene sulfonic acid dope) / manufactured by Bayer) was spin-coated on this ITO glass substrate, and then vacuum-dried at 100 ° C. for 1 hour. An injection layer was formed (film thickness of about 40 nm).
The coating solution B was spin-coated on this in a glove box (dew point -68 degrees, oxygen concentration 10 ppm) to form a light emitting layer (film thickness of about 40 nm).
Subsequently, Balq was vapor-deposited to a film thickness of 40 nm by a vacuum vapor deposition method to form an electron injection layer.
And 1 nm of lithium fluoride was vapor-deposited on this, and also metal aluminum was vapor-deposited 70 nm, and it was set as the cathode.
The produced laminate was put in a glove box substituted with argon gas, and sealed with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by CHIBA NAGASE Co., Ltd.).

(Performance evaluation)
Evaluation was performed in the same manner as in Example 1.

(Evaluation results)
The results obtained are shown in Table 4.

[Comparative Example 4]
In preparing the light-emitting device of Example 4, the compound No. 1 of the present invention was used. A light emitting device was produced in the same manner as in Example 4 except that Comparative Compound 1 was used instead of 35. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 4.

Example 5
(Adjustment of coating liquid C)
Iridium complex (Ir (ppy) ₃ ) 0.23% by mass, host compound no. 1. 1.77% by mass of a solvent (a solvent obtained by mixing N-methyl-2-pyrrolidone, 2-n-butoxyethanol, and ethylene glycol at a mass ratio of 55/35/10) The organic electroluminescent element coating liquid (coating liquid C) was obtained.

(Production of organic EL element)
A transparent support substrate was obtained by depositing ITO to a thickness of 150 nm on a 25 mm × 25 mm × 0.7 mm glass substrate. This transparent support substrate was etched and washed.
A hole injection layer (PEDOT-PSS solution (polyethylenedioxythiophene-polystyrene sulfonic acid dope) / manufactured by Bayer) was spin-coated on this ITO glass substrate, and then vacuum-dried at 100 ° C. for 1 hour. An injection layer was formed (film thickness of about 40 nm).
The coating liquid C was spin-coated on this in a glove box (dew point -68 degrees, oxygen concentration 10 ppm) to form a light emitting layer (film thickness of about 40 nm).
Subsequently, Balq was vapor-deposited to a film thickness of 40 nm by a vacuum vapor deposition method to form an electron injection layer.
And 1 nm of lithium fluoride was vapor-deposited on this, and also metal aluminum was vapor-deposited 70 nm, and it was set as the cathode.
The produced laminate was put in a glove box substituted with argon gas, and sealed with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by CHIBA NAGASE Co., Ltd.). Evaluation was performed in the same manner as in Example 1. The obtained results are shown in Table 5.

[Comparative Example 5]
In preparing the light-emitting device of Example 5, the compound No. 1 of the present invention was used. A light emitting device was produced in the same manner as in Example 5 except that the following comparative compounds 2 to 4 were used instead of 1. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 5.

Example 6
(Adjustment of coating solution D)
Iridium complex (Ir (ppy) ₃ ) 0.23% by mass, host compound no. 18 1.77% by mass, a solvent (a solvent obtained by mixing N-methyl-2-pyrrolidone, 2-n-butoxyethanol, and ethylene glycol at a mass ratio of 55/35/10) is a mass ratio of 55/35/10. The organic electroluminescent element coating liquid (coating liquid D) was obtained.

(Production of organic EL element)
A transparent support substrate was obtained by depositing ITO to a thickness of 150 nm on a 25 mm × 25 mm × 0.7 mm glass substrate. This transparent support substrate was etched and washed.
A hole injection layer (PEDOT-PSS solution (polyethylenedioxythiophene-polystyrene sulfonic acid dope) / manufactured by Bayer) was spin-coated on this ITO glass substrate, and then vacuum-dried at 100 ° C. for 1 hour. An injection layer was formed (film thickness of about 40 nm).
The coating solution D was spin-coated on this in a glove box (dew point -68 degrees, oxygen concentration 10 ppm) to form a light emitting layer (film thickness of about 40 nm).
Subsequently, Balq was vapor-deposited to a film thickness of 40 nm by a vacuum vapor deposition method to form an electron injection layer.
And 1 nm of lithium fluoride was vapor-deposited on this, and also metal aluminum was vapor-deposited 70 nm, and it was set as the cathode.
The produced laminate was put in a glove box substituted with argon gas, and sealed with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by CHIBA NAGASE Co., Ltd.). Evaluation was performed in the same manner as in Example 1. The results obtained are shown in Table 6.

[Comparative Example 6]
In preparing the light-emitting device of Example 6, the compound No. 1 of the present invention was used. A light emitting device was produced in the same manner as in Example 6 except that the following comparative compound 5 was used instead of 18. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 6.

Example 7
(Adjustment of coating liquid E)
Iridium complex (Ir (ppy) ₃ ) 0.23% by mass, host compound no. 52 1.77% by mass, 98% by mass of a solvent (a solvent obtained by mixing N-methyl-2-pyrrolidone, 2-n-butoxyethanol, and ethylene glycol at a mass ratio of 55/35/10) was mixed with organic An electroluminescent element coating liquid (coating liquid E) was obtained.

(Production of organic EL element)
A transparent support substrate was obtained by depositing ITO to a thickness of 150 nm on a 25 mm × 25 mm × 0.7 mm glass substrate. This transparent support substrate was etched and washed.
A hole injection layer (PEDOT-PSS solution (polyethylenedioxythiophene-polystyrene sulfonic acid dope) / manufactured by Bayer) was spin-coated on this ITO glass substrate, and then vacuum-dried at 100 ° C. for 1 hour. An injection layer was formed (film thickness of about 40 nm).
The coating liquid E was spin-coated on this in a glove box (dew point -68 degrees, oxygen concentration 10 ppm) to form a light emitting layer (film thickness of about 40 nm).
Subsequently, Balq was vapor-deposited to a film thickness of 40 nm by a vacuum vapor deposition method to form an electron injection layer. And 1 nm of lithium fluoride was vapor-deposited on this, and also metal aluminum was vapor-deposited 70 nm, and it was set as the cathode.
The produced laminate was put in a glove box substituted with argon gas, and sealed with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by CHIBA NAGASE Co., Ltd.). Evaluation was performed in the same manner as in Example 1. The results obtained are shown in Table 7.

[Comparative Example 7]
In preparing the light emitting device of Example 7, the compound No. 1 of the present invention was used. A light emitting device was produced in the same manner as in Example 7 except that the following comparative compound 6 was used instead of 52. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 7.

  As a result of the evaluation, it was found that the organic electroluminescence device using the compound of the present invention has high durability such as durability over time of wet heat and small change in luminance at the beginning of driving.

Claims (11)

A composition used for an organic electroluminescent device having a pair of electrodes and at least one organic layer including a light emitting layer between the electrodes on a substrate, comprising a compound represented by the following general formula (1) A composition characterized by comprising:
General formula (1)

(In General Formula (1), Ar ₁ represents a 4-biphenyl group. R ₁ , R ₂ , and R _{4 to} R ₈ are each independently a hydrogen atom, an unsubstituted alkyl group having 1 to 18 carbon atoms, or carbon. A substituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 20 carbon atoms, a halogen atom, a cyano group, a carboxyl group, and a phosphoric acid group , Sulfo group, hydroxy group, carbamoyl group having 1 to 10 carbon atoms, sulfamoyl group having 0 to 10 carbon atoms, nitro group, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, carbon number 1 ˜20 acyl group, C 1-20 acyloxy group, C 1-20 acylamino group, C 1-20 sulfonyl group, C 1-20 sulfinyl group, C 1-20 sulfo Ruamino group, substituted or unsubstituted amino group having 0 to 20 carbon atoms, ammonium group having 0 to 15 carbon atoms, hydrazino group having 0 to 15 carbon atoms, ureido group having 1 to 15 carbon atoms, 1 to 15 carbon atoms An imide group, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 80 carbon atoms, a heteroarylthio group having 1 to 80 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms A substituent selected from the group consisting of a roxycarbonyl group is represented, and R ₃ represents the following substituent (2).)
Substituent (2)

(In General Formula (2), R ₉ , R ₁₀ , and R ₁₁ each independently represents an alkyl group, an aryl group, or a heteroaryl group, and at least one of R ₉ , R ₁₀ , and R ₁₁ is an alkyl group. And R ₉ , R ₁₀ and R ₁₁ do not all represent the same substituent at the same time (the wavy line represents the bonding position). 2. The composition according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).



(In General Formula (3), Ar ₂ represents 4-biphenylene. R ₁₆ , R ₁₇ , and R _{19 to} R ₂₃ are each independently a hydrogen atom, an unsubstituted alkyl group having 1 to 18 carbon atoms, or a carbon number. A substituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 20 carbon atoms, a halogen atom, a cyano group, a carboxyl group, a phosphate group, Sulfo group, hydroxy group, carbamoyl group having 1 to 10 carbon atoms, sulfamoyl group having 0 to 10 carbon atoms, nitro group, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, 1 to carbon atoms 20 acyl groups, C1-C20 acyloxy groups, C1-C20 acylamino groups, C1-C20 sulfonyl groups, C1-C20 sulfinyl groups, C1-C20 Sulfonylamino group, substituted or unsubstituted amino group having 0 to 20 carbon atoms, ammonium group having 0 to 15 carbon atoms, hydrazino group having 0 to 15 carbon atoms, ureido group having 1 to 15 carbon atoms, 1 to 15 carbon atoms An imide group, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 80 carbon atoms, a heteroarylthio group having 1 to 80 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and a 6 to 20 carbon atom And represents a substituent selected from the group consisting of an aryloxycarbonyl group, R ₁₈ represents the above substituent (2), and n represents an integer of 2 or more.)   In the said General formula (3), n is 2, The composition of Claim 2 characterized by the above-mentioned.   An organic electroluminescent element comprising a substrate and a pair of electrodes and at least one organic layer including a light emitting layer between the electrodes, wherein any one of the organic layers is defined in any one of claims 1 to 3. An organic electroluminescent device comprising a compound represented by any one of the general formula (1) or (3) described in 1.   The light emitting layer contains a compound represented by any one of the general formulas (1) and (3) according to any one of claims 1 to 3 and a phosphorescent material. The organic electroluminescent element as described.   6. The organic electroluminescent device according to claim 5, wherein the phosphorescent material is Ir or Pt complex.   The organic electroluminescent element according to any one of claims 4 to 6, wherein any one of the organic layers is formed using the composition according to any one of claims 1 to 3. .   The organic electric field according to any one of claims 4 to 7, wherein any one of the organic layers is formed by wet film formation using the composition according to any one of claims 1 to 3. Light emitting element.   The organic electroluminescence device according to claim 8, wherein the wet film formation is selected from a coating method, an inkjet method, and a spray coating method. A method for producing a compound represented by the following general formula (3) by linking a compound represented by the following general formula (4) and a halogen compound by a coupling reaction.



(In General Formula (3), Ar ₂ represents 4-biphenylene. R ₁₆ , R ₁₇ , and R _{19 to} R ₂₃ are each independently a hydrogen atom, an unsubstituted alkyl group having 1 to 18 carbon atoms, or a carbon number. A substituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 20 carbon atoms, a halogen atom, a cyano group, a carboxyl group, a phosphate group, Sulfo group, hydroxy group, carbamoyl group having 1 to 10 carbon atoms, sulfamoyl group having 0 to 10 carbon atoms, nitro group, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, 1 to carbon atoms 20 acyl groups, C1-C20 acyloxy groups, C1-C20 acylamino groups, C1-C20 sulfonyl groups, C1-C20 sulfinyl groups, C1-C20 Sulfonylamino group, substituted or unsubstituted amino group having 0 to 20 carbon atoms, ammonium group having 0 to 15 carbon atoms, hydrazino group having 0 to 15 carbon atoms, ureido group having 1 to 15 carbon atoms, 1 to 15 carbon atoms An imide group, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 80 carbon atoms, a heteroarylthio group having 1 to 80 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and a 6 to 20 carbon atom A substituent selected from the group consisting of an aryloxycarbonyl group is represented, R ₁₈ represents the following substituent (2), and n represents an integer of 2 or more.
Substituent (2)

(In General Formula (2), R ₉ , R ₁₀ , and R ₁₁ each independently represents an alkyl group, an aryl group, or a heteroaryl group, and at least one of R ₉ , R ₁₀ , and R ₁₁ is an alkyl group. And R ₉ , R ₁₀ and R ₁₁ do not all represent the same substituent at the same time (the wavy line represents the bonding position).

(In general formula (4), R ₁ , R ₂ , R _{4 to} R ₈ represent a hydrogen atom or a substituent, and R ₃ represents the substituent (2).) A carbazole compound represented by the following structural formula.