JP5753658B2 - Charge transport material and organic electroluminescent device - Google Patents

Description

  The present invention relates to a charge transport material and an organic electroluminescent device.

  Organic electroluminescent elements (hereinafter also referred to as “organic EL elements”, “light emitting elements”, “EL elements”, or “elements”) are actively researched and developed because they can emit light with high brightness when driven at a low voltage. Has been done. 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. Inventions relating to phosphorescent light-emitting elements using iridium complexes or platinum complexes as phosphorescent light-emitting materials have been disclosed (see, for example, Patent Documents 1 and 2). However, an element that achieves both high efficiency and high durability has not been developed yet.

One of the reasons why high efficiency and high durability cannot be achieved at the same time in phosphorescent light emitting devices is high in chemical stability and carrier injection / transport properties, and the lowest excited triplet energy (“T ₁ energy”, “T ₁ ”). In other words, a large amount of charge transport material is also limited. Charge T ₁ of the transport material is a large T ₁ is obtained from the phosphorescent material to the charge-transporting material for thereby quench T ₁ is less than the light emission of the phosphorescent material. Even when T ₁ of the charge transporting material is greater than T ₁ of the phosphorescent material, partly when T ₁ difference between the two is small, since the reverse energy transfer from the phosphorescent material to the charge-transporting material occurs, efficiency It causes a decrease in durability and durability. Accordingly, there is a need for a charge transport material having a sufficiently large T ₁ and high chemical stability and carrier injection / transport properties.

An invention relating to an organic electroluminescent device using a material composed of a compound in which a nitrogen-containing heterocyclic group is bonded to a phenylcarbazolyl group as shown below as a material for forming a light emitting layer together with a phosphorescent material is disclosed ( For example, see Patent Document 3). These materials have a large T ₁ and have relatively high hole / electron injection / transport properties and stability to holes and electrons, but the drive voltage and durability of the device are insufficient, and further improvements have been demanded.

  Patent Document 4 describes an organic EL device using a material having a structure in which a phenylcarbazolyl group as shown below and 2-phenylpyridine are connected by a silicon atom.

However, according to the study of the present inventor, the above materials have low chemical stability, insufficient driving durability, and improvement has been demanded.
Patent Document 5 describes an organic EL device using a material having a structure in which phenylcarbazolyl groups are connected by silicon atoms as shown below.

  However, since the above materials have low electron injection / transport properties and low stability to electrons, there are problems such as an increase in driving voltage when used in an element and insufficient driving durability.

  In addition, when there is a large change in voltage (in many cases, voltage increase) during driving, the charge balance in the device is lost, causing emission chromaticity shifts and difficult to use in circuit design. was there. Therefore, an element having a small voltage change during driving is demanded.

In the production of an organic electroluminescent device, as a method for forming a thin film which is an organic layer provided between a pair of electrodes, vacuum deposition is used as a vapor deposition method, spin coating method, printing method, ink jet method is used as a wet method. It has been broken.
In particular, when a wet method is used, it is possible to use high molecular organic compounds that are difficult to form in a dry process such as vapor deposition. When used in flexible displays, durability such as flex resistance and film strength is possible. This is suitable, especially when the area is increased.
However, the organic electroluminescent element obtained by the wet method has a problem that the luminous efficiency and the element durability are inferior.

US Pat. No. 6,303,238 International Publication No. 00/57676 International Publication No. 03/080760 JP 2009-152571 A US Patent Application Publication No. 2005/0064238

An object of the present invention, the chemical stability is high, is that T ₁ is to provide a large charge transporting material. Another object of the present invention is to provide an organic EL device that uses the charge transport material and has high efficiency, low driving voltage, high driving durability, and low voltage increase rate during driving.

The present invention is as follows.
1.
A charge transport material represented by the following general formula (1).

{(In General Formula (1), R ^{1 to} R ⁴ each independently represents a substituent, n 1 represents an integer of 0 to 5, and L ^A1 and L ^B1 each independently represent a single bond or a divalent linking group. the stands, ^{R 1} and ^{R 2} are bonded may form a ring ^.R 3 together, ^{R 4,} and at least two good .R ⁴ be bonded to each other to form a ring of ^{L A1} When a plurality of R ⁴ are present, the plurality of R ⁴ may be the same or different, and G ^B1 represents a structure represented by the following general formula (B1-1) or the following general formula (B2-1).

(In general formula (B1-1), each X independently represents a nitrogen atom or a carbon atom to which R ⁷ is bonded. Any one of R ^{5 to} R ⁷ is a bonding point with L ^B1 in general formula (1). , R ^{5 to} R ⁶ each independently represents a substituent, and among R ⁷ , the remaining represents a hydrogen atom or a substituent, provided that in the general formula (B1-1), next to the nitrogen atom at least if but a carbon atom, the carbon atom to .R ⁷ having a substituent as R ⁷ there are a plurality, a plurality of R ⁷ each of the good .R ⁵ to R ⁷ may be the same or different The two may be bonded to each other to form a ring, wherein in formula (B2-1), * is the point of attachment to L ^B1 in formula (1), E is a halogen atom, a perfluoroalkyl group , nitro group, selected from any one of a cyano group, R ⁸ is table substituents , N2 represents an integer of 1 to 5, n3 if the .E and ^{R 8} represents an integer of 0 to 4 there are a plurality, the plurality of E and ^{R 8} may be the same or different. However, generally (In formula (1), the partial structure represented by the following general formula (A1) and the partial structure represented by the following general formula (B1) do not represent the same structure.)

(In the general formula (A1) and the general formula (B1), R ^{3 to} R ⁴ , n1, L ^A1 , L ^B1 , and G ^B1 are R ^{3 to} R ⁴ , n1, and L ^A1 in the general formula (1), respectively. , L ^B1 and G ^B1 .)}
2.
2. The charge transport material according to 1 above, wherein the general formula (1) is represented by the following general formula (2).

{(In General Formula (2), R ^{9 to} R ¹² each independently represent a substituent, L ^A2 and L ^B2 each independently represent a single bond or a divalent linking group, and n4 and n5 each independently represent It represents an integer of 0 to 4, n6 and n7 ^{If .R} 9 ^{to R 12} each independently an integer of 0 to 5. there are a plurality, a plurality of ^R 9 ^{to R 12} may be the same or different. X 'represents a single bond, or .R ¹ and R ² represents a divalent linking group independently represent a substituent, R ¹ and R ² may be bonded to each other to form a ring .G ^B2 Represents a structure represented by the following general formula (B1-2) or the following general formula (B2-2).

(In General Formula (B1-2), each X independently represents a nitrogen atom or a carbon atom to which R ⁷ is bonded. Any one of R ^{5 to} R ⁷ is a bonding point with ^LB 2 in General Formula (2). , R ^{5 to} R ⁶ each independently represents a substituent, and among R ⁷ , the remaining represents a hydrogen atom or a substituent, provided that in the general formula (B1-1), next to the nitrogen atom at least if but a carbon atom, the carbon atom to .R ⁷ having a substituent as R ⁷ there are a plurality, a plurality of R ⁷ each of the good .R ⁵ to R ⁷ may be the same or different The two may be bonded to each other to form a ring, wherein in formula (B2-2), * represents a point of attachment to L ^B2 in formula (2), R ¹³ represents a substituent, and n8 represents an integer of 0 to 5, n9 if the ^{.R 13} represents an integer of 0 to 4 there are multiple , Or different in each plurality of R ¹³ are the same. However, in the general formula (2), and a partial structure represented by the partial structure and the following general formula represented by the following general formula (A2) (B2) It does not represent the same structure.)

(In General Formula (A2) and General Formula (B2), X ′, R ^{9 to} R ¹² , n4 to n7, L ^A2 , L ^B2 , and G ^B2 are X ′ and R ⁹ in General Formula (2), respectively. To R ¹² , n4 to n7, L ^A2 , L ^B2 , and G ^B2 .)}
3.
3. The charge transport material according to 2 above, wherein the general formula (2) is represented by the following general formula (3).

{(In the general formula (3), R ^{9 to} R ¹² each independently represents a substituent, n4 and n5 each independently represent an integer of 0 to 4, and n6 and n7 each independently represent an integer of 0 to 5) ^{If .R} 9 ^{to R 12} representing a presence of a plurality, the plurality of ^R 9 ^{to R 12} good be the same or different .X 'represents a single bond, or .R ¹ represents a divalent linking group and R ² each independently represents a substituent, R ¹ and R ² may .G ^B2 be bonded to each other to form a ring has the same meaning as G ^B2 in the formula (2). However, the general formula ( In 3), the partial structure represented by the following general formula (A3) and the partial structure represented by the following general formula (B3) do not represent the same structure.)

(In General Formula (A3) and General Formula (B3), X ′, R ^{9 to} R ¹² , n4 to n7, and G ^B2 are X ′, R ^{9 to} R ¹² , and n4 to R in General Formula (2), respectively. n7 and G ^B2 are synonymous.)}
4).
4. The charge transport material according to any one of 1 to 3, wherein the lowest excited triplet (T ₁ ) energy in the film state is 2.8 eV or more and 3.2 eV or less.
5.
The charge transport material according to any one of 1 to 4 above, which has a molecular weight of 600 or more and 1200 or less.
6).
6. A film comprising the charge transport material according to any one of 1 to 5 above.
7).
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 at least one of the organic layers is any one of the above 1 to 5 An organic electroluminescent device comprising the charge transport material described.
8).
8. The organic electroluminescent device according to 7 above, wherein the light emitting layer contains a phosphorescent light emitting material.
9.
9. The organic electroluminescent device according to 8 above, wherein the phosphorescent luminescent material has a maximum emission wavelength of 400 nm or more and 470 nm or less.
10.
10. The organic electroluminescence device according to any one of 7 to 9, which comprises the charge transport material according to any one of 1 to 5 in a light emitting layer or a layer adjacent to the light emitting layer.
11.
The organic electroluminescence device according to any one of 7 to 10, wherein the organic layer containing the charge transport material according to any one of 1 to 5 is a layer formed by a wet process.
12
A compound represented by the following general formula (1).

{(In General Formula (1), R ^{1 to} R ⁴ each independently represents a substituent, n 1 represents an integer of 0 to 5, and L ^A1 and L ^B1 each independently represent a single bond or a divalent linking group. the stands, ^{R 1} and ^{R 2} are bonded may form a ring ^.R 3 together, ^{R 4,} and at least two good .R ⁴ be bonded to each other to form a ring of ^{L A1} When a plurality of R ⁴ are present, the plurality of R ⁴ may be the same or different, and G ^B1 represents a structure represented by the following general formula (B1-1) or the following general formula (B2-1).

(In general formula (B1-1), each X independently represents a nitrogen atom or a carbon atom to which R ⁷ is bonded. Any one of R ^{5 to} R ⁷ is a bonding point with L ^B1 in general formula (1). , R ^{5 to} R ⁶ each independently represents a substituent, and among R ⁷ , the remaining represents a hydrogen atom or a substituent, provided that in the general formula (B1-1), next to the nitrogen atom at least if but a carbon atom, the carbon atom to .R ⁷ having a substituent as R ⁷ there are a plurality, a plurality of R ⁷ each of the good .R ⁵ to R ⁷ may be the same or different The two may be bonded to each other to form a ring, wherein in formula (B2-1), * is the point of attachment to L ^B1 in formula (1), E is a halogen atom, a perfluoroalkyl group , nitro group, selected from any one of a cyano group, R ⁸ is table substituents , N2 represents an integer of 1 to 5, n3 if the .E and ^{R 8} represents an integer of 0 to 4 there are a plurality, the plurality of E and ^{R 8} may be the same or different. However, generally (In formula (1), the partial structure represented by the following general formula (A1) and the partial structure represented by the following general formula (B1) do not represent the same structure.)

(In the general formula (A1) and the general formula (B1), R ^{3 to} R ⁴ , n1, L ^A1 , L ^B1 , and G ^B1 are R ^{3 to} R ⁴ , n1, and L ^A1 in the general formula (1), respectively. , L ^B1 and G ^B1 .)}
13.
A compound represented by the following general formula (2 ′).

{(In the general formula (2 ′), R ^{9 to} R ¹² each independently represent a substituent, L ^A2 and L ^B2 each independently represent a single bond or a divalent linking group, and n4 and n5 each independently a represents an integer of 0 to 4, n6 and n7 ^{If .R} 9 ^{to R 12} each independently an integer of 0 to 5. there are a plurality, a plurality of ^R 9 ^{to R 12} may be the same or different R ¹ and R ² each independently represent a substituent and may be bonded to each other to form a ring, X ′ represents a single bond or a divalent linking group, and G ^B2 represents the following general formula ( B1-2) or represents a structure represented by the following general formula (B2-2). ^However, if ^{G B2} has a structure represented by the following formula (B1-2) ^is, -L B2 ^{-G B2} Is bonded to the meta or para position with respect to the silicon atom.)

(In General Formula (B1-2), each X independently represents a nitrogen atom or a carbon atom. Any of R ^{5 to} R ⁷ is a bonding point with ^LB 2 in General Formula (2 ′), and R ⁵ to The remaining ones of R ⁶ each independently represent a substituent, and the remaining ones of R ⁷ represent a hydrogen atom or a substituent, provided that a carbon atom is adjacent to the nitrogen atom in the general formula (B1-1). some cases, the carbon atom if .R ⁷ having a substituent as R ⁷ there is a plurality, at least two of the good .R ⁵ to R ⁷ be different in each plurality of R ⁷ are identical to each other In general formula (B2-2), * is a point of attachment to L ^B2 in general formula (2 ′), R ¹³ represents a substituent, and n8 is 0 to 0. represents 5 integers, n9 if the ^{.R 13} represents an integer of 0 to 4 there are a plurality, a plurality of R ³ may be the same or different. However, in the general formula (2 '), the partial structure represented by the partial structure and the following general formula represented by the following general formula (A2) (B2) is identical in structure Is not represented.)

(In General Formula (A2) and General Formula (B2), X ′, R ^{9 to} R ¹² , n4 to n7, L ^A2 , L ^B2 , and G ^B2 are X ′ and R in General Formula (2 ′), respectively. ^{9 ~R 12, n4~n7,} the same meaning as ^{L A2,} L ^B2, and ^{G B2.)}}
14
14. The compound according to 13, wherein the general formula (2 ′) is represented by the following general formula (3 ′).

{( 'In), X' formula ^{(3, R 9 ~R 12,} n4~n7, and ^{G B2} 'X in)' is the general formula ^{(2, R 9 ~R 12,} n4~n7, and ^{G B2} and if synonymous ^{.G B2} has a structure represented by the general formula (B1-2) is, ^{-G B2} is in meta or para position with respect to the silicon atom. However, the general formula (3 In '), the partial structure represented by the following general formula (A3) and the partial structure represented by the following general formula (B3) do not represent the same structure.)

(In General Formula (A3) and General Formula (B3), X ′, R ^{9 to} R ¹² , n4 to n7, and GB ² are X ′, R ^{9 to} R ¹² , and n4 in General Formula (2 ′), respectively. ～N7, and it is synonymous with ^{G B2.)}}
15.
The light-emitting device using the organic electroluminescent element in any one of said 7-11.
16.
The display apparatus using the organic electroluminescent element in any one of said 7-11.
17.
The illuminating device using the organic electroluminescent element in any one of said 7-11.

According to the present invention, a charge transport material having high chemical stability and a large T ₁ is provided. In addition, according to the present invention, there is provided an organic EL device using the charge transport material, having high efficiency, low driving voltage, high driving durability, and low voltage increase rate during driving.

It is the schematic which shows an example (1st Embodiment) of the layer structure of the organic EL element which concerns on this invention. It is the schematic which shows an example (2nd Embodiment) of the light-emitting device which concerns on this invention. It is the schematic which shows an example (3rd Embodiment) of the illuminating device which concerns on this invention.

[Charge Transport Material Represented by General Formula (1)]
Hereinafter, the charge transport material represented by the general formula (1) will be described.
Charge transporting material represented by the general formula (1) may, because of a large high T ₁ chemical stability and carrier transportability, it is particularly suitable for the organic EL element.

{(In General Formula (1), R ^{1 to} R ⁴ each independently represents a substituent, n 1 represents an integer of 0 to 5, and L ^A1 and L ^B1 each independently represent a single bond or a divalent linking group. the stands, R ^3, if ^{R 4,} and at least two of good .R ⁴ be bonded to each other to form a ring of L ^A1 there are a plurality, or different in each plurality of R ⁴ are the same G ^B1 represents a structure represented by the following general formula (B1-1) or the following general formula (B2-1).

(In general formula (B1-1), each X independently represents a nitrogen atom or a carbon atom to which R ⁷ is bonded. Any one of R ^{5 to} R ⁷ is a bonding point with L ^B1 in general formula (1). , R ^{5 to} R ⁶ each independently represents a substituent, and among R ⁷ , the remaining represents a hydrogen atom or a substituent, provided that in the general formula (B1-1), next to the nitrogen atom at least if but a carbon atom, the carbon atom to .R ⁷ having a substituent as R ⁷ there are a plurality, a plurality of R ⁷ each of the good .R ⁵ to R ⁷ may be the same or different The two may be bonded to each other to form a ring, wherein in formula (B2-1), * is the point of attachment to L ^B1 in formula (1), E is a halogen atom, a perfluoroalkyl group , nitro group, selected from any one of a cyano group, R ⁸ is table substituents , N2 represents an integer of 1 to 5, n3 is an integer of 0-4.
If E and R ⁸ there are a plurality of, or different in each plurality of E and R ⁸ are the same. However, in the general formula (1), the partial structure represented by the following general formula (A1) and the partial structure represented by the following general formula (B1) do not represent the same structure. )

(In the general formula (A1) and the general formula (B1), R ^{3 to} R ⁴ , n1, L ^A1 , L ^B1 , and G ^B1 are R ^{3 to} R ⁴ , n1, and L ^A1 in the general formula (1), respectively. , L ^B1 and G ^B1 .)}

The charge transport material represented by the general formula (1) has a structure in which the partial structure represented by the general formula (A1) and the partial structure represented by the general formula (B1) are connected by a silicon atom. The partial structure represented by the general formula (A1) and the partial structure represented by the general formula (B1) are different from each other, and the partial structure represented by the general formula (A1) functions as a hole transport site. The partial structure represented by the general formula (B1) can function as an electron transporting site.
The charge transport material represented by the general formula (1) exhibits both carrier (electron / hole) transport properties by having an electron transport site and a hole transport site in the molecule, and also against oxidation (radical cation state). It is also a chemically stable material against reduction (radical anion state).
In addition, by connecting the electron transport site and the hole transport site via a silicon atom, they can be connected without conjugating them, and the electron transport site and the hole transport in the molecule can be maintained while maintaining high T ₁ energy. The functions of the parts are more clearly assigned and exhibit good characteristics (such as durability and light emission efficiency) when used in an element.

By selecting R ^{1 to} R ⁴ , L ^A1 , L ^B1 , and G ^{B1 in} the general formula (1), the molecular assembly state, ionization potential energy (Ip), T ₁ energy, and the like in the film can be controlled. Although it depends on the application, Ip is preferably 5.0 to 7.0, more preferably 5.3 to 6.5, and particularly preferably from the viewpoint of chemical stability and hole transportability of the compound. 5.5-6.2. Moreover, the the _{T 1} energy in the film state is preferably 2.5～4.0EV, more preferably 2.7～3.7EV, particularly preferably 2.8～3.2EV.
Note that Ip can be measured by atmospheric photoelectron spectroscopy of a thin film of material (for example, measured using a Riken Keiki AC-2). In addition, Ip is known to correlate with the redox potential in the solution state of the material (for example, Macromol. 1995, 28, 1180-1196. Etc.), and is estimated from the oxidation potential in CV (cyclic voltammetry) measurement. You can also. 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 a vacuum deposition method, and the phosphorescence emission spectrum of the thin film is F-7000 Hitachi Spectrofluorimeter (Hitachi High-Technologies) under 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.

As the substituent represented by R ^{1 to} R ⁴ in the general formula (1), those exemplified as the following substituent group A can be applied.

(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.
In the present invention, the “carbon number” of a substituent such as an alkyl group includes a case where a substituent such as an alkyl group may be substituted by another substituent, and also includes the carbon number of the other substituent. Used to mean

The charge transport material represented by the general formula (1) is preferably an alkyl group having 1 to 18 carbon atoms as R ^{1 to} R ⁴ from the viewpoint of chemical stability, carrier transport ability, and T ₁ energy. An aryl group having 6 to 18 carbon atoms, an amino group having 2 to 12 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, a heterocyclic oxy group having 2 to 10 carbon atoms, and the number of carbon atoms An acyl group having 1 to 18 carbon atoms, an acylamino group having 1 to 18 carbon atoms, a sulfonylamino group having 1 to 18 carbon atoms, a sulfamoyl group having 2 to 18 carbon atoms, a carbamoyl group having 2 to 18 carbon atoms, and 1 to 18 carbon atoms Alkylthio group, C2-C10 heterocyclic thio group, C1-C18 sulfonyl group, halogen atom, cyano group, nitro group, C2-C10 heterocyclic group, C3-C18 silyl group , With 3-18 carbon atoms A silyloxy group, a phosphoryl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an amino group having 2 to 12 carbon atoms, a halogen atom, and a cyano group. , A nitro group, a heterocyclic group having 2 to 10 carbon atoms, a silyl group having 3 to 18 carbon atoms, and a phosphoryl group having 1 to 18 carbon atoms, particularly preferably an alkyl group having 1 to 18 carbon atoms, a halogen atom, and cyano. A silyl group having 3 to 18 carbon atoms.
R ¹ and R ² are preferably an alkyl group, an aryl group, a heteroaryl group, a silyloxy group, or a thienyl group, and are an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Is more preferable, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms is more preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group is particularly preferable. . R ¹ and R ² may be bonded to each other to form a ring.
R ³ is preferably an alkyl group, an alkenyl group, or an aryl group, and is preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. More preferably, it is more preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and an ethyl group, an allyl group, a phenyl group, or a biphenyl group. It is particularly preferred.
R ⁴ is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, Or it is still more preferable that it is a C6-C12 aryl group, and it is especially preferable that it is a phenyl group or a biphenyl group. R ⁴ may be bonded to each other to form a ring, and preferably forms a naphthalene ring.
In the general formula (1), n1 is preferably 0 to 3, more preferably 0 to 2, still more preferably 0 to 1, particularly preferably 0 from the viewpoint of carrier injection and transportability. is there.
R ³ and R ⁴ are preferably bonded to each other to form a ring. Moreover, this ring may contain atoms other than a carbon atom and a nitrogen atom, for example, a sulfur atom, an oxygen atom, a silicon atom, etc. are mentioned. The ring formed by combining R ³ and R ⁴ with each other is preferably a ring having 4 to 30 carbon atoms, more preferably a ring having 4 to 20 carbon atoms, and still more preferably forming a carbazolyl group.
R ^{1 to} R ⁴ may further have a substituent, and examples of the substituent include the substituent group A, and preferably an alkyl group, an aryl group, a halogen atom, a fluoroalkyl group, or It is a silyl group, More preferably, it is a C1-C20 alkyl group or a C6-C20 aryl group.

The charge transport material represented by the general formula (1) is preferably a single bond, alkylene having 1 to 18 carbon atoms, as L ^A1 and L ^B1 from the viewpoints of chemical stability, carrier transport ability, and T ₁ energy. An aryl group substituted with an arylene group having 6 to 24 carbon atoms, a divalent heterocyclic group having 2 to 10 carbon atoms, an alkyl group or an aryl group having 1 to 20 carbon atoms (-NR- (R: an alkyl group or an aryl group); Group)), a silylene group substituted with an alkyl group having 2 to 30 carbon atoms or an aryl group, a phosphoryl group, a carbonyl group, a sulfonyl group, an oxy group (—O—), and a thio group (—S—). These linking groups can be used in combination.
More preferably, it is a linking group arbitrarily selected from a single bond, an alkylene group having 1 to 18 carbon atoms, and an arylene group having 6 to 24 carbon atoms, and a single bond, a phenylene group or a biphenylene group is still more preferable.
L ^A1 is preferably bonded to R ³ or R ⁴ to form a ring.
Preferred specific examples of L ^A1 and L ^B1 are shown below. A structure obtained by combining a plurality selected from the following structures is also preferable. * Represents a binding site.

In the general formula ^{(1), G B1} represents a structure represented by the following general formula (B1-1) or the following general formula (B 2 - 1).

(In general formula (B1-1), each X independently represents a nitrogen atom or a carbon atom to which R ⁷ is bonded. Any one of R ^{5 to} R ⁷ is a bonding point with L ^B1 in general formula (1). , R ^{5 to} R ⁶ each independently represents a substituent, and among R ⁷ , the remaining represents a hydrogen atom or a substituent, provided that in the general formula (B1-1), next to the nitrogen atom If there is a carbon atom, said carbon atom if .R ⁷ having a substituent as R ⁷ there are a plurality, a plurality of R ⁷ may be the same or different. formula (B 2 - 1) in * is the point of attachment to the L ^B1 in the formula (1), E is selected from one halogen atom, a perfluoroalkyl group, a nitro group, a cyano group, R ⁸ represents a substituent, n2 is represents an integer of 1 to 5, n3 is .E and ^{R 8} represents an integer of 0 to 4 If the number present may be different in each plurality of E and R ⁸ are the same.)

  The structure represented by the general formula (B1) has an electron deficiency and can function as an electron transporting site in the charge transporting material of the present invention.

In General Formula (B1-1), each X independently represents a nitrogen atom or a carbon atom to which R ⁷ is bonded. As general formula (B1-1), the structure of the following general formula (B1-1-1)-general formula (B1-1-8) is preferable, General formula (B1-1-3), General formula (B- 1-5), the structure of any of general formula (B-1-6) and general formula (B-1-8) is more preferable.

(In the general formula (b1-1-1) ~ formula ^(B1-1-8), becomes a point of attachment to ^{L B1} or in the general formula (1) ^{R 5 ~R 7, R 5 ~R} 6 The remaining of each independently represents a substituent, and the remaining of R ⁷ represents a hydrogen atom or a substituent, provided that in the general formula (B1-1), the nitrogen atom is adjacent to a carbon atom. is carbon atom if .R ⁷ having a substituent as R ⁷ there is a plurality, or different in each plurality of R ⁷ are the same.)

  In general formula (B1-1), it is preferable that 1-2 X represents a nitrogen atom. As general formula (B1-1), general formula (B1-1-2)-general formula (B1-1-7) are preferable.

In the general formulas (B1-1) and (B2-1), when R ^{5 to} R ⁷ represent a substituent, those exemplified as the substituent group A can be applied as the substituent.
R ^{5 to} R ⁷ in the general formula (B1-1) each independently represent a substituent when R ^{5 to} R ⁶ do not ^serve as a bonding point with L ^B1 in the general formula (1), and R ^{5 7} represents a hydrogen atom or a substituent, and in the general formula (B1-1), when the nitrogen atom is adjacent to a carbon atom, the carbon atom has a substituent as R ⁷ . As a result, when the charge transport material of the present invention is used in a device, the light emission efficiency and durability of the device are improved. Although the reason for the improvement in luminous efficiency and durability is not clearly understood, in the charge transport material of the present invention, the carbon atom next to the nitrogen atom in the general formula (B1-1) is a reactive site. Therefore, it is preferable to protect with a substituent from the viewpoint of chemical stability, or the lone pair of chemically active nitrogen atom is sterically protected when the substituent is bulkier than the hydrogen atom. From the above, it can be considered preferable. From the viewpoint of chemical stability of the material, when R ^{5 to} R ⁷ represent a substituent, an alkyl group, an aryl group, or a heteroaryl group is preferable, and an alkyl group having 1 to 20 carbon atoms and 6 to 20 carbon atoms is preferable. Are more preferable, t-butyl group or phenyl group is more preferable, and phenyl group is particularly preferable.
E is selected from a halogen atom, a perfluoroalkyl group, a nitro group, and a cyano group, and can function as an electron withdrawing group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. As a perfluoroalkyl group, a C1-C20 perfluoroalkyl group is preferable and a trifluoromethyl group is more preferable. E is particularly preferably a cyano group from the viewpoint of stability against oxidation and reduction.
n2 is preferably 1 to 4, more preferably 1 to 3, from the viewpoint of carrier injection and transportability.
R ⁸ is preferably an alkyl group, an aryl group, or a halogen atom, more preferably an alkyl group having 1 to 10 carbon atoms or a halogen atom, and still more preferably a methyl group or a fluorine atom.
n3 is preferably 0 to 3, more preferably 0 to 2, still more preferably 0 to 1, and particularly preferably 0 from the viewpoint of carrier injection and transportability.

When G ^B1 represents the general formula (B1-1), the general formula (1) is preferably the following general formula (1-1) to general formula (1-5), and the general formula (1-1) or general formula Either (1-2) or general formula (1-4) is more preferable. The following general formula (1-1) is a case where R ⁵ is a bonding point with L ^B1, and the following general formula (1-2) is a case where R ⁶ is a bonding point with L ^B1. Formulas (1-3) to (1-5) are cases where R ⁷ is a bonding point with L ^B1 .

(In General Formulas (1-1) to (1-5), R ^{1 to} R ⁴ each independently represents a substituent, n1 represents an integer of 0 to 5, and L ^A1 and L ^B1 each independently represent a single group. Represents a bond or a divalent linking group, and R ¹ and R ² may be bonded to each other to form a ring, and at least two of R ³ , R ⁴ and L ^A1 may be bonded to each other to form a ring; and if even a good .R ⁴ there are a plurality, the plurality of R ⁴ are each selected from the same or different .X each independently represent a nitrogen atom, or a carbon atom to which R ⁷ is bonded .R ⁵ and R ⁶ each independently represents a substituent, and R ⁷ represents a hydrogen atom or a substituent, provided that in general formulas (1-1), (1-2), (1-3), and (1-5), If either X represents a nitrogen atom, X next to the nitrogen atom represents a carbon atom to which R ⁷ is bonded, the R ⁷ represents a substituent .R If is there is a plurality, a plurality of R ⁷ are each at least two of the good .R ⁵ to R ⁷ may be the same or different may be bonded to each other to form a ring.)

If G ^B1 represents a general formula (B1-2), the following formula is a general formula (1) (1-6) is preferred.

(In General Formula (1-6), R ^{1 to} R ⁴ each independently represents a substituent, n 1 represents an integer of 0 to 5, and L ^A1 and L ^B1 each independently represent a single bond or a divalent linkage. R ¹ and R ² may be bonded to each other to form a ring, and at least two of R ³ , R ⁴ and L ^A1 may be bonded to each other to form a ring. ^{When a} plurality of ⁴ are present, the plurality of R ⁴ may be the same or different, E is selected from a halogen atom, a perfluoroalkyl group, a nitro group, and a cyano group, and R ⁸ represents a substituent. , n2 represents an integer of 1 to 5, n3 if the .E and ^{R 8} represents an integer of 0 to 4 there are a plurality, the plurality of E and ^{R 8} may be the same or different.)

In the general formula (1), when L ^B1 is an arylene group and G ^B1 has a structure represented by the general formula (B1-1), G ^B1 is meta-position to the silicon atom of L ^B1 or Bonding at the para position is preferred. By binding to the meta or para position, the strain of the molecule is reduced, and the luminous efficiency and durability of the device are improved as compared with the case of binding to the ortho position. In particular, this effect is remarkable in an element in which an organic layer containing the charge transport material represented by the general formula (1) is manufactured by a wet process.

In the general formula (1), preferred specific examples of the structure represented by ^GB1 are shown below. In the structures of the following specific examples, * represents a bonding point with ^LB1 in the general formula (1).

In the above structure, E is selected from a halogen atom, a perfluoroalkyl group, a nitro group, and a cyano group.
In the compound represented by the general formula (1), the partial structure represented by the general formula (A1) can function as a hole transporting site. The preferred range of the partial structure represented by the general formula (A1) is in accordance with the preferred ranges of R ³ , R ⁴ , n1 and L ^A1 .

  Preferred specific examples of the partial structure represented by formula (A1) are shown below. In the structures of the following specific examples, * represents a bonding point with a silicon atom in the general formula (1).

  However, in the present invention, in the general formula (1), the partial structure represented by the following general formula (A1) and the partial structure represented by the following general formula (B1) do not represent the same structure. In the general formula (1), a compound in which the partial structure represented by the general formula (A1) and the partial structure represented by the general formula (B1) have the same structure is used when the organic EL device is used. It is inferior in luminous efficiency and durability as compared with the case of using the compound of the invention.

In general formula (A1) and general formula (B1), R ^{3 to} R ⁴ , n 1, L ^A1 , L ^B1 , and G ^B1 are R ^{3 to} R ⁴ , n1, L ^A1 , and R 1 in general formula (1), respectively. It is synonymous with L ^B1 and G ^B1 , and the preferred range is also the same.

  The charge transport material represented by the general formula (1) is preferably a charge transport material represented by the following general formula (2) from the viewpoint of chemical stability and carrier transport property.

[Charge transport material represented by formula (2)]
Hereinafter, the charge transport material represented by the general formula (2) will be described.

{(In General Formula (2), R ^{9 to} R ¹² each independently represent a substituent, L ^A2 and L ^B2 each independently represent a single bond or a divalent linking group, and n4 and n5 each independently represent It represents an integer of 0 to 4, n6 and n7 ^{If .R} 9 ^{to R 12} each independently an integer of 0 to 5. there are a plurality, a plurality of ^R 9 ^{to R 12} may be the same or different. R ¹ and ^{R 2} have the same meanings as ^{R 1} and ^{R 2} in the general formula (1) .X 'represents a single bond, or a divalent linking group ^{.G B2} is the following formula (B1-2), or (The structure represented by the following general formula (B2-2) is represented.)

In (formula (B1-2), X and ^R 5 to R ⁷ is a general formula (synonymous with X and ^R 5 to R ⁷ in B1-1). In the general formula (B2-2), * the general a point of attachment to ^{L B2} in the formula ^{(2), R 13} represents a substituent, n8 represents an integer of 0 to 5, n9 if the ^{.R 13} represents an integer of 0 to 4 there are a plurality of , or different in each plurality of R ¹³ are the same. However, in the general formula (2), and a partial structure represented by the partial structure and the following general formula represented by the following general formula (A2) (B2) It does not represent the same structure.)

(In General Formula (A2) and General Formula (B2), X ′, R ^{9 to} R ¹² , n4 to n7, L ^A2 , L ^B2 , and G ^B2 are X ′ and R ⁹ in General Formula (2), respectively. To R ¹² , n4 to n7, L ^A2 , L ^B2 , and G ^B2 .)}

In the general formula (2), ^{R 1} and ^{R 2} have the same meanings as ^{R 1} and ^{R 2} in the general formula (1), and preferred ranges are also the same.

Examples of R ^{9 to} R ¹² include the substituent group A. R ⁹ and R ¹⁰ are preferably the same as R ⁸ . R ¹¹ and R ¹² are preferably the same as R ⁴ .
n4 to n7 are preferably 0 to 3, more preferably 0 to 2, still more preferably 0 to 1, and particularly preferably 0 from the viewpoint of carrier injection and transportability.
^Examples of L ^A2 and L ^B2 include the same as L ^A1 and L ^B1, and preferred ranges are also the same.
X ′ represents a single bond or a divalent linking group. As the divalent linking group, an alkylene group, a cycloalkylene group, an arylene group, -S-, -O-, and a divalent linking group obtained by combining these are preferable. X ′ is preferably a single bond, an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 30 carbon atoms, —S— or —O—, and more preferably a single bond, carbon An alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, and -S- are more preferable, and a single bond is particularly preferable.

In General Formula (2), G ^B2 represents a structure represented by General Formula (B1-2) or General Formula (B2-2).
In the general formula (B1-2), X and ^R 5 to R ⁷ has the same meaning as X and ^R 5 to R ⁷ in the general formula (B1-1), and preferred ranges are also the same.
In General Formula (B2-2), R ¹³ represents a substituent, n8 represents an integer of 0 to 5, and n9 represents an integer of 0 to 4. R ¹³ in the presence of two or more may be different in each plurality of R ¹³ are the same.
A preferred range for R ¹³ is the same as R ⁸ described above. The preferable ranges of n8 and n9 are the same as those of n2 and n3, respectively.

However, in the general formula (2), the partial structure represented by the general formula (A2) and the partial structure represented by the general formula (B2) do not represent the same structure.
In general formula (A2) and general formula (B2), X ′, R ^{9 to} R ¹² , n4 to n7, L ^A2 , L ^B2 , and G ^B2 are X ′, R ⁹ to R in General Formula (2), respectively. ^{R 12, n4~n7, L A2,} L B2, and has the same meaning as ^{G B2,} preferred ranges are also the same.

  The compound represented by the general formula (2) is more preferably a compound represented by the following general formula (3) from the viewpoint of chemical stability and carrier transport ability.

[Charge Transport Material Represented by General Formula (3)]
Hereinafter, the charge transport material represented by the general formula (3) will be described.

{(In the general formula ^{(3), X ', R} 9 ~R 12, n4~n7, and ^{G B2} X in the general formula ^{(2)', R 9 ~R} 12, n4~n7, and ^{G B2} synonymous However, in the general formula (3), the partial structure represented by the following general formula (A3) and the partial structure represented by the following general formula (B3) do not represent the same structure.)

(In General Formula (A3) and General Formula (B3), X ′, R ^{9 to} R ¹² , n4 to n7, and G ^B2 are X ′, R ^{9 to} R ¹² , and n4 to R in General Formula (2), respectively. n7 and G ^B2 are synonymous.)}

In the general formula ^{(3), X ', R} 9 ~R 12, n4~n7, and ^{G B2} X in the general formula ^{(2)', R 9 ~R} 12, n4~n7, and ^{G B2} and interchangeably The preferred range is also the same.
In the general formula (A3) and the general formula (B3), X ′, R ^{9 to} R ¹² , n4 to n7, and GB ² are X ′, R ^{9 to} R ¹² , and n4 to n7 in the general formula (2), respectively. , and have the same meaning as G ^B2, preferred ranges are also the same.

T ₁ energy generally decreases as the π-conjugated system spreads in the molecule. In addition, since the T ₁ energy of a molecule is determined by a partial structure in which the T ₁ energy is the smallest in the molecule, if there is a portion where the π-conjugated system is wide even at one location in the molecule, the T ₁ energy is determined at that portion. Thus for general T ₁ is made smaller to have a structure in which biaryl structure or an aromatic ring is condensed in a molecule in the molecule, using short-wavelength emission wavelength (maximum emission wavelength below 500 nm) in combination with phosphorescent material The case is not preferred.
In addition, the charge transport material of the present invention has a large T ₁ because the electron transport site and the hole transport site are linked via a silicon atom, so that the π-conjugated system is cut by the silicon atom.

The molecular weight of the charge transport material of the present invention is preferably 600 to 1200, more preferably 600 to 1100, and particularly preferably 600 to 1000. If the molecular weight is in this range, the stability of the film state is excellent, and it is easy to achieve high purity in terms of solubility in a solvent and sublimation temperature. As an index of film state stability, there is a glass transition temperature Tg, and Tg is preferably 60 to 400 ° C, more preferably 100 to 400 ° C, and particularly preferably 130 to 400 ° C.
Here, Tg can be confirmed by thermal measurement such as differential scanning calorimetry (DSC) and differential thermal analysis (DTA), X-ray diffraction (XRD), and polarization microscope observation. In addition, since the charge transport material of the present invention has a low purity, it functions as a trap for charge transport. Therefore, the higher the purity of the charge transport material of the present invention, the better. The purity can be measured by, for example, high performance liquid chromatography (HPLC), and the area ratio when detected with a light absorption intensity of 254 nm is preferably 95.0% or more, more preferably 97.0% or more, Preferably it is 99.0% or more, Most preferably, it is 99.5% or more. In the present invention, from the viewpoint of device durability, it is preferable not to contain a halogen compound other than the charge transport material of the present invention, and it is preferable that no halogen compound is detected other than the charge transport material of the present invention by HPLC.

  As known for the carbazole-based material described in WO2008 / 117889, a material in which part or all of the hydrogen atoms in the charge transport material of the present invention are substituted with deuterium atoms can also be preferably used as the charge transport material.

  Specific examples of the charge transport material of the present invention are illustrated below, but the present invention is not limited thereto.

The charge transport material of the present invention can be synthesized by combining various known synthesis methods. Hereinafter, the synthesis method will be described.
Literature Asian J.M. Chem. , 2009, 21, 2516. A carbazole derivative having various substituents can be synthesized with reference to the description of the
Reference J.M. Chem. Soc. , 1931, 2568. , J .; Am. Chem. Soc. , 1936, 58, 1278. , J .; Am. Chem. Soc. 1938, 60, 1458. , J .; Chem. Soc. C, 1971, 2537. , Angew. Chem. Int. Ed. 1991, 30, 1646. , J .; Mater. Chem. , 2007, 17, 1209. , And acridan derivatives having various substituents can be synthesized with reference to the description of WO2007 / 110228 and the like.
Reference Chem. Rev. 2005, 105, 2873. Etc., indole derivatives having various substituents can be synthesized.
Reference Angew. Chem. Int. Ed. , 2003, 42, 5400. Various arylamine derivatives can be synthesized with reference to the description of the above.
A nitrogen-containing aromatic heterocyclic compound can be synthesized with reference to the descriptions of documents WO2003 / 080760, WO2005 / 085387, WO2005 / 022962, and the like.
A silicon compound can be synthesized with reference to the descriptions in documents US2005214572 and JP2009-152571A.
The charge transport material of the present invention can be synthesized by combining the reactions described in the above documents.

  The charge transport material of the present invention is excellent in chemical stability and carrier transport ability, and can be preferably used in various organic electronic devices. Any electronic device may be used, and examples thereof include organic electroluminescent elements, organic transistors, organic photoelectric conversion elements, gas sensors, organic rectifying elements, organic inverters, and information recording elements. The organic photoelectric conversion element can be used for both optical sensor applications (solid-state imaging elements) and energy conversion applications (solar cells). Preferred are organic electroluminescent elements, organic photoelectric conversion elements and organic transistors, more preferred are organic electroluminescent elements and organic photoelectric conversion elements, and particularly preferred are organic electroluminescent elements.

The present invention also relates to a film containing the charge transport material represented by the general formula (1). The film of the present invention can be used as an organic layer in an organic electroluminescence device.
The present invention also relates to a compound represented by the following general formula (2 ′).

{(In the general formula (2 ′), R ^{9 to} R ¹² each independently represent a substituent, L ^A2 and L ^B2 each independently represent a single bond or a divalent linking group, and n4 and n5 each independently a represents an integer of 0 to 4, n6 and n7 ^{If .R} 9 ^{to R 12} each independently an integer of 0 to 5. there are a plurality, a plurality of ^R 9 ^{to R 12} may be the same or different R ¹ and R ² each independently represent a substituent and may be bonded to each other to form a ring, X ′ represents a single bond or a divalent linking group, and G ^B2 represents the following general formula ( B1-2) or represents a structure represented by the following general formula (B2-2). ^However, if ^{G B2} has a structure represented by the following formula (B1-2) ^is, -L B2 ^{-G B2} Is bonded to the meta or para position with respect to the silicon atom.)

(In General Formula (B1-2), each X independently represents a nitrogen atom or a carbon atom. Any of R ^{5 to} R ⁷ is a bonding point with ^LB 2 in General Formula (2 ′), and R ⁵ to The remaining ones of R ⁶ each independently represent a substituent, and the remaining ones of R ⁷ represent a hydrogen atom or a substituent, provided that a carbon atom is adjacent to the nitrogen atom in the general formula (B1-1). In some cases, the carbon atom has a substituent as R ^{7. In} general formula (B2-2), * represents a point of attachment to L ^B2 in general formula (2 ′), and R ¹³ represents a substituent. , n8 represents an integer of 0 to 5, n9 if the ^{.R 13} represents an integer of 0 to 4 there are a plurality, a plurality of ^{R 13} may be the same or different. However, the general formula (2 ' ), A partial structure represented by the following general formula (A2) and a partial structure represented by the following general formula (B2) The structure does not represent the same structure.)

(In General Formula (A2) and General Formula (B2), X ′, R ^{9 to} R ¹² , n4 to n7, L ^A2 , L ^B2 , and G ^B2 are X ′ and R in General Formula (2 ′), respectively. ^{9 ~R 12, n4~n7,} the same meaning as ^{L A2,} L ^B2, and ^{G B2.)}}

The preferred range and specific examples of the compound represented by the general formula (2 ′) are the same as those described above as the preferred range and specific examples of the general formula (2). The compound of the present invention can be used as, for example, a charge transport material.
The general formula (2 ′) is preferably represented by the following general formula (3 ′).

{( 'In), X' formula ^{(3, R 9 ~R 12,} n4~n7, and ^{G B2} 'X in)' is the general formula ^{(2, R 9 ~R 12,} n4~n7, and ^{G B2} and if synonymous ^{.G B2} has a structure represented by the general formula (B1-2) is, ^{-G B2} is in meta or para position with respect to the silicon atom. However, the general formula (3 In '), the partial structure represented by the following general formula (A3) and the partial structure represented by the following general formula (B3) do not represent the same structure.)

(In General Formula (A3) and General Formula (B3), X ′, R ^{9 to} R ¹² , n4 to n7, and GB ² are X ′, R ^{9 to} R ¹² , and n4 in General Formula (2 ′), respectively. ～N7, and it is synonymous with ^{G B2.)}}

  Preferred ranges and specific examples of the compound represented by the general formula (3 ′) are the same as those described above as the preferred ranges and specific examples of the general formula (3).

  Next, an organic electroluminescent element will be described.

[Organic electroluminescence device]
The organic electroluminescent device of the present invention is 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, and at least one of the organic layers. Includes a charge transport material represented by the general formula (1).
In the organic electroluminescent element of the present invention, the charge transport material represented by the general formula (1) is preferably contained in the light emitting layer or a layer adjacent to the light emitting layer.
The organic electroluminescent element of the present invention has at least one organic layer between the light emitting layer and the cathode, and the charge transport material represented by the general formula (1) is used as the organic layer between the light emitting layer and the cathode. It is preferable to contain.

In the organic electroluminescent element of the present invention, the light emitting layer is an organic layer, but may further have a plurality of organic layers.
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 device 10 according to the present invention shown in FIG. 1, a light emitting layer 6 is sandwiched between an anode 4 and a cathode 9 on a support substrate 12. Specifically, the hole injection layer 4, the hole transport layer 5, the light emitting layer 6, the hole block layer 7, and the electron transport layer 8 are laminated in this order between the anode 4 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 / 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 suitable for any of dry film forming methods such as vapor deposition and sputtering, and wet film forming methods (wet processes) such as transfer, printing, and spin coating. Can be formed.
In the present invention, the charge transport material represented by the general formula (1) is easily dissolved in an aromatic organic solvent such as toluene or a halogen organic solvent such as chloroform and has low crystallinity. It is preferable from the viewpoint of manufacturing cost reduction. In addition, it is preferable to form the organic layer containing the charge transport material represented by the general formula (1) by a wet process because the performance of the element such as durability is improved.

(Light emitting layer)
The light emitting layer contains at least one light emitting material.
<Light emitting material>
The light emitting material in the present invention may use light emitted from excited singlet (fluorescence) or light emitted from excited triplet (phosphorescence), but from the viewpoint of light emission efficiency, the one using phosphorescence. Is preferred.
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. At least one of the light emitting materials is preferably a phosphorescent light emitting material.
It is preferable that at least one of the light emitting materials is a platinum complex or an iridium complex.
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.

In the present invention, the phosphorescent light emitting material, the effect when combined with the charge transport material (in the larger i.e. T ₁₎ that the more the present invention short wavelength is remarkable, maximum emission wavelength of the phosphorescent light emitting material is 400nm The maximum emission wavelength is preferably 400 nm or more and 465 nm or less, and more preferably 400 nm or more and 460 nm or less.
Moreover, as a phosphorescent luminescent material, a phosphorescent platinum complex or a phosphorescent iridium complex is preferable.

The phosphorescent platinum complex will be described.
In the present invention, the platinum complex is preferably a compound 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 represents a carbon atom or a nitrogen atom. 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 the general formula (C-1), and the preferred ranges are 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 following substituent group B can be applied.

(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, trifluoromethyl, pentafluoroethyl, etc.), alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably carbon number). 2-10, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably carbon number). 2-10, for example, propargyl, 3-pentynyl, etc.), aryl groups (preferably Or 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl, anthranyl, and pentafluorophenyl. An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group ( Preferably it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and the like, and an aryloxycarbonyl group (preferably having a carbon number). 7 to 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms For example, phenyloxycarbonyl, etc.), acyloxy groups (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). 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, And carbamoyl 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, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenyl Carbamoyl, etc.), heterocyclic groups (preferably Or a hetero atom, for example, a nitrogen atom, an oxygen atom, or a sulfur atom, specifically, imidazolyl, pyridyl, quinolyl, furyl, thienyl, Examples include piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group and the like. )

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 the nitrogen atom 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 each other to form a condensed ring. Examples of the ring formed include a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. 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. 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 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 the nitrogen atom 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 each other to form a condensed ring. Examples of the ring formed include a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. Ring, thiophene ring, furan ring and the like.

  Of the platinum complexes represented by the general formula (C-2), one of the more preferable embodiments is a platinum complex represented by the following general formula (C-3).

(In the formula, A ^{301 to} A ³¹³ each independently represent C—R or a nitrogen atom. R represents a hydrogen atom or a substituent. L ³¹ represents a single bond or a divalent linking group.)

General formula (C-3) is demonstrated. L ³¹ has the same meaning as L ²¹ in formula (C-2), and the preferred range is also the same. A ^{301 to} A ³⁰⁶ each independently represent C—R or a nitrogen atom. R represents a hydrogen atom or a substituent. As the substituent represented by R, those exemplified as the substituent group A can be applied.
A ^{301 to} A ³⁰⁶ are preferably C—R, and Rs may be connected to each other to form a ring. When A ^{301 to} A ³⁰⁶ are C—R, R in A ³⁰² and A ³⁰⁵ 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 ³⁰¹ , A ³⁰³ , A ³⁰⁴ and A ³⁰⁶ 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. A ³⁰⁷ , A ³⁰⁸ , A ³⁰⁹ and A ³¹⁰ each independently represent C—R or a nitrogen atom. 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 ³⁰⁷ , A ³⁰⁸ , A ³⁰⁹ and A ³¹⁰ are C—R, R is preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diaryl. An amino group, an alkyloxy group, a cyano group, and a halogen atom, more preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, a dialkylamino group, a cyano group, a fluorine atom, still more preferably a hydrogen atom, An alkyl group, a trifluoromethyl group, and a fluorine atom; If possible, the substituents may be linked to form a condensed ring structure. When the emission wavelength is shifted to the short wavelength side, A ³⁰⁸ is preferably an N atom.

When A ^{307 to} A ³¹⁰ are selected as described above, the 6-membered ring formed from two carbon atoms and A ³⁰⁷ , A ³⁰⁸ , A ³⁰⁹ and A ³¹⁰ includes a benzene ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring. , A pyridazine ring and a triazine ring, more preferably a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring and a pyridazine ring, and particularly preferably a benzene ring and a pyridine ring. When the 6-membered ring is a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring (particularly preferably a pyridine ring), a hydrogen atom present at a position where a metal-carbon bond is formed as compared with a benzene ring. Since the acidity is improved, it is advantageous in that a metal complex is more easily formed.

A ³¹¹ , A ³¹² and A ³¹³ 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 ³¹¹ , A ³¹² and A ³¹³ are C—R, R is preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, An alkyloxy group, a cyano group, and a halogen atom, more preferably a hydrogen atom, an alkyl group, a polyfluoroalkyl group, an aryl group, a dialkylamino group, a cyano group, and a fluorine atom, more preferably a hydrogen atom, an alkyl group, A trifluoromethyl group and a fluorine atom. If possible, the substituents may be linked to form a condensed ring structure. At least one of A ³¹¹ , A ³¹² and A ³¹³ is preferably N, and A ³¹¹ is particularly preferably N.

  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 the general formula (C-4), A ^{401 to} A ⁴¹⁴ each independently represents C—R ²⁴ or a nitrogen atom. R ²⁴ represents a hydrogen atom or a substituent. L ⁴¹ represents a single bond or a divalent linkage. Represents a group.)

General formula (C-4) is demonstrated.
A ^{401 to} A ⁴¹⁴ each independently represent C—R or a nitrogen atom. R represents a hydrogen atom or a substituent. A ^{401 to} A ⁴⁰⁶ and L ⁴¹ have the same meanings as A ^{301 to} A ³⁰⁶ and L ³¹ in the general formula (C-3), and preferred ranges thereof are also the same.

As A ^{407 to} A ⁴¹⁴ , the number of nitrogen atoms in each of A ^{407 to} A ⁴¹⁰ and A ^{411 to} A ⁴¹⁴ is preferably 0 to 2, and more preferably 0 to 1. In the case of shifting the emission wavelength to the short wavelength side, A ⁴⁰⁸ and A ⁴¹² are preferably nitrogen atoms, and both A ⁴⁰⁸ and A ⁴¹² are more preferably nitrogen 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 the general formula (C-5), A ^{501 to} A ⁵¹² each independently represents C—R or a nitrogen atom, R represents a hydrogen atom or a substituent, and L ⁵¹ represents a single bond or a divalent linkage. Represents a group.)

General formula (C-5) is demonstrated. A ⁵⁰¹ to A ⁵⁰⁶ and ^{L 51} have the same meanings as ^A 301 ^{to A 306} and ^{L 31} in the formula (C-3), and preferred ranges are also the same.

A ⁵⁰⁷ , A ^508, A ⁵⁰⁹ , A ⁵¹⁰ , A ^511, and A ⁵¹² are each independently the same as A ³¹¹ , A ^312, and A ³¹³ in the general formula (C-3), and the preferred ranges are also the same. is there.

  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 a carbon atom or a nitrogen atom. Z ⁶¹ and Z ⁶² each independently represent a nitrogen-containing aromatic heterocyclic ring. Z ⁶³ independently represents a benzene ring or an aromatic heterocyclic ring, 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 a carbon atom or a nitrogen atom. In view of the stability of the complex and the light emission quantum yield of the complex, A ⁶¹ is preferably a carbon atom.

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 a nitrogen atom. R represents a hydrogen atom or a substituent. L ⁷¹ represents a single bond or a divalent linking group. Y represents An anionic acyclic ligand that binds to Pt.)

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 ^{301 to} A ³¹⁰ in formula (C-3), 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. Compounds described in JP-A-2006-256999, [0065] to [0083], compounds described in JP-A-2006-93542, [0065] to [0090], JP-A-2007-73891 [0063] to [0071] of JP-A No. 2007-324309, compounds described in [0079] to [0083] of JP-A 2007-324309, and [0055] to [0071] of JP-A 2007-96255. And [0043] to [0046] of JP-A-2006-313796, and other platinum complexes exemplified below. That.

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).

  In this invention, when making the light emitting layer contain the compound represented by general formula (C-1), it is preferable that the content is 1-30 mass% in a light emitting layer, and it is 3-25 mass%. Is more preferable, and it is still more preferable that it is 5-20 mass%.

The phosphorescent iridium complex will be described.
In the present invention, the iridium complex is preferably a compound represented by the following general formula (T-1).

(In General Formula (T-1), R ₃ ′ represents an alkyl group, a heteroalkyl group, an aryl group, or a heteroaryl group, and may further have a substituent Z.
R ₅ represents an aryl group or a heteroaryl group, and may be further substituted with a non-aromatic group.
Ring Q represents an aromatic heterocyclic ring or a condensed aromatic heterocyclic ring having at least one nitrogen atom coordinated to Ir, and may be further substituted with a non-aromatic group.
R ₃ , R ₄ and R ₆ are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, —CN, —CF ₃ , —C _n F _{2n + 1} , a trifluorovinyl group, —CO ₂ R, —C (O). R, —NR ₂ , —NO ₂ , —OR, a halogen atom, an aryl group or a heteroaryl group may be represented, and may further have a substituent Z.
R ₃ and R ₄ may be bonded to each other to form a fused 4 to 7 membered ring, and the fused 4 to 7 membered ring is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl, and the fused 4 The -7 membered ring may further have a substituent Z.
_{R 6} and R _{3 'are, -CR 2 -CR 2 -, -} CR = CR -, - CR 2 -, - O -, - NR -, - O-CR 2 -, - NR-CR 2 - and N May be linked to each other by a linking group selected from ═CR—, and each R independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group, a heteroaryl group or 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, per A haloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group;
(XY) represents an auxiliary ligand.
m is an integer of 1 to 3. n represents an integer of 0 to 2.
m + n is 3. )

  General formula (T-1) is a complex which has iridium (Ir) as a metal, and is excellent in terms of high emission quantum yield.

The alkyl group represented by R ₃ ′ and R _{3 to} R ₆ may have a substituent, may be saturated or unsaturated, and may be substituted. The substituent Z mentioned above can be mentioned. The alkyl group represented by Ra ₂ is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 6 carbon atoms in total, such as a methyl group, an ethyl group, i- A propyl group, a cyclohexyl group, a t-butyl group, etc. are mentioned.

Examples of the heteroalkyl group represented by R ₃ ′ include a group in which at least one carbon of the alkyl group is replaced with O, NR, or S.

The aryl group represented by R ₃ ′, R ₅ , R _{3 to} R ₆ is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a tolyl group, a naphthyl group, and the like. Can be mentioned.

The heteroaryl group represented by R ₃ ′, R ₅ and R _{3 to} R ₆ is preferably a heteroaryl group having 5 to 8 carbon atoms, and more preferably 5 or 6-membered substituted or unsubstituted. 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 , Isoxazolyl group Benzisoxazolyl group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, an imidazolidinyl group, a thiazolinyl group and a sulfolanyl group.
Preferable examples of the heterocyclic group represented by R ₃ ′ are a pyridyl group, a pyrimidinyl group, an imidazolyl group, and a thienyl group, and more preferably a pyridyl group and a pyrimidinyl group.

R ₃ ′ is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

R ₅ represents aryl or heteroaryl, and the aryl or heteroaryl may be substituted with one or more non-aromatic groups.
As the non-aromatic group for R ₅ , an alkyl group, an alkoxy group, a fluoro group, a cyano group, an alkylamino group, and a diarylamino group are preferable, an alkyl group, a fluoro group, and a cyano group are more preferable, and an alkyl group is still more preferable.
R ₅ is preferably a phenyl group, a p-tolyl group, or a naphthyl group, and more preferably a phenyl group.

R ₃ , R ₄ and R ₆ are preferably a hydrogen atom, an alkyl group, a cyano group, a trifluoromethyl group, a perfluoroalkyl group, a dialkylamino group, a fluoro group, an aryl group or a heteroaryl group, more preferably a hydrogen atom. An atom, an alkyl group, a cyano group, a trifluoromethyl group, a fluoro group, and an aryl group, and more preferably a hydrogen atom, an alkyl group, and an aryl group.
As the substituent Z in R _3, R _{4 and} R ₆ , 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.

  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. A pyridine ring and a pyrazine ring are preferable, and a pyridine ring is more preferable.

  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.

  As the non-aromatic group in the ring Q, an alkyl group, an alkoxy group, a fluoro group, a cyano group, an alkylamino group, and a diarylamino group are preferable, and an alkyl group, a fluoro group, and a cyano group are more preferable.

m is preferably 1 to 3, more preferably 2 to 3, and still more preferably 2.
n is preferably 0 to 1, and more preferably 1.
More preferably, m is 2 and n is 1.

(X—Y) represents an auxiliary ligand. These ligands are called “auxiliary” because they are believed to be able to alter the photoactive properties of the molecule rather than directly contributing to the photoactive properties. The definitions of photoactivity and auxiliary are for non-limiting theory. For example, in the case of Ir, n may be 0, 1, or 2 for a bidentate ligand. The auxiliary ligand used in the luminescent material can be selected from those known in the art. Non-limiting examples of auxiliary ligands are described on pages 89-90 of Lamansky et al., PCT application WO 02/15645 A1, incorporated by reference. In addition, “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 (eg, bipyridyl, phenanthroline, etc.), diketone ligands (eg, acetylacetone, etc.), preferably diketones or picolinic acid derivatives.
Although the example of an auxiliary ligand is specifically mentioned below, this invention is not limited to these.

  In the examples of the auxiliary ligand, Rx, Ry and Rz each independently represent a hydrogen atom or a substituent. Examples of the substituent include the substituent group A, preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms. And more preferably an alkyl group having 1 to 4 carbon atoms.

  Preferred auxiliary ligands include acetylacetonate (acac) and picolinate (pic), and derivatives thereof. In the present invention, the auxiliary ligand is preferably acetylacetonate from the viewpoint of obtaining stability of the complex and high luminous efficiency.

  One of the preferable forms of the compound represented by the general formula (T-1) is a compound represented by the following general formula (T-2).

(In General Formula (T-2), R ₃ ′ represents an alkyl group, a heteroalkyl group, an aryl group, or a heteroaryl group, and may further have a substituent Z.
R ₄ ′ to R ₆ ′ each 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.
R ₃ ′ and R ₄ ′, R ₄ ′ and R ₅ ′, and R ₅ ′ and R ₆ ′ may be independently bonded to each other to form a condensed 4- to 7-membered ring. The 7-membered ring is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl, and the fused 4- to 7-membered ring may further have a substituent Z.
_{R 6} and R _{3 'are, -CR 2 -CR 2 -, -} CR = CR -, - CR 2 -, - O -, - NR -, - O-CR 2 -, - NR-CR 2 - and N ═CR— may be linked to each other to form a ring, and 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.
R ₅ represents an aryl group or a heteroaryl group, and may be further substituted with a non-aromatic group.
R ₃ , R ₄ and R ₆ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, —CN, —CF ₃ , —C _n F _{2n + 1} , a trifluorovinyl group, —CO ₂ R, — C (O) R, —NR ₂ , —NO ₂ , —OR, a halogen atom, an aryl group, or a heteroaryl group, which may further have a substituent Z.
R ₃ and R ₄ may be bonded to each other to form a fused 4 to 7 membered ring, and the fused 4 to 7 membered ring is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl, and the fused 4 The -7 membered ring 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, per A haloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group;
(XY) represents an auxiliary ligand.
m is an integer of 1 to 3. n represents an integer of 0 to 2.
m + n is 3. )

R ₃ ′, R _{3 to} R ₆ , (X—Y), m and n in the general formula (T-2) are R ₃ ′, R _{3 to} R ₆ , (X— Y) is synonymous with m and n, and preferred ones are also the same.
R ₄ ′ to R ₆ ′ are synonymous with R ₃ ′.
R ₄ ′ is preferably a hydrogen atom, an alkyl group, an aryl group or a fluoro group, more preferably a hydrogen atom.
R ₅ ′ and R ₆ ′ each 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 cycloalkyl, cyclohetero More preferred is alkyl, aryl, or heteroaryl, and even more preferred is aryl.
The substituent Z in R ₄ ′ to R ₆ ′ is preferably an alkyl group, an alkoxy group, a fluoro group, a cyano group, an alkylamino group, or a diarylamino group, and more preferably an alkyl group.

  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 definition and preferred range 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 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.

Other light emitting materials will be described.
(Fluorescent material)
Examples of fluorescent light-emitting materials that can be used in the present invention include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives. , Condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styryl Complexes of amine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives and pyromethene derivatives Various complexes represented, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

(Phosphorescent material)
Examples of phosphorescent light-emitting materials that can be used in the present invention include US Pat. / 19373A2, JP 2001-247859, JP 2002-302671, JP 2002-117978, JP 2003-133074, JP 2002-235076, JP 2003-123982, JP 2002-170684 No., EP 12111257, JP 2002-226495, JP 2002-234894, JP 2001-247859, JP 2001-298470, JP 2002-173684, JP 2002-203678, JP 2002-203679, JP 2004-357771, JP 2006-256999, JP 2007-19462, JP 2007-84635, JP 2007. Phosphorescent compounds described in Patent Documents such as No. -96259, among others, more preferable luminescent dopants include Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd Complexes, Os complexes, Eu complexes, Tb complexes, Gd complexes, Dy complexes, and Ce complexes can be mentioned. Particularly preferred is an Ir complex, a Pt complex, or a Re complex, among which an Ir complex or a Pt complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond. Or Re complexes are preferred. Furthermore, from the viewpoints of luminous efficiency, driving durability, chromaticity, etc., an Ir complex, a Pt complex, or a Re complex containing a tridentate or higher polydentate ligand is particularly preferable.

  The light emitting material in the light emitting layer is preferably contained in an amount of 0.1% by mass to 50% by mass with respect to the mass of all the compounds generally forming the light emitting layer in the light emitting layer. In view of the above, it is more preferably contained in an amount of 1% by mass to 40% by mass, and further preferably 2% by mass to 30% 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 have a mixed layer of a light emitting material and a host 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. As such a material, a hydrocarbon-based material is preferable, and a material having an adamantane skeleton is particularly preferable. 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 organic EL device of the present invention may contain the following compound as a host material. 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 copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, organic silane, carbon film, pyridine, pyrimidine, triazine, imidazo , Pyrazole, triazole, oxazole, oxadiazol, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, fluorine-substituted aromatic compounds , Metal complexes of heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, phthalocyanine, 8-quinolinol derivatives and metal complexes represented by metal phthalocyanine, benzoxazole and benzothiazole ligands And derivatives thereof (which may have a substituent or a condensed ring).

In the light emitting layer, the triplet lowest excitation energy (T ₁ energy) of the host material 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. It is preferable _{T 1} is greater 0.1eV higher than the _{T 1} of the phosphorescent material of the host material, more preferably at least 0.2eV higher, and further preferably more than 0.3eV large.
T ₁ of the host material is a large T ₁ is obtained from the phosphorescent material to the host material for thereby quench T ₁ is less than the light emission of the phosphorescent material. Even if the T _{1 of} the host material is larger than the phosphorescent light emitting material, if the difference in T ₁ between the two is small, the reverse energy transfer from the phosphorescent light emitting material to the host material occurs in part, resulting in a decrease in efficiency and durability. Cause. Therefore, there is a demand for a host material having a sufficiently large T ₁ and high chemical stability and carrier injection / transport properties.

The charge transport material represented by the general formula (1) can also be used as the host material in the light emitting layer.
Further, the content of the host material in the light emitting layer is not particularly limited, but from the viewpoint of light emission efficiency and driving voltage, it is 15% by mass or more and 95% by mass or less with respect to the total compound mass forming the light emitting layer. Preferably there is.
The charge transport material represented by the general formula (1) in the light emitting layer is 15% by mass or more and 95% by mass or less based on the total mass of the compound forming the light emitting layer from the viewpoints of light emission efficiency and driving voltage in the light emitting layer. It is preferable that it is 40 mass% or more and 96 mass% or less.

-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.
Regarding the hole injection layer, the hole transport layer, the electron injection layer, and the electron transport layer, the matters described in paragraph numbers [0165] to [0167] of JP-A-2008-270736 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, aluminum (III) bis (2-methyl-8-quinolinato) 4-phenylphenolate (Aluminum (III) bis (2-methyl-8-quinolinato) 4- aluminum complexes such as phenylphenolate (abbreviated as BAlq), triazole derivatives, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-Dimethyl-4,7-diphenyl-1,10-) phenanthroline derivatives such as 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.
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.

(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 light-emitting element of the present invention can improve the light extraction efficiency by various known devices. For example, by processing the substrate surface shape (for example, forming a fine concavo-convex pattern), controlling the refractive index of the substrate / ITO layer / organic layer, controlling the film thickness of the substrate / ITO layer / organic layer, etc. It is possible to improve light extraction efficiency and external quantum efficiency.

  The light emitting element of the present invention may be a so-called top emission method in which light emission is extracted from the anode side.

The organic EL element in the present invention may have a resonator structure. For example, a multilayer mirror made of a plurality of laminated films having different refractive indexes, a transparent or translucent electrode, a light emitting layer, and a metal electrode are superimposed on a transparent substrate. The light generated in the light emitting layer resonates repeatedly with the multilayer mirror and the metal electrode as a reflection plate.
In another preferred embodiment, a transparent or translucent electrode and a metal electrode each function as a reflecting plate on a transparent substrate, and light generated in the light emitting layer repeats reflection and resonates between them.
In order to form a resonant structure, the optical path length determined from the effective refractive index of the two reflectors and the refractive index and thickness of each layer between the reflectors is adjusted to an optimum value to obtain the desired resonant wavelength. Is done. The calculation formula in the case of the first embodiment is described in JP-A-9-180883. The calculation formula in the case of the second aspect is described in Japanese Patent Application Laid-Open No. 2004-127795.

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 500 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 350 nm to 600 nm, still more preferably 400 nm to 520 nm, particularly preferably. It is 400 nm or more and 465 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 where light emission luminance is high, such as a light emitting device, a lighting device, and a display 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.

Following reduction compounds 1 to 17, and comparative compound 1-6 was synthesized. Of the following compounds 1 to 17, compounds 3, 5, 7, 9 to 11 are compounds of the present invention, and compounds 1, 2, 4, 6, 8, 12, 13, 15 to 17 are reference examples. It is this compound.

<Synthesis example>
Synthesis Example 1: Synthesis of Compound 1

Bis (4-bromophenyl) diphenylsilane (9.00 g, 18.2 mmol), carbazole (2.74 g, 16.4 mmol), palladium acetate (165 mg, 0.72 mmol), 2- (di-t-butylphosphino ) Biphenyl (858 mg, 2.88 mmol), rubidium carbonate (12.6 g, 54.6 mmol) and xylene (90 mL) were mixed and heated to reflux for 3 hours under a nitrogen atmosphere. After the reaction solution was filtered through Celite, the solvent was distilled off under reduced pressure, and further purified by silica gel column chromatography (developing solvent: toluene / hexane = 1: 2). The obtained solid was washed with ethanol and vacuum-dried to obtain a synthetic intermediate M-1 as a white powder (yield 2.70 g, yield 59%).
Synthesis intermediate M-1 (2.70 g, 4.65 mmol), bis (pinacolato) diboron (1.42 g, 5.58 mmol), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride Dichloromethane complex (1: 1) (114 mg, 0.14 mmol), potassium acetate (1.05 g, 10.7 mmol), N, N-dimethylformamide (30 mL) were mixed, and the mixture was stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. did. After returning the reaction solution to room temperature, pure water and ethyl acetate were added for liquid separation, and the organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The product was purified by silica gel column chromatography (developing solvent: toluene) and vacuum dried to obtain a synthetic intermediate M-2 as a white powder (yield 1.35 g, yield 46%).
Synthetic intermediate M-2 (1.26 g, 20.0 mmol), 4-bromo-2,6-diphenylpyrimidine (622 mg, 20.0 mmol), palladium acetate (225 mg, 1.0 mmol), triphenylphosphine (1. 05 g, 4.0 mmol), sodium carbonate (6.36 g, 60.0 mmol), 1,2-dimethoxyethane (15 mL), and pure water (10 mL) were mixed and heated to reflux for 4 hours under a nitrogen atmosphere. The reaction solution was returned to room temperature, ethyl acetate was added, and the mixture was filtered through celite. The organic solvent was distilled off under reduced pressure, and the precipitated solid was filtered and washed with water. Thereafter, the product was purified by silica gel column chromatography (developing solvent: toluene / hexane = 1: 1), and the obtained solid was washed with hexane and vacuum dried to obtain Compound 1 as a white powder (yield 1. 16 g, 79% yield).
¹ H NMR (300 MHz, DMSO) δ = 8.70-8.48 (m, 7H), 8.26 (d, 2H), 7.87-7.77 (m, 6H), 7.69-7 .43 (m, 20H), 7.31 (dd, 2H). MS (MALDI-TOF): m / z = 732.2 ([M + H] ^< +>).

Synthesis Example 2: Synthesis of Compound 2 Compound 2 was synthesized in the same manner except that 4-bromo-2,6-diphenylpyrimidine in Synthesis Example 1 was replaced with 4-bromo-2,6-diphenylpyridine. MS (MALDI-TOF): m / z = 731.3 ([M + H] ^< +>).

Synthesis Example 3: Synthesis of Compound 3 The same procedure was performed except that 4-bromo-2,6-diphenylpyrimidine in Synthesis Example 1 was replaced with 2-chloro-4,6-diphenyl- [1,3,5] triazine. 3 was synthesized. MS (MALDI-TOF): m / z = 733.3 ([M + H] ^< +>).

Synthesis Example 4: Synthesis of Compound 4 Compound 4 was synthesized in the same manner except that 4-bromo-2,6-diphenylpyrimidine in Synthesis Example 1 was replaced with 3-bromobenzonitrile. MS (MALDI-TOF): m / z = 603.2 ([M + H] ^< +>).

Synthesis Example 5: Synthesis of Compound 5 In Synthesis Example 1, bis (4-bromophenyl) diphenylsilane was changed to bis (4-bromophenyl) dimethylsilane, carbazole was changed to 9,9-dimethyl-9,10-dihydroacridine, carbonic acid A synthetic intermediate corresponding to synthetic intermediate M-1 was synthesized in the same manner except that rubidium was replaced with t-butoxy sodium, and then compound 5 was synthesized in the same manner as in Synthetic Example 1. MS (MALDI-TOF): m / z = 774.3 ([M + H] ^< +>).

Synthesis Example 6: Synthesis of Compound 6 In Synthesis Example 1, carbazole was changed to 4- (9-carbazolyl) phenylboronic acid, bis (4-bromophenyl) diphenylsilane was changed to bis (4-bromophenyl) dimethylsilane, and 2- ( Synthetic intermediate M- except that di-t-butylphosphino) biphenyl is replaced by triphenylphosphine, rubidium carbonate is replaced by sodium carbonate, and xylene is replaced by 1,2-dimethoxyethane and water (2: 1). A synthetic intermediate corresponding to 1 was synthesized, and then compound 6 was synthesized in the same manner as in Synthesis Example 1. MS (MALDI-TOF): m / z = 684.3 ([M + H] ^< +>).

Synthesis Example 7: Synthesis of Compound 7 A synthesis intermediate corresponding to the synthesis intermediate M-1 was synthesized in the same manner as in Synthesis Example 1 except that carbazole was replaced with α-phenylnaphthylamine and rubidium carbonate was replaced with t-butoxy sodium. Thereafter, Compound 7 was synthesized in the same manner as in Synthesis Example 1. MS (MALDI-TOF): m / z = 784.3 ([M + H] ^< +>).

Synthesis Example 8: Synthesis of Compound 8 After 3-bromo-9-ethylcarbazole (1.37 g, 5.0 mmol), magnesium powder (146 mg, 6.0 mmol), iodine pieces, and THF (10 mL) were stirred at room temperature, Heated to reflux for 1 hour. Only the liquid component of this reaction solution was mixed with a solution of chlorodiphenyl (pentafluorophenyl) silane (1.92 g, 5.0 mmol) in THF (10 mL) and stirred for 4 hours. Pure water and ethyl acetate were added to the reaction solution, and the organic layer was extracted by liquid separation. After drying over sodium sulfate and concentrating under reduced pressure, compound 8 was obtained by purification by column chromatography (developing solvent: hexane / ethyl acetate) (yield 1.01 g, yield 37%). MS (MALDI-TOF): m / z = 544.2 ([M + H] ^< +>).

Synthesis Example 9: Synthesis of Compound 9 A synthesis intermediate corresponding to synthesis intermediate M-1 was synthesized in the same manner as in Synthesis Example 1 except that carbazole was replaced with 3-t-butylindole and rubidium carbonate was replaced with t-butoxysodium. Thereafter, compound 9 can be synthesized in the same manner as in Synthesis Example 1.

Synthesis Example 10: Synthesis of Compound 10 The same as Synthesis Example 1 except that carbazole is replaced with phenothiazine, bis (4-bromophenyl) diphenylsilane is replaced with bis (3-bromophenyl) diphenylsilane, and rubidium carbonate is replaced with t-butoxysodium. Then, a synthetic intermediate corresponding to the synthetic intermediate M-1 is synthesized, and then the compound 10 can be synthesized by the same method as in Synthetic Example 1.

Synthesis Example 11: Synthesis of Compound 11 A synthesis intermediate corresponding to the synthesis intermediate M-1 was synthesized in the same manner as in Synthesis Example 1 except that carbazole was replaced with tribenzazepine and rubidium carbonate was replaced with t-butoxy sodium. Can synthesize Compound 11 in the same manner as in Synthesis Example 1.

Synthesis Example 12: Synthesis of Compound 12 By replacing bis (4-bromophenyl) diphenylsilane of Synthesis Example 1 with bis (4-bromophenyl) diisopropylsilane, a synthesis intermediate corresponding to synthesis intermediate M-1 was synthesized. Thereafter, compound 12 can be synthesized in the same manner as in Synthesis Example 1 except that 4-bromo-2,6-diphenylpyrimidine is replaced with 5-bromo-1,2,3-trifluorobenzene.

Synthesis Example 13: Synthesis of Compound 13 By replacing bis (4-bromophenyl) diphenylsilane of Synthesis Example 1 with bis (4-bromophenyl) dibutylsilane, a synthesis intermediate corresponding to synthesis intermediate M-1 was synthesized. Thereafter, compound 13 can be synthesized in the same manner as in Synthesis Example 1 except that 4-bromo-2,6-diphenylpyrimidine is replaced with 4-bromo-4′-trifluoromethylbiphenyl.

Synthesis Example 14: Synthesis of Compound 14 Compound 14 can be synthesized by the following synthesis route (experimental conditions and the like are the same as those of Synthesis Example 1).

Synthesis Example 15: Synthesis of Compound 15 Compound 15 was synthesized by the following synthesis route.

Synthesis Example 16: Synthesis of Compound 16 Compound 16 was synthesized by the following synthesis route.

Synthesis Example 17: Synthesis of Compound 17 Compound 17 was synthesized by the following synthesis route.

  All materials used for device fabrication were purified by sublimation, and the purity (absorption intensity ratio at 254 nm) was 99.5% or higher by high performance liquid chromatography (HPLC), and halogen-containing compounds among the synthetic intermediates were detected. It was confirmed that the amount was below the limit amount.

Cyclic voltammetry (CV) measurement of each compound is performed under the following conditions. From the oxidation peak value E _ox and the reduction peak value E _red , the ionization potential Ip (eV) = E _ox (V) +4.5, the electron affinity Ea (eV ) = E _red (V) +4.8 and calculated in the table ( _Eox and E _{red of} CV correlate with Ip and Ea in the solid film state. Macromol. 1995, 28, 1180- 1196, etc. The correction values used (+4.5, +4.8) were obtained by forming several material monolayer films (deposited on a glass substrate with a film thickness of 50 nm by vacuum deposition) into RIKEN KEIKI AC -Ip value measured using -2 and the Ea value obtained from the band gap Eg obtained from the absorption long wavelength end of the material single layer film by the relationship of Ea = Ip-Eg. Used the same value).
Solvent: N, N-dimethylformamide Concentration: 1.0 × 10 ⁻³ mol / L
Supporting electrolyte: 0.1 mol / L n-BuNPF ₆
Working electrode: Glassy carbon Counter electrode: Platinum Reference electrode: Ag / AgCl
Further, a F-7000 Hitachi spectrofluorometer (Hitachi High-Technologies Corporation) was prepared by preparing a single layer film (film thickness of about 50 nm) of the charge transport material of the present invention or a comparative material on a glass substrate by a vacuum deposition method as a measurement sample. ) Was used to measure the phosphorescence spectrum at the liquid nitrogen temperature, and the T ₁ (eV) of each material was determined by converting the energy at the short wavelength end. The results are shown in Table 1.

<Example 1>
[Production of Element 1-1]
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, subjected to ultrasonic cleaning 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: 4,4 ′, 4 ″ -tris (2-naphthylphenylamino) triphenylamine (2-TNATA) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano Quinodimethane (F4-TCNQ) (mass ratio 99.7: 0.3): film thickness 120 nm
Second layer: NPD: film thickness 7 nm
Third layer: C-1: film thickness 3 nm
Fourth layer (light emitting layer): H-1 and the following compound 9-16 (mass ratio 85:15): film thickness 30 nm
Fifth layer: Compound 1: film thickness 27 nm
Sixth layer: BCP: film thickness 3 nm
On top of this, 0.1 nm of lithium fluoride and 100 nm of metallic aluminum were vapor-deposited in this order to form a cathode.
The laminated body thus obtained was put in a glove box substituted with nitrogen gas without being exposed to the atmosphere, and a glass sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by CHIBA NAGASE Co., Ltd.) The organic electroluminescent element 1-1 of the reference example was obtained.

[Preparation of Elements 1-2 to 1-11 and Comparative Elements 1-1 to 1-6]
In the manufacture of the element 1-1, by using the material shown in the following Table 2 instead of the compound 1 as the material of the fifth layer, the elements 1-2 to 1-11 and the comparative elements 1-1 to 1-6 are obtained. It was.

  These elements were evaluated in terms of efficiency, drive voltage, durability, drive voltage increase rate, and maximum emission wavelength by the following methods. The results are shown in Table 2.

[Evaluation of device]
(A) Efficiency Using a source measure unit 2400 manufactured by Toyo Technica, a direct current 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 around the luminance of 360 cd / m ² was calculated by the luminance conversion method and described as a relative value. The higher the number, the better the efficiency.

(B) Driving voltage Each element is caused to emit light by applying a DC voltage so that the luminance is 360 cd / m ² . The applied voltage at this time was used as an index for evaluating the drive voltage, and was described as a relative value. The driving voltage is preferably as small as possible.

(C) Durability Each element continued to emit light by applying a DC voltage so that the luminance was 1000 cd / m ² , and the time taken until the luminance became 500 cd / m ² was used as a durability index, and the relative value It was described in. The higher the durability, the better.

(D) The driving voltage measured at the driving voltage increase rate (b) is V, and (c) the voltage necessary for obtaining a luminance of 360 cd / m ² is obtained as V ′ in the element after evaluation as in (b). V ′ / V at the time was shown as the drive voltage increase rate. The drive voltage increase rate is preferably as the number is smaller.

(E) Maximum emission wavelength Each element was caused to emit light by applying a DC voltage so that the luminance was 1000 cd / m ² , and the maximum emission wavelength was obtained from the emission spectrum at this time.

  As can be seen from Table 2, the device of the present invention using the charge transporting material of the present invention is superior to the comparative device in all aspects of efficiency, drive voltage, durability, and drive voltage increase rate.

<Examples 2 to 23>
[Preparation of Elements 2-1 to 23-1, Comparative Elements 2-1 to 23-1]
The third layer material, fourth layer material, and fifth layer material in Example 1 were changed to those shown in Table 3 below, and elements (elements 2-1 to 23-1, comparative elements 2-1 to 23-1) were used. Table 3 shows the results of device evaluation performed in the same manner as in Example 1.

  As can be seen from Table 3, the charge transport material of the present invention can be used in combination with various materials for any of the hole transport layer, the light emitting layer host, and the electron transport layer to produce a high-performance device. .

Example 24
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, subjected to ultrasonic cleaning in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. Went. On this transparent anode (ITO film), PEDOT (poly (3,4-ethylenedioxythiophene)) / PSS (polystyrene sulfonic acid) aqueous solution (BaytronP (standard product)) was spin-coated (4000 rpm, 60 seconds), 120 A hole transporting buffer layer was formed by drying at a temperature of 10 ° C. for 10 minutes.
Next, a toluene solution containing 1% by mass of Compound 1 and 0.05% by mass of TM-3 was spin-coated (2000 rpm, 60 seconds) on the previous buffer layer to form a light emitting layer.
On this light emitting layer, BAlq was vapor-deposited with a thickness of 50 nm by a vacuum vapor deposition method to form an electron transport layer, and lithium fluoride 0.1 nm and metal aluminum 100 nm were vapor-deposited in this order to form a cathode.
This product 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.). Thus, an organic electroluminescent element 24-1 was obtained. Moreover, except having changed the material which comprises a light emitting layer into the material of Table 4, it carried out similarly and obtained the element 24-2-25-2 and the comparison element 24-1-25-1.

Above-mentioned example using the reduction compound 1～8,15～17, even devices using of compound 9-14 show similarly high device performance.

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 device (organic EL device)
DESCRIPTION OF SYMBOLS 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 32... Fine particle 40.

Claims (17)

A charge transport material represented by the following general formula (1).
{(In General Formula (1), R ¹ and R ² each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms , and R ³ represents an alkyl group having 1 to 20 carbon atoms, It represents a substituent capable of forming a three-ring structure represented by an indole ring or the following formula with a phenyl group in the general formula (1) bonded aryl group having 6 to 20 carbon atoms, or a following R ^4, R ⁴ is The two are bonded to each other to form a benzene ring that condenses with the phenyl group in general formula (1), and is bonded to R ³ together with the phenyl group in general formula (1) to be represented by the indole ring or the following formula A substituent that forms a tricyclic structure, or a substituent that combines with the following L ^A1 to form a carbazole ring or an acridan ring together with the phenyl group in the general formula (1), n1 represents an integer of 0 to 5, ^A1 is bonded to an arylene group having 6 to 24 carbon atoms, a biphenylene group, or R ⁴ to form a valent linking group that forms a carbazole ring or an acridan ring together with the phenyl group in the general formula (1), or these rings. represents a divalent linking group composed of a divalent linking group and phenylene group, L ^B1 of the arylene group having 6 to 24 carbon atoms, when it represents a biphenylene group. R ⁴ there are a plurality, the plurality of R ⁴ is G ^B1 represents a structure represented by the following general formula (B1-1) or the following general formula (B2-1), provided that a carbazole ring is present in the following general formula (A1). G ^B1 is represented by the following general formula (B1-1), and represents a structure in which at least two of X are nitrogen atoms.)
(The above formula represents the tricyclic structure, wherein * is the point of attachment to ^LA 1 in the general formula (1) , X ′ is a single bond, an alkylene group having 1 to 10 carbon atoms, 6 carbon atoms. Represents ~ 20 arylene group or -S-).
(In General Formula (B1-1), each X independently represents a nitrogen atom or a carbon atom to which R ⁷ is bonded.
Any of R ^{5 to} R ⁷ is a bonding point with ^LB 1 in the general formula (1), and the remaining ones of R ^{5 to} R ⁶ are each independently an alkyl group having 1 to 20 carbon atoms or 6 to 6 carbon atoms. 20 represents an aryl group, and the remaining R ⁷ represents a hydrogen atom , an alkyl group having 1 to 20 carbon atoms , or an aryl group having 6 to 20 carbon atoms . However, in the general formula (B1-1), when the nitrogen atom is adjacent to a carbon atom, the carbon atom has R ⁷ as an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms . If R ⁷ there is a plurality, or different in each plurality of R ⁷ are the same. One in general formula (B 2 - 1), * is the point of attachment to the L ^B1 in the formula (1), E is selected from one halogen atom, a perfluoroalkyl group, a nitro group, a cyano radical, R ⁸ represents a substituent, n2 represents an integer of 1 to 5, and n3 represents 0 . When a plurality of E are present, the plurality of E may be the same or different. However, in the general formula (1), the partial structure represented by the following general formula (A1) and the partial structure represented by the following general formula (B1) do not represent the same structure. )
(In the general formula (A1) and the general formula (B1), R ^{3 to} R ⁴ , n1, L ^A1 , L ^B1 , and G ^B1 are R ^{3 to} R ⁴ , n1, and L ^A1 in the general formula (1), respectively. , L ^B1 and G ^B1 .)} The charge transport material according to claim 1, wherein the general formula (1) is represented by the following general formula (2).
{(In General Formula (2), R ^{9 to} R ¹² each independently represent a substituent, L ^A2 and L ^B2 each independently represent a single bond or a phenylene group , and n4 to n7 represent 0. X ′ Represents a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or —S— , wherein R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms or a carbon number. Represents an aryl group of 6 to 20. G ^B2 represents a structure represented by the following general formula (B1-2) or the following general formula (B2-2), provided that when X ′ is a single bond, G ^B2 Is represented by the following general formula (B1-2), and represents a structure in which two Xs are nitrogen atoms.)
(In General Formula (B1-2), each X independently represents a nitrogen atom or a carbon atom to which R ⁷ is bonded.
Any of R ^{5 to} R ⁷ serves as a bonding point with ^LB 2 in the general formula (2), and the remaining ones of R ^{5 to} R ⁶ are each independently an alkyl group having 1 to 20 carbon atoms or 6 to 6 carbon atoms. 20 represents an aryl group, and the remaining R ⁷ represents a hydrogen atom , an alkyl group having 1 to 20 carbon atoms , or an aryl group having 6 to 20 carbon atoms . However, if the neighboring nitrogen atom is a carbon atom in the general formula (B1- 2), the carbon atom has an alkyl group or an aryl group having 6 to 20 carbon atoms having 1 to 20 carbon atoms as ^{R 7.} If R ⁷ there is a plurality, or different in each plurality of R ⁷ are the same. In one general formula (B2-2), * is the point of attachment to the ^{L B2} in the general formula ^{(2), R 13} represents a substituent, n8 represents an integer of 0 to 5, n9 is 0 . However, in the general formula (2), does not have a partial structure represented by the partial structural and following general formula represented by the following general formula (A2) (B2) represent the same structure. )
(In General Formula (A2) and General Formula (B2), X ′, R ^{9 to} R ¹² , n4 to n7, L ^A2 , L ^B2 , and G ^B2 are X ′ and R ⁹ in General Formula (2), respectively. To R ¹² , n4 to n7, L ^A2 , L ^B2 , and G ^B2 .)} The charge transport material according to claim 2, wherein the general formula (2) is represented by the following general formula (3).
{(In General Formula (3), R ^{9 to} R ¹² each independently represents a substituent, and n 4 to n ⁷ each represents 0. X ′ represents a single bond, an alkylene group having 1 to 10 carbon atoms, or 6 carbon atoms. 20 arylene group, or -S- .R ¹ and ^{R 2} represents a represents an alkyl group or an aryl group having 6 to 20 carbon atoms having 1 to 20 carbon atoms each independently ^{.G B2} is the formula (2 ) is synonymous with ^{G B2} in. However, when X 'is a single ^{bond, G B2} is represented by the general formula (B1-2), 2 one X represents the structure is a nitrogen atom. formula ( In 3), the partial structure represented by the following general formula (A3) and the partial structure represented by the following general formula (B3) do not represent the same structure.)
(In General Formula (A3) and General Formula (B3), X ′, R ^{9 to} R ¹² , n4 to n7, and G ^B2 are X ′, R ^{9 to} R ¹² , and n4 to R in General Formula (2), respectively. n7 and G ^B2 are synonymous.)} The charge transport material according to claim 1, wherein the lowest excited triplet (T ₁ ) energy in the film state is 2.8 eV or more and 3.2 eV or less.   The charge transport material according to claim 1, which has a molecular weight of 600 or more and 1200 or less.   A film comprising the charge transport material according to claim 1.   An organic electroluminescent element comprising a pair of electrodes and at least one organic layer including a light emitting layer between the electrodes on a substrate, wherein at least one of the organic layers is any one of claims 1 to 5. An organic electroluminescent device comprising the charge transport material described in 1.   The organic electroluminescent element according to claim 7, wherein the light emitting layer contains a phosphorescent light emitting material.   The organic electroluminescent element according to claim 8, wherein the phosphorescent light emitting material has a maximum emission wavelength of 400 nm or more and 470 nm or less.   The organic electroluminescent element in any one of Claims 7-9 which contains the electric charge transport material in any one of Claims 1-5 in the light emitting layer or the layer adjacent to a light emitting layer.   The organic electroluminescent element according to any one of claims 7 to 10, wherein the organic layer containing the charge transport material according to any one of claims 1 to 5 is a layer formed by a wet process. A compound represented by the following general formula (1).
{(In General Formula (1), R ¹ and R ² each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms , and R ³ represents an alkyl group having 1 to 20 carbon atoms, It represents a substituent capable of forming a three-ring structure represented by an indole ring or the following formula with a phenyl group in the general formula (1) bonded aryl group having 6 to 20 carbon atoms, or a following R ^4, R ⁴ is The two are bonded to each other to form a benzene ring that condenses with the phenyl group in general formula (1), and is bonded to R ³ together with the phenyl group in general formula (1) to be represented by the indole ring or the following formula A substituent that forms a tricyclic structure, or a substituent that combines with the following L ^A1 to form a carbazole ring or an acridan ring together with the phenyl group in the general formula (1), n1 represents an integer of 0 to 5, ^A1 is bonded to an arylene group having 6 to 24 carbon atoms, a biphenylene group, or R ⁴ to form a valent linking group that forms a carbazole ring or an acridan ring together with the phenyl group in the general formula (1), or these rings. represents a divalent linking group composed of a divalent linking group and phenylene group, L ^B1 of the arylene group having 6 to 24 carbon atoms, when it represents a biphenylene group. R ⁴ there are a plurality, the plurality of R ⁴ is G ^B1 represents a structure represented by the following general formula (B1-1) or the following general formula (B2-1), provided that a carbazole ring is present in the following general formula (A1). G ^B1 is represented by the following general formula (B1-1), and represents a structure in which at least two of X are nitrogen atoms.)
(The above formula represents the tricyclic structure, wherein * is the point of attachment to ^LA 1 in the general formula (1) , X ′ is a single bond, an alkylene group having 1 to 10 carbon atoms, 6 carbon atoms. Represents ~ 20 arylene group or -S-).
(In General Formula (B1-1), each X independently represents a nitrogen atom or a carbon atom to which R ⁷ is bonded.
Any of R ^{5 to} R ⁷ is a bonding point with ^LB 1 in the general formula (1), and the remaining ones of R ^{5 to} R ⁶ are each independently an alkyl group having 1 to 20 carbon atoms or 6 to 6 carbon atoms. 20 represents an aryl group, and the remaining R ⁷ represents a hydrogen atom , an alkyl group having 1 to 20 carbon atoms , or an aryl group having 6 to 20 carbon atoms . However, in the general formula (B1-1), when the nitrogen atom is adjacent to a carbon atom, the carbon atom has R ⁷ as an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms . If R ⁷ there is a plurality, or different in each plurality of R ⁷ are the same. One in general formula (B 2 - 1), * is the point of attachment to the L ^B1 in the formula (1), E is selected from one halogen atom, a perfluoroalkyl group, a nitro group, a cyano radical, R ⁸ represents a substituent, n2 represents an integer of 1 to 5, and n3 represents 0 . When a plurality of E are present, the plurality of E may be the same or different. However, in the general formula (1), the partial structure represented by the following general formula (A1) and the partial structure represented by the following general formula (B1) do not represent the same structure. )
(In the general formula (A1) and the general formula (B1), R ^{3 to} R ⁴ , n1, L ^A1 , L ^B1 , and G ^B1 are R ^{3 to} R ⁴ , n1, and L ^A1 in the general formula (1), respectively. , L ^B1 and G ^B1 .)} A compound represented by the following general formula (2 ′).
{(In General Formula (2 ′), R ^{9 to} R ¹² each independently represent a substituent, L ^A2 and L ^B2 each independently represent a single bond or a phenylene group , and n4 to n7 represent 0. R ¹ and R ² each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ′ represents a single bond, an alkylene group having 1 to 10 carbon atoms , or an alkyl group having 6 to 20 carbon atoms. Represents an arylene group or —S—, and G ^B2 represents a structure represented by the following general formula (B1-2) or the following general formula (B2-2), provided that when X ′ is a single bond, G ^B2 is represented by the following general formula (B1-2), and represents a structure in which two Xs are nitrogen atoms, and when G ^B2 is a structure represented by the following general formula (B1-2), -L ^B2 -G ^B2 are in meta or para position with respect to the silicon atom.)
(In General Formula (B1-2), each X independently represents a nitrogen atom or a carbon atom. Any one of R ^{5 to} R ⁷ is a bonding point with L ^B2 in General Formula (2 ′), and R ⁵ to The remaining ones of R ⁶ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms , and the remaining ones of R ⁷ are hydrogen atoms and alkyl groups having 1 to 20 carbon atoms . or an aryl group having 6 to 20 carbon atoms. However, if adjacent nitrogen atom is a carbon atom in the general formula (B1- 2), the carbon atom of the alkyl group having 1 to 20 carbon atoms as ^{R 7} or if .R ⁷ having an aryl group having 6 to 20 carbon atoms there are a plurality, a plurality of ^{R 7} may be the same or different. in one general formula (B2-2), * the general formula (2 ') in a point of attachment to ^{L B2, R 13} represents a substituent, the n8 Represents an integer of to 5, n9 is. Was however represents 0, in the general formula (2 '), the partial structure represented by the partial structure and the following general formula represented by the following general formula (A2) (B2) Do not represent the same structure.)
(In General Formula (A2) and General Formula (B2), X ′, R ^{9 to} R ¹² , n4 to n7, L ^A2 , L ^B2 , and G ^B2 are X ′ and R in General Formula (2 ′), respectively. ^{9 ~R 12, n4~n7,} the same meaning as ^{L A2,} L ^B2, and ^{G B2.)}} The compound according to claim 13, wherein the general formula (2 ') is represented by the following general formula (3').
{(In the general formula (3 ′), X ′, R ^{9 to} R ¹² , n4 to n7, and GB ² represent the general formula (2 ′)
X ^'in, R ^{9 ~R 12,} the same meanings as N4 to N7, and ^{G B2.} However, when X ′ is a single bond, G ^B2 is represented by the general formula (B1-2), and represents a structure in which two Xs are nitrogen atoms. If G ^B2 has a structure represented by the general formula (B1-2) is, ^{-G B2} is in meta or para position with respect to the silicon atom. However, in the general formula (3 ′), the partial structure represented by the following general formula (A3) and the partial structure represented by the following general formula (B3) do not represent the same structure. )
(In General Formula (A3) and General Formula (B3), X ′, R ^{9 to} R ¹² , n4 to n7, and GB ² are X ′, R ^{9 to} R ¹² , and n4 in General Formula (2 ′), respectively. ～N7, and it is synonymous with ^{G B2.)}}   The light-emitting device using the organic electroluminescent element in any one of Claims 7-11.   The display apparatus using the organic electroluminescent element in any one of Claims 7-11.   The illuminating device using the organic electroluminescent element in any one of Claims 7-11.