KR20190114794A - Organic electroluminescence device - Google Patents

Abstract

Provided is an organic electroluminescent device having a net structure having higher practicality and superior electron injection properties than a device using polyethyleneimine. The organic electroluminescent device has a structure in which a plurality of organic compound layers stacked between a cathode and an anode are formed on a substrate. A layer, adjacent to the cathode, among the organic compound layers is a coating layer of a solution containing an amino group-containing compound having a structure represented by the following general formula (1): (X)-[(L)-(NR^1R^2)]_n (1) (where X represents an n-valent group derived from an electron transporting compound, L represents a coupling group which bonds an amino group represented by X and NR^1R^2, or a direct bond, R^1 and R^2 are the same or different and represent a hydrocarbon group which may have a substituent, and n represents the number of 1-8.).

Description

Organic electroluminescent element {ORGANIC ELECTROLUMINESCENCE DEVICE}

The present invention relates to an organic electroluminescent device. In more detail, it is related with the organic electroluminescent element which can be used as a display apparatus, such as a display part of an electronic device, an illumination device, etc.

Organic electroluminescent devices (organic EL devices) are expected as new light emitting devices that can be applied to thin, flexible and flexible display devices and lighting.

The organic electroluminescent device has a structure in which one or more types of layers including a light emitting layer formed between a positive electrode and a negative electrode comprises a light emitting layer formed between the positive electrode and the negative electrode. Energy at the time of recombination is used to excite the luminescent organic compound to obtain luminescence. An organic electroluminescent element is a current-driven element, and in order to utilize the flowing current more efficiently, the element structure and the material of the layer which comprise an element are examined variously.

The organic electroluminescent element in which the layers between the cathode and the anode are both made of an organic compound is likely to be degraded by oxygen or water as a result, and rigid sealing is indispensable in order to prevent their intrusion. This causes the complicated manufacturing process of the organic electroluminescent element.

Moreover, in recent years, in order to improve durability, ensuring the performance of an organic electroluminescent element, as an electron injection layer which does not contain an alkali metal, Non-patent document 1 has organic electroluminescence which has an electron injection layer which consists of polyethyleneimine, for example. The device is described. In addition, Non-Patent Document 2 describes that the electrolyte membrane is effective for improving the electron injection speed, and Non-Patent Document 3 describes the effect of these amino groups on the electron injection at the electrode and the organic layer interface.

 Jiangshan Chen and six others Journal of Materials Chemistry, Vol. 22, 2012, p5164-5170  Hyosung Choi and 8 others Advanced Materials, Vol. 23, 2011, p2759  Yinhua Zho et al 21 `` Science '', Vol. 336, 2012, p327

As described above, the use of polyethyleneimine or the like as the material of the electron injection layer is disclosed, but since polyethyleneimine has no conductivity, it can only be used as an ultra-thin film, and the film thickness has a small allowable range or comes from lack of conductivity. For reasons of low durability, the device using polyethyleneimine as the material of the electron injection layer is not suitable for practical use. For this reason, the organic electroluminescent element which is high in practical use and excellent in electron injection property is calculated | required compared with the element using polyethyleneimine. Particularly, organic electroluminescent devices have a forward structure in which an anode is formed on a substrate and an inverse structure in which a cathode is formed on a substrate, but a device having a more general forward structure has higher practicality than a device using polyethyleneimine, There is also a demand for a device having excellent electron injection properties.

This invention is made | formed in view of the said phenomenon, and an object of this invention is to provide the organic electroluminescent element of the pure structure which has higher practicality than the element using polyethyleneimine, and is excellent in electron injection property.

MEANS TO SOLVE THE PROBLEM This inventor studies the organic electroluminescent element of the pure structure excellent in practicality and electron injection property, has an electron transport performance as a center skeleton, and can express the dipole moment which becomes an electron injection property in the terminal with an electrode metal. It was noted that the compound having a specific structure having a tertiary amine has conductivity and is excellent in electron injection property and electron transport property. And as a result of various examination about the organic electroluminescent element using this compound, when the layer adjacent to a cathode is formed by apply | coating the solution containing this compound, the organic electroluminescent element obtained is an element excellent in electron injection property. I found out to be. It is thought that this is because the liquid phase process which is a coating film forming process rather than a vapor phase process like vapor deposition has higher structural freedom in the film | membrane of the amino group containing compound after film forming. Moreover, since the compound of this specific structure has electroconductivity, since the element which has the layer of the coating film of the compound of this specific structure has a larger film thickness tolerance range than the case where polyethyleneimine is used, it also turns out that it becomes a highly practical element. The present invention has been reached.

That is, this invention is an organic electroluminescent element which has a structure in which the some organic compound layer was laminated | stacked between the cathode and the anode formed on the board | substrate, The layer adjacent to a cathode among the organic compound layers is following General formula (1);

(X)-[(L)-(NR ¹ R ² )] _n (1)

(Wherein, X represents an n-valent group derived from an electron transporting compound. L represents a linking group or a direct bond which bonds an amino group represented by X and NR ¹ R ^2. R ¹ and R ² are the same or different. The hydrocarbon group which may have a substituent is represented, n represents the number of 1-8.) It is an organic electroluminescent element characterized by the layer of the coating film of the solution containing the amino-group containing compound which has a structure shown by these.

In the said General formula (1), it is preferable that the structure of the terminal part couple | bonded with L with the n-valent group derived from the electron carrying compound represented by X is a pyridine ring.

The present invention is also a display device comprising the organic electroluminescent element of the present invention.

The present invention is also an illumination device comprising the organic electroluminescent element of the present invention.

The present invention also provides a method for producing an organic electroluminescent device having a structure in which a plurality of organic compound layers are laminated between a cathode and an anode formed on a substrate, the production method of which is represented by the following general formula (1);

(X)-[(L)-(NR ¹ R ² )] _n (1)

(Wherein, X represents an n-valent group derived from an electron transporting compound. L represents a linking group or a direct bond which bonds an amino group represented by X and NR ¹ R ^2. R ¹ and R ² are the same or different. The hydrocarbon group which may have a substituent is represented, n shows the number of 1-8. The process of apply | coating the solution containing the amino-group-containing compound which has a structure shown by (), and forming a layer, and this amino-group-containing compound are included. It is also a method for producing an organic electroluminescent device, comprising the step of forming a cathode adjacent to a layer to be formed.

The organic electroluminescent element of the present invention is an organic electroluminescent element of a forward structure in which an anode is formed on a substrate, and can be suitably used as a material of a display device or a lighting device in view of excellent electron injection property.

1 is a schematic view showing an example of a laminated structure of an organic electroluminescent element of the present invention.
FIG. 2 is a diagram showing measurement results of voltage-current density and luminance characteristics of the organic electroluminescent device produced in Example 1. FIG.
FIG. 3 is a diagram showing measurement results of voltage-current density and luminance characteristics of the organic electroluminescent device produced in Comparative Example 1. FIG.

The present invention is described in detail below.

Moreover, what combined two or more individual preferable aspects of this invention described below is also a preferable aspect of this invention.

The organic electroluminescent device of the present invention has a structure in which a plurality of organic compound layers are laminated between a cathode and an anode formed on a substrate, and a layer adjacent to the cathode includes the following general formula (1);

(X)-[(L)-(NR ¹ R ² )] _n (1)

(Wherein, X represents an n-valent group derived from an electron transporting compound. L represents a linking group or a direct bond which bonds an amino group represented by X and NR ¹ R ^2. R ¹ and R ² are the same or different. The hydrocarbon group which may have a substituent is represented, n is a layer of the coating film of the solution containing the amino-group-containing compound which has a structure shown by (). Although the organic electroluminescent element of the present invention has high practicality and is excellent in electron injectability, since the use of an electron injection layer produced by coating film production leads to a reduction in cost, this point is also an organic electroluminescent element of the present invention. Is an excellent point.

As a method of forming the layer of the amino group containing compound which has a structure represented by General formula (1), in addition to the method of apply | coating the solution containing this compound and forming a layer of a coating film, the method by vapor deposition mentioned later, etc., In the organic electroluminescent element of the pure structure which has an anode on a board | substrate, it is obtained by making an amino-group containing compound which has such a specific structure into a solution, apply | coating this solution, forming a layer of a coating film, and forming a cathode on it. The organic electroluminescent element is particularly excellent in electron injection property. It is thought that this is because the terminal N atoms are arranged during the coating film formation time so as to favor the charge injection, and thus the light emitting start voltage is estimated to be low. In addition, as a candidate for the arrangement, a dipole between metals constituting a cathode adjacent to the layer of the coating film is considered, and the number of dipoles is considered to be a factor causing a difference in device characteristics. It is difficult to observe the dipole directly.

Below, the amino group containing compound represented by General formula (1) is demonstrated first, and then, the structure of the organic electroluminescent element of this invention, and materials other than an amino group containing compound are demonstrated.

1. Amino Group Containing Compound

The amino group containing compound of this invention has a structure represented by the said General formula (1).

X in General formula (1) represents the n-valent group derived from an electron carrying compound. An electron transport compound is an n-type organic semiconductor which has a heterocyclic ring whose lowest unoccupied orbital (LUMO) level is 2.0 eV-4.0 eV. Especially, the compound whose LUMO level is 2.5 eV-3.5 eV, or the compound whose hetero ring is a nitrogen-containing hetero ring is preferable.

As the electron transporting compound for forming an n-valent group derived from the electron transporting compound represented by X in the general formula (1), any compound that can be commonly used as a material for the electron transporting layer can be used.

In the said General formula (1), it is one of the preferable aspects of this invention that X is represented by following General formula (2).

[Formula 1]

In the general formula (2), Z represents a group in which n hydrogen atoms are removed from a triazine ring, a benzene ring, or a pyrimidine ring, and P represents an alkylene group, an arylene group, or a hetero ring. Q represents a heterocyclic ring, and is couple | bonded with L of General formula (1), respectively. n1 represents the repeating unit of P and is a number of 0-3. n2 represents the repeating unit of Q and is 0 or 1; n represents the number of substituents represented by following General formula (3) which Z has, and is the same number as n in Formula (1). When two or more P and Q exist in n, the repeating unit and structure of P and Q may be the same respectively, and may differ, and Q may exist in at least one of several n.

[Formula 2]

P, Q, n1, n2 in General formula (3) is the same as that of General formula (2).

It is preferable that the alkylene group, arylene group, heterocyclic ring, and heterocyclic ring in Q in P in the said General formula (2) are group of C3-C15.

The heterocyclic ring in Q in the general formula (2) is preferably an electron transporting group, and for example, an imidazole ring, thiazole ring, oxazole ring, oxadiazole ring, triazole ring, pyrazole It is preferable to have two hydrogen atoms removed from a ring, a pyridine ring, a pyrazine ring, a triazine ring, a benzoimidazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring and a benzothiadiazole ring. And it is more preferable that it is the group which removed two hydrogen atoms from the pyridine ring.

The alkylene group, arylene group, heterocyclic ring in the said P, and the heterocyclic ring in Q may have 1 or 2 or more substituents. As a substituent, the thing similar to the substituent of R <^1> , R <^2> of the said General formula (1) is illustrated.

As an example of the electron carrying compound which forms the n-valent group derived from the electron carrying compound represented by X in the said General formula (1), Tris-1,3,5- (3 '-(pyridin-3' '-yl) phenyl Pyridine derivatives such as benzene (TmPhPyB), 2,4-bis (4-biphenyl) -6- (4 '-(2-pyridinyl) -4-biphenyl)-[1,3,5] triazine And triazine derivatives such as (MPT).

Other examples include phosphine oxide derivatives such as phenyl-dipyrenylphosphineoxide (POPy ₂ ), quinoline derivatives such as (2- (3- (9-carbazolyl) phenyl) quinoline (mCQ), 2 Pyrimidine derivatives such as -phenyl-4,6-bis (3,5-dipyridylphenyl) pyrimidine (BPyPPM), pyrazine derivatives, phenanthroline derivatives such as vasophenanthroline (BPhen), 3-phenyl- Triazole derivatives, such as 4- (1'-naphthyl) -5-phenyl-1,2,4-triazole (TAZ), oxazole derivatives, 2- (4-biphenylyl) -5- (4- oxadiazole derivatives such as tert-butylphenyl-1,3,4-oxadiazole) (PBD), 2,2 ', 2''-(1,3,5-bentriyl) -tris (1-phenyl Imidazole derivatives such as -1-H-benzimidazole) (TPBI), 2,5-bis (6 '-(2', 2 ''-bipyridyl))-1,1-dimethyl-3,4 Organic silane derivatives represented by silol derivatives such as diphenylsilol (PyPySPyPy), Japanese Patent Application No. 2012-228460, Japanese Patent Application No. 2015-503053, Japanese Patent Application No. 2015-053872, Japanese Patent The boron containing compound etc. which were described in the application 2015-081108 and the Japanese patent application 2015-081109 are mentioned.

Among these, the pyridine derivative which has a pyridyl group in the terminal like TmPhPyB is preferable. In other words, it is preferable that X is an n-valent group derived from a pyridine derivative having a pyridyl group at the terminal, and is bonded to L of the general formula (1) at a portion of the terminal pyridyl group.

That is, in General formula (1), it is one of the preferable aspects of this invention that the structure of the terminal part which n-valent group derived from the electron transport compound represented by X couple | bonds with L is a pyridine ring.

In the said General formula (1), L represents the coupling group or direct bond which couple | bonds X and an amino group. When L is a linking group, this linking group is group which connects the atom and the amino group of arbitrary positions which comprise n-valent group derived from the electron transport compound represented by X. When L is a direct bond, the bond position of the n-valent group derived from an electron carrying compound, and an amino group is also arbitrary.

As an example of the coupling group represented by L in the said General formula (1), C1-C18 alkylene coupling group (for example, methylene group, ethylene group, propylene group, butylene group, etc.), C6-C18 arylene A linking group (for example, a phenylene group, a naphthylene group, etc.), a heterocyclic linking group having 2 to 18 carbon atoms (for example, a furyl group, thienylene group, pyridyl group, pyrimidyl group, triazyl group, imidazolyl group, Pyrazolyl group, oxazolyl group, morpholinyl group, etc.), a C1-C4 alkenylene coupling group (vinylene group etc.), an alkynylene coupling group, a nitrogen atom, an oxygen atom, etc. are mentioned. The coupling group represented by L may combine two or more from the above-mentioned coupling group.

As a coupling group represented by L, a C1-C6 alkylene coupling group is especially preferable among the said coupling groups. If the coupling group represented by L is an alkylene coupling group, solubility of an organic material can be improved and it is preferable. In addition, the hydrogen atom contained in the linking group L may be substituted with a monovalent substituent. In addition, carbon number of the said linking group means carbon number of only the linking group which does not have a substituent, and does not include carbon number of the substituent in the case where a linking group has a monovalent substituent.

In said general formula (1), R <^1> , R <^2> is the same or different and represents the hydrocarbon group which may have a substituent. As a hydrocarbon group, it is preferable that it is C1-C6. More preferably, they are C1-C2. In addition, carbon number here means carbon number of only a hydrocarbon group, and does not include carbon number of the substituent in case a hydrocarbon group has a substituent.

The hydrocarbon group may be any of an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.

In General formula (1), although n shows the number of 1-8, it is preferable that it is 1-6, More preferably, it is 2 or 3.

In the said General formula (1), the linking group L may have the same or different monovalent substituent, respectively. In the linking group L, the position and number which a monovalent substituent couple | bonds are not specifically limited. Although it does not restrict | limit especially as a monovalent substituent which may couple | bond with any 1 or more of the linking group L, For example, a halogen atom, a C1-C20 hydrocarbon group, a C1-C12 halogenated hydrocarbon group, C1-C12 A heterocyclic group, a cyano group, a C1-C12 alkoxy group, a C2-C12 alkoxycarbonyl group, a C6-C12 aryloxy group, a C2-C30 N-2 substituted amino group, etc. are mentioned.

The substituent in the case where the hydrocarbon group of R <^1> , R <^2> of General formula (1) has a substituent is also the same as these.

It is preferable that the said halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

The C1-C20 hydrocarbon group is a straight or branched chain having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group and octyl group Type alkyl group; C2-C12 alkenyl groups, such as a vinyl group, a 1-propenyl group, an allyl group, and a styryl group; Alkynyl groups having 2 to 12 carbon atoms such as an ethynyl group, a 1-propynyl group, and a propargyl group; C5-C12 cyclic alkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; The C6-C20 aryl group which may be substituted by the alkyl group, alkenyl group, alkynyl group, etc. are mentioned.

It is preferable that the C1-C20 hydrocarbon group is C1-C8 among the above-mentioned thing, More preferably, it is C1-C6, More preferably, it is C1-C4. It is especially preferable that the said C1-C20 hydrocarbon group is carbon number among the above-mentioned thing.

The said C1-C12 halogenated hydrocarbon group is C1-C12 haloalkyl groups, such as a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group; A C6-C12 aryl group substituted by the halogen atom is mentioned.

It is preferable that the said C1-C12 halogenated hydrocarbon group is C1-C8 among the above-mentioned thing, More preferably, it is 1-6.

The heterocyclic group having 0 to 12 carbon atoms may be a 5-membered ring nitrogen-containing ring group such as pentazole; 5-membered ring heterocyclic groups such as triazole, tetrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, pyrazole, pyrrole, pyrrolidine, oxazoline, furan and thiophene; 6-membered ring heterocyclic groups, such as a pyridine, a pyrazine, a piperidine, a morpholine, a thiazine, are mentioned as a preferable thing. In addition, these heterocyclic groups may be substituted by a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkenyl group, an alkynyl group, or the like.

The heterocyclic group having 0 to 12 carbon atoms is preferably 1 to 8, more preferably 1 to 6, among the above-mentioned ones.

The alkoxy group having 1 to 12 carbon atoms is a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyl octa The thing of linear or branched chain type, such as a timing, is mentioned as a preferable thing.

It is preferable that carbon number of the said C1-C12 alkoxy group is C1-C8 among the thing mentioned above, More preferably, it is 1-6, More preferably, it is 1-3.

Examples of the alkoxycarbonyl group having 2 to 12 carbon atoms include linear or branched chains such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group and octyloxycarbonyl group.

It is preferable that carbon number of the said C2-C12 alkoxycarbonyl group is two among the above-mentioned thing.

A phenyloxy group, a benzyloxy group, etc. are mentioned as said C6-C12 aryloxy group. The said C6-C12 aryloxy group may be substituted by the halogen atom, the alkyl group, the aryl group, the alkoxy group, the alkenyl group, the alkynyl group, etc., for example in the part of the aryl group of an aryloxy group.

The C6-C12 aryloxy group has preferable C6-C10 among the above-mentioned thing, More preferably, it is 6-8, More preferably, it is 6.

As said C2-C30 N-2 substituted amino group, C2-C12 dialkylamino groups, such as a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a morpholinyl group; N-alkyl-N-arylamino groups having 6 to 20 carbon atoms such as an N-methyl-N-phenylamino group and an N-ethyl-N-naphthylamino group; C1-C30 acyclic diarylamino group or cyclic diarylamino group, such as a diphenylamino group, a carbazolyl group, a phenoxazinyl group, and a phenothiazinyl group, etc. are mentioned as a preferable thing.

In addition, an acyclic diarylamino group means what does not have ring structure other than an aromatic ring. A cyclic diarylamino group means what has ring structures other than an aromatic ring. The said C2-C30 N-2 substituted amino group may be substituted by the halogen atom, the alkyl group, the alkoxy group, the alkenyl group, the alkynyl group etc., for example in the part of the alkyl group or aryl group of N-2 substituted amino group. .

It is preferable that the C2-C12 dialkylamino group is C2-C8 among the above-mentioned thing. More preferably, it is 2-6. More preferably, it is 2-4.

It is preferable that the C6-C20 N-alkyl-N-arylamino group has 7-18 carbon atoms among the above-mentioned thing. More preferably, it is 7-15. More preferably, they are 7-11.

The acyclic diarylamino group or the cyclic diarylamino group having 11 to 30 carbon atoms described above is preferably 11 to 20 carbon atoms, more preferably 12 to 18, and even more preferably 12 16.

In addition, the monovalent substituent which may couple | bond with any one or more of the linking groups L, and the substituent in case the hydrocarbon group of R <^1> , R <^2> has a substituent are acyl groups, such as an acetyl group, a propionyl group, butyryl group; N, N-dialkyl carbamoyl groups, such as N, N- dimethyl carbamoyl group and N, N-diethyl carbamoyl group; Thiocarbonyl groups such as thioacetyl group, thiobenzoyl group, and methoxythiocarbonyl group; A dioxabororanyl group, a stanyl group, a silyl group, an ester group, a formyl group, a thioether group, an epoxy group, an isocyanate group, a sulfo group, a sulfonyl group, a phosphoryl group, etc. may be sufficient.

In addition, the said monovalent substituent (monovalent substituent which may be couple | bonded with 1 or more of the linking group L, and substituent in the case where the hydrocarbon group of R <^1> , R <^2> has a substituent) is a halogen atom as long as it can exhibit the effect of this invention, It may be substituted by monovalent substituents, such as a hetero atom, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, and an aromatic ring. When the said monovalent substituent (monovalent substituent which may couple | bond with 1 or more of the linking group L, and the substituent when the hydrocarbon group of R <^1> , R <^2> has a substituent) further has a monovalent substituent, either 1 of the linking groups L The position and the number of monovalent substituents bonded to the monovalent substituents which may be bonded to the above are not particularly limited.

2. Organic electroluminescent device

Next, the structure of the organic electroluminescent element of this invention and materials other than the said amino group containing compound are demonstrated.

The organic electroluminescent device of the present invention has a structure in which a plurality of organic compound layers are laminated between a cathode and an anode formed on a substrate.

Although the structure of the organic electroluminescent element of the present invention is not particularly limited, the element having an anode, a hole transporting layer and / or a hole injection layer, a light emitting layer, and optionally an electron transporting layer, an electron injection layer, and a cathode, in this order, are adjacent to each other. Is preferably. In addition, each of these layers may consist of one layer, and may consist of two or more layers.

In the organic electroluminescent element of the said structure, when an element does not have an electron carrying layer, an electron injection layer and a light emitting layer adjoin. When the device has only one of the hole transporting layer and the hole injection layer, the one layer is laminated adjacent to the light emitting layer and the anode, and when the device has both the hole transporting layer and the hole injection layer, the anode, These layers are stacked adjacent to each other in the order of a hole injection layer, a hole transport layer, and a light emitting layer.

The organic electroluminescent element of this invention may be a top emission type which takes out light to the opposite side to a board | substrate, or may be a bottom emission type which takes out light to the board | substrate side.

In the organic electroluminescent device of the present invention, the layer of the coating film formed by applying a solution containing the amino group-containing compound represented by the general formula (1) is formed as a layer adjacent to the cathode, so that the amino group-containing compound The layer of the coating film containing this becomes an electron injection layer. Since the amino group containing compound represented by General formula (1) is a compound which is excellent in electron injection property, by having the layer containing this compound as an electron injection layer, an element becomes a device which has a low drive voltage and excellent characteristic.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing for demonstrating an example of the organic electroluminescent element of the forward structure of this invention. The organic electroluminescent element of this embodiment shown in FIG. 1 has the light emitting layer 5 between the anode 2 and the cathode 8. In the organic electroluminescent element shown in FIG. 1, the electron injection layer 7 is provided between the cathode 8 and the light emitting layer 5.

The organic electroluminescent device of the present embodiment includes, on the substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, and an electron transport layer 6. The electron injection layer 7 and the cathode 8 have a laminated structure formed in this order.

"Board"

As a material of the board | substrate in the organic electroluminescent element of this invention, a resin material, a glass material, etc. are mentioned.

Examples of the resin material used for the substrate include polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyether sulfone, polymethyl methacrylate, polycarbonate, and polyarylate. When a resin material is used as a material of a board | substrate, since the organic electroluminescent element excellent in flexibility is obtained, it is preferable.

As a glass material used for a board | substrate, quartz glass, soda glass, etc. are mentioned.

When the organic electroluminescent element of the present invention is a bottom emission type, a transparent substrate is used as the material of the substrate.

When the organic electroluminescent element of the present invention is of the top emission type, not only a transparent substrate but also an opaque substrate may be used as the material of the substrate. As an opaque board | substrate, the board | substrate which consists of ceramic materials, such as alumina, the board | substrate which formed the oxide film (insulating film) in the surface of the metal plate, such as stainless steel, the board | substrate comprised of resin material, etc. are mentioned, for example.

The average thickness of the said board | substrate can be determined according to the material of a board | substrate, etc., It is preferable that it is 0.1-30 mm, and it is more preferable that it is 0.1-10 mm.

The average thickness of a board | substrate can be measured with a digital multimeter and a vernier caliper.

"anode"

In the organic electroluminescent device of the present invention, examples of the material used for the anode include ITO, IZO, Au, Pt, Ag, Cu, Al, or alloys containing them. Among these, it is preferable to use ITO, IZO, Au, Ag, Al as a material of an anode.

Although the average thickness of the said anode is not specifically limited, It is preferable that it is 10-1000 nm, and it is more preferable that it is 30-150 nm. Moreover, also when using an impermeable material as a material of an anode, it can be used as a transparent anode in a top emission type organic electroluminescent element by making an average thickness about 10-30 nm, for example.

The average thickness of the positive electrode can be measured at the time of forming the positive electrode by means of a crystal oscillator film thickness meter.

`` Hole injection layer ''

In the organic electroluminescent device of the present invention, as a material used for the hole injection layer, dipyrazino [2,3-f: 2 ', 3'-h] quinoxaline-2,3,6,7,10 , 11-hexacarbonitrile (HAT-CN), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane (F4-TCNQ), etc. are mentioned.

Although the average thickness of the said hole injection layer is not specifically limited, It is preferable that it is 1-1000 nm, and it is more preferable that it is 5-50 nm.

The average thickness of the hole injection layer can be measured at the time of film formation by a crystal oscillator film thickness meter.

`` Hole transport layer ''

In the organic electroluminescent device of the present invention, as the hole transporting organic material used for the hole transporting layer, various p-type polymer materials (organic polymers) and various p-type low molecular materials can be used alone or in combination.

Specifically, as a material of the hole transport layer, for example, N, N'-di (1-naphthyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine ( α-NPD), N4, N4'-bis (dibenzo [b, d] thiophen-4-yl) -N4, N4'-diphenylbiphenyl-4,4'-diamine (DBTPB), polyarylamine , Fluorene-arylamine copolymer, fluorene-bithiophene copolymer, poly (N-vinylcarbazole), polyvinylpyrene, polyvinylanthracene, polythiophene, polyalkylthiophene, polyhexylthiophene, poly ( p-phenylenevinylene), polytinylenevinylene, pyreneformaldehyde resin, ethylcarbazole formaldehyde resin or derivatives thereof. The material of these hole transport layers 4 can also be used as a mixture with other compounds. As an example, as a mixture containing polythiophene used as a material of the hole transport layer 4, poly (3,4-ethylenedioxythiophene / styrenesulfonic acid) (PEDOT / PSS) and the like can be mentioned.

Although the average thickness of the said hole transport layer is not specifically limited, It is preferable that it is 10-150 nm, and it is more preferable that it is 20-100 nm.

The average thickness of the hole transport layer can be measured by, for example, a stylus stepometer and spectroscopic ellipsometry.

`` Light emitting layer ''

In the organic electroluminescent element of the present invention, any material which can be used as a material of the light emitting layer may be used as the material for forming the light emitting layer, or a mixture thereof may be used. Specifically, for example, bis [2- (2-benzothiazolyl) phenolato] zinc (II) (Zn (BTZ) ₂ ) and tris [1-phenylisoquinoline] iridium (III) as light emitting layers (Ir (piq) ₃ ) can be included.

Moreover, a low molecular weight compound may be sufficient as the material which forms a light emitting layer, and a high molecular compound may be sufficient as it. In addition, in this invention, a low molecular material means the material which is not a polymeric material (polymer), and does not necessarily mean the organic compound with low molecular weight.

As a polymeric material which forms the said light emitting layer, For example, polyacetylene type compounds, such as a trans type polyacetylene, a cis type polyacetylene, a poly (di-phenyl acetylene) (PDPA), a poly (alkylphenyl acetylene) (PAPA) ; Poly (para-phenvinylene) (PPV), poly (2,5-dialkoxy-para-phenylenevinylene) (RO-PPV), cyano-substituted-poly (para-phenvinylene) (CN- PPV), poly (2-dimethyloctylsilyl-para-phenylenevinylene) (DMOS-PPV), poly (2-methoxy-5- (2'-ethylhexoxy) -para-phenylenevinylene) ( Polyparaphenylene vinylene-based compounds such as MEH-PPV); Polythiophene-based compounds such as poly (3-alkylthiophene) (PAT) and poly (oxypropylene) triol (POPT); Poly (9,9-dialkylfluorene) (PDAF), poly (dioctylfluorene-alt-benzothiadiazole) (F8BT), α, ω-bis [N, N'-di (methylphenyl) aminophenyl ] -Poly [9,9-bis (2-ethylhexyl) fluorene-2,7-diyl] (PF2 / 6am4), poly (9,9-dioctyl-2,7-divinylenefluorenyl- Polyfluorene compounds such as ortho-co (anthracene-9,10-diyl); poly (para-phenylene) (PPP), poly (1,5-dialkoxy-para-phenylene) (RO-PPP) Polyparaphenylene compounds such as; polycarbazole compounds such as poly (N-vinylcarbazole) (PVK); poly (methylphenylsilane) (PMPS), poly (naphthylphenylsilane) (PNPS), poly (non Polysilane-based compounds such as phenylylphenylsilane) (PBPS), and further, boron compound-based polymer materials described in Japanese Patent Application No. 2010-230995 and Japanese Patent Application No. 2011-6457.

As a low molecular material which forms the said light emitting layer, For example, a tri coordination iridium complex which has 2,2'-bipyridine-4,4'- dicarboxylic acid in a ligand, and a pactless (2-phenylpyridine) Iridium (Ir (ppy) ₃ ), 8-hydroxyquinolinealuminum (Alq ₃ ), tris (4-methyl-8quinolinolate) aluminum (III) (Almq ₃ ), 8-hydroxyquinolinezinc (Znq ₂ ), (1,10-phenanthroline) -tris (4,4,4-trifluoro-1- (2-thienyl) -butane-1,3-dionate) europium (III) (Eu (TTA ) ₃ (phen)), various metal complexes such as 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphine platinum (II); Benzene-based compounds such as distyrylbenzene (DSB) and diaminodistyrylbenzene (DADSB); Naphthalene-based compounds such as naphthalene and nired; Phenanthrene-based compounds such as phenanthrene; Chrysene-based compounds such as chrysene and 6-nitrocriscene; Perylene-based compounds such as perylene and N, N'-bis (2,5-di-t-butylphenyl) -3,4,9,10-perylene-di-carboxyimide (BPPC); Coronene-based compounds such as coronene; Anthracene-based compounds such as anthracene and bisstyrylanthracene; Pyrene-based compounds such as pyrene; Pyranic compounds such as 4- (di-cyanomethylene) -2-methyl-6- (para-dimethylaminostyryl) -4H-pyran (DCM); Acridine-based compounds such as acridine; Stilbene compounds such as stilbene; Thiophene type compounds, such as 2, 5- dibenzo oxazole thiophene; Benzoxazole type compounds, such as benzoxazole; Benzoimidazole type compounds, such as benzoimidazole; Benzothiazole compounds such as 2,2 '-(para-phenylenedivinylene) -bisbenzothiazole; Butadiene type compounds, such as bistyryl (1, 4- diphenyl- 1, 3- butadiene) and tetraphenyl butadiene; Naphthalimide-based compounds such as naphthalimide; Coumarin-based compounds such as coumarin; Perinone compounds such as perinone; Oxadiazole type compounds, such as oxadiazole; Aldazine-based compounds; Cyclopentadiene compounds such as 1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene (PPCP); Quinacridone compounds such as quinacridone and quinacridone red; Pyridine compounds such as pyrrolopyridine and thiadiazolopyridine; Spiro compounds such as 2,2 ', 7,7'-tetraphenyl-9,9'-spirobifluorene; Phthalocyanine compounds of metals or metals such as phthalocyanine (H ₂ Pc) and copper phthalocyanine; Furthermore, the boron compound material etc. which were described in Unexamined-Japanese-Patent No. 2009-155325, Unexamined-Japanese-Patent No. 2011-184430, and Unexamined-Japanese-Patent Application 2011-6458 are mentioned.

Although the average thickness of the said light emitting layer is not specifically limited, It is preferable that it is 10-150 nm, and it is more preferable that it is 20-100 nm.

The average thickness of the light emitting layer may be measured by a tactile stepmeter or may be measured at the time of film formation of the light emitting layer by a crystal oscillator film thickness meter.

`` Electron transport layer ''

In the organic electroluminescent element of the present invention, as the material of the electron transporting layer, any material which can be commonly used as the material of the electron transporting layer may be used.

Specific examples of the material that can be commonly used as the material of the electron transport layer include phosphine oxide derivatives such as phenyl-dipyrenylphosphineoxide (POPy ₂ ), tris-1,3,5- (3 '-(pyridine-) Pyridine derivatives such as 3 ''-yl) phenyl) benzene (TmPhPyB), quinoline derivatives such as (2- (3- (9-carbazolyl) phenyl) quinoline (mCQ)), 2-phenyl-4,6- Pyrimidine derivatives such as bis (3,5-dipyridylphenyl) pyrimidine (BPyPPM), pyrazine derivatives, phenanthroline derivatives such as vasophenanthroline (BPhen), 2,4-bis (4-biphenyl) Triazine derivatives such as -6- (4 '-(2-pyridinyl) -4-biphenyl)-[1,3,5] triazine (MPT), 3-phenyl-4- (1'-naphthyl Triazole derivatives, such as) -5-phenyl-1,2,4-triazole (TAZ), oxazole derivatives, 2- (4-biphenylyl) -5- (4-tert-butylphenyl-1,3 Oxadiazole derivatives such as, 4-oxadiazole) (PBD), 2,2 ', 2''-(1,3,5-bentriyl) -tris (1-phenyl-1-H-benzimidazole Already like (TPBI) Aromatic ring tetracarboxylic anhydrides, such as a diazole derivative, naphthalene, and perylene, bis [2- (2-hydroxyphenyl) benzothiazolato] zinc (Zn (BTZ) ₂ ), tris (8-hydroxyquinolina) Various metal complexes represented by, for example, aluminum (Alq ₃ ), 2,5-bis (6 '-(2', 2 ''-bipyridyl))-1,1-dimethyl-3,4-diphenyl Organic silane derivatives represented by silol derivatives such as silol (PyPySPyPy), Japanese Patent Application 2012-228460, Japanese Patent Application 2015-503053, Japanese Patent Application 2015-053872, Japanese Patent Application 2015-081108 and Japanese Patent Application 2015-081109 The boron-containing compound described, etc. are mentioned, These 1 type, or 2 or more types can be used.

Among the materials of these electron transporting layers, it is particularly preferable to use phosphine oxide derivatives such as POPy ₂ , metal complexes such as Alq _3, and pyridine derivatives such as TmPhPyB.

Although the average thickness of the said electron carrying layer is not specifically limited, It is preferable that it is 10-150 nm, and it is more preferable that it is 20-100 nm.

The average thickness of an electron carrying layer can be measured with a stylus type stepmeter and spectroscopic ellipsometry.

`` Electron injection layer ''

In the organic electroluminescent device of the present invention, the electron injection layer is a layer that improves the rate and electron transportability of electron injection from the cathode to the light emitting layer, and contains an amino group-containing compound represented by the general formula (1) as described above. It is a layer.

It is preferable that it is 5-100 nm, and, as for the average thickness of an electron injection layer, it is more preferable that it is 10-50 nm. When the average thickness of an electron injection layer is 100 nm or less, the raise of the drive voltage of an organic electroluminescent element by forming an electron injection layer can fully be suppressed.

The average thickness of an electron injection layer can be measured with a stylus type stepmeter and spectroscopic ellipsometry.

When the organic electroluminescent element of this invention uses the layer containing the amino-group containing compound represented by the said General formula (1) as an electron injection layer, for example, when using the alkali metal which is an unstable material in air | atmosphere as an electron injection layer, In comparison with this, excellent durability is obtained.

"cathode"

In the organic electroluminescent device of the present invention, as the material of the cathode, the use of an alkali metal or an alkaline earth metal is not essential as in the case of a general cathode material. A metal having a medium work function such as Al, gold having an inert large work function, or the like can be used by itself.

Although the average thickness of the said negative electrode is not specifically limited, It is preferable that it is 10-500 nm, and it is more preferable that it is 100-200 nm.

The average thickness of a negative electrode can be measured with a stylus type stepmeter and spectroscopic ellipsometry.

"bag"

The organic electroluminescent element of this invention may be sealed as needed.

Although the sealing method in particular is not restrict | limited, For example, you may be sealed by the sealing container which has a concave space which accommodates an organic electroluminescent element, and the adhesive agent which adhere | attaches the edge part of a sealing container, and a board | substrate. Moreover, you may encapsulate by accommodating an organic electroluminescent element in a sealing container, and filling the sealing material which consists of ultraviolet-ray (UV) hardening resin etc .. Moreover, the sealing member which consists of a plate member arrange | positioned on the cathode, the frame member arrange | positioned along the edge part of the side which opposes the cathode of a plate member, and the adhesive agent which bonds between a plate member and a frame member, and between a frame member and a board | substrate It may be sealed using.

When sealing an organic electroluminescent element using the said sealing container or sealing member, you may arrange | position the drying material which absorbs moisture in a sealing container or inside of a sealing member. Moreover, you may use the material which absorbs water as a sealing container or sealing member. Moreover, the space may be formed in the sealed sealing container or inside of the sealing member.

A resin material, a glass material, etc. can be used as a material of the sealing container or sealing member used when sealing the said organic electroluminescent element. Examples of the resin material and glass material used for the sealing container or the sealing member include the same materials as those used for the substrate.

In the organic electroluminescent device of the present invention, the method of forming the layer formed of the organic compound is not particularly limited, and various methods can be suitably used in accordance with the properties of the material. Method, casting method, microgravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, slit coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method It can form into a film using various coating methods, such as a method and the inkjet printing method. Among these, the spin coat method and the slit coat method are preferable at the point which makes it easier to control a film thickness. If not applied or solvent solubility is low, sputtering, vacuum deposition, sol-gel, spray pyrolysis (SPD), atomic layer deposition (ALD), vapor deposition, liquid deposition, ESDUS (Evaporative Spray Deposition from Ultra) -dilute solution) method can be used.

When forming the layer formed from the organic compound containing the amino group containing compound represented by the said General formula (1) by apply | coating and forming an organic compound solution, As a solvent used in order to dissolve an organic compound, For example, nitric acid Inorganic solvents such as sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, carbon tetrachloride and ethylene carbonate, methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl ketone (MIBK) and methyl isopropyl ketone (MIPK) Ketone solvents such as cyclohexanone, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol (DEG), glycerin, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane ( Ethers such as DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), diethylene glycol ethyl ether (carbitol) Cellosolve solvents such as le-based solvents, methyl cellosolve, ethyl cellosolve, and phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene, xylene, and benzene Amides such as solvents, aromatic heterocyclic compound solvents such as pyridine, pyrazine, furan, pyrrole, thiophene and methylpyrrolidone, N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMA) Halogen solvents such as chlorobenzene, dichloromethane, chloroform and 1,2-dichloroethane, ester solvents such as ethyl acetate, methyl acetate, and ethyl formate, sulfur such as dimethyl sulfoxide (DMSO) and sulfolane Various organic solvents such as a compound solvent, a nitrile solvent such as acetonitrile, propionitrile and acrylonitrile, and an organic acid solvent such as formic acid, acetic acid, trichloroacetic acid and trifluoroacetic acid, or Mixed solvents containing these, etc. are mentioned.

Among these, as the solvent, a nonpolar solvent is preferable, and for example, aromatic hydrocarbon solvents such as xylene, toluene, cyclohexylbenzene, dihydrobenzofuran, trimethylbenzene, tetramethylbenzene, pyridine, pyrazine, furan, And aromatic heterocyclic compound solvents such as pyrrole, thiophene and methylpyrrolidone, and aliphatic hydrocarbon solvents such as hexane, pentane, heptane and cyclohexane, and the like, and these may be used alone or in combination.

The cathode and the anode can be formed by a sputtering method, a vacuum deposition method, a sol-gel method, a spray pyrolysis (SPD) method, an atomic layer deposition (ALD) method, a vapor deposition method, a liquid film formation method, or the like. Bonding of metal foil can also be used for formation of an anode and a cathode. It is preferable to select these methods according to the characteristic of the material of each layer, and a manufacturing method may differ for every layer. When forming a metal oxide layer on an organic compound layer, it is more preferable to form using a vapor-phase film forming method among these. According to the vapor phase film forming method, it is possible to form a clean contact with good contact with the adjacent layer without damaging the surface of the organic compound layer.

3. Manufacturing method of organic electroluminescent element

As mentioned above, in the organic electroluminescent element of a pure structure, the organic electroluminescence which is excellent in electron injection property is formed by apply | coating the solution containing the amino group containing compound which has a structure represented by the said General formula (1), and forming a layer. The device is obtained.

A method of manufacturing such an organic electroluminescent device, that is, a method of manufacturing an organic electroluminescent device having a structure in which a plurality of organic compound layers are laminated between a cathode and an anode formed on a substrate, the production method being represented by the following general formula (1) );

(X)-[(L)-(NR ¹ R ² )] _n (1)

(Wherein, X represents an n-valent group derived from an electron transporting compound. L represents a linking group or a direct bond which bonds an amino group represented by X and NR ¹ R ^2. R ¹ and R ² are the same or different. The hydrocarbon group which may have a substituent is represented, n shows the number of 1-8. The process of apply | coating the solution containing the amino-group-containing compound which has a structure shown by (), and forming a layer, and this amino-group-containing compound are included. The manufacturing method of the organic electroluminescent element characterized by including the process of forming a cathode adjacent to the said layer is also one of this invention.

In the manufacturing method of the organic electroluminescent element of this invention, the solvent used when preparing the solution containing the amino-group containing compound represented by General formula (1), and the method of forming the layer of the coating film of this solution are mentioned above. You can use one.

The manufacturing method of the organic electroluminescent element of this invention is the process of apply | coating the solution containing the amino group containing compound which has a structure represented by the said General formula (1), and forming a layer, and adjoining the layer containing this amino group containing compound. As long as it includes the process of forming a cathode, you may include other processes. As another process, the process of forming other layers other than the layer of the coating film of the solution containing an amino-group containing compound, the process of sealing an element, etc. are mentioned.

In the organic electroluminescent device of the present invention, the emission color can be changed by appropriately selecting the material of the organic compound layer, and a desired emission color can also be obtained by using a color filter or the like. Therefore, it can use suitably as a light emitting site | part or an illumination device of a display apparatus. In particular, when the organic electroluminescent element is an inverse structure element, a display device combined with an oxide TFT is preferable from the characteristic of inverse structure.

Such a display device comprising the organic electroluminescent element of the present invention and an illumination device comprising the organic electroluminescent element of the present invention are also one of the present inventions.

Example

Although an Example is given to the following and this invention is demonstrated in more detail, this invention is not limited only to these Examples. In addition, "part" means "weight part" and "%" shall mean "mass%" unless there is particular notice.

¹ H-NMR measurement about the compound synthesize | combined in the synthesis example was performed as follows.

( ¹ H-NMR measurement)

The sample was dissolved in heavy chloroform containing tetramethylsilane and measured by a nuclear magnetic resonance apparatus (Varian 600 MHz).

Synthesis Example 1

Synthesis of Organic Compound A

By reaction 1-5 shown below, the organic compound A represented by following formula (i) was synthesize | combined.

[Formula 3]

(Reaction 1) The following compound 1 was synthesized by the following reaction.

[Formula 4]

In a 500 ml three-necked flask under nitrogen atmosphere, 3-allyl-5-bromopyridine (7.6 g, 38.4 mmol) and THF synthesized according to Angelwandte Chemie International Edition, 2004, 43, p.3333 (200 mL) was added, and boron trifluoride diethyl ether complex (BF ₃ · OEt ₂ ) (4.8 mL, 38.2 mmol) was slowly added while stirring at 0 ° C. 9-vorabicyclo [3,3,1] nonane (9-BBN) (1.0 M THF solution, 100 mL, 100 mmol) was added dropwise, and the temperature was raised to room temperature, followed by stirring at 50 ° C for 20 hours. The reaction solution was cooled to 0 ° C, N, N, N ', N'-tetramethylethylenediamine (TMEDA) (2.9 mL, 19.2 mmol) was added, and the mixture was stirred at room temperature for 2 hours. It cooled to 0 degreeC again, the aqueous sodium hydroxide solution (thing which melt | dissolved 9.3 g in 93 mL of water) was added gradually, and after adding 35% hydrogen peroxide solution (93 mL), it stirred at room temperature for 3 hours. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate, the organic layer was washed with saturated brine, dried over sodium sulfate and filtered. The filtrate was concentrated, and the obtained residue was purified by silica gel column chromatography to obtain 7.9 g of compound 1. (36.6 mmol, 95%)

(Reaction 2) The compound 2 was synthesize | combined from the following reaction by the following reaction.

[Formula 5]

Compound 1 (13.0 g, 60.2 mmol), THF (170 mL), triethylamine (12.5 mL, 90.2 mmol) was added to a 300 mL eggplant flask under nitrogen atmosphere, and methanesulfonyl chloride (7.0 was cooled to 0 ° C. Ml, 90.4 mmol) was added slowly. After stirring overnight at room temperature, water was added and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate and filtered. The residue obtained by concentrating the filtrate was purified by silica gel column chromatography to obtain 14.4 g of compound 2. (48.9 mmol, 81%)

(Reaction 3) The compound 3 was synthesize | combined from the following reaction by the following reaction.

[Formula 6]

Compound 2 (14.4 g, 48.9 mmol) and THF (100 mL) were placed in a 300 mL flask, and 50% aqueous dimethylamine solution was added while stirring at room temperature. After stirring overnight, it was concentrated, water was added to the residue, and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, filtered and the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 11.5 g of compound 3. (47.3 mmol, 97%)

(Reaction 4) The compound 4 was synthesize | combined from the compound 3 by the following reaction.

[Formula 7]

Compound 3 (11.5 g, 47.3 mmol) and diethyl ether (300 mL) were put into a 500 mL three-necked flask, and the mixture was cooled to -78 deg. N-butyllithium (1.63 M, 33 mL, 52 mmol) was slowly added dropwise thereto, and after stirring for 1 hour, tributyltin chloride (14.1 mL, 52 mmol) was slowly added. After stirring at room temperature overnight, saturated aqueous ammonium chloride solution was added and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, filtered and the filtrate was concentrated, and the obtained residue was purified by silica gel column chromatography to obtain 18.4 g of compound 4. (40.6 mmol, 86%)

(Reaction 5) The compound 5 (organic compound A) was synthesize | combined from the compound 4 by the following reaction.

[Formula 8]

In a 200 ml two-necked flask under nitrogen atmosphere, compound 4 (10.8 g, 24 mmol), tris (3-bromophenyl) -1,3,5-triazine (3.0 g, 5.5 mmol), toluene (60 ml) ). Tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ) (800 mg, 0.69 mmol) was added thereto, stirred at 110 ° C. for 24 hours, followed by addition of dioxane (60 mL). Stirred for 17 hours. After cooling to room temperature, water was added, extraction was performed with ethyl acetate, and the organic layer was dried over magnesium sulfate and filtered. The filtrate was concentrated and purified by silica gel column chromatography to obtain a crude product. This was suspended in acetone, the insoluble compound was collected by filtration, washed with ethyl acetate, and the obtained white solid was recrystallized from toluene to obtain 1.13 g of compound 5 (organic compound A). (1.42 mmol, 26%)

The ¹ H-NMR measurement results of the obtained organic compound A are as follows.

(Production of organic electroluminescent element)

(Example 1)

[1] A transparent glass substrate on which a commercially available ITO electrode layer having an average thickness of 0.7 mm was formed was prepared. At this time, the ITO electrode (anode) of the board | substrate used what was patterned by width 2mm. This board | substrate was ultrasonically cleaned in acetone in isopropanol for 10 minutes, respectively, and vapor-washed in isopropanol for 5 minutes. This board | substrate was dried by nitrogen blow, and UV ozone washing was performed for 20 minutes.

[2] The substrate was set in a spin coater, and an aqueous dispersion of poly (3,4-ethylenedioxythiophene / styrenesulfonic acid) (PEDOT / PSS) (CH8000, manufactured by Hereus) was added dropwise at 2000 revolutions per minute. It was rotated for 60 seconds and further dried for 10 minutes on a 130 degreeC hotplate, and the hole injection layer which consists of PEDOT / PSS was formed on the anode. The average thickness of the hole injection layer was 50 nm. The average thickness of the hole injection layer was measured by a stylus step meter.

[3] A 2% xylene solution of poly (dioctylfluorene-alto-benzothiadiazole) (F8BT) (molecular weight 54000) was prepared. The board | substrate produced by the said process [2] was set to the spin coater. The F8BT-xylene solution was dripped on the hole injection layer formed in the said process [2], it rotated for 60 second at 2,000 rotations per minute, and the light emitting layer which consists of F8BT was formed on the interlayer layer. The average thickness of the light emitting layer was 50 nm. The average thickness of the light emitting layer was measured by a stylus step meter.

[4] The substrate produced in Step [3] was set in a spin coater. The ethanol solution (0.5 wt%) of the organic compound A synthesized in Synthesis Example 1 was added dropwise onto the light emitting layer formed in the step [3], rotated at 2000 rotations per minute for 60 seconds to form an electron injection layer on the light emitting layer. . The average thickness of the electron injection layer was 10 nm. The average thickness of the electron injection layer was measured by a tactile stepmeter.

[5] The substrate produced in Step [4] was fixed to the substrate holder of the vacuum deposition apparatus. Aluminum wire (Al) was put into an alumina crucible and set in the vapor deposition source. The inside of a vacuum vapor deposition apparatus was decompressed to about 1 * 10 <^-4> Pa, and Al (cathode) was deposited on the electron injection layer so that average thickness might be 100 nm, and the organic electroluminescent element was produced. The average thickness of the cathode was measured at the time of film formation with a crystal oscillator film thickness meter.

(Comparative Example 1)

An organic electroluminescent element was produced in the same manner as in Example 1 except that Step [4] of Example 1 was changed to Step [4-1] below.

[4-1] The substrate produced in Step [3] was fixed to the substrate holder of the vacuum deposition apparatus. At the same time, the organic compound A synthesized in Synthesis Example 1 was placed in a crucible and set in a vapor deposition source. The inside of a vacuum vapor deposition apparatus was decompressed to about 1 * 10 <^-4> Pa, and organic compound A was deposited on the light emitting layer formed in the said process [3] so that an average thickness might be set to 10 nm. The average thickness of an electron injection layer was measured at the time of film-forming by the crystal oscillator film thickness meter.

(Measurement of emission characteristics of organic electroluminescent element)

About the organic electroluminescent element produced in Example 1 and the comparative example 1, voltage application and electric current measurement to the element were performed with Keithley's "2400 type source meter". Moreover, the luminescence brightness was measured by "BM-7" by Topcon Corporation. The measurement was performed in argon atmosphere. The results are shown in FIGS. 2 and 3.

In the organic electroluminescent element of Example 1 having a coating film of organic compound A, while the applied voltage starts to emit light from about 2.8 V, in the organic electroluminescent element of Comparative Example 1 in which organic compound A was formed by vapor deposition, It did not emit light unless a voltage was applied to around 3.5 V. Moreover, when the brightness | luminance at the applied voltage 6V was compared, the organic electroluminescent element of Example 1 was about 10 times higher than the organic electroluminescent element of Comparative Example 1. From these results, it was confirmed that it becomes the element excellent in the electron injection property by forming the layer of the coating film of organic compound A.

1: substrate
2: anode
3: hole injection layer
4: hole transport layer
5: light emitting layer
6: electron transport layer
7: electron injection layer
8: cathode

Claims (5)

An organic electroluminescent device having a structure in which a plurality of organic compound layers are laminated between a cathode and an anode formed on a substrate,
In the organic compound layer, the layer adjacent to the cathode,
The following general formula (1);
(X)-[(L)-(NR ¹ R ² )] _n (1)
(Wherein, X represents an n-valent group derived from an electron transporting compound. L represents a linking group or a direct bond which bonds an amino group represented by X and NR ¹ R ^2. R ¹ and R ² are the same or different. The hydrocarbon group which may have a substituent is represented, n represents the number of 1-8.) It is an organic electroluminescent element characterized by the layer of the coating film of the solution containing the amino-group-containing compound which has a structure shown by these. The method of claim 1,
In said general formula (1), the n-valent group derived from the electron transport compound represented by X is a structure of the terminal part couple | bonded with L, The organic electroluminescent element characterized by the above-mentioned. The organic electroluminescent element of Claim 1 or 2 is provided, The display apparatus characterized by the above-mentioned. The organic electroluminescent element of Claim 1 or 2 is provided, The illuminating device characterized by the above-mentioned. A method of manufacturing an organic electroluminescent device having a structure in which a plurality of organic compound layers are laminated between a cathode and an anode formed on a substrate,
The manufacturing method is following General formula (1);
(X)-[(L)-(NR ¹ R ² )] _n (1)
(Wherein, X represents an n-valent group derived from an electron transporting compound. L represents a linking group or a direct bond which bonds an amino group represented by X and NR ¹ R ^2. R ¹ and R ² are the same or different. And a hydrocarbon group which may have a substituent, n represents a number from 1 to 8. A process of forming a layer by applying a solution containing an amino group-containing compound having a structure represented by
A method of producing an organic electroluminescent device, comprising the step of forming a cathode adjacent to a layer containing the amino group-containing compound.

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