Organic compound and organic electroluminescent element containing the same

Abstract

The present invention relates to a novel organic compound and an organic light-emitting element comprising the organic compound, and more particularly, to an organic electroluminescent element with low driving voltage and significantly improved luminous efficiency and lifespan.

Description

Technical Field

[0001] The present invention relates to an organic compound and an organic electroluminescent element comprising the organic compound. Background Art

[0002] Compared with other flat panel display elements such as existing liquid crystal displays (LCDs), plasma display panels (PDPs) and field emission displays (FEDs), organic electroluminescent elements (OLEDs) have a simple structure and various advantages in the manufacturing process. They have high brightness and excellent field of view characteristics, fast response speed and low driving voltage. Therefore, they are actively developed and commercialized so that they can be used as light sources for flat panel displays such as wall-mounted TVs or display backlights, lighting, billboards, etc.

[0003] As for organic electroluminescent elements, the initial organic EL element was reported by CW Tang et al. of Eastman Kodak Company (CW Tang, SAVanslyke, Applied Physics Letters, Vol. 51, p. 913, 1987). The luminescence principle thereof is generally based on that, when voltage is applied, holes injected from the anode and electrons injected from the cathode recombine to form excitons, i.e., electron-hole pairs, and the energy of the excitons is converted into light by transferring the energy of the excitons to the luminescent material.

[0004] More specifically, the organic electroluminescent element has a structure including a cathode (electron injection electrode) and an anode (hole injection electrode) and one or more organic layers between the two electrodes. At this time, the organic electroluminescent element is stacked in the order of a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EML), an electron transport layer (ETL) or an electron injection layer (EIL) starting from the anode. In order to improve the efficiency of the light emitting layer, a hole transport auxiliary layer or a hole blocking layer (HBL) can be further included before and after the light emitting layer.

[0005] Materials used as organic layers in organic electronic devices can be divided into light-emitting materials and charge transport materials according to their functions, for example, hole injection materials, hole transport materials, electron transport materials, electron injection materials, etc.

[0006] Lifespan and efficiency are the biggest issues for organic electronic light-emitting elements, and as displays become larger, these efficiency and lifespan issues must be resolved. Efficiency, lifespan, and driving voltage are interrelated. When efficiency increases, driving voltage decreases relatively. As driving voltage decreases, crystallization of organic substances due to Joule heating generated during driving decreases, resulting in a tendency for lifespan to increase.

[0007] However, simply improving the organic layer cannot maximize efficiency because long life and high efficiency can only be achieved when the energy levels and T1 values ​​between the organic layers, the inherent properties of the material (mobility, interface properties, etc.) are optimally combined.

[0008] Furthermore, in recent years, in organic electroluminescent elements, in order to solve the luminescence problem in the hole transport layer, a luminescence auxiliary layer must exist between the hole transport layer and the luminescent layer, and different luminescence auxiliary layers must be developed according to each luminescent layer (red (R), green (G), blue (B)).

[0009] Generally, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer, and excitons are generated through recombination.

[0010] However, as for the materials used for the hole transport layer, since they need to have a low HOMO value, most of them have a low T1 value. As a result, the excitons generated in the light-emitting layer are transferred to the hole transport layer, resulting in charge unbalance in the light-emitting layer, which leads to light emission at the hole transport layer interface.

[0011] When the hole transport layer interface emits light, the color purity and efficiency of the organic electrical element decrease, and the life span becomes shorter. Therefore, there is an urgent need for a light-emitting auxiliary layer with a high T1 value and a HOMO energy level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light-emitting layer.

[0012] Prior art literature

[0013] Non-patent literature

[0014] (Non-patent document 1) Krebs, Frederik C., et al., "Synthesis, Structure, and Properties of 4,8,12-Trioxa-12c-phospha-4,8,12,12c-tetrahydrodibenzo[cd,mn]pyrene, a Molecular Pyroelectric." Journal of the American Chemical Society, 119.6 (1997): 1208-1216. Summary of the invention

[0015] Problem that the invention aims to solve

[0016] An object of the present invention is to provide a novel organic compound and an organic electroluminescent device including the organic compound.

[0017] Another object of the present invention is to provide a novel organic compound having a high glass transition temperature and thermal stability.

[0018] Another object of the present invention is to provide an organic electroluminescent element having excellent hole transport properties, and by reducing the HOMO energy level difference between the hole transport layer and the light-emitting layer, adjusting the hole injection properties, and reducing the hole accumulation at the interface of the light-emitting layer, thereby reducing the driving voltage and significantly improving the luminous efficiency and life characteristics.

[0019] Means used to solve problems

[0020] In order to achieve the above-mentioned different purposes of the present invention, the present invention provides a compound represented by the following chemical formula 1:

[0021] [Chemical formula 1]

[0022]

[0023] in,

[0024] n, m and o are the same or different from each other and are each independently an integer from 0 to 5,

[0025] p is an integer of 0 or 1,

[0026] X1 is N, O or S,

[0027] Ring A, Ring B and Ring C are the same or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms,

[0028] R1 to R4 are the same as or different from each other, and are each independently selected from hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkylthio having 1 to 4 carbon atoms, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 5 to 60 carbon atoms, substituted or unsubstituted cycloalkyl having 6 to 30 carbon atoms, The present invention relates to a group consisting of a substituted or unsubstituted heteroarylalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and can bond to adjacent groups to form a substituted or unsubstituted ring.

[0029] Furthermore, the present invention relates to an organic electroluminescent element, comprising: a first electrode; a second electrode opposite to the first electrode; and one or more organic layers between the first electrode and the second electrode, wherein the one or more organic layers contain the compound represented by the chemical formula 1.

[0030] In the present invention, unless otherwise specified, "hydrogen" means hydrogen, protium, deuterium or tritium.

[0031] In the present invention, the "halogen group" is fluorine, chlorine, bromine or iodine.

[0032] In the present invention, "alkyl" refers to a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, and hexyl.

[0033] In the present invention, "alkenyl" refers to a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples include vinyl, allyl, isopropenyl, 2-butenyl, etc., but are not limited thereto.

[0034] In the present invention, "alkynyl" refers to a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon triple bonds. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.

[0035] In the present invention, the "alkylthio group" refers to the above-mentioned alkyl group bonded via a sulfur bond (-S-).

[0036] In the present invention, "aryl" refers to a monovalent substituent of an aromatic hydrocarbon having 6 to 60 carbon atoms in a single ring or two or more rings. In addition, it may include two or more rings in a pendant or fused form, specifically, naphthyl, anthracenyl, phenanthrenyl, triphenyl, pyrenyl, phenalenyl, peryl, chrysene, fluorenyl, etc., but not limited thereto. The fluorenyl may be substituted, and adjacent groups may be combined with each other to form a ring.

[0037] In the present invention, "heteroaryl" refers to a monovalent substituent derived from a monocyclic or polycyclic aromatic hydrocarbon having 6 to 30 carbon atoms. At this time, one or more carbons in the ring, preferably 1 to 3 carbons, are replaced by heteroatoms such as N, O, S or Se. In addition, it can include a form in which two or more rings are pendant or fused to each other, and can also include a form fused with an aromatic group. As examples of such heteroaryl groups, 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl, 2-pyrimidinyl, etc., but are not limited thereto.

[0038] In the present invention, "aryloxy" is a monovalent substituent represented by RO-, where R is an aryl group having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenoxy, naphthoxy, and diphenoxy.

[0039] In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R' refers to an alkyl group having 1 to 40 carbon atoms, and may include a linear, branched or cyclic structure. Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, tert-butoxy, n-butoxy, pentyloxy, and the like.

[0040] In the present invention, "alkoxy" can be a straight chain, a branched chain or a cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, and preferably the number of carbon atoms is 1 to 20. Specifically, it can be a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, an isopropoxy group, an i-propyloxy group, a n-butoxy group, an isobutoxy group, a tert-butoxy group, a sec-butoxy group, a n-pentoxy group, a neopentoxy group, an isopentyl group, a n-hexyl group, a 3,3-dimethylbutoxy group, a 2-ethylbutoxy group, an n-octyloxy group, a n-nonyloxy group, a n-decyloxy group, a benzyloxy group, a p-methylbenzyloxy group, etc., but it is not limited thereto.

[0041] In the present invention, "aralkyl" refers to an aryl-alkyl group as described above consisting of an aryl group and an alkyl group. Preferred aralkyl groups include lower alkyl groups. Non-limiting examples of preferred aralkyl groups include benzyl, 2-phenylethyl and naphthylmethyl. The bonding to the parent residue is achieved through the alkyl group.

[0042] In the present invention, the "arylamino group" refers to an amine substituted with an aryl group having 6 to 30 carbon atoms.

[0043] In the present invention, the "alkylamino group" refers to an amine substituted by an alkyl group having 1 to 30 carbon atoms.

[0044] In the present invention, the "aralkylamino group" refers to an amine substituted with an aryl-alkyl group having 6 to 30 carbon atoms.

[0045] In the present invention, "heteroarylamino" refers to an amino group substituted by an aryl group having 6 to 30 carbon atoms and a heterocyclic group.

[0046] In the present invention, "heteroaralkyl" refers to an aryl-alkyl group substituted by a heterocyclic group.

[0047] In the present invention, "cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

[0048] In the present invention, "heterocycloalkyl" refers to a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 carbon atoms, wherein one or more carbon atoms, preferably 1 to 3 carbon atoms, in the ring are substituted by heteroatoms such as N, O, S or Se. Examples of such heterocycloalkyl include morpholine, piperazine, etc., but are not limited thereto.

[0049] In the present invention, an “alkylsilyl group” refers to a silyl group substituted by an alkyl group having 1 to 40 carbon atoms, and an “arylsilyl group” refers to a silyl group substituted by an aryl group having 6 to 60 carbon atoms.

[0050] In the present invention, the "fused ring" refers to a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, a fused heteroaromatic ring or a combination thereof.

[0051] In the present invention, "bonding with adjacent groups to form a ring" means bonding with adjacent groups to form a substituted or unsubstituted aliphatic hydrocarbon ring; a substituted or unsubstituted aromatic hydrocarbon ring; a substituted or unsubstituted aliphatic heterocycle; a substituted or unsubstituted aromatic heterocycle; or a condensed ring thereof.

[0052] In the present invention, examples of the "aromatic hydrocarbon ring" include phenyl, naphthyl, anthracenyl and the like, but are not limited thereto.

[0053] In the present invention, "aliphatic heterocycle" refers to an aliphatic ring containing one or more heteroatoms.

[0054] In the present invention, the "aromatic heterocycle" refers to an aromatic ring containing one or more heteroatoms.

[0055] In the present invention, "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced by other substituents. As for the position of substitution, as long as it is a position where the hydrogen atom can be substituted, that is, a position where the substituent can be substituted, there is no limitation on the position of substitution. When two or more substituents are substituted, the two or more substituents are the same or different from each other. As for the above-mentioned substituents, they can be selected from hydrogen, cyano, nitro, halogen, hydroxyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 24 carbon atoms, heteroalkyl having 2 to 30 carbon atoms, aralkyl having 6 to 30 carbon atoms, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, heteroaralkyl having 3 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, The amino group may be substituted with one or more substituents selected from the group consisting of, but not limited to, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an arylalkylamino group having 7 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0056] Effects of the Invention

[0057] The present invention relates to a novel organic compound with a relatively high glass transition temperature and thermal stability. The novel organic compound is used as a material for an organic electroluminescent element and has excellent hole transport properties. The novel organic compound reduces the HOMO energy level difference between the hole transport layer and the light-emitting layer, adjusts the hole injection properties, and reduces the hole accumulation at the interface of the light-emitting layer, thereby reducing the driving voltage and significantly improving the luminous efficiency and life characteristics. DETAILED DESCRIPTION

[0058] The embodiments of the present invention are described in detail below to facilitate implementation by those skilled in the art. However, the present invention can be implemented in various forms and is not limited to the embodiments described in this specification.

[0059] The novel organic compound according to the present invention can have a high glass transition temperature and thermal stability, and in particular, because it has a HOMO energy level that facilitates hole transport, it can be used as a hole transport auxiliary layer material of an organic electroluminescent element having excellent hole transport properties to the light-emitting layer.

[0060] Even if the compound structure of the present invention has the characteristic of decreased crystallinity, the structure forms a stereo rigid fused ring structure with each other, so the mobility of the molecule can be reduced. On the contrary, compared to structures such as cycloalkyl or aryl, with respect to simple molecular structures, the molecule is a non-planar structure, and generally, a non-planar structure like an alkyl group with a long chain may cause energy loss due to the mobility caused by the characteristics such as the rotational motion or vibrational motion of the molecule. As described above, due to the characteristics of the present invention that form a stereo rigid fused ring structure with each other, it has high heat resistance and can reduce the energy loss caused by mobility.

[0061] Specifically, the compound represented by the following chemical formula 1 is as follows:

[0062] [Chemical formula 1]

[0063]

[0064] in,

[0065] n, m and o are the same or different from each other and are each independently an integer from 0 to 5,

[0066] p is an integer of 0 or 1,

[0067] X1 is N, O or S,

[0068] Ring A, Ring B and Ring C are the same or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms,

[0069] R1 to R4 are the same as or different from each other, and are each independently selected from hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkylthio having 1 to 4 carbon atoms, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 5 to 60 carbon atoms, substituted or unsubstituted cycloalkyl having 6 to 30 carbon atoms, The present invention relates to a group consisting of a substituted or unsubstituted heteroarylalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and can bond to adjacent groups to form a substituted or unsubstituted ring.

[0070] The C ring may be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

[0071] Specifically, the compound represented by the above Chemical Formula 1 may be a compound represented by the following Chemical Formula 9:

[0072] [Chemical formula 9]

[0073]

[0074] in,

[0075] n, m, p, Ring A, Ring B, X1, and R1 to R4 are the same as defined in the above Chemical Formula 1.

[0076] The A ring may be selected from the group consisting of substituents represented by the following chemical formulas 2 to 4:

[0077] [Chemical formula 2]

[0078]

[0079] [Chemical formula 3]

[0080]

[0081] [Chemical formula 4]

[0082]

[0083] in,

[0084] * indicates the bonding part,

[0085] q is an integer from 0 to 5,

[0086] r and s are the same or different from each other and are each independently an integer from 0 to 7,

[0087] Y1 is selected from O, S, Se, N(R8) and C(R9) (R 10 ),

[0088] R5 to R 10 The same as or different from each other, and each independently selected from hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkylthio having 1 to 4 carbon atoms, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 5 to 60 carbon atoms, substituted or unsubstituted 6 to 3 The present invention relates to a group consisting of a substituted or unsubstituted heteroarylalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, which may be bonded to adjacent groups to form a substituted or unsubstituted ring.

[0089] The B ring may be selected from the group consisting of substituents represented by the following chemical formulas 5 to 8:

[0090] [Chemical formula 5]

[0091]

[0092] [Chemical formula 6]

[0093]

[0094] [Chemical formula 7]

[0095]

[0096] [Chemical formula 8]

[0097]

[0098] in,

[0099] * indicates the bonding part,

[0100] t is an integer from 0 to 5,

[0101] u and x are the same or different from each other and are each independently an integer from 0 to 7,

[0102] v and w are the same or different from each other, and are each independently an integer from 0 to 4,

[0103] Y2 is selected from O, S, Se, N (R 16 ) and C(R 17 )(R 18 ),

[0104] R 11 To R 18 The same as or different from each other, and each independently selected from hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkylthio having 1 to 4 carbon atoms, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 5 to 60 carbon atoms, substituted or unsubstituted 6 to 3 The present invention relates to a group consisting of a substituted or unsubstituted heteroarylalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, which may be bonded to adjacent groups to form a substituted or unsubstituted ring.

[0105] Wherein, the R3 is a substituted or unsubstituted adamantyl group.

[0106] The compound represented by Chemical Formula 1 according to the present invention is selected from the group consisting of the following compounds, but is not limited thereto:

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132] The compound represented by the above Chemical Formula 1 of the present invention may be usefully used as a hole transport layer or a hole transport auxiliary layer.

[0133] The above-mentioned compound contains a substituent that can increase and fine-tune the HOMO. Therefore, when the compound of the present invention is used as a hole transport layer or hole transport auxiliary layer material in an organic electroluminescent element, the hole mobility can be adjusted to the optimum according to the mobility of electrons injected into the light-emitting layer.

[0134] Due to these characteristics, when the above-mentioned organic compound is used as a material for an organic electroluminescent element, it can exhibit equivalent or superior characteristics in most element characteristics such as luminous efficiency and life.

[0135] The present invention provides an organic electroluminescent device including the compound represented by the above Chemical Formula 1.

[0136] The organic compound of the present invention can be usefully used as a hole transport layer or hole transport auxiliary layer material.

[0137] Furthermore, the present invention relates to an organic electroluminescent element in which an organic thin film layer composed of one or more layers including at least a light-emitting layer is stacked between a cathode and an anode, wherein the organic thin film layer is a hole transport layer and / or a hole transport auxiliary layer between the first electrode and the light-emitting layer.

[0138] The hole transport layer and / or the hole transport auxiliary layer is a compound represented by the chemical formula 1.

[0139] The hole transport auxiliary layer controls the hole injection characteristics by reducing the HOMO energy level difference between the hole transport auxiliary layer and the light-emitting layer, thereby reducing the hole accumulation at the interface between the hole transport auxiliary layer and the light-emitting layer, and can reduce the quenching phenomenon (quenching) of the exciton disappearance at the interface caused by polarons. Thus, the degradation phenomenon of the element is reduced and the element is stabilized, thereby improving efficiency and life.

[0140] The organic electroluminescent element may have a structure of stacking an anode, a hole injection layer, a hole transport layer, a hole transport auxiliary layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode, and may further stack an electron transport auxiliary layer as required.

[0141] Hereinafter, the organic electroluminescent device of the present invention will be described with examples, but the contents of the following examples do not limit the organic electroluminescent device of the present invention.

[0142] The organic electroluminescent element of the present invention may have a structure in which an anode (hole injection electrode), a hole injection layer (HIL), a hole transport layer (HTL), a hole transport auxiliary layer, a light emitting layer (EML) and a cathode (electron injection electrode) are stacked in sequence. Preferably, a hole transport auxiliary layer may be further included between the anode and the light emitting layer, and an electron transport layer (ETL) and an electron injection layer (EIL) may be further included between the cathode and the light emitting layer. In addition, an electron transport auxiliary layer may be further included between the cathode and the light emitting layer.

[0143] As the manufacture method of organic electroluminescent element according to the present invention, first, anode is formed by applying anode material on substrate surface in a conventional manner. At this time, the substrate used is preferably a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling and water resistance. And, as anode material, transparent and excellent conductive indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO) etc. can be used.

[0144] Next, a hole injection layer (HIL) material is formed on the surface of the anode by vacuum thermal deposition or spin coating in a conventional manner. Examples of such a hole injection layer material include copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylamino)triphenylamine (m-MTDATA), 4,4',4"-tris(3-methylphenylamino)phenoxybenzene (m-MTDAPB), 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA) as a starburst amine, 4,4',4"-tris(N-(2-naphthyl)-N-phenylamino)-triphenylamine (2-TNATA), or IDE406 available from Idemitsu Kosan Co., Ltd.

[0145] The hole transport layer is formed by vacuum thermal evaporation or spin coating of a hole transport layer material on the surface of the hole injection layer in a conventional manner. The hole transport layer material can be a commonly used hole transport layer material or a compound represented by the above chemical formula 1 according to the present invention.

[0146] The hole transport auxiliary layer is formed by vacuum thermal evaporation or spin coating on the surface of the hole transport layer the compound represented by the above chemical formula 1 according to the present invention. As described above, the hole transport auxiliary layer can use the compound according to the present invention as the hole transport auxiliary layer material, and can also use commonly used hole transport auxiliary layer materials to form the hole transport auxiliary layer.

[0147] The light-emitting layer (EML) material is formed by vacuum thermal evaporation or spin coating on the surface of the hole transport auxiliary layer in a conventional manner. At this time, among the light-emitting layer materials used, a single light-emitting material or a light-emitting main material can use tris(8-hydroxyquinolyl)aluminum (Alq3) and the like for green, and Alq3, 4,4'-N,N'-dicarbazole-biphenyl (4,4'-N,N'-dicabazole-biphenyl, CBP), poly(n-vinylcabazole), PVK, 9,10-di(naphthalene-2-yl)anthracene (9,10-di(naphthalene-2-yl)anthracene, ADN), 4,4',4"-tri(4,4'-N,N'-dicarbazole-biphenyl, CBP), poly(n-vinylcabazole), PVK, 9,10-di(naphthalene-2-yl)anthracene, ADN, ... (N-carbazole-9-yl)triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene, TPBI), 3-tert-butyl-9,10-di(naphth-2-yl)anthracene (3-tert-butyl-9,10-di(naphth-2-yl)anthracene, TBADN), E3, distyrylarylene (DSA) or a mixture of two or more thereof, but not limited thereto.

[0148] As for the dopant that can be used together with the light-emitting main body in the light-emitting layer material, IDE102 and IDE105 that can be purchased from Idemitsu Kosan can be used. As the phosphorescent dopant, tris(2-phenylpyridine)iridium(III) (Ir(ppy)3), bis[(4,6-difluorophenyl)pyridyl-N,C-2']picolinyliridium(III) (FIrpic) (reference [Chihaya Adachi et al., Appl.Phys.Lett., 2001, 79, 3082-3084]), octaethylporphyrinplatinum(II) (PtOEP), TBE002 (Corbion Co., Ltd.), etc. can be used.

[0149] The electron transport layer (ETL) material is formed by vacuum thermal evaporation or spin coating on the surface of the light emitting layer in a conventional manner. At this time, there is no particular limitation on the electron transport layer material used, and preferably, tris(8-hydroxyquinoline)aluminum (Alq3) can be used.

[0150] Optionally, a hole blocking layer (HBL) is further formed between the light emitting layer and the electron transport layer, and a phosphorescent dopant is used in the light emitting layer to prevent triplet excitons or holes from diffusing into the electron transport layer.

[0151] The formation of the hole blocking layer can be carried out by vacuum thermal evaporation or spin coating of the hole blocking layer material by conventional methods. There is no particular limitation on the hole blocking layer material, but (8-hydroxyquinolyl) lithium (Liq), bis(8-hydroxy-2-methylquinolyl)-biphenyloxyaluminum (BAlq), bathocuproine (BCP) and lithium fluoride (LiF) can be preferably used.

[0152] The electron injection layer (EIL) material is formed by vacuum thermal evaporation or spin coating on the surface of the electron transport layer in a conventional manner. At this time, the electron injection layer material can use LiF, Liq, Li2O, BaO, NaCl, CsF and other materials.

[0153] A cathode material is formed by vacuum thermal evaporation on the surface of the electron injection layer in a conventional manner.

[0154] At this time, the cathode material used may include lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), etc. In addition, the front-emitting organic electroluminescent element may use indium tin oxide (ITO) or indium zinc oxide (IZO) to form a transparent cathode that can transmit light.

[0155] A covering layer (CPL) can be formed on the surface of the cathode using a covering layer-forming composition.

[0156] Hereinafter, the synthesis method of the above-mentioned compound will be described by representative examples. However, the synthesis method of the compound of the present invention is not limited to the method exemplified below, and the compound of the present invention can be prepared by the method exemplified below and methods known in the art.

[0157] [Synthesis example]

[0158] <Synthesis Example 1: Synthesis of Compound 32>

[0159] 1-1) Synthesis of Compound 1-1

[0160]

[0161] Under a nitrogen stream, 1-bromoadamantane (215.1 g, 1000 mmol) was dissolved in 1,3-dichlorobenzene (220.5 g, 1500 mmol). After that, aluminum chloride (4.0 g, 30 mmol) was added and stirred at 60 ° C for 8 hours. After the reaction was completed, the organic layer was extracted with water and dichloromethane. The extracted solution was treated with MgSO4 to remove moisture, and after drying and concentration, it was purified by column chromatography. After that, 182.8 g (yield: 65%) of compound 1-1 was obtained by recrystallization using methanol.

[0162] 1-2) Synthesis of Compound 1-2

[0163]

[0164] Under a nitrogen stream, N-phenyl-[1,1'-biphenyl]-4-amine (21.0 g, 85.60 mmol), compound 1-1 (26.48 g, 94.16 mmol), t-BuONa (16.45 g, 171.2 mmol), Pd2(dba)3 (1.57 g, 1.71 mmol), Sphos (1.41 g, 3.42 mmol) and toluene (350 mL) were added to a round-bottom flask, and the mixture was stirred at 100°C to react. After the reaction was completed, the organic layer was extracted with toluene and water. The extracted solution was treated with MgSO4 to remove moisture, and after reduced pressure concentration, it was purified by column chromatography and recrystallization to prepare 31.46 g (yield: 75%) of compound 1-2.

[0165] 1-3) Synthesis of Compound 32

[0166]

[0167] Under a nitrogen stream, compound 1-2 (10.0 g, 20.40 mmol), [1,1'-biphenyl]-4-ylboronic acid (4.85 g, 24.49 mmol), K3PO4 (10.83 g, 51.01 mmol), Pd(OAc)2 (0.09 g, 0.41 mmol), Sphos (0.34 g, 0.82 mmol), toluene (100 mL) and water (10 ml) were added to a round-bottom flask, and the mixture was stirred at 100°C to react. After the reaction was completed, the organic layer was extracted with toluene and water. The extracted solution was treated with MgSO4 to remove moisture, and after reduced pressure concentration, it was purified by column chromatography and recrystallization to prepare 7.44 g (yield: 60%) of compound 32.

[0168] <Synthesis Example 2: Synthesis of Compound 39>

[0169]

[0170] 7.54 g (yield: 57%) of compound 39 was prepared in the same manner as the synthesis method of compound 32, except that (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (5.83 g, 24.49 mmol) was used instead of [1,1'-biphenyl]-4-ylboronic acid.

[0171] <Synthesis Example 3: Synthesis of Compound 47>

[0172]

[0173] 7.82 g (yield: 55%) of compound 47 was prepared in the same manner as the synthesis method of compound 32, except that (9-phenyl-9H-carbazol-3-yl)boronicacid (7.03 g, 24.49 mmol) was used instead of [1,1'-biphenyl]-4-ylboronic acid.

[0174] <Synthesis Example 4: Synthesis of Compound 905>

[0175]

[0176] 7.11 g (yield: 50%) of Compound 905 was prepared in the same manner as the synthesis method of Compound 32, except that (4-(9H-carbazol-9-yl)phenyl)boronic acid (7.03 g, 24.49 mmol) was used instead of [1,1'-biphenyl]-4-ylboronic acid.

[0177] <Synthesis Example 5: Synthesis of Compound 191>

[0178] 5-1) Synthesis of Compound 5-1

[0179]

[0180] 10.53 g (yield: 72%) of compound 5-1 was prepared in the same manner as the synthesis method of compound 1-2, except that 4-(naphthalen-1-yl)-N-phenylaniline (8.0 g, 27.08 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0181] 5-2) Synthesis of Compound 191

[0182]

[0183] 6.82 g (yield: 52%) of compound 191 was prepared in the same manner as the synthesis method of compound 32, except that compound 5-1 (10.0 g, 18.51 mmol) and (4-(naphthalen-1-yl)phenyl)boronic acid (5.51 g, 22.22 mmol).

[0184] <Synthesis Example 6: Synthesis of Compound 208>

[0185] 6-1) Synthesis of Compound 6-1

[0186]

[0187] 11.26 g (yield: 77%) of compound 6-1 was prepared in the same manner as the synthesis method of compound 1-2, except that 4-(naphthalen-2-yl)-N-phenylaniline (8.0 g, 27.08 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0188] 6-2) Synthesis of Compound 208

[0189]

[0190] 7.24 g (yield: 56%) of compound 208 was prepared in the same manner as the synthesis method of compound 32, except that compound 6-1 (10.0 g, 18.51 mmol) and (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (5.29 g, 22.22 mmol) were used.

[0191] <Synthesis Example 7: Synthesis of Compound 67>

[0192] 7-1) Synthesis of Compound 7-1

[0193]

[0194] 21.70 g (yield: 73%) of compound 7-1 was prepared in the same manner as the synthesis method of compound 1-2, except that 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (16.0 g, 56.06 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0195] 7-2) Synthesis of Compound 67

[0196]

[0197] 7.83 g (yield: 58%) of compound 67 was prepared in the same manner as the synthesis method of compound 32, except that compound 7-1 (10.0 g, 18.86 mmol) and (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (5.39 g, 22.64 mmol).

[0198] <Synthesis Example 8: Synthesis of Compound 69>

[0199]

[0200] 6.52 g (yield: 51%) of compound 69 was prepared in the same manner as the synthesis method of compound 32, except that compound 7-1 (10.0 g, 18.86 mmol) and dibenzo[b,d]thiophen-3-ylboronic acid (5.16 g, 22.64 mmol) were used.

[0201] <Synthesis Example 9: Synthesis of Compound 90>

[0202] 9-1) Synthesis of Compound 9-1

[0203]

[0204] 10.89 g (yield: 70%) of compound 9-1 was prepared in the same manner as the synthesis method of compound 1-2, except that N-phenyldibenzo[b,d]furan-3-amine (8.0 g, 30.85 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0205] 9-2) Synthesis of Compound 90

[0206]

[0207] 6.54 g (yield: 53%) of Compound 90 was prepared in the same manner as the synthesis method of Compound 32, except that Compound 9-1 (10.0 g, 19.84 mmol) and [1,1'-biphenyl]-4-ylboronic acid (4.71 g, 23.81 mmol) were used.

[0208] <Synthesis Example 10: Synthesis of Compound 356>

[0209] 10-1) Synthesis of Compound 10-1

[0210]

[0211] 34.35 g (yield: 78%) of compound 10-1 was prepared in the same manner as the synthesis method of compound 1-2, except that di([1,1'-biphenyl]-4-yl)amine (25.0 g, 77.78 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0212] 10-2) Synthesis of Compound 356

[0213]

[0214] 6.64 g (yield: 55%) of Compound 356 was prepared in the same manner as the synthesis method of Compound 32, except that Compound 10-1 (10.0 g, 17.66 mmol) and [1,1'-biphenyl]-4-ylboronic acid (4.20 g, 21.19 mmol) were used.

[0215] <Synthesis Example 11: Synthesis of Compound 362>

[0216]

[0217] 7.42 g (yield: 58%) of compound 362 was prepared in the same manner as the synthesis method of compound 32, except that compound 10-1 (10.0 g, 17.66 mmol) and (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (5.05 g, 21.19 mmol).

[0218] <Synthesis Example 12: Synthesis of Compound 364>

[0219]

[0220] 6.43 g (yield: 51%) of compound 364 was prepared in the same manner as the synthesis method of compound 32, except that compound 10-1 (10.0 g, 17.66 mmol) and dibenzo[b,d]thiophen-3-ylboronic acid (4.83 g, 21.19 mmol) were used.

[0221] <Synthesis Example 13: Synthesis of Compound 383>

[0222] 13-1) Synthesis of Compound 13-1

[0223]

[0224] 26.83 g (yield: 80%) of compound 13-1 was prepared in the same manner as the synthesis method of compound 1-2, except that N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (20.0 g, 55.33 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0225] 13-2) Synthesis of Compound 383

[0226]

[0227] 6.09 g (yield: 57%) of Compound 383 was prepared in the same manner as the synthesis method of Compound 32, except that Compound 13-1 (10.0 g, 16.49 mmol) and phenylboronic acid (2.41 g, 19.79 mmol) were used.

[0228] <Synthesis Example 14: Synthesis of Compound 390>

[0229]

[0230] 7.56 g (yield: 60%) of compound 390 was prepared in the same manner as the synthesis method of compound 32, except that compound 13-1 (10.0 g, 16.49 mmol) and (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (4.71 g, 19.79 mmol) were used.

[0231] <Synthesis Example 15: Synthesis of Compound 906>

[0232] 15-1) Synthesis of Compound 15-1

[0233]

[0234] 25.25 g (yield: 73%) of compound 15-1 was prepared by the same method as the synthesis method of compound 1-2, except that N-([1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-3-amine (20.0 g, 59.63 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0235] 15-2) Synthesis of Compound 906

[0236]

[0237] 5.77 g (yield: 48%) of Compound 906 was prepared in the same manner as the synthesis method of Compound 32, except that Compound 15-1 (10.0 g, 17.24 mmol) and [1,1'-biphenyl]-2-ylboronic acid (4.10 g, 20.68 mmol) were used.

[0238] <Synthesis Example 16: Synthesis of Compound 424>

[0239]

[0240] 6.14 g (yield: 50%) of compound 424 was prepared in the same manner as the synthesis method of compound 32, except that compound 15-1 (10.0 g, 17.24 mmol) and dibenzo[b,d]furan-4-ylboronic acid (4.39 g, 20.68 mmol) were used.

[0241] <Synthesis Example 17: Synthesis of Compound 907>

[0242] 17-1) Synthesis of Compound 17-1

[0243]

[0244] 23.75 g (yield: 70%) of compound 17-1 was prepared in the same manner as the synthesis method of compound 1-2, except that 4-(dibenzo[b,d]thiophen-2-yl)-N-phenylaniline (4-(dibenzo[b,d]thiophen-2-yl)-N-phenylaniline, 20.0 g, 56.90 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0245] 17-2) Synthesis of Compound 907

[0246]

[0247] 5.14 g (yield: 48%) of Compound 907 was prepared in the same manner as the synthesis method of Compound 32 except that Compound 17-1 (10.0 g, 16.77 mmol) and phenylboronic acid (2.45 g, 20.13 mmol) were used.

[0248] <Synthesis Example 18: Synthesis of Compound 908>

[0249]

[0250] 6.00 g (yield: 52%) of Compound 908 was prepared in the same manner as the synthesis method of Compound 32 except that Compound 17-1 (10.0 g, 16.77 mmol) and naphthalen-2-ylboronic acid (3.46 g, 20.13 mmol) were used.

[0251] <Synthesis Example 19: Synthesis of Compound 911>

[0252] 19-1) Synthesis of Compound 19-1

[0253]

[0254] 11.96 g (yield: 75%) of compound 19-1 was prepared by the same method as the synthesis method of compound 1-2, except that N-(4-(dibenzo[b,d]furan-2-yl)phenyl)-[1,1'-biphenyl]-4-amine (10.0 g, 24.30 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0255] 19-2) Synthesis of Compound 911

[0256]

[0257] 5.96 g (yield: 56%) of Compound 911 was prepared in the same manner as the synthesis method of Compound 32 except that Compound 19-1 (10.0 g, 15.24 mmol) and phenylboronic acid (2.23 g, 18.29 mmol) were used.

[0258] <Synthesis Example 20: Synthesis of Compound 909>

[0259] 20-1) Synthesis of Compound 20-1

[0260]

[0261] 11.33 g (yield: 71%) of compound 20-1 was prepared in the same manner as the synthesis method of compound 1-2, except that N-phenyl-4-(9-phenyl-9H-carbazol-3-yl)aniline (10.0 g, 24.36 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0262] 20-2) Synthesis of Compound 909

[0263]

[0264] 5.32 g (yield: 50%) of Compound 909 was prepared in the same manner as the synthesis method of Compound 32 except that Compound 20-1 (10.0 g, 15.26 mmol) and phenylboronic acid (2.23 g, 18.31 mmol) were used.

[0265] <Synthesis Example 21: Synthesis of Compound 620>

[0266] 21-1) Synthesis of Compound 21-1

[0267]

[0268] 31.79 g (yield: 79%) of compound 21-1 was prepared in the same manner as the synthesis method of compound 1-2, except that bis(9,9-dimethyl-9H-fluoren-2-yl)amine (25.0 g, 62.26 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0269] 21-2) Synthesis of Compound 620

[0270]

[0271] 6.17 g (yield: 58%) of Compound 620 was prepared in the same manner as the synthesis method of Compound 32, except that Compound 21-1 (10.0 g, 15.47 mmol) and phenylboronic acid (2.26 g, 18.57 mmol) were used.

[0272] <Synthesis Example 22: Synthesis of Compound 910>

[0273]

[0274] 6.84 g (yield: 55%) of compound 910 was prepared in the same manner as the synthesis method of compound 32, except that compound 21-1 (10.0 g, 15.47 mmol) and (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (4.42 g, 18.57 mmol).

[0275] <Synthesis Example 23: Synthesis of Compound 622>

[0276]

[0277] 5.08 g (yield: 43%) of Compound 622 was prepared in the same manner as the synthesis method of Compound 32, except that Compound 21-1 (10.0 g, 15.47 mmol) and [1,1'-biphenyl]-3-ylboronic acid (3.68 g, 18.57 mmol) were used.

[0278] <Synthesis Example 24: Synthesis of Compound 649>

[0279] 24-1) Synthesis of Compound 24-1

[0280]

[0281] 12.22 g (yield: 74%) of compound 24-1 was prepared in the same manner as the synthesis method of compound 1-2, except that N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-3-amine (10.0 g, 26.63 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0282] 24-2) Synthesis of Compound 649

[0283]

[0284] 5.34 g (yield: 50%) of Compound 649 was prepared in the same manner as the synthesis method of Compound 32 except that Compound 24-1 (10.0 g, 16.12 mmol) and phenylboronic acid (2.36 g, 19.35 mmol) were used.

[0285] <Synthesis Example 25: Synthesis of Compound 316>

[0286] 25-1) Synthesis of Compound 25-1

[0287]

[0288] 11.66 g (yield: 73%) of compound 25-1 was prepared in the same manner as the synthesis method of compound 1-2, except that N,9,9-triphenyl-9H-fluoren-2-amine (10.0 g, 24.42 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0289] 25-2) Synthesis of Compound 316

[0290]

[0291] 5.59 g (yield: 49%) of Compound 316 was prepared in the same manner as the synthesis method of Compound 32 except that Compound 25-1 (10.0 g, 15.28 mmol) and naphthalen-2-ylboronic acid (3.15 g, 18.34 mmol) were used.

[0292] <Synthesis Example 26: Synthesis of Compound 335>

[0293] 26-1) Synthesis of Compound 26-1

[0294]

[0295] 12.17 g (yield: 76%) of compound 26-1 was prepared in the same manner as the synthesis method of compound 1-2, except that N-phenyl-9,9'-spirobi[fluoren]-2-amine (10.0 g, 24.54 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0296] 26-2) Synthesis of compound 335

[0297]

[0298] 5.93 g (yield: 52%) of Compound 335 was prepared in the same manner as the synthesis method of Compound 32, except that Compound 26-1 (10.0 g, 15.33 mmol) and naphthalen-1-ylboronic acid (3.16 g, 18.40 mmol) were used.

[0299] <Synthesis Example 27: Synthesis of Compound 344>

[0300] 27-1) Synthesis of Compound 27-1

[0301]

[0302] 10.68 g (yield: 71%) of compound 27-1 was prepared by the same method as the synthesis method of compound 1-2, except that N-(naphthalen-2-yl)-10,11-dihydrospiro[dibenzo[a,d][7]annulene-5,9'-fluoren]-2'-amine (10.0 g, 20.59 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0303] 27-2) Synthesis of compound 344

[0304]

[0305] 4.86 g (yield: 46%) of Compound 344 was prepared in the same manner as the synthesis method of Compound 32, except that Compound 27-1 (10.0 g, 13.69 mmol) and phenylboronic acid (2.00 g, 16.43 mmol) were used.

[0306] <Synthesis Example 28: Synthesis of Compound 725>

[0307] 28-1) Synthesis of Compound 28-1

[0308]

[0309] 13.09 g (yield: 77%) of compound 28-1 was prepared in the same manner as the synthesis method of compound 1-2, except that bis(dibenzo[b,d]furan-3-yl)amine (10.0 g, 28.62 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0310] 28-2) Synthesis of Compound 725

[0311]

[0312] 6.47 g (yield: 54%) of Compound 725 was prepared in the same manner as the synthesis method of Compound 32, except that Compound 28-1 (10.0 g, 16.83 mmol) and [1,1'-biphenyl]-4-ylboronic acid (4.00 g, 20.13 mmol) were used.

[0313] <Synthesis Example 29: Synthesis of Compound 29>

[0314] 29-1) Synthesis of Compound 29-1

[0315]

[0316] 13.09 g (yield: 70%) of compound 29-1 was prepared in the same manner as the synthesis method of compound 1-2, except that bis(4-(tert-butyl)phenyl)amine (10.0 g, 35.53 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0317] 29-2) Synthesis of Compound 29

[0318]

[0319] 7.06 g (yield: 46%) of compound 29 was prepared in the same manner as the synthesis method of compound 32, except that compound 29-1 (10.0 g, 19.00 mmol) and (9,9-diphenyl-9H-fluoren-2-yl)boronic acid (7.44 g, 22.80 mmol) were used.

[0320] <Synthesis Example 30: Synthesis of Compound 30>

[0321] 30-1) Synthesis of Compound 30-1

[0322]

[0323] 10.72 g (yield: 73%) of compound 30-1 was prepared in the same manner as compound 1-2 except that diphenylamine (6.0 g, 35.45 mmol) was used instead of N-phenyl-[1,1′-biphenyl]-4-amine.

[0324] 30-2) Synthesis of Compound 30

[0325]

[0326] 8.38 g (yield: 50%) of compound 30 was prepared in the same manner as the synthesis method of compound 32, except that compound 30-1 (10.0 g, 24.16 mmol) and 9,9'-spirobi[fluoren]-2-ylboronic acid (10.44 g, 28.99 mmol) were used.

[0327] <Synthesis Example 31: Synthesis of Compound 331>

[0328] 31-1) Synthesis of Compound 31-1

[0329]

[0330] 11.18 g (yield: 70%) of compound 31-1 was prepared in the same manner as the synthesis method of compound 1-2, except that N,9,9-triphenyl-9H-fluoren-4-amine (10.0 g, 24.42 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0331] 31-2) Synthesis of compound 331

[0332]

[0333] 5.00 g (yield: 47%) of Compound 331 was prepared in the same manner as the synthesis method of Compound 32, except that Compound 31-1 (10.0 g, 15.28 mmol) and phenylboronic acid (2.24 g, 18.34 mmol) were used.

[0334] <Synthesis Example 32: Synthesis of Compound 594>

[0335] 32-1) Synthesis of Compound 32-1

[0336]

[0337] 11.30 g (yield: 75%) of compound 32-1 was prepared in the same manner as the synthesis method of compound 1-2, except that N-([1,1'-biphenyl]-4-yl)-9,9'-spirobi[fluoren]-4-amine (10.0 g, 20.68 mmol) was used instead of N-phenyl-[1,1'-biphenyl]-4-amine.

[0338] 32-2) Synthesis of Compound 594

[0339]

[0340] 5.50 g (yield: 52%) of Compound 594 was prepared in the same manner as the synthesis method of Compound 32, except that Compound 32-1 (10.0 g, 13.73 mmol) and phenylboronic acid (2.01 g, 16.47 mmol) were used.

[0341] <Synthesis Example 33: Synthesis of Compound 410>

[0342] 33-1) Synthesis of Compound 33-1

[0343]

[0344] 80.4 g (yield: 52%) of compound 33-1 was prepared in the same manner as compound 1-1, except that 1-bromo-3,5-dimethyladamantane (121.6 g, 500 mmol) was used instead of 1-bromoadamantane.

[0345] 33-2) Synthesis of Compound 33-2

[0346]

[0347] Except for using compound 33-1 (9.41 g, 30.43 mmol) and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine, 10.0 g, 27.66 mmol), 12.46 g (yield: 71%) of compound 33-2 was prepared in the same manner as the synthesis method of compound 1-2.

[0348] 33-3) Synthesis of Compound 410

[0349]

[0350] 5.19 g (yield: 45%) of compound 410 was prepared in the same manner as the synthesis method of compound 32, except that compound 33-2 (10.0 g, 15.77 mmol) and (4-(tert-butyl)phenyl)boronic acid (3.37 g, 18.92 mmol) were used.

[0351] <Synthesis Example 34: Synthesis of Compound 374>

[0352] 34-1) Synthesis of Compound 34-1

[0353]

[0354] In addition to using compound 33-1 (10.58 g, 34.22 mmol) and N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine (N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine, 10.0 g, 31.11 mmol), 12.76 g (yield: 69%) of compound 34-1 was prepared in the same manner as the synthesis method of compound 1-2.

[0355] 34-2) Synthesis of compound 374

[0356]

[0357] 5.82 g (yield: 47%) of Compound 374 was prepared in the same manner as the synthesis method of Compound 32, except that Compound 34-1 (10.0 g, 16.83 mmol) and phenanthren-9-ylboronic acid (4.48 g, 20.19 mmol) were used.

[0358] <Synthesis Example 35: Synthesis of Compound 912>

[0359] 35-1) Synthesis of Compound 35-1

[0360]

[0361] 10.35 g (yield: 70%) of compound 35-1 was prepared in the same manner as the synthesis method of compound 1-2, except that compound 33-1 (9.71 g, 31.39 mmol) and N-phenyl-[1,1'-biphenyl]-4-amine (7.0 g, 28.53 mmol) were used.

[0362] 35-2) Synthesis of Compound 912

[0363]

[0364] Except for using compound 35-1 (10.0 g, 19.30 mmol) and (4-(dibenzo[b,d]furan-4-yl)phenyl)boronic acid ((4-(dibenzo[b,d]furan-4-yl)phenyl)boronic acid, 6.67 g, 23.16 mmol), 6.31 g (yield: 45%) of compound 912 was prepared in the same manner as the synthesis method of compound 32.

[0365] [Example 1: Production of organic electroluminescent element (red)]

[0366] An anode was formed using ITO on a substrate having a reflective layer, and the surface was treated with N2 plasma or ultraviolet (UV)-ozone. HAT-CN was deposited on the top with a thickness of 10 nm as a hole injection layer (HIL). Next, N4,N4,N4',N4'-tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine (N4,N4,N4',N4'-tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine) was deposited with a thickness of 100 nm to form a hole transport layer (HTL).

[0367] The compound 32 of the present invention is vacuum-deposited on the upper portion of the hole transport layer with a thickness of 85 nm to form a hole transport auxiliary layer, and 4,4'-N,N'-dicarbazole-biphenyl (4,4'-N,N'-dicarbazole-biphenyl, CBP) is vapor-deposited on the upper portion of the hole transport auxiliary layer with a thickness of 35 nm as a light-emitting layer (EML), and about 3% of bis(1-phenylisoquinolyl)iridium(III)acetylacetonate (piq)2Ir(acac) is doped as a dopant.

[0368] An anthracene derivative and LiQ were mixed in a ratio of 1:1 and deposited on the light-emitting layer (EML) with a thickness of 30 nm as an electron transport layer (ETL), and LiQ was deposited on the electron transport layer (ETL) with a thickness of 1 nm as an electron injection layer (EIL). Subsequently, a mixture of magnesium and silver (Ag) mixed in a ratio of 1:4 was deposited with a thickness of 16 nm as a cathode, and N4,N4'-bis[4-[bis(3-methylphenyl)amino]phenyl]-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (DNTPD) was deposited on the cathode with a thickness of 60 nm as a capping layer. A seal cap containing a moisture absorbent was attached thereto using an ultraviolet curable adhesive to protect the organic electroluminescent element from the influence of O2 or moisture in the atmosphere, thereby manufacturing an organic electroluminescent element.

[0369] [Examples 2 to 35]

[0370] Organic electroluminescent elements of Examples 2 to 35 and organic electroluminescent elements of Comparative Examples 1 to 3 were manufactured in the same manner as in Example 1 except that the hole transport auxiliary layer compounds were used as shown in Table 1 below.

[0371] [Compound A]

[0372]

[0373] [Compound B]

[0374]

[0375] [Compound C]

[0376]

[0377] [Experimental Example 1: Component Performance Analysis]

[0378] In the above, for the organic electroluminescent elements manufactured according to Examples 1 to 35 and Comparative Examples 1 to 3, the measured 2 The electro-optical characteristics when driven by a current of 20 mA / cm 2 The life span is reduced by 95% when driven with constant current and is shown in Table 1.

[0379] [Table 1]

[0380]

[0381]

[0382] According to the experimental results in Table 1, when the compound of the present invention is used as a hole transport auxiliary layer material of an organic electroluminescent element, the driving voltage shows an equivalent or lower level compared with the comparative example, but it exhibits excellent element efficiency characteristics and long life characteristics.

[0383] [Example 36: Production of organic electroluminescent element (green)]

[0384] An anode was formed on a substrate with a reflective layer using ITO, and the surface was treated with N2 plasma or ultraviolet (UV)-ozone. HAT-CN was deposited on top of the substrate to a thickness of 10 nm as a hole injection layer (HIL). Next, N4,N4,N4',N4'-tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine (N4,N4,N4',N4'-tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine) was deposited to a thickness of 110 nm to form a hole transport layer (HTL).

[0385] The compound 32 of the present invention is vacuum-deposited on the upper portion of the hole transport layer with a thickness of 40 nm to form a hole transport auxiliary layer, and 4,4'-N,N'-dicarbazole-biphenyl (4,4'-N,N'-dicarbazole-biphenyl, CBP) is vapor-deposited on the upper portion of the hole transport auxiliary layer with a thickness of 35 nm as a light-emitting layer (EML), and tris(2-phenylpyridine)-iridium (tris(2-phenylpyridine)-iridium, Ir(ppy)3) is doped with about 5% as a dopant.

[0386] Furthermore, as an electron transport layer (ETL), an anthracene derivative and LiQ mixed in a mass ratio of 1:1 were vapor-deposited at a thickness of 30 nm on the light-emitting layer (EML), and LiQ was vapor-deposited at a thickness of 1 nm thereon as an electron injection layer (EIL). Subsequently, a mixture of magnesium and silver (Ag) mixed in a ratio of 1:4 was vapor-deposited at a thickness of 16 nm as a cathode, and N4,N4'-bis[4-[bis(3-methylphenyl)amino]phenyl]-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (DNTPD) was vapor-deposited at a thickness of 60 nm on the cathode as a capping layer. A seal cap containing a moisture absorbent was attached thereto using an ultraviolet curable adhesive to protect the organic electroluminescent element from the influence of O2 or moisture in the atmosphere, thereby manufacturing an organic electroluminescent element.

[0387] [Examples 36 to 70]

[0388] Organic electroluminescent elements of Examples 36 to 70 and organic electroluminescent elements of Comparative Examples 4 to 6 were manufactured in the same manner as in Example 36 except that the hole transport auxiliary layer compounds were used as shown in Table 2 below.

[0389] [Experimental Example 2]

[0390] In the above, for the organic electroluminescent elements manufactured according to Examples 36 to 70 and Comparative Examples 4 to 6, the measured 2 The electro-optical characteristics when driven by a current of 20 mA / cm 2 The lifetime is reduced by 95% when driven with constant current and is shown in Table 2.

[0391] [Table 2]

[0392]

[0393]

[0394]

[0395] According to the experimental results in Table 2, when the compound of the present invention is used as a hole transport auxiliary layer material of an organic electroluminescent element, the driving voltage is equal to or lower than that of the comparative example, but excellent element efficiency characteristics and long life characteristics are exhibited.

[0396] [Example 71: Production of organic electroluminescent element (HTL)]

[0397] An anode was formed on a substrate with a reflective layer using ITO, and the surface was treated with N2 plasma or ultraviolet (UV)-ozone. HAT-CN was deposited on top of the anode to a thickness of 10 nm as a hole injection layer (HIL). Next, compound 67 was deposited to a thickness of 110 nm to form a hole transport layer (HTL).

[0398] On the upper part of the hole transport layer, 4,4'-N,N'-dicarbazole-biphenyl (4,4'-N,N'-dicarbazole-biphenyl, CBP) was vapor-deposited with a thickness of 35nm as a light-emitting layer (EML), and tris(2-phenylpyridine)-iridium (Ir(ppy)3) was doped at about 5% as a dopant.

[0399] Furthermore, as an electron transport layer (ETL), an anthracene derivative and LiQ mixed in a mass ratio of 1:1 were vapor-deposited at a thickness of 30 nm on the light-emitting layer (EML), and LiQ was vapor-deposited at a thickness of 1 nm thereon as an electron injection layer (EIL). Subsequently, a mixture of magnesium and silver (Ag) mixed in a ratio of 1:4 was vapor-deposited at a thickness of 16 nm as a cathode, and N4,N4'-bis[4-[bis(3-methylphenyl)amino]phenyl]-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (DNTPD) was vapor-deposited at a thickness of 60 nm on the cathode as a capping layer. A seal cap containing a moisture absorbent was attached thereto using an ultraviolet curable adhesive to protect the organic electroluminescent element from the influence of O2 or moisture in the atmosphere, thereby manufacturing an organic electroluminescent element.

[0400] [Examples 72 to 80]

[0401] Organic electroluminescent elements of Examples 72 to 80 and organic electroluminescent elements of Comparative Examples 7 to 9 were manufactured in the same manner as in Example 71, except that the hole transport layer compounds were used as shown in Table 3 below.

[0402] [Experimental Example 3: Component Performance Analysis]

[0403] In the above, for the organic electroluminescent elements manufactured according to Examples 71 to 80 and Comparative Examples 7 to 9, the 2 The electro-optical characteristics when driven by a current of 20 mA / cm 2 The lifetime is reduced by 95% when driven with constant current and is shown in Table 3.

[0404] [Table 3]

[0405]

[0406] According to the experimental results in Table 3, when the compound of the present invention is used as a hole transport layer material of an organic electroluminescent element, the driving voltage is equal to or lower than that of the comparative example, but excellent element efficiency characteristics and long life characteristics are exhibited.

[0407] The preferred embodiments of the present invention are described in detail above, but the protection scope of the claims of the present invention is not limited thereto. Various modifications and improvements made by those skilled in the art using the basic concepts of the present invention defined in the claims of the present invention are also included in the scope of the rights to be protected by the present invention.

Claims

1. An organic electroluminescent element, wherein: include: The first electrode, a second electrode, opposite to the first electrode, and One or more organic layers are disposed between the first electrode and the second electrode; The organic layer includes a hole transport auxiliary layer, At least one of the hole transport auxiliary layers includes a compound represented by the following Chemical Formula 9, [Chemical formula 9] In the chemical formula 9, n and m are the same or different from each other and are each independently an integer from 0 to 5, p is an integer of 1, X1 is N, Ring A is a substituent selected from Chemical Formula 4, [Chemical formula 4] In the chemical formula 4, * refers to the bonding part, Y1 is C(R9)(R 10 ), s is an integer from 0 to 7, R7, R9 and R 10 The same as or different from each other, and each independently selected from hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, unsubstituted alkylthio having 1 to 4 carbon atoms, unsubstituted alkyl having 1 to 30 carbon atoms, unsubstituted cycloalkyl having 3 to 20 carbon atoms, unsubstituted alkenyl having 2 to 30 carbon atoms, unsubstituted alkynyl having 2 to 24 carbon atoms, unsubstituted aralkyl having 7 to 30 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 5 to 60 carbon atoms, unsubstituted The group consisting of an unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, an unsubstituted alkoxy group having 1 to 30 carbon atoms, an unsubstituted alkylamino group having 1 to 30 carbon atoms, an unsubstituted arylamino group having 6 to 30 carbon atoms, an unsubstituted arylalkylamino group having 7 to 30 carbon atoms, an unsubstituted heteroarylamino group having 2 to 24 carbon atoms, an unsubstituted alkylsilyl group having 1 to 30 carbon atoms, an unsubstituted arylsilyl group having 6 to 30 carbon atoms and an unsubstituted aryloxy group having 6 to 30 carbon atoms, Ring B is selected from the group consisting of substituents consisting of the following chemical formulas 5 to 8, [Chemical formula 5] [Chemical formula 6] [Chemical formula 7] [Chemical formula 8] In the chemical formula 5 to the chemical formula 8, * refers to the bonding part, t is an integer from 0 to 5, u and x are the same or different from each other and are each independently an integer from 0 to 7, v and w are the same or different from each other, and are each independently an integer from 0 to 4, Y2 is selected from O, S, Se, N (R 16 ) and C(R 17 )(R 18 ), R4 is selected from unsubstituted aryl groups having 6 to 30 carbon atoms, R 11 is selected from an unsubstituted aryl group having 6 to 30 carbon atoms or an unsubstituted heteroaryl group having 5 to 60 carbon atoms, R3 is an unsubstituted adamantyl group, R1 and R2 are both hydrogen, R 12 To R 18 The same as or different from each other, and each independently selected from hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, unsubstituted alkylthio having 1 to 4 carbon atoms, unsubstituted alkyl having 1 to 30 carbon atoms, unsubstituted cycloalkyl having 3 to 20 carbon atoms, unsubstituted alkenyl having 2 to 30 carbon atoms, unsubstituted alkynyl having 2 to 24 carbon atoms, unsubstituted aralkyl having 7 to 30 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 5 to 60 carbon atoms, unsubstituted The present invention relates to a group consisting of an unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, an unsubstituted alkoxy group having 1 to 30 carbon atoms, an unsubstituted alkylamino group having 1 to 30 carbon atoms, an unsubstituted arylamino group having 6 to 30 carbon atoms, an unsubstituted arylalkylamino group having 7 to 30 carbon atoms, an unsubstituted heteroarylamino group having 2 to 24 carbon atoms, an unsubstituted alkylsilyl group having 1 to 30 carbon atoms, an unsubstituted arylsilyl group having 6 to 30 carbon atoms and an unsubstituted aryloxy group having 6 to 30 carbon atoms.

2. The organic electroluminescent element according to claim 1, wherein The compound represented by the chemical formula 9 is selected from the group consisting of the following compounds:

3. The organic electroluminescent element according to claim 1, wherein The organic layer further includes at least one selected from the group consisting of a hole injection layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a covering layer.

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