KR20190088158A - Acridine derivative and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides an acridine derivative represented by chemical formula 1 and an organic light emitting device comprising the same. The acridine derivative according to an embodiment of the present specification can be used as a material of an organic matter layer of the organic light emitting device, and by using the same, it is possible to improve efficiency, low driving voltage, and/or lifespan characteristics in the organic light emitting device.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic light emitting diode (OLED) and an organic light emitting diode (OLED)

The present invention relates to an acridine derivative and an organic light emitting device comprising the same.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out.

Development of new materials for such organic light emitting devices has been continuously required.

U.S. Patent Application Publication No. 2004-0251816

The present invention provides an acridine derivative and an organic light emitting device comprising the same.

According to one embodiment of the present invention, there is provided an acridine derivative represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

And R < 2 > may be hydrogen or may be bonded to each other,

R3 to R6 are the same or different from each other and each independently represents a hydrogen atom, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

L1 to L3 are the same or different and are each independently a direct bond or a substituted or unsubstituted arylene group,

Ar 1 and Ar 2 may be the same or different and each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group or may combine with each other to form a ring,

a is an integer of 0 to 4,

b is an integer of 0 to 7,

c is an integer of 0 to 5,

d is an integer of 0 to 4,

When a is plural, R3 is the same or different from each other,

And when b is plural, R4 is the same or different from each other,

And when c is plural, R5 are the same or different from each other,

When d is plural, R6 are the same or different from each other.

According to an embodiment of the present invention, there is also provided a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And at least one organic compound layer provided between the first electrode and the second electrode, wherein at least one of the organic compound layers comprises an acridine derivative represented by Formula 1, Lt; / RTI >

The acridine derivative according to one embodiment of the present invention can be used as a material for an organic material layer of an organic light emitting device and by using it, it is possible to improve the efficiency, the driving voltage and / or the lifetime characteristics of the organic light emitting device.

1 shows an organic light emitting device according to an embodiment of the present invention.
2 shows an organic light emitting device according to another embodiment of the present invention.
FIG. 3 illustrates an organic light emitting device according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

The present specification provides an acridine derivative represented by the above formula (1).

In this specification, when a part is referred to as "including " an element, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In this specification, when a member is located on another member, it includes not only the case where the member is in contact with the other member but also the case where another member exists between the two members.

Examples of substituents in the present specification are described below, but are not limited thereto.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.

As used herein, the term " substituted or unsubstituted " A nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group, or that at least two of the substituents exemplified above are substituted with a substituent to which they are linked, or have no substituent. For example, the "substituent group to which at least two substituents are connected" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, or the like.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, Cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably a group having 3 to 30 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, But are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, sec-butyl, It is not.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, But is not limited thereto.

In this specification, the amine group is -NH ₂ ; An alkylamine group; N-alkylarylamine groups; An arylamine group; An N-arylheteroarylamine group; An N-alkylheteroarylamine group, and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine, dimethylamine, ethylamine, diethylamine, phenylamine, naphthylamine, biphenylamine, anthracenylamine, 9-methyl- , Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group; N-phenylnaphthylamine group; An N-biphenylnaphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; An N-biphenyl phenanthrenyl amine group; N-phenylfluorenylamine group; An N-phenyltriphenylamine group; N-phenanthrenyl fluorenylamine group; And an N-biphenylfluorenylamine group, but are not limited thereto.

In the present specification, the N-alkylarylamine group means an amine group in which N of the amine group is substituted with an alkyl group and an aryl group.

In the present specification, the N-arylheteroarylamine group means an amine group in which N in the amine group is substituted with an aryl group and a heteroaryl group.

In the present specification, the N-alkylheteroarylamine group means an amine group in which N in the amine group is substituted with an alkyl group and a heteroaryl group.

In the present specification, the alkyl group in the alkylamine group, the N-arylalkylamine group, the alkylthio group, the alkylsulfoxy group and the N-alkylheteroarylamine group is the same as the alkyl group described above.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, However, the present invention is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. Specific examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and the like, but are not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably 10 to 30 carbon atoms. Specific examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, triphenyl, pyrenyl, phenalenyl, perylenyl, no.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.

,

,

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

And

And the like. However, the present invention is not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group having at least two aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the aryl group in the aryloxy group, the N-arylalkylamine group, and the N-arylheteroarylamine group is the same as the aforementioned aryl group. Specific examples of the aryloxy group include a phenoxy group, a p-tolyloxy group, a m-tolyloxy group, a 3,5-dimethyl-phenoxy group, a 2,4,6- trimethylphenoxy group, a p- Naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group and the like.

In the present specification, the heteroaryl group includes at least one non-carbon atom and at least one hetero atom. Specifically, the hetero atom may include one or more atoms selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, , An isoquinolinyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzocarbazolyl group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group ), An isoxazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but the present invention is not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group having two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the above-mentioned heteroaryl group.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the above-mentioned heteroaryl group.

According to one embodiment of the present invention, the acridine derivative represented by the following general formula (1) can be represented by any one of the following general formulas (2) to (7).

 (2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In formulas (2) to (7), R 1 to R 6, L 1 to L 3, Ar 1, Ar 2, and a to d are as defined in Formula 1.

According to one embodiment of the present disclosure, R1 and R2 are bonded to each other.

According to one embodiment of the present disclosure, R3 to R6 are hydrogen.

According to one embodiment of the present invention, L1 to L3 are the same or different from each other, and are each independently a direct bond; Or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

According to one embodiment of the present invention, L1 to L3 are the same or different from each other, and are each independently a direct bond; Or an arylene group substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms.

According to one embodiment of the present invention, L1 to L3 are the same or different from each other, and are each independently a direct bond; A phenylene group; A divalent naphthyl group; A divalent biphenyl group; A divalent terphenyl group; A divalent spirobifluorene group; A divalent triphenylene group; A divalent dimethylfluorene group; Or a divalent diphenylfluorene group.

According to one embodiment of the present invention, L1 to L3 are the same or different and are each independently a direct bond or a phenylene group.

According to one embodiment of the present invention, Ar1 and Ar2 are the same or different and each independently represent an aryl group having 6 to 20 carbon atoms, which is substituted or unsubstituted with an alkyl group or an aryl group.

According to one embodiment of the present invention, Ar 1 and Ar 2 are the same or different and each independently represent an aryl group having 6 to 20 carbon atoms, which is substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms .

According to one embodiment of the present invention, Ar1 and Ar2 are the same or different from each other and each independently represents a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorene group, a pyrene group, a triphenylene group, A phenanthrene group or an anthracene group and the above aryl groups are substituted with at least one substituent selected from the group consisting of deuterium, nitrile group, halogen group, alkyl group, aryl group, heteroaryl group, silyl group and phosphine oxide group Or is unsubstituted.

According to one embodiment of the present invention, Ar1 and Ar2 are the same or different from each other and each independently represents a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorene group, a pyrene group, a triphenylene group, Anthracene group, and the aryl groups listed above are substituted or unsubstituted with an alkyl group or an aryl group.

According to one embodiment of the present invention, Ar 1 and Ar 2 are the same or different and each independently represents a phenyl group, naphthyl group, biphenyl group, terphenyl group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, Or a fluorene group substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms, or a triphenylene group.

According to one embodiment of the present invention, Ar1 and Ar2 are the same or different and are each independently a heteroaryl group containing at least one of N, O, and S having 3 to 20 carbon atoms.

According to one embodiment of the present invention, Ar1 and Ar2 are the same or different from each other and each is a monocyclic or polycyclic heteroaryl group containing at least one of N, O, and S having 3 to 20 carbon atoms.

According to one embodiment of the present invention, Ar1 and Ar2 are the same or different from each other, and each independently represents a pyridine group, a pyrimidine group, a thraazyl group, a carbazole group, a thiophene group, a furan group, a benzothiophene group, A furan group, a dibenzothiophene group, or a dibenzofurane group.

According to one embodiment of the present invention, Ar1 and Ar2 are the same or different from each other, and each independently is a dibenzothiophene group or a dibenzofurane group.

According to one embodiment of the present invention, Ar1 and Ar2 are the same or different and each independently represent an aryl group having 6 to 20 carbon atoms, which is substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms; Or a heteroaryl group containing at least one of N, O, and S having 3 to 20 carbon atoms.

According to one embodiment of the present invention, Ar1 and Ar2 are the same or different and each independently represents a phenyl group, a biphenyl group, a naphthyl group, a terphenyl group, a dimethylfluorene group, a diphenylfluorene A dibenzofurane group, or a dibenzothiophene group.

According to another embodiment of the present invention, - (L1) N (L2-Ar1) (L3-Ar2) which is a combination of L1 to L3, Ar1 and Ar2 may be any one of the following substituents, It is not.

는 코어와 결합하는 부위이다.remind

Is a site that binds to the core.

According to another embodiment of the present invention, the compounds of Formulas 1 to 7 may be represented by the following structural formulas.

According to one embodiment of the present invention, intermediates of the compounds of Formulas 1 to 7 may be prepared according to the following reaction scheme, but are not limited thereto. In the following reaction formula, the kind and number of substituents can be variously synthesized by appropriately selecting starting materials known to those skilled in the art. The type of reaction and the reaction conditions may be those known in the art.

The compounds of formulas (1) to (7) described in the present specification can be prepared by appropriately combining the above-described formulas and the above-described intermediates on the basis of common technical knowledge.

According to one embodiment of the present disclosure, there is provided a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; And one or more organic layers disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes the above-mentioned acridine derivative, to provide.

According to one embodiment of the present disclosure, the organic material layer of the organic light emitting device may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transporting layer, an electron restraining layer, a light emitting layer, a hole blocking layer, an electron transporting layer, and an electron injecting layer as organic layers. However, the structure of the organic light emitting device is not limited thereto and may include fewer or more organic layers.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in FIGS. 1 and 2, but the present invention is not limited thereto.

FIG. 1 illustrates a structure of an organic light emitting device in which a first electrode 2, a light emitting layer 3, and a second electrode 4 are sequentially stacked on a substrate 1. 1 is an exemplary structure of an organic light emitting diode according to an embodiment of the present invention, and may further include another organic layer.

2 shows a structure in which a first electrode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 3, an electron transporting layer 7, an electron injecting layer 8 and a second electrode 4) are sequentially stacked on a substrate. 2 is an exemplary structure according to an embodiment of the present invention, and may further include another organic layer.

3 shows a structure in which a first electrode 2, a hole injecting layer 5, a hole transporting layer 6, an electron restraining layer 9, a light emitting layer 3, a hole blocking layer 10, The structure of the organic light emitting element in which the transport layer 11 and the second electrode 4 are sequentially laminated is illustrated. 3 is an exemplary structure according to an embodiment of the present invention, and may further include another organic layer.

According to an embodiment of the present invention, the organic material layer includes a hole injection layer, a hole transport layer or an electron restraining layer, and the hole injection layer, the hole transporting layer or the electron restraining layer includes the acridine derivative represented by the above formula do.

According to one embodiment of the present invention, the organic layer includes an electron suppressing layer, and the electron suppressing layer includes an acridine derivative represented by the general formula (1).

According to an embodiment of the present invention, the organic material layer includes an electron injection layer, an electron transport layer or a hole blocking layer, and the electron injection layer, electron transport layer or hole blocking layer contains an acridine derivative represented by the above formula do.

According to an embodiment of the present invention, the organic layer includes a light emitting layer, and the light emitting layer includes an acridine derivative represented by the general formula (1).

According to an embodiment of the present invention, the organic material layer may further include at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

The organic light emitting device of the present invention may be formed by a material and a method known in the art except that at least one of the organic material layers includes the acridine derivative of the present specification, that is, the acridine derivative represented by the above formula .

When the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

For example, the organic light emitting device of the present invention can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation Forming a first electrode, forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer on the first electrode, and depositing a material usable as a second electrode thereon. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a second electrode material, an organic material layer, and a first electrode material on a substrate. According to one embodiment of the present invention, the first electrode is an anode and the second electrode is a cathode.

According to another embodiment of the present invention, the first electrode is a cathode and the second electrode is a cathode.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al, LiO ₂ / Al, and Mg / Ag, but are not limited thereto.

The hole injecting layer is a layer for injecting holes from the electrode as a hole injecting material and a hole injecting effect for injecting holes in the anode as a hole injecting material and an excellent hole injecting effect for a light emitting layer or a light emitting material , The migration of excitons generated in the light emitting layer to the electron injection layer or the electron injection material, and also the ability to form thin films is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer. The hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material of the light emitting layer is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Benzoxazole, benzothiazole and benzimidazole compounds; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocyclic compound include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting material of the electron transporting layer is a layer that transports electrons from the electron injecting layer to the electron transporting layer and transports electrons from the cathode to the light emitting layer. This large material is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The organic light emitting device according to the present invention may be of a top emission type, a back emission type, or a both-side emission type, depending on the material used.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

Manufacturing example  One

Compound A (6.50 g, 14.74 mmol) and compound a1 (7.48 g, 16.95 mmol) were dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by the addition of 2M aqueous potassium carbonate solution (120 mL) , And tetrakis- (triphenylphosphine) palladium (0.51 g, 0.44 mmol) were added thereto, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (210 mL) to obtain Compound 1 (9.78 g, 83%).

MS [M + H] < ⁺ > = 803

Manufacturing example  2

Compound A (5.50 g, 12.47 mmol) and compound a2 (6.90 g, 14.34 mmol) were completely dissolved in 220 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by the addition of 2M aqueous potassium carbonate solution (110 mL) , And tetrakis- (triphenylphosphine) palladium (0.43 g, 0.37 mmol) were added thereto, followed by heating with stirring for 2 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (160 mL) to give Compound 2 (7.12 g, 68%).

MS [M + H] < ⁺ > = 843

Manufacturing example  3

Compound A (4.50 g, 10.20 mmol) and Compound a3 (6.23 g, 11.73 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by addition of 2M aqueous potassium carbonate solution (120 mL) , And tetrakis- (triphenylphosphine) palladium (0.35 g, 0.31 mmol) were added thereto, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 250 mL of tetrahydrofuran to obtain Compound 3 (6.95 g, 76%).

MS [M + H] < ⁺ > = 893

Manufacturing example  4

Compound A (5.0 g, 11.34 mmol) and compound a4 (5.75 g, 13.04 mmol) were completely dissolved in 160 mL of tetrahydrofuran in a 500 mL round bottom flask under nitrogen atmosphere, followed by addition of a 2M aqueous potassium carbonate solution (80 mL) , And tetrakis- (triphenylphosphine) palladium (0.39 g, 0.34 mmol) were added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (210 mL) to obtain Compound 4 (4.69 g, 52%).

MS [M + H] < ⁺ > = 803

Manufacturing example  5

Compound A (6.50 g, 14.74 mmol) and compound a5 (5.44 g, 16.95 mmol) were completely dissolved in 220 mL of xylene and then NaOtBu (2.27 g, 23.58 mmol) was added to a 500 mL round- (Tri-tert-butylphosphine) palladium (0) (0.15 g, 0.29 mmol) was added thereto, followed by heating and stirring for 3 hours. After the temperature was lowered to room temperature and the base was removed by filtration, the xylene was concentrated under reduced pressure and recrystallized from ethyl acetate (210 mL) to obtain Compound 5 (8.61 g, yield: 80%).

MS [M + H] < ⁺ > = 727

Manufacturing example  6

Compound A (6.50 g, 14.74 mmol) and compound a6 (6.12 g, 16.95 mmol) were completely dissolved in 200 mL of xylene and then NaOtBu (2.27 g, 23.58 mmol) was added to a 500 mL round- (Tri-tert-butylphosphine) palladium (0) (0.15 g, 0.29 mmol) was added thereto, followed by heating and stirring for 2 hours. After the temperature was lowered to room temperature and the base was removed by filtration, the xylene was concentrated under reduced pressure and recrystallized from ethyl acetate (220 mL) to obtain Compound 6 (6.67 g, yield: 59%).

MS [M + H] < ⁺ > = 767

Manufacturing example  7

Compound A (5.50 g, 12.47 mmol) and Compound a7 (4.60 g, 14.34 mmol) were completely dissolved in 160 mL of xylene and then NaOtBu (1.92 g, 19.95 mmol) was added to a 500 mL round- (Tri-tert-butylphosphine) palladium (0) (0.13 g, 0.25 mmol) was added thereto, followed by heating and stirring for 4 hours. After the temperature was lowered to room temperature and the base was removed by filtration, the xylene was concentrated under reduced pressure, and recrystallized from 230 mL of ethyl acetate to obtain 7 (7.12 g, yield: 79%).

MS [M + H] < ⁺ > = 727

Manufacturing example  8

Compound A (3.50 g, 7.94 mmol) and Compound a8 (3.66 g, 9.13 mmol) were completely dissolved in 150 mL of xylene and then NaOtBu (1.22 g, 12.70 mmol) was added to a 500 mL round- (Triphenylphosphine) palladium (0) (0.08 g, 0.16 mmol) was added thereto, followed by heating and stirring for 1 hour. After the temperature was lowered to room temperature and the base was removed by filtration, the xylene was concentrated under reduced pressure and recrystallized from ethyl acetate (210 mL) to obtain Compound 8 (3.45 g, yield: 54%).

MS [M + H] < ⁺ > = 807

Manufacturing example  9

Compound A9 (6.33 g, 14.34 mmol) was completely dissolved in 210 mL of tetrahydrofuran in a 500 mL round-bottomed flask under nitrogen atmosphere, followed by addition of 2M aqueous potassium carbonate solution (100 mL) , And tetrakis- (triphenylphosphine) palladium (0.43 g, 0.37 mmol) were added thereto, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from ethyl acetate (350 mL) to obtain Compound 9 (8.86 g, 88%).

MS [M + H] < ⁺ > = 803

Manufacturing example  10

Compound A10 (3.77 g, 11.73 mmol) was completely dissolved in 160 mL of xylene and then NaOtBu (1.57 g, 16.33 mmol) was added to a 500 mL round bottom flask in a nitrogen atmosphere. (Tri-tert-butylphosphine) palladium (0) (0.10 g, 0.20 mmol) was added thereto, followed by heating and stirring for 2 hours. After the temperature was lowered to room temperature and the base was removed by filtration, the xylene was concentrated under reduced pressure and recrystallized from ethyl acetate (180 mL) to obtain Compound 10 (5.56 g, yield: 75%).

MS [M + H] < ⁺ > = 727

Manufacturing example  11

Compound C (5.0 g, 11.34 mmol) and compound a11 (5.10 g, 13.04 mmol) were completely dissolved in 160 mL of xylene and then NaOtBu (1.74 g, 18.14 mmol) was added to a 500 mL round- (Tri-tert-butylphosphine) palladium (0) (0.12 g, 0.23 mmol) was added thereto, followed by heating and stirring for 3 hours. After the temperature was lowered to room temperature and the base was removed by filtration, the xylene was concentrated under reduced pressure and recrystallized from ethyl acetate (210 mL) to obtain Compound 11 (6.23 g, yield 69%).

MS [M + H] < ⁺ > = 797

Example  1-1

The glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1,000 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, Fischer Co. product was used as a detergent, and distilled water filtered by a filter (filtration) manufactured by Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

On the thus-prepared ITO transparent electrode, a compound represented by the following chemical formula HAT was thermally vacuum deposited to a thickness of 100 Å to form a hole injection layer. A compound (1250 ANGSTROM) represented by the following formula (HT1) was vacuum-deposited on the hole injection layer to form a hole transport layer. Subsequently, the compound of Preparation Example 1 prepared above was vacuum deposited on the hole transport layer to a thickness of 150 ANGSTROM to form an electron inhibition layer. Subsequently, a compound represented by the following formula (BH) and a compound represented by the following formula (BD) were vacuum deposited on the electron suppression layer to a thickness of 200 angstroms at a weight ratio of 25: 1 to form a light emitting layer. A hole blocking layer was formed on the light emitting layer by vacuum evaporation of a compound represented by the following formula HB1 to a film thickness of 50 ANGSTROM. Subsequently, a compound represented by the following formula (ET1) and a compound represented by the following formula (LiQ) were vacuum deposited on the hole blocking layer at a weight ratio of 1: 1 to form an electron injection and transport layer having a thickness of 310 Å. Lithium fluoride (LiF) and aluminum having a thickness of 1,000 Å were sequentially deposited on the electron injecting and transporting layer to form a cathode.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, the degree of vacuum upon deposition 2ⅹ10 ^-7 ~ Lt; ^-6 > ^-6 torr. Thus, an organic light emitting device was fabricated.

Example  1-2 Example  1-11

An organic light emitting device was prepared in the same manner as in Example 1-1 except that the compound described in the following Table 1 was used in place of the compound of Preparation Example 1. [

Comparative Example  1-1 to 1-3

An organic light emitting device was prepared in the same manner as in Example 1-1 except that the compound described in the following Table 1 was used in place of the compound of Preparation Example 1. [ The compounds of EB1, EB2 and EB3 used in Table 1 are as follows.

Experimental Example  One

The voltage, efficiency, color coordinates and lifetime of the organic light-emitting device manufactured in Examples and Comparative Examples were measured, and the results are shown in Table 1 below. T95 means the time required for the luminance to decrease from the initial luminance (1600 nits) to 95%.

compound
(Electron inhibiting layer) Voltage
(V @ 10mA
/ cm ² ) efficiency
(cd / A @ 10mA
/ cm ² ) Color coordinates
(x, y) T95
(hr) Example 1-1 Production Example 1 4.51 6.30 (0.140, 0.045) 275 Examples 1-2 Production Example 2 4.33 6.46 (0.141, 0.047) 310 Example 1-3 Production Example 3 4.56 6.34 (0.143, 0.047) 295 Examples 1-4 Production Example 4 4.41 6.42 (0.139, 0.043) 285 Examples 1-5 Production Example 5 4.50 6.33 (0.140, 0.047) 275 Examples 1-6 Production Example 6 4.73 6.15 (0.141, 0.046) 310 Examples 1-7 Production Example 7 4.64 6.29 (0.140, 0.044) 290 Examples 1-8 Production Example 8 4.46 6.44 (0.141, 0.046) 260 Examples 1-9 Production Example 9 4.41 6.42 (0.138, 0.044) 280 Example 1-10 Production Example 10 4.50 6.33 (0.139, 0.043) 295 Example 1-11 Production Example 11 4.43 6.41 (0.140, 0.043) 285 Comparative Example 1-1 EB1 5.67 5.01 (0.139, 0.043) 125 Comparative Example 1-2 EB2 5.12 5.75 (0.142, 0.045) 165 Comparative Example 1-3 EB3 7.25 3.16 (0.150, 0.049) 20

As shown in Table 1, the organic light emitting device using the compound of the present invention as the electron suppressing layer exhibited excellent characteristics in terms of efficiency, driving voltage and stability of the organic light emitting device. The low-voltage, high-efficiency and high-efficiency organic electroluminescent devices manufactured by using the compound of the core dihydroacridine of the present invention as the electron restraining layer at the 9th position of the phenyl group and the EB3 group of which the amine group is substituted for both of the phenyl group and the EB3 group, Long life. Particularly, the reason for the increase of the voltage is that the amine group is located on both sides and the HOMO value increases and the barrier with the light emitting layer becomes higher. In addition, the organic light emitting device manufactured by using EB3 compound in which the phosphine oxide was substituted for the phenyl group in the 9th phenyl group as the electron inhibiting layer showed a remarkably deteriorated lifetime characteristic. In general, it was confirmed that the absence of an amine group as a substituent can not be used as a hole transporting layer and an electron blocking layer.

As shown in Table 1, it was confirmed that the compound of the present invention is excellent in electron blocking ability and applicable to organic light emitting devices.

Although the preferred embodiments of the present invention (electron suppression layer) have been described above, the present invention is not limited thereto, but can be variously modified and embodied within the scope of the claims and the detailed description of the invention. It belongs to the invention.

1: substrate
2: first electrode
3: light emitting layer
4: Second electrode
5: Hole injection layer
6: hole transport layer
7: Electron transport layer
8: electron injection layer
9: Electronic inhibiting layer
10: hole blocking layer
11: electron injection and transport layer

Claims (7)

An acridine derivative represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
And R < 2 > may be hydrogen or may be bonded to each other,
R3 to R6 are the same or different from each other and each independently represents a hydrogen atom, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,
L1 to L3 are the same or different and are each independently a direct bond or a substituted or unsubstituted arylene group,
Ar 1 and Ar 2 may be the same or different and each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group or may combine with each other to form a ring,
a is an integer of 0 to 4,
b is an integer of 0 to 7,
c is an integer of 0 to 5,
d is an integer of 0 to 4,
When a is plural, R3 is the same or different from each other,
And when b is plural, R4 is the same or different from each other,
And when c is plural, R5 are the same or different from each other,
When d is plural, R6 are the same or different from each other. The acridine derivative according to claim 1, wherein the formula (1) is represented by any one of the following formulas (2) to (7)
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the general formulas (2) to (7), R1 to R6, L1 to L3, Ar1, Ar2, and a to d are as defined in claim 1. The compound according to claim 1, wherein Ar1 and Ar2 are the same or different and each independently represents an aryl group having 6 to 20 carbon atoms, which is substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; Or an acridine derivative which is a heteroaryl group containing N, O, or S having 3 to 20 carbon atoms. [3] The compound according to claim 1, wherein L1 to L3 are the same or different from each other and each independently is a direct bond; Or an arylene group substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms. [Claim 2] The acridine derivative according to claim 1, wherein the formula (1) is any one selected from the following compounds:

A first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the acridine derivative of any one of claims 1 to 5 Lt; / RTI > 7. The organic light emitting device according to claim 6, wherein the organic material layer includes a hole injecting layer, a hole transporting layer, or an electron blocking layer, and the hole injecting layer, the hole transporting layer, or the electron blocking layer includes the acridine derivative.

Images