KR101421521B1 - Amine derivative compounds and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a novel amine derivative compound and an organic electroluminescent device comprising the same as a light emitting material. More specifically, the present invention relates to an amine derivative compound represented by the following formula 1 or 2 and an organic electroluminescent device comprising the same. An excellent light emitting property such as a driving voltage and a current efficiency, and an excellent thermal stability even in a high temperature manufacturing process.
[Chemical Formula 1] < EMI ID =

Description

[0001] The present invention relates to an amine derivative compound and an organic electroluminescent device including the same,

The present invention relates to a novel amine derivative compound and an organic electroluminescent device including the same as a light emitting material. More particularly, the present invention relates to an amine derivative compound having excellent light emitting properties such as driving voltage and current efficiency, To an organic electroluminescent device.

In recent years, organic light emitting devices capable of being driven by a low voltage in a self-emission type have superior viewing angles and contrast ratios as compared with liquid crystal displays (LCDs), which are the mainstream of flat panel display devices, and require no backlight, It is attracting attention as a next-generation display device because it is advantageous in terms of power and has a wide color reproduction range.

In organic light emitting diodes (OLEDs), when electrons are injected into an organic light emitting layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode), electrons and holes are paired, to be.

An organic electroluminescent device using an organic light emitting phenomenon usually has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electroluminescent 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, . When a voltage is applied between the two electrodes in the structure of the organic electroluminescent device, holes are injected into the anode, electrons are injected into the organic layer, and excitons are formed when injected holes and electrons meet. When it falls back to the ground state, the light comes out.

The organic electroluminescent device can be formed on a flexible transparent substrate such as a plastic substrate and can be driven at a voltage as low as 10 V or less as compared with a plasma display panel or inorganic electroluminescence display The power consumption is relatively low, and the color is excellent. In addition, organic electroluminescent devices can display three colors of green, blue, and red, making them an object of interest for a large number of people as a next-generation rich color display device.

In order for the organic electroluminescent device to sufficiently exhibit the above-described excellent characteristics, materials constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material are supported by a stable and efficient material However, development of an organic material layer material for an organic electroluminescence device has not been sufficiently developed yet, and development of an organic material layer material having excellent light emitting properties is required.

Generally, in order to produce a product in the production of an OLED panel, since the organic material layer is exposed to the deposition condition of the production line for a long time, the thermal stability of the material is essential for commercialization of the organic material. Particularly, even when a material having excellent performance as an organic material used in an organic electroluminescent device is exposed to a high temperature for a long time in the manufacturing process, pyrolysis occurs.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a novel amine derivative compound having excellent luminous efficiency, such as a driving voltage and a current efficiency, and having excellent thermal stability.

A second object of the present invention is to provide an organic electroluminescent device including the amine derivative compound.

In order to achieve the first technical object,

The present invention provides an amine derivative compound represented by the following formula (1) or (2).

[Chemical Formula 1] < EMI ID =

In the above Chemical Formula 1 or Chemical Formula 2,

Z and A are each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms,

B is a substituted or unsubstituted cycloalkylene having 3 to 8 carbon atoms,

R ₁ To R ₄ each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, Or an unsubstituted or substituted alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 40 carbon atoms, a cyano group, and a halogen group,

R ₁ To R < ₄ > are each independently connected to an adjacent substituent with an alkylene having 3 to 60 carbon atoms and an alkenylene having 3 to 60 carbon atoms, with or without a fused ring, to form an alicyclic ring and a monocyclic or polycyclic aromatic ring And,

n is an integer of 1 to 6,

When n is 2 or more, the plurality of amine derivative compounds may be independently the same or different.

According to one embodiment of the present invention, in the amine derivative compound of the above Chemical Formula 1 or 2, Z may be naphthalene, anthracene, pyrene, triphenylene, fluoranthene or spiro compound, May be any one selected from the compounds represented by the following structural formulas.

[constitutional formula]

In order to solve the second technical problem,

The present invention relates to an anode; Cathode; And a layer containing an amine derivative compound represented by the formula (1) or (2) interposed between the anode and the cathode.

According to the present invention, the amine derivative compound represented by the formula (1) or (2) has excellent thermal stability and excellent luminescent characteristics as compared with the existing materials, and thus the organic electroluminescent device including the same is stable and has excellent luminous efficiency The organic electroluminescent device fabricated according to the present invention not only can realize high performance, but also has excellent thermal stability and can be used commercially.

1 is a graph showing a measurement result (HPLC) of a change in purity of [Formula 185] with exposure time at 340 ° C.
2 is a graph showing a measurement result (HPLC) of a change in purity of [Formula 185] with exposure time at 360 ° C.
3 is a graph showing a measurement result (HPLC) of a change in purity of [Formula 186] with exposure time at 305 ° C.
4 is a graph showing a measurement result (HPLC) of a change in purity of [Formula 186] with exposure time at 330 ° C.
5 is a graph showing a measurement result (HPLC) of a change in purity of [Formula 186] with exposure time at 350 ° C.
6 is a graph showing a measurement result (HPLC) of a change in purity of [Formula 214] with exposure time at 330 ° C.
7 is a graph showing a measurement result (HPLC) of a change in purity of [Formula 214] with exposure time at 355 ° C.
8 is a graph showing a measurement result (HPLC) of a change in purity of [Formula 214] with exposure time at 380 ° C.
9 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.

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

The present invention relates to an amine derivative compound which is characterized by being represented by the above-mentioned formula (1) or (2), and particularly has a novel structure in which the molecular structure of the amine derivative compound is newly designed to have thermal stability .

The amine derivative compound according to the present invention is characterized in that it is a heterocyclic compound of the above formulas (1) and (2), which has no double bond on one side of a pentagonal ring containing nitrogen in order to obtain a luminescent material having a narrower line width and a short wavelength region R ₁ to R ₄ in the above formulas (1) and (2) are structures which do not contain hydrogen and form a structure capable of inhibiting the aromatization reaction by resonance stabilization under high temperature conditions .

In the amine derivative compound of the above formula (1) or (2) according to the present invention, the substituent will be described in more detail as follows.

In the above formula (1) or (2), R ₁ To R _4, Z and A are each independently a heavy hydrogen atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkylamino group having 1 to 40 alkyl group, a C 1 -C 40 alkoxy group, having 1 to 40 carbon atoms of the carbon number 6 An aryloxy group having 3 to 40 carbon atoms, a heteroarylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an aryloxy group having 3 to 40 carbon atoms, A heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, and boron, and may be further substituted by such a substituent.

Specific examples of the alkyl group as the substituent used in the present invention include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, a hexyl group, a heptyl group, A halogen atom, a hydroxyl group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (in this case, a " alkylsilyl group "hereinafter), a substituted or unsubstituted amino group _{(-NH 2, -NH (R)} , -N (R ') (R''), where R, R' and R" are each independently a carbon number A hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms (for example, an alkyl group having 1 to 24 carbon atoms , An alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, An aryl group having from 5 to 24 carbon atoms, an aryl group having from 5 to 24 carbon atoms, an arylalkyl group having from 6 to 24 carbon atoms, a heteroaryl group having from 3 to 24 carbon atoms, or a heteroarylalkyl group having from 3 to 24 carbon atoms.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, isoamyloxy, And can be substituted with substituents similar to those in the case of the alkyl group.

Specific examples of the halogen group which is a substituent used in the compound of the present invention include fluorine (F), chlorine (Cl), bromine (Br) and the like.

Specific examples of the aryl group as the substituent group used in the compound of the present invention include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, Examples of the aryl group include phenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, , Anthryl group, phenanthryl group, pyrenyl group, fluorenyl group, tetrahydronaphthyl group and the like, which may be substituted with the same substituents as those in the case of the alkyl group.

Specific examples of the heteroaryl group used as the substituent in the compound of the present invention include pyridinyl, pyrimidinyl, triazinyl, indolinyl, quinolinyl, pyrrolidinyl, piperidinyl, An oxazolyl group, an oxadiazolyl group, a benzoxazolyl group, a thiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a triazolyl group, an imidazolyl group, a benzoimidazole group, And at least one of the hydrogen atoms of the heteroaryl group may be substituted with the same substituent as the alkyl group.

Examples of the aralkyl group which is a substituent group used in the compound of the present invention include benzyl group, 2-phenylethyl group, 2-phenylisopropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 2- (1-naphthyl) Fluorobenzyl group, 4-fluorobenzyl group, 2-chlorobenzyl group, 2-fluorobenzyl group, 2-fluorobenzyl group, 2- A 3-chlorobenzyl group, a 4-chlorobenzyl group, a 2-bromobenzyl group, a 3-bromobenzyl group, a 4-bromobenzyl group, and the like.

In the present invention, the term "substituted or unsubstituted" means a group selected from the group consisting of a cyano group, a halogen group, a hydroxyl group, a nitro group, an alkyl group, an alkoxy group, an alkylamino group, an arylamino group, a heteroarylamino group, an alkylsilyl group, Substituted or unsubstituted with at least one substituent selected from the group consisting of an oxygen atom, an aryl group, a heteroaryl group, germanium, phosphorus, boron, hydrogen and deuterium.

The present invention is not limited by the specific examples of the amine derivative compound according to the above-mentioned formula (1) or (2) having the above-mentioned structure, but specifically, the compound represented by the following formulas (3) to Lt; / RTI >

[Chemical Formula 3]

[Chemical Formula 5]

[Chemical Formula 7]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 13]

[Chemical Formula 15]

[Chemical Formula 17]

[Chemical Formula 19]

[Chemical Formula 21]

[Chemical Formula 23]

[Chemical Formula 25]

[Chemical Formula 27]

[Chemical Formula 30]

(32)

[Chemical Formula 33]

[Chemical Formula 35]

[Chemical Formula 37]

[Chemical Formula 39]

[Chemical Formula 41]

[Chemical Formula 43]

[Chemical Formula 45]

[Chemical Formula 47]

[Chemical Formula 49]

[Chemical Formula 51]

(54)

[Chemical Formula 55]

[Chemical Formula 57]

[Chemical Formula 60]

[Chemical Formula 61]

(63)

[Chemical Formula 65]

[Chemical Formula 67]

(70)

[Chemical Formula 71]

[Chemical Formula 73]

[Chemical Formula 75]

[Formula 77]

[Formula 79]

[Formula 81]

[Chemical Formula 83]

[Chemical Formula 85]

[Chemical Formula 87]

(90)

[Chemical Formula 91]

[Chemical Formula 95] [Chemical Formula 95]

[Chemical Formula 98] [Chemical Formula 98]

[Formula 100] < EMI ID =

(105) < RTI ID = 0.0 >

≪ EMI ID = 106.1 >

(110)

[Formula 111]

(115)

(117)

(119)

(120)

[124] [124] [124]

[Formula 125]

(129)

[Formula 130]

(133)

(135)

(137)

[Chemical Formula 138]

[Formula 140]

[Chemical Formula 142]

(145)

[Chemical Formula 146]

[Chemical Formula 148]

[Formula 150]

[Chemical Formula 152]

[Chemical Formula 154]

(157)

(159) < RTI ID = 0.0 >

[Formula 161]

[163]

[Formula 164]

(167)

[169]

[171]

[173]

(175)

[177]

[179]

[Formula 181]

[Formula 182]

[Formula 184]

[Formula 186]

[Formula 188] [Formula 189]

[Chemical Formula 190]

[193]

[Chemical Formula 194] [Chemical Formula 195]

[197] [197]

(198)

[Formula 200]

[Chemical Formula 202]

(205)

[Chemical Formula 206]

[Chemical Formula 209]

[Chemical Formula 210]

[Chemical Formula 212]

[Formula 214]

[217]

[218]

The method for producing the amine derivative compound according to the present invention is specifically shown in the following Examples.

The present invention also relates to a fuel cell comprising an anode; Cathode; And a layer containing an amine derivative compound represented by the formula (1) or (2) interposed between the anode and the cathode.

In this case, the layer containing the amine derivative compound is preferably a light emitting layer between the anode and the cathode, and a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer, ≪ RTI ID = 0.0 > and / or < / RTI >

In addition, according to another embodiment of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 ANGSTROM, and the light emitting layer may further include various phosphorescent host materials.

As a specific example, a hole transport layer (HTL) may be further stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic emission layer. An electron donor molecule having a low ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative having a basic skeleton of triphenylamine is used as the material of the hole transport layer. It is widely used.

In the present invention, the material for the hole transport layer is not particularly limited as long as it is commonly used in the art. For example, N, N'-bis (3-methylphenyl) -N, N'- , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (a-NPD).

A hole injection layer (HIL) may be additionally formed on the lower portion of the hole transport layer. The material for the hole injection layer is not particularly limited as long as it is commonly used in the art. For example, (4,4 ', 4 "-tri (N-carbazolyl) triphenyl-amine) or m-MTDATA (4,4' -methylphenylphenylamino) triphenylamine) can be used.

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention can transport electrons supplied from the cathode smoothly to the organic luminescent layer and inhibit the movement of holes which are not bonded in the organic luminescent layer, .

The material of the electron transport layer is not particularly limited as long as it is commonly used in the art. For example, oxadiazole derivative PBD, BMD, BND or Alq ₃ can be used.

Meanwhile, an electron injection layer (EIL) may be further formed on the electron transport layer to facilitate injection of electrons from the cathode to ultimately improve power efficiency. The electron injection layer material As long as it is commonly used in the art, it can be used without any particular limitation. For example, materials such as LiF, NaCl, CsF, Li ₂ O, and BaO can be used.

The organic electroluminescent device according to the present invention can be used for a display device, a display device, an element for a single color or a white light, and the like.

9 is a cross-sectional view showing the structure of an organic electroluminescent device of the present invention. The organic electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic emission layer 50, an electron transport layer 60 and a cathode 80, The electron injecting layer 70 may be further formed. In addition, one or two intermediate layers may be further formed, or a hole blocking layer or an electron blocking layer may be further formed.

The organic electroluminescent device of the present invention and a method of manufacturing the same will be described with reference to FIG. First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

A hole injection layer 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30.

A hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

According to another embodiment of the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer is formed by a single molecular deposition method or a solution process And the organic electroluminescent device according to the present invention can be used for a display device, a display device, and a monochromatic or white illumination device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further illustrating the present invention and that the scope of the present invention is not limited thereby.

Synthesis Example 1 Synthesis of Compound Represented by Formula 185

(1) Synthesis of the compound represented by the formula (1-a) and the formula (1-b)

[Chemical Formula 1-a] and [Chemical Formula 1-b] were synthesized by the following Reaction Scheme 1.

[Reaction Scheme 1]

[Chemical Formula 1] < EMI ID =

60.1 g (0.282 mol) of 4-tert-butylbromobenzene and 250 ml of THF were placed in a 1 L round bottom flask, and after cooling to -78 ° C, 163 ml (0.2613 mol) of n-butyllithium was slowly added dropwise, After stirring for 1 hour, 30 g (0.1045 mol) of 2,6-dibromoanthraquinone was added. The reaction product was warmed to room temperature, stirred for 12 hours, and 300 ml of 2N hydrochloric acid was added to the reaction mixture. The resultant was separated, and the organic layer was dried over MgSO ₄ , filtered and concentrated to give a compound represented by the general formula [1-a].

After adding a compound represented by the general formula [1-a] to a 1 L round bottom flask, KI 52g (0.3135 mol), NaH ₂ PO ₂ -H ₂ O 66.5 g (0.627 mol) and acetic acid 600 ml were added, Lt; / RTI > The resultant was cooled to room temperature, filtered, and washed with excess water and methanol. The washed product was dried and then recrystallized with toluene. The resulting solid was filtered and dried under reduced pressure to give 23 g (36.5%) of a compound represented by the formula (1-b)

(2) Synthesis of a compound represented by the formula (1-c).

[Chemical Formula 1-c] was synthesized by the following Reaction Scheme 2.

[Reaction Scheme 2]

[Chemical Formula 1-c]

40 g (0.3699 mol) of phenylhydrazine, 41.5 g (0.3699 mol) of 2-methylcyclohexanone and 240 ml of acetic acid were placed in a 500 ml round bottom flask and refluxed for 6 hours. After completion of the reaction, the reaction solution was basified with sodium hydroxide, extracted with water and ethylene acetate, and neutralized. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by column chromatography using hexane and methylene chloride as eluent To obtain 57.5 g (84%) of a compound represented by the formula (1-c).

(3) Synthesis of a compound represented by the formula (1-d).

[Chemical Formula 1-d] was synthesized by the following Reaction Scheme 3.

[Reaction Scheme 3]

[Chemical formula 1-d]

50 g (0.269, 9 mol) of [Formula 1-a] obtained above was dissolved in 150 ml of toluene in a 500 ml round-bottomed flask under nitrogen atmosphere, and the temperature was lowered to -20 ° C. 260 ml (0.1753 mol) of 1.6 M methyl lithium was slowly added dropwise to the above solution and reacted at -20 ° C for 3 hours. After completion of the reaction, 200 ml of a 1: 1 solution of toluene and water was slowly poured into the reaction mixture, and the mixture was separated. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and then subjected to column chromatography using hexane and methylene chloride as eluent 47.3 g (87%) of [Formula 1-d] was prepared.

(4) Synthesis of Compound Represented by Formula 185

A compound represented by the formula (185) was synthesized by the following reaction scheme [4].

[Reaction Scheme 4]

[185]

10 g (0.0205 mol) of the above-synthesized compound 1-b, 9.9 g (0.0492 mol) of the compound represented by the formula 1-d, 0.18 g (0.82 mmol) of palladium acetate, 0.51 g mmol), 7.8 g (0.082 mol) of sodium alginate butoxide and 80 ml of toluene were added, and the mixture was refluxed for 12 hours. Upon completion of the reaction, celite was placed on a Buchner funnel under a hot condition, and the mixture was filtered. The filtrate was concentrated, and then recrystallized from toluene. The recrystallization method was repeated several times to obtain a compound represented by the formula (185) as a pale yellow solid. (3.4 g, 19.7%).

m.p. : 380.7 DEG C

^{1 H NMR (300 MHz, CDCl} 3) d 7.80 (d, 2H), 7.65 (d, 4H), 7.50 (td, 4H), 7.40 (d, 4H), 7.08 (d, 2H), 7.00 (t, 2H), 6.78 (d, 2H), 6.65 (d, 2H), 1.80 (m, 4H), 1.49 )

Synthesis Example 2 Synthesis of a compound represented by the formula (186).

186] was obtained in the same manner as in [Synthesis Example 1], except that 1-bromo-p-biphenyl was used instead of 4-tert-butylbromobenzene in [Reaction Scheme 1] of <Synthesis Example 1> The compound to be displayed was prepared. (4.6 g, 23.4%).

m.p. : 303.4 DEG C

^{1 H NMR (300 MHz, CDCl} 3) d 7.88 (t, 4H), 7.80 (d, 6H), 7.65 (m, 4H), 7.55 (t, 6H), 7.45 (t, 4H), 7.05 (d, 2H), 7.00 (t, 2H), 6.76 (t, 2H), 6.65 (d, 2H), 1.80 (m, 4H) )

Synthesis Example 3 Synthesis of Comparative Example Compound

In order to measure and evaluate the high-temperature thermal stability of the amine derivative compound according to the present invention, a compound represented by the following formula (219) was synthesized as a comparative compound.

219] was obtained in the same manner as in [Synthesis Example 1], except that 2,3,3-trimethylindoline was used in place of the compound [Formula 1-d] in [Reaction Scheme 3] of the above Synthesis Example 1 &Lt; / RTI > (5.5 g, 30.2%)

m.p. : 347.7 DEG C

^{1 H NMR (300 MHz, CDCl} 3) d 7.78 (d, 2H), 7.65 (d, 4H), 7.49 (m, 4H), 7.38 (dd, 2H), 7.34 (s, 2H), 7.50 (d, (S, 6H), 1.21 (s, 6H), 7.20 (d, 2H), 6.85 ), 1.15 (d, 6H)

[219]

&Lt; Examples 1 to 2 > High-temperature thermal stability measurement

The purity of the material was analyzed by HPLC after the deposition temperature (Ts) for producing the light emitting device of the amine derivative compound according to the present invention was exposed to heat for a long time at a temperature higher than the deposition temperature.

The analytical instrument used for purity measurement was a Waters 600 controller system, a Waters 600 pump, and a Waters 486 detector. The column used was Shiseido capcell pack C18 UG 120 4.6 ID × 250 mm.

1 mg of each sample was dissolved in 2 mL of tetrahydrofuran (THF), and then 5 mL of the sample was injected. The mobile phase used was a mixed solution of acetonitrile: tetrahydrofuran = 85: 15 and a flow rate of 0.8 mL / min Respectively.

<Example 1> Measurement of high-temperature thermal stability of [Formula 185]

The thermal stability of the compound represented by Formula 185, which is the amine derivative compound according to the present invention, was measured, and the results are shown in Table 1 below.

Exposure temperature (℃)
The deposition temperature (Ts) HPLC Purity (%) according to High Temperature Exposure Time 0 hr 24 hr 72 hr - - - - Ts 340 99.33 99.37 99.46 - - - - Ts + 20 ° C 360 99.33 99.56 99.46 - - - -

As shown in Table 1, the initial purity was maintained at a high temperature without changing the purity, and the results of HPLC analysis according to each temperature and exposure time were shown in FIG. 1 and FIG. 2, respectively.

Example 2 Measurement of high-temperature thermal stability of [Formula 186]

The thermal stability of the compound represented by Formula 186, which is an amine derivative compound according to the present invention, was measured, and the results are shown in Table 2 below.

Exposure temperature (℃)
The deposition temperature (Ts) HPLC Purity (%) according to High Temperature Exposure Time 0h 25h 50h 75h 100h 125h 150h Ts 305 99.71 99.36 99.56 99.52 99.79 99.77 - Ts + 25 ° C 330 99.71 99.15 99.33 99.45 99.61 99.75 99.65 Ts + 50 ° C 355 99.71 99.63 99.46 99.00 99.54 99.40 -

As shown in Table 2, the initial purity was maintained at a high temperature without changing the purity as shown in Table 2, and the results of HPLC analysis according to each temperature and exposure time are shown in FIGS. 3 to 5.

Comparative Example 1 Measurement of high-temperature thermal stability of [Formula 219]

In the measurement of the high-temperature thermal stability of the above Examples 1 and 2, the high-temperature thermal stability was measured in the same manner as in the above Example using the compound of Comparative Example synthesized in Synthesis Example 3, instead of the amine derivative compound of the present invention And the results are shown in Table 3 below.

Exposure temperature (℃)
The deposition temperature (Ts) HPLC Purity (%) according to High Temperature Exposure Time 0 hr 25 hr 50 hr 75 hr 100 hr 125 hr 150 hr Ts 330 99.00 96.85 96.11 94.84 95.59 89.56 90.88 Ts + 25 ° C 355 99.00 78.86 94.84 93.40 91.35 91.06 90.03 Ts + 50 ° C 380 99.00 80.53 54.41 -

As shown in Table 3, the purity of [Formula 219] was about 10% lower than the initial purity at the high temperature exposure condition, and the HPLC spectrum with time at each temperature was shown in FIG. 6 to FIG.

&Lt; Examples 3 to 4 > Preparation of an organic electroluminescent device containing the compound synthesized by Synthesis Examples 1 and 2

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the substrate was mounted in a vacuum chamber, the substrate was adjusted to have a pressure of 1 × 10 ^-6 torr. Then, organic substances were injected onto the ITO by DNTPD (700 Å), NPD (300 Å), ADN + 300 Å), Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å).

[DNTPD]

[NPD]

[ADN]

[Alq ₃ ]

&Lt; Comparative Examples 2 to 3 > The high-temperature thermal stability measurement of [Formula 219] and [Formula 220]

The organic light emitting diode device for the comparative example was fabricated in the same manner except that the following compound was used in place of the compound prepared according to the invention in the device structure of the present invention and the following compound was used in the following formula .

[219]

(220)

The results of the characteristics of the organic electroluminescent device for Examples 3 to 4 and Comparative Examples 2 to 3 of the amine derivative compound according to the present invention are shown in Table 4 below.

division The Host V Cd / A Luminous color Example 3 185 ADN 3.76 21.25 green Example 4 186 ADN 3.73 23.56 green Comparative Example 2 214 ADN 3.88 23.61 green Comparative Example 3 215 ADN 4.09 18.46 green

As shown in [Table 1] to [Table 4] and Figures 1 to 8, the compound according to the present invention exhibits device characteristics with a low driving voltage and excellent current efficiency compared with the conventional compound [220] Compared with the target compound [Formula 219], the device characteristics are similar, but the device is characterized by its excellent thermal stability at a high temperature, so that it can be used commercially as well as realizing a high performance organic electroluminescent device.

10: substrate 20: anode
30: Hole injection layer 40: Hole transport layer
50: organic light emitting layer 60: electron transporting layer
70: electron injection layer 80: cathode

Claims (9)

An amine derivative compound represented by the following formula 1 or 2:
[Chemical Formula 1] &lt; EMI ID =

In the above Chemical Formula 1 or Chemical Formula 2,
Z and A are each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms,
B is a substituted or unsubstituted cycloalkylene having 3 to 8 carbon atoms,
R ₁ to R ₄ each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, A substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C7 to C50 aralkyl group , A substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 40 carbon atoms, a cyano group, and a halogen group,
n is an integer of 1 to 6, and when n is 2 or more, the plurality of amine derivative compounds may be independently the same or different. The method according to claim 1,
Wherein Z is any one selected from the compounds represented by the following structural formulas:
[constitutional formula]

The method according to claim 1,
R ₁ of the above formula (1) or (2) To R _4, Z and A are each independently a heavy hydrogen atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkylamino group having 1 to 40 alkyl group, a C 1 -C 40 alkoxy group, having 1 to 40 carbon atoms of the carbon number 6 An aryloxy group having 3 to 40 carbon atoms, a heteroarylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an aryloxy group having 3 to 40 carbon atoms, A heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, and boron. The method according to claim 1,
The amine derivative compound represented by the above formula (1) or (2) is any one selected from the group consisting of the following formulas (3) to (218)

[Chemical Formula 3]

[Chemical Formula 5]

[Chemical Formula 7]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 13]

[Chemical Formula 15]

[Chemical Formula 17]

[Chemical Formula 19]

[Chemical Formula 21]

&Lt; EMI ID =

[Chemical Formula 25]

[Chemical Formula 27]

[Chemical Formula 30]

(32)

[Chemical Formula 33]

[Chemical Formula 35]

[Chemical Formula 37]

[Chemical Formula 39]

[Chemical Formula 41]

[Chemical Formula 43]

[Chemical Formula 45]

[Chemical Formula 47]

[Chemical Formula 49]

[Chemical Formula 51]

(54)

[Chemical Formula 55]

[Chemical Formula 57]

[Chemical Formula 60]

[Chemical Formula 61]

(63)

[Chemical Formula 65]

[Chemical Formula 67]

(70)

[Chemical Formula 71]

[Chemical Formula 73]

[Chemical Formula 75]

[Formula 77]

[Formula 79]

[Formula 81]

[Chemical Formula 83]

[Chemical Formula 85]

[Chemical Formula 87]

(90)

[Chemical Formula 91]

[Chemical Formula 95] [Chemical Formula 95]

[Chemical Formula 98] [Chemical Formula 98]

[Formula 100] &lt; EMI ID =

(105) &lt; RTI ID = 0.0 &gt;

&Lt; EMI ID = 106.1 &gt;

(110)

[Formula 111]

(115)

(117)

(119)

(120)

[124] [124] [124]

[Formula 125]

(129)

[Formula 130]

(133)

(135)

(137)

[Chemical Formula 138]

[Formula 140]

[Chemical Formula 142]

(145)

[Chemical Formula 146]

[Chemical Formula 148]

[Formula 150]

[Chemical Formula 152]

[Chemical Formula 154]

(157)

(159) &lt; RTI ID = 0.0 &gt;

[Formula 161]

[163]

[Formula 164]

(167)

[169]

[171]

[173]

(175)

[177]

[179]

[Formula 181]

[Formula 182]

[Formula 184]

[Formula 186]

[Formula 188] [Formula 189]

[Chemical Formula 190]

[193]

[Chemical Formula 194] [Chemical Formula 195]

[197] [197]

(198)

[Formula 200]

[Chemical Formula 202]

(205)

[Chemical Formula 206]

[Chemical Formula 209]

[Chemical Formula 210]

[Chemical Formula 212]

[Formula 214]

[217]

[218] Anode;
Cathode;
And a layer containing the amine derivative compound of any one of claims 1 to 4 interposed between the anode and the cathode. 6. The method of claim 5,
Wherein the amine derivative compound is contained in the light emitting layer between the anode and the cathode. The method according to claim 6,
Wherein at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer and an electron injecting layer is further interposed between the anode and the cathode. 8. The method of claim 7,
Wherein at least one layer selected from the group consisting of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer is formed by a single molecular deposition method or a solution process. 6. The method of claim 5,
Wherein the organic electroluminescent device is used in a display device, a display device, or a device for monochromatic or white illumination.

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