KR20080062807A - Polymeric compounds containing phenylcarbazole group and polymer light emitting diode employing the same - Google Patents

Abstract

A polymer compound having a phenylcarbazole group, and a polymer electroluminescent device containing the polymer compound are provided to improve hole and electron transport property and to enhance brightness and color reproduction range. A polymer compound having a phenylcarbazole group is represented by the formula 1, 2 or 3, wherein R1 to R11 are identical or different one another and are H, a halogen atom, an alkyl group, an alkoxy group, a cyano group, a nitro group, an acyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero ring having at least one halogen, nitrogen, oxygen or sulfur atom as a ring member; X1 to X4 are identical or different one another and are an alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted hetero arylene group, or their combination; Y1 to Y3 are a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group, or a substituted or unsubstituted fluorene group; a, b, c and d are 0 or 1; and n, m and p are an integer of 1-50,000.

Description

Polymer Compounds Containing Phenylcarbazole Group and Polymer Light Emitting Diode Employing the Same

1 is a view showing the structure of an organic light emitting diode (OLED).

Figure 2 shows a specific implementation method of a polymer electroluminescent device using a polymer compound having a phenylcarbazole group according to the present invention.

In Figure 3 is an intermediate for synthesizing the polymer compound containing a phenyl carbazole according to the invention N - [4- (2- ethyl-hexyl-oxyl) -3,5-dibromo-phenyl-methylene] - of carbazole ¹ H NMR spectrum.

4 is an absorption of poly [ N- (4- (2-ethylhexyloxy) -3,5-dimethylene-phenyl) -carbazole-alt-aniline] which is an example of the compound represented by the formula (1) of the present invention. And blue emission spectrum.

5 is a poly [ N- (4- (2-ethylhexyloxy) -3,5-dimethylene-phenyl) -carbazole-alt-aniline] as an example of the compound represented by the formula (1) of the present invention; Green emission spectrum of binary compound obtained using as host material for dopant.

6 is a ¹ H NMR spectrum of N- (2-ethylhexyloxylphenyl) -3,6-dibromocarbazole which is an intermediate for synthesizing a high molecular compound having a phenylcarbazole group according to the present invention.

7 is an absorption and blue emission spectrum of poly [( N- (2-ethylhexyloxy) -phenyl) -3,6-carbazole-alt-aniline] which is an example of a compound represented by Formula 2 of the present invention. .

8 is a host material for a green dopant of poly [( N- (2-ethylhexyloxy) -phenyl) -3,6-carbazole-alt-aniline], which is an example of the compound represented by Formula 2 of the present invention. It is the green emission spectrum of the binary compound obtained by using.

9 is a host material for a red dopant of poly [( N- (2-ethylhexyloxy) -phenyl) -3,6-carbazole-alt-aniline], which is an example of the compound represented by Formula 2 of the present invention; Red emission spectrum of the binary compound obtained by using.

FIG. 10 is ¹³ C-NMR of bis [6-bromo- N- (2-ethylhexyloxylphenyl) -carbazol-3-yl as an intermediate for synthesizing a polymer compound having a phenylcarbazole group according to the present invention. Spectrum.

11 is a poly [bis (6- N- (4- (2-ethylhexyloxy) -phenyl) -carbazol-3-yl) -alt- which is an example of another compound represented by the general formula (2) of the present invention. Absorption and blue emission spectrum of aniline.

12 is a poly [bis (6- N- (4- (2-ethylhexyloxy) -phenyl) -carbazol-3-yl) -alt- which is an example of another compound represented by the general formula (2) of the present invention. Green emission spectra of binary compounds obtained using aniline as the host material for the green dopant.

FIG. 13 is a poly [bis (6- N- (4- (2-ethylhexyloxy) -phenyl) -carbazol-3-yl) -alt- which is an example of another compound represented by Chemical Formula 2 of the present invention; FIG. Red emission spectrum of the binary compound obtained using aniline as a host material for the red dopant.

14 is a ¹ H NMR spectrum of N- (4-aminophenyl) -carbazole, which is an intermediate for synthesizing a polymer compound having a phenylcarbazole group according to the present invention.

15 is a ¹ H NMR spectrum of N- (2-ethylhexyl) -3,6-dibromo-carbazole as an intermediate for synthesizing a polymer compound having a phenylcarbazole group according to the present invention.

FIG. 16 shows absorption of poly [ N- (4-aminophenyl) -carbazole-alt- N- (2-ethylhexyl) -3,6-carbazole], which is an example of the compound represented by Formula 3 of the present invention; Blue emission spectrum.

17 is a green dopant of poly [ N- (4-aminophenyl) -carbazole-alt- N- (2-ethylhexyl) -3,6-carbazole] as an example of the compound represented by Formula 3 of the present invention; Green emission spectrum of binary compound obtained using as host material for.

FIG. 18 shows a poly [ N- (4-aminophenyl) -carbazole-alt- N- (2-ethylhexyl) -3,6-carbazole], which is an example of a compound represented by Formula 3, as a host for a red dopant. It is the red emission spectrum of the binary compound obtained using it as a material.

19 is a poly ( N- (2-ethylhexyloxylphenyl) -3,6-carbazole-alt- N- (4-aminophenyl) -carbazole which is an example of another compound represented by Chemical Formula 3 of the present invention. ) Is the green emission spectrum of the binary compound obtained using as host material for the green dopant.

20 is a poly ( N- (2-ethylhexyloxylphenyl) -3,6-carbazole-alt- N- (4-aminophenyl) -carbazole which is an example of another compound represented by Chemical Formula 3 of the present invention. ) Is the red emission spectrum of the binary compound obtained using as host material for the red dopant.

<Explanation of symbols for the main parts of the drawings>

1, 11: cathode 2: electron injection layer

3: electron transport layer 4: light emitting layer

5: hole transport layer 6: hole injection layer

7, 14: anode 8: red light emitting layer

9: green light emitting layer 10: blue light emitting layer

12: organic bank 13: inorganic bank

15: hole injection / transport layer

The present invention relates to a polymer compound and a polymer electroluminescent device using the same. More specifically, at least two amine groups having excellent hole transport characteristics as repeating units are included, and at least one of the two or more amine groups is carba. The present invention relates to a polymer compound having excellent hole and electron transport characteristics and a polymer electroluminescent device using the same because it is a slum.

CRT was the mainstream until 2000, but as the demand for flat panel displays increased due to the demand for light weight, low power consumption, portability, and flattening, it was rapidly replaced by liquid crystal display (LCD). Currently, organic light emitting diodes (OLEDs) are attracting attention as next-generation flat panel displays. OLED is a display that can realize characters or images of various colors by emitting organic materials by itself when voltage is applied to organic material (polymer or low molecule) thin film. Self-emitting type, ultra thin type (1/3 of LCD), fast Its response speed (1000 times of LCD), low power consumption (1/2 of LCD), high sharpness and flexibility make it a popular small mobile display for mobile phones and PDAs. In the future, it is expected to develop into notebook PCs, wall-mounted TVs, and displays of simpler and clearer scroll TVs like paper after 2010.

OLED emits visible light by recombination of holes and electrons, and has a form in which a plurality of organic layers are stacked between a cathode and an anode. Generally, substrates for OLED devices are made of glass, but in some cases, bendable plastic or film types are used. The anode on the substrate mainly uses indium tin oxide (ITO) formed by vacuum deposition or sputtering, and the organic layer is vacuum deposited for low molecular weight compounds, spin coating for high molecular weight compounds, spin coating, or inkjet printing. A thin film is formed using such as. The negative electrode requires magnesium or lithium having a small work function, but mainly uses aluminum in consideration of stability with moisture and oxygen in the air.

Looking briefly at the structure of OLEDs using low molecular weight organic materials, the organic material with semiconductor properties has a sandwich structure between the cathode and the anode in the form of a thin film, and when a direct current electric field is applied to both electrodes, electrons and holes It is injected into the light emitting layer formed of the low molecular organic material to emit light in the visible light region. In general, in order to improve the luminous efficiency of OLEDs, as shown in FIG. 1, various types of organic materials are formed in a multilayer between a cathode and an anode. For example, a hole injection layer (HIL) is formed on the anode, followed by a hole transporting layer (HTL), an emitting layer (EML), an electron transporting layer (ETL), and an electron. An injection layer (EIL) and a cathode electrode are sequentially formed. In addition, the light emitting layer is generally composed of a host material and a dopant material, and light emission efficiency can be greatly improved by doping a small amount of dopant of 0.5 to 20%. In the case of an OLED using a low molecular organic material, each of the above layers is formed by a vacuum deposition method, and a cathode electrode made of a metal is also formed by vacuum deposition. The reason for forming a multi-layer OLED of HIL / HTL / EML / ETL / EIL between the cathode and the anode is to inject a lot of electrons and holes from the cathode and the anode and to move the injected electrons and holes to the EML layer quickly. In order to increase the formation efficiency of an electron-hole pair (exciton) in the light emitting layer. As a result, high-efficiency OLED can be realized.

Currently, OLED is applied to small-scale applications, and like other displays, R & D is focused on large-area OLED implementation as part of the expansion of its application field and formation of large-scale OLED market. The most important field of application of large area OLED is TV field. Active technology development is being made to realize large-area OLED for such TV use, development of low temperature polysilicon-thin film transistor (LTPS-TFT), development of large-area response OLED equipment, formation of RGB (red, green, blue) pattern Technology development is currently in progress for large area. Among these, development of RGB pattern forming technology replaces the conventional vacuum deposition method, and inkjet printing technology, LITI (laser induced thermal imaging) technology, and the method of applying color filter to white OLED are examined, and inkjet printing technology is a large-area substrate. Applicability to is evaluated to be the best.

In order to complete the inkjet printing technology, it is important to ink the electroluminescent material. However, low molecular weight OLED materials, which are mainly used, are difficult to ink. The electroluminescent material suitable for the inkjet method is suitable for a polymer, and a polymer light emitting diode (PLED) using a polymer occupies a major field in the electroluminescent display industry. That is, when the polymer is used, it is possible to form an RGB pattern by an inkjet method having a large area, and is also in an advantageous position for implementing a flexible display beyond a TV application in the future. In order to implement such an electroluminescent device, the development of a polymer electroluminescent material of high brightness, high efficiency and high color purity should be preceded.

The electroluminescent device using the polymer organic material has a structure in which a polymer material is formed of a multilayer thin film on the cathode and the anode as in the case of the OLED using the low molecular organic material. In other words, except that the organic material used is a polymer, the principle and concept thereof are the same as OLEDs using low molecules. In the case of the electroluminescent device, the hole injection / transport layer and the electron injection / transport layer may be selectively introduced or removed according to the characteristics of the polymer material constituting the light emitting layer, or may be used in combination with the low molecular material. In addition, in order to improve the luminous efficiency and color reproduction range, the light emitting layer is composed of a polymer host and a low molecular phosphorescent dopant, and the polymer host material itself must be a polymer material capable of emitting blue light because the band gap must be large.

OLEDs using low-molecular organic materials have entered the prototyping stage because many low-molecular materials with high brightness, high efficiency and high color purity have been developed. However, the electroluminescent device is still at the R & D level, which is insufficient in the commercialization level, and many researches are being conducted for high efficiency and high color purity. In particular, the research direction for the commercialization of the electroluminescent device is to improve the efficiency of the electroluminescent device and to implement a full color display by implementing various colors. Various color (green, red and blue) implementations for full colors can be achieved by changing the structure of the light emitting polymer. Among the polymer luminescent materials, poly (p-phenylene vinylene) [PP (V)] shows green light emission. <PL Burn, DDC Bradley, RH Friend, DA Halliday, AB Holmes, RW Jackson, A. Kraft, J. Chem . Soc , Perkin Trans , Vol. 1, p. 3225, 1992>, poly (2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene), a derivative of PPV [poly (2-methoxy-5 (2-ethylhexyloxy) -1,4-phenylene vinylene): EH-PPV] is a structure in which two alkoxy groups are introduced into the phenyl group of PPV, and unlike the PPV, it is known that light emission of red region is possible (US Pat. No. 5,189,136). In this way, the main chain of the conjugated polymer is the same and the emission color is changed even if only the side chain structure is changed. Alternatively, as mentioned above, a polymer host and a low molecular dopant may be used. In other words, the polymer host uses a material with a blue band with a large band gap, and the dopant is made of phosphorescent red, green, and blue low molecular materials with high efficiency, thereby enabling high efficiency and realizing various colors.

The color emitted from the polymer is very important for producing color displays. In order to obtain a natural color in a color display, red light, blue light and green light having excellent color purity must be mixed in an appropriate ratio. Full-color displays such as CRT (cathod ray tube), LCD, and plasma display panel (PDP), which are widely used at present, are formed with a fine pattern of fluorescent materials capable of emitting red, blue and green light with excellent color purity. In the case of devices, high purity trichromatic light emitting polymer materials have to be developed to have a display. Currently, light emitting polymers of various colors have been developed, but there are not many high purity red, blue and green light emitting polymers suitable for full color displays. In particular, in the electroluminescent device, the blue light emitting polymer has a low lifespan, poor efficiency and color purity, and thus is unsuitable for commercialization. In the case of OLEDs using low-molecules, the prototype is in the commercial stage, whereas in the case of electroluminescent devices, commercialization is delayed.

The present invention has been made to solve the problems of the prior art such as the above, at least two or more amine groups having excellent hole transport properties as a repeating unit, at least one or more of the two or more amine groups It is an object to provide a high molecular compound which is a carbazole group.

In addition, the present invention, in the electroluminescent device comprising at least one organic layer between the cathode and the anode, at least one layer of the organic layer includes a high molecular compound having the phenylcarbazole group, high efficiency, high color purity is possible It is an object to provide a polymer electroluminescent device.

The polymer compound having a phenylcarbazole group according to the present invention is represented by the following formula (1).

(Wherein

R ₁ , R ₂ and R ₃ are the same as or different from each other, hydrogen atom, halogen atom, alkyl group, alkoxy group, cyano group, nitro group, acyl group, substituted amino group, unsubstituted amino group, substituted aryl group, unsubstituted aryl group, A substituted heterocyclic group or an unsubstituted heterocyclic group,

X ₁ , and X ₂ are the same or different as the linking group, and are a group selected from an alkylene group, a substituted arylene group, an unsubstituted arylene group, a substituted hetero arylene group, an unsubstituted hetero arylene group and a linking group thereof, and

Y ₁ is an aryl group having 6 to 60 carbon atoms which may have a substituent, a heteroaryl group having 3 to 60 carbon atoms which may have a substituent, or a fluorene group which may have a substituent,

a and b are the same or different and are 0 or 1,

n is an integer from 1 to 50,000.)

According to another aspect of the invention, the polymer compound having a phenylcarbazole group is represented by the following formula (2).

(Wherein

R ₄ , R ₅ and R ₆ are the same as or different from each other, hydrogen atom, halogen atom, alkyl group, alkoxy group, cyano group, nitro group, acyl group, substituted amino group, unsubstituted amino group, substituted aryl group, unsubstituted aryl group, A substituted heterocyclic group or an unsubstituted heterocyclic group,

X ₃ , and X ₄ are the same or different as the linking group, and are a group selected from an alkylene group, a substituted arylene group, an unsubstituted arylene group, a substituted hetero arylene group, an unsubstituted hetero arylene group, and a linking group thereof, and a combination thereof

Y ₂ is an aryl group having 6 to 60 carbon atoms which may have a substituent, a heteroaryl group having 3 to 60 carbon atoms which may have a substituent, or a fluorene group which may have a substituent,

c and d are the same or different and are 0 or 1,

m is an integer from 1 to 50,000.)

According to another aspect of the present invention, the polymer compound having a phenylcarbazole group is represented by the following formula (3).

(Wherein

R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are the same as or different from each other, hydrogen atom, halogen atom, alkyl group, alkoxy group, cyano group, nitro group, acyl group, substituted amino group, unsubstituted amino group, substituted aryl group , An unsubstituted aryl group, a substituted heterocyclic group, or an unsubstituted heterocyclic group,

Y ₃ is an aryl group having 6 to 60 carbon atoms which may have a substituent, a heteroaryl group having 3 to 60 carbon atoms which may have a substituent, a fluorene group having a substituent, or an alkyl group having 1 to 20 carbon atoms,

p is an integer from 1 to 50,000.)

As X ₁ , X ₂ , which is the linking group of Formula 1, and X ₃ , X _{4, which} is the linking group of Formula 2,

등을 예로 들 수 있으며, 상기 제시 구조 이외에도 그 예는 무수히 많을 수 있다.

And the like, and there may be numerous examples other than the above-described structure.

R ₁₂ to R ₄₁ shown in the linking group examples are hydrogen atom, halogen atom, alkyl group, alkoxy group, cyano group, nitro group, acyl group, substituted amino group, unsubstituted amino group, substituted aryl group, unsubstituted aryl group, substituted hetero Ventilation, and unsubstituted heterocyclic groups.

As Y ₁ , Y _{2 which} is a substituent of Formula 1, 2 according to the present invention,

And the like, and there may be numerous examples other than the above-described structure.

In addition, as Y ₃ which is a substituent of the formula (3) according to the present invention,

And the like, and there may be numerous examples other than the above-described structure.

R ₄₂ to R ₅₇ shown in the substituent examples are hydrogen atom, halogen atom, alkyl group, alkoxy group, cyano group, nitro group, acyl group, substituted amino group, unsubstituted amino group, substituted aryl group, unsubstituted aryl group, substituted hetero Selected from the group consisting of ventilated and unsubstituted heterocyclic groups.

Formula 1 to Formula 3 according to the present invention is a high molecular compound containing at least two amine groups having excellent hole transport properties in a repeating unit, and is a new structure which is not known until now. That is, Chemical Formulas 1 to 3 of the present invention are composed of secondary / tertiary amines including one or more carbazole groups, and thus have excellent hole injection / transport characteristics. In addition, in Formulas 1 to 3, at least one of the two or more amines has a short conjugation length since the amine is included in the polymer backbone, thereby increasing the band gap and enabling blue light emission. In addition, in the case of phosphorescent materials, which are emerging in recent years, light emission occurs in a triplet state, a conventional host material used for fluorescent OLED devices (light emission in a singlelet state) can be applied to phosphorescent devices. none. That is, there is a need for a material capable of energy transfer from the triplet state to the phosphorescent dopant. Conventionally, fluorene-based materials have been applied as host materials for phosphorescent devices, but energy levels in the triplet state are not suitable for interacting with energy levels of the dopant, and carbazole-based materials have been reported instead. . Therefore, the novel high molecular compound according to the present invention has an advantage that it can also function as a host material for phosphorescent devices because it contains a carbazole group.

When the present inventors synthesized and evaluated the polymer compounds having various structures as examples of Formula 1 and Formula 2, the electron affinity was found in the range of 1.97 to 2.59 eV according to the linking group and the substituent, and the ionization potential ( ionization potential) ranged from 5.1 ~ 5.64eV and bandgap energy was 3.05 ~ 3.32eV. In addition, the present inventors synthesized and evaluated the polymer compound of various structures as an example of the formula (3), the electron affinity appeared in the region of 2.5 ~ 1.9 eV according to the substituent, the ionization potential is 5.5 ~ 5.0 eV, band gap energy Was 2.9 ~ 3.3eV.

From the above formulas (1) to (3) according to the present invention, as well as the application as a blue light emitting material according to the substituents and linking groups, hole injection / transport layer (hole injection / transport port), phosphorescent element host material (for red, green, blue) It was confirmed that it can be applied as. Of course, when various substituents are applied to Formulas 1 to 3 of the present invention, the range of electron affinity, ionization potential, and band gap energy will be wider.

In another aspect of the present invention, there is provided a polymer electroluminescent device comprising a compound represented by Formula 1 to Formula 3.

The polymer electroluminescent device according to the present invention is a polymer electroluminescent device of a form in which a first electrode, an organic material layer including one or more layers including a light emitting layer, and a second electrode are sequentially stacked, wherein at least one layer of the organic material layer is It includes at least one compound selected from the group consisting of a compound represented by the formula (1), a compound represented by the formula (2), a compound represented by the formula (3).

In the polymer electroluminescent device according to the present invention, the organic material layer comprises a hole transport layer, the hole transport layer is composed of a compound represented by the formula (1), a compound represented by the formula (2), a compound represented by the formula (3) At least one compound selected from the group.

In the polymer electroluminescent device according to the present invention, the light emitting layer is composed of a binary compound of a host and a phosphorescent dopant or a fluorescent dopant, and the host material is a compound represented by Formula 1, a compound represented by Formula 2, or Mixtures of these compounds.

In the polymer electroluminescent device according to the present invention, the organic material layer comprises an electron transport layer, the electron transport layer is composed of a compound represented by Formula 1, a compound represented by Formula 2, a compound represented by Formula 3 At least one compound selected from the group.

A detailed embodiment of the polymer electroluminescent device including the compound represented by Chemical Formulas 1 to 3 of the present invention will be described with reference to FIG. 2. First, a transparent electrode (anode) pattern is formed as a first electrode on a substrate, and then a bank structure for distinguishing red, green, and blue regions is formed. The formation of such a bank is a prior art Republic of Korea Patent Publication No. 10-2004-0012484, Publication No. 10-2003-0055121, Registration No. 10-0424731, Registration No. 10-0436303, Registration No. 10 It is well represented in -0426680.

The transparent electrode is mainly used ITO having both electrical conductivity and transparency at the same time. In addition, the substrate may be provided with a thin film transistor (TFT), and when the TFT is provided, an active matrix type electroluminescent device may be manufactured, and when the TFT is not provided, the passive matrix may be passive. type) Electroluminescent device can be manufactured. In the present invention, either an active drive type or a passive drive type may be used. In addition, the substrate can be used, such as glass, plastic, metal foil, and is not particularly limited.

The hole injection / transport layer is not particularly limited, and it is preferable that the material has a good interfacial property with the transparent electrode while serving as a smoothing function on the surface of the transparent electrode and can easily give electrons to the transparent electrode. A process of first printing a water-insoluble or water-dispersible hole injection / transport layer ink on a substrate having a transparent electrode pattern and a bank formed thereon is required. The ink for the hole injection / transport layer is discharged through an inkjet head to each pixel (top of the anode). The ink of the hole injection / transport material is disposed. Of course, it is also possible by a spin coating method. After the printing is completed, the hole injection / transport layer is completed by first drying in vacuum and removing the solvent through heat treatment for several minutes at 200 ° C. atmospheric pressure. The ink for hole injection / transport layer used at this time is poly (3,4-ethylene dioxythiophene): poly (4-styrenesulfonate) [poly (3,4-ethylene dioxythiophene): poly (4 In addition to poly (3,4-ethylenedioxythiophene): poly (4-styrenesulfonate): polyglycol (glycerol) [poly (3,4-ethylenedioxythio-phene): poly ( 4-styrenesulfonate): polyglycol (glycerol), G-PEDOT], polyaniline camphor sulfonic acid (PANI: CSA), poly (4,4'-dimethoxy bitophene) [poly (4,4 '-dimethoxy bithophene), PDBT] and the like can be used.

After the hole injection / transport layer is completed, a process of forming a light emitting layer by discharging a polymer ink such as an electroluminescent ink (eg, a red light emitting ink, a green light emitting ink, or a blue light emitting ink) having electroluminescent properties from an inkjet head is followed. Similar to the injection / transport layer formation, the formation of the electroluminescent layer is completed by drying the discharged substrate.

The electroluminescent ink used in the present invention may be used as a blue light emitting material alone as a compound represented by the formula (1) to (3) according to the present invention, and also using the compound represented by the formula (1) to (3) as a host material The compound represented by Formula 5 may be used as a blue light emitting ink by using as a dopant. The blue light emitting dopant is numerous in addition to the compound represented by the following formula (5).

In addition, when the compound represented by Formula 1 to Formula 3 of the present invention is used as a host material and the compound represented by Formula 6 as a dopant, it may be used as a red light emitting ink. The red light emitting dopant is innumerable in addition to the compound represented by the following formula (6).

In addition, when the compound represented by Formula 1 to Formula 3 of the present invention is used as a host material, and the compound represented by the following Formula 7 is used as a dopant, a green light emitting ink can be realized, and the green light emitting dopant is represented by the following Formula 7. In addition to the compounds shown are numerous.

In the polymer electroluminescent device according to the present invention, an electron transport layer may be formed on the light emitting layer. That is, when the low molecular weight material, such as the compound represented by the following formula (8), is formed to a thickness of about 200 to 400 Pa by vacuum deposition, the efficiency of the electroluminescent device increases. Of course, the formation of the electron transport layer in the electroluminescent device may be omitted.

An electron injection layer is formed on the electron transport layer, and LiF is used a lot in industry. A cathode, which is a second electrode, is formed on the electron injection layer. A single metal such as Al, Ma, Ag, etc. may be used as the cathode, and LiF / Ca (or Ba) / Al structure is formed by forming several tens of nm of Ca, Ba, etc., between the electron injection layer LiF and Al, the cathode electrode. It also utilizes the cathode of. After the cathode formation, the polymer electroluminescent device is completed through an encapsulation process to block the atmosphere.

As described above, the structural features of the compounds represented by Chemical Formulas 1 to 3 according to the present invention and the method of implementing the polymer electroluminescent device using the same are described, but the present invention is not limited to the above-described range. That is, according to the types of substituents and linking groups in the formula (1) and (2), it is also possible to apply to the polymer light emitting material, RGB host material, charge injection / transport material.

Hereinafter, the method for preparing the novel compound and the method for implementing the polymer electroluminescent device according to the present invention will be embodied by examples, but the present invention is not limited to the following examples, which are only presented to aid the understanding of the present invention.

<Example 1>

As a specific example of the compound represented by the formula (1), poly [ N- (4- (2-ethylhexyloxy) -3,5-dimethylene-phenyl) -carbazole-alt-aniline represented by the following formula (9) ] (poly [N - (4- (2-ethylhexyloxy) -3,5-dimethylene-phenyl) - carbazole- alt - aniline]) was synthesized.

An outline of the synthesis process of the compound represented by Formula 9 is shown in Scheme 1 below.

The synthesis process is summarized with reference to Scheme 1 as follows.

First, the monomer N- [4- (2-ethylhexyloxyl) -3,5-dibromo-methylenephenyl] -carbazole ( N- [4- (2-ethylhexyloxyl) -3,5-dibromo-methylenephenyl] -carbazole) (hereinafter referred to as 'monomer 4') was synthesized in three steps. First, as a first step, 4-bromo-2, in suspension solution prepared by vigorous stirring by adding potassium hydroxide (0.06 mol) to 200 ml of acetonitrile under a nitrogen stream for 30 minutes. 50 ml of acetonitrile in which 6-dimethyl-phenol (0.02 mol) was dissolved was added slowly. Then 2-ethylhexyl bromide (0.02 mol) was added followed by reflux for 48 hours. After the reaction, potassium hydroxide was filtered off, the solvent was removed, and the crude product was washed with water and dried under MgSO ₄ . As a hexane eluent, 5-bromo-2- (2-ethylhexyloxyl) -1,3-dimethyl benzene (Compound ( 4 ) of Scheme 1) was obtained by column chromatography. (Yield 63%). ¹ H NMR (300 MHz in CDCl ₃ ): δ 7.15 (2H, Ar- H ), 3.6 (2H, -OC H _2- ), 2.26 (6H, Ar-C H ₃ ), 2.18 (9H, -C H -, -C H ₂ ), 0.91 (6H, -C H ₃ ).

In the second step, 5-bromo-2- (2-ethylhexyloxyl) -1,3-dimethyl benzene (112.79 mmol), carbazole (15.24 mmol), K ₃ PO ₄ as compound ( 4 ) of Scheme 1 (26.72 mmol), CuI (0.64 mmol) and trans-1,2-cyclohexanediamine (2.54 mmol) were used. The reaction mixture was refluxed for 48 hours and then purified to give pure N- [4- (2-ethylhexyloxyl) -3,5-dimethyl-phenyl] -carbazole (Compound ( 5 ) of Scheme 1). (Yield 25%). ¹ H NMR (300 MHz in CDCl ₃ ): δ 7.38 (4H, Ar- H ), 7.26 (4H, Ar- H ), 7.16 (2H, Ar- H ), 3.6 (2H, -OC H _2- ), 2.30 (6H , Ar-C H ₃ ), 2.18 (9H, -C H- , -C H _2- ), 0.91 (6H, -C H ₃ ).

As a third step, the compound of Scheme 1 N at room temperature, (5) - [4- (2-ethyl-hexyl-oxyl) -3,5-dimethyl-phenyl] carbazole (3.68mmol), NBS (8.09mmol) and BPO (0.1618 mmol) was dissolved in CCl ₄ . Reaction and purification were performed using the method used in the general bromination (bromination) to obtain a pure monomer 4 and its ¹ H NMR analysis (spectrum) is shown in FIG. (Yield 45%). ¹ H NMR (300 MHz in CDCl ₃ ): δ 7.48 (4H, Ar- H ), 7.45 (4H, Ar- H ), 7.35 (2H, Ar- H ), 4.6 (4H, C H ₂ Br-), 3.96 (2H, -OC H _2- ), 2.25 (9H, -C H- , -C H _2- ), 0.95 (6H, -C H ₃ ).

Thereafter, the compound of Formula 9 was synthesized using the monomer 4. Specifically, the monomer 4 (2.60 mmol) and aniline (2.60 mmol) were dissolved in 30 ml of toluene. NaO- t -Bu (7.8mmol), with _{Pd 2 (dba) 3 (0.066mmol} ) and _{P (t-Bu) 3 (} 0.4mmol) was added at room temperature. The reaction proceeded at 100 ° C. for 48 hours. After cooling to room temperature, ammonia water (50 ml) was added to stop the reaction, and the reaction was extracted with CHCl ₃ . The organic layer was concentrated and then reprecipitated with CHCl ₃ / methanol. The reaction was filtered and dried in vacuo to afford a polymer. Characterization of the polymerized compound of formula 9 was carried out and the results are summarized in Table 1 below.

division PDI T d (° C) T g (° C) λmax, UV (nm) λmax, PL (nm) Band gap (eV) HOMO (eV) LUMO (eV) Formula 9 1.56 327 --- 304 451 3.05 -5.64 -2.59

An absorption spectrum and a blue emission spectrum of the compound of Formula 9 are shown in FIG. 4.

The conditions for the preparation of PHOLED (Phosphorescent OLED) constituting EML by using the synthesized Formula 9 as a host matrix and applying the compound Ir (ppy) ₃ of Formula 7 as a dopant as a green phosphor, are shown in Table 2 below. Summarized in

Stratified Ingredients and Methods HIL PEDOT ( 1% by weight in IPA ) Spin coated at 1000 rpm for 20 seconds and dried on a hot plate at 80 ° C for 10 minutes EML Compound of formula 9 + spin coated at 10 wt% Ir ( ppy ) ₃ ] 1200rpm in [1,1,2,2 -tetrachloroethane for 10 seconds, dried for 10 minutes on a hot plate at 100 ° C HBL BAlq (30 nm ) thermal evaporation at 140 ° C ETL Thermal Deposition at Alq ₃ (20 nm ) 200 ℃ EIL LiF (1 nm) Cathode electrode Al  (120 nm )

Green light emission (color coordinates x = 0.31, y = 0.50) having the highest emission peak at 528 nm was observed with respect to the PHOLED manufactured under the above conditions, and blue, which is an inherent emission region of the compound of Formula 9, was not observed. This green emission spectrum is shown in FIG. 5. This is because the electrons and holes injected into the compound of Formula 9 can be effectively transferred to Ir (ppy) ₃ as a dopant in the electrode, whereby the compound of Formula 9 has a sufficient function as a host material for phosphorescent devices.

<Example 2>

As a specific example of Formula 2, poly [( N- (2-ethylhexyloxy) -phenyl) -3,6-carbazole-alt-aniline] (poly [( N- (2) -ethylhexyloxy) -phenyl) -3,6-carbazole- alt -aniline]) was synthesized.

A schematic of the synthesis process of the compound represented by Chemical Formula 10 is shown in Scheme 2 below.

The synthesis process is summarized with reference to Scheme 2 as follows.

First, N- (2-ethylhexyloxylphenyl) -3,6-dibromocarbazole (hereinafter referred to as 'monomer 2') was synthesized as a monomer, and the synthesis was composed of three steps. In the first step, 4-bromophenol (1.5 mmol) was dissolved in 100 ml of acetonitrile and then K ₂ CO ₃ (4.5 mmol) was added. After reacting for 30 minutes under a nitrogen stream at 60 ° C, a solution of 2-ethylhexyl bromide (4.5 mmol) in 25 ml of acetonitrile was slowly added dropwise. After reacting for 48 hours, after removing K ₂ CO ₃ and solvent, the crude product was washed with water and dried using MgSO ₄ . Silica column chromatography using hexane as eluent gave pure 4-bromo- (2-ethylhexyloxyl) -benzene (Compound ( 1 ) in Scheme 2). (Yield 66%). ¹ H NMR (300 MHz in CDCl ₃ ): δ 7.33 (2H, Ar- H ), 6.79 (2H, Ar- H ), 3.79 (2H, -OC H _2- ), 1.71 (1H, -C H- ) , 1.29-1.46 (8H, -C H _2- ), 0.91 (6H, -C H ₃ ) ¹³ C NMR (300 MHz in CDCl ₃ ): 158.4, 132.0, 116.2, 112.4, 70.6, 39.2, 30.4, 29.0, 23.8, 23.0, 14.1, 11.1.

In the second step, 4-bromo- (2-ethylhexyloxyl) -benzene (56.4 mmol), carbazole (7.6 mmol), K ₃ PO ₄ (13.4 mmol), CuI (0.32), which is Compound ( 1 ) of Scheme 2 mmol) and trans-1,2-cyclo-hexane-diamine (1.27 mmol) to give pure N- (2-ethylhexyloxylphenyl) -carbazole (Compound 2 in Scheme 2 ). (Yield 29%). ¹ H NMR (300 MHz in CDCl ₃ ): δ 8.15 (2H, Ar- H ), 7.44 ~ 7.24 (8H, Ar- H ), 7.08 (2H, Ar- H ), 3.94 (2H, -OC H _2- ), 1.77 (1H, -C H- ), 1.26-1.57 (8H, -C H _2- ), 0.91 (6H, -C H ₃ ) ¹³ C NMR (300 MHz in CDCl ₃ ): 158.6, 141.3, 129.9 , 128.5, 125.8, 123.0, 120.2, 119.5, 115.5, 109.7, 70.8, 39.2, 30.4, 29.0, 23.8, 23.0, 14.1, 11.1.

As a third step, N- (2-ethylhexyloxylphenyl) -carbazole (2.43 mmol), which is Compound ( 2 ) of Scheme 2, was dissolved in 60 ml of THF, and then cooled to 0 ° C. NBS (N-bromosuccimide) (4.86 mmol) was added in small portions, and then the temperature was raised to room temperature, followed by overnight. After removing the solvent, the reaction was extracted with diethyl ether and water. After drying the organic layer under MgSO ₄ Monomer 2 was obtained by column chromatography using hexane / methylene chloride eluent. (Yield 59%). ¹ H NMR (300 MHz in CDCl ₃ ): δ 8.18 (2H, Ar- H ), 7.47 (2H, Ar- H ), 7.36 (2H, Ar- H ) 7.16 (2H, Ar- H ), 7.08 (2H , Ar- H ), 3.94 (2H, -OC H _2- ), 1.77 (1H, -C H- ), 1.26-1.57 (8H, -C H _2- ), 0.91 (6H, -C H ₃ ); ¹³ C NMR (300 MHz in CDCl ₃ ): 159.1, 140.3, 129.2, 128.9, 128.3, 123.6, 123.1, 115.7, 112.7, 111.5, 70.8, 39.3, 30.5, 29.1, 23.8, 23.1, 14.1, 11.1. ¹ H-NMR spectrum of Monomer 2 is shown in FIG. 6.

Thereafter, the compound of Formula 10 was synthesized using the monomer 2. Specifically, the monomer 2 (2.60 mmol) and aniline (2.60 mmol) were dissolved in 30 ml of toluene. NaO- t -Bu (7.8mmol), with _{Pd 2 (dba) 3 (0.066mmol} ) and _{P (t-Bu) 3 (} 0.4mmol) was added at room temperature. The reaction proceeded at 100 ° C. for 48 hours. After cooling to room temperature, ammonia water (50 ml) was added to stop the reaction, and the reaction was extracted with CHCl ₃ . The organic layer was concentrated and then reprecipitated with CHCl ₃ / methanol. The reaction was filtered and dried in vacuo to give a polymer of formula (10). Characterization of the polymerized compound of Formula 10 was carried out and the results are summarized in Table 3 below.

division PDI T d (℃) T g (℃) λmax, UV (nm) λmax, PL (nm) Band gap (eV) HOMO (eV) LUMO (eV) Formula 10 1.67 415 --- 300 445 3.14 -5.10 -1.96

An absorption spectrum and a blue emission spectrum of the compound of Formula 10 are shown in FIG. 7.

Using the compound of Formula 10 as a host matrix and applying the green phosphor, Ir (ppy) ₃ as a dopant, the conditions for fabricating the PHOLED constituting the EML are summarized in Table 4 below.

Stratified Ingredients and Methods HIL PEDOT ( 1% by weight in IPA ) Spin coated at 1000 rpm for 20 seconds and dried on a hot plate at 80 ° C for 10 minutes EML Compound (10 ) spin coated for 10 seconds at 8 wt% Ir ( ppy ) ₃ ] 1000 rpm in [1,1,2,2 -tetrachloroethane for 10 seconds, dried for 10 minutes on a hot plate at 100 ℃ HBL BAlq (30 nm ) thermal evaporation at 140 ° C ETL Thermal Deposition at Alq ₃ (20 nm ) 200 ℃ EIL LiF (1 nm) Cathode electrode Al  (120 nm )

Green luminescence (color coordinates x = 0.33, y = 0.43) having the highest emission peak at 512 nm was observed from the PHOLED fabricated under the above conditions, and blue, which was an inherent emission region of the compound of Formula 10, was not observed. This green emission spectrum is shown in FIG. 8. This is because electrons and holes injected into the compound of Formula 10 can be effectively transferred to Ir (ppy) ₃ as a dopant in the electrode, whereby the compound of Formula 10 was found to function sufficiently as a host material for phosphorescent devices.

In addition, instead of the green dopant Ir (ppy) ₃ , the red phosphorescent dopant IR-PIQC-1 <2 phenyl isoquinoloine and one 2-acetyl-1,3-cyclohexanedione (2- a phosphorescent red dopant in which an acetyl-1,3-cyclohexanedione ligand is complexed with Ir; DU Kim et. al, Current Applied Physics , 6, 805-807, 2006> was applied to fabricate the PHOLED device constituting the EML. Table 5 summarizes the fabrication conditions.

Stratified Ingredients and Methods HIL PEDOT ( 1% by weight in IPA ) Spin coated at 1000 rpm for 20 seconds and dried on a hot plate at 80 ° C for 10 minutes EML Spin coating for 10 seconds at 1000 rpm of 10 % by weight of a compound of formula 10 + [1,1,2,2 -tetrachloroethane at 10 rpm by weight of IR - PIQC -1] and dried for 10 minutes on a hot plate at 100 ° C. HBL BAlq (30 nm ) thermal evaporation at 140 ° C ETL Thermal Deposition at Alq ₃ (20 nm ) 200 ℃ EIL LiF (1 nm) Cathode electrode Al  (120 nm )

Red luminescence having the highest luminescence peak at 620 nm and green luminescence near 500 nm resulting from ETL Alq3 were simultaneously obtained from the red PHOLED fabricated under the above conditions, which is shown in FIG. 9. The green light emission is because the thickness of the ETL is so thick that excitons are formed not only in the light emitting layer but also in the ETL. The peak of the red region corresponding to 620 nm is because the electrons and holes injected into the compound of Formula 10 can be effectively transferred to the dopant IR-PIQC-1, similar to the green PHOLED, so that the compound of Formula 10 is a host material for phosphorescent devices. It was found that it functions as enough. In addition, by controlling the thickness of the ETL, it was found that the white light emission is possible by implementing red and green simultaneously.

<Example 3>

As another specific example of Formula 2, poly [bis (6- N- (4- (2-ethylhexyloxy) -phenyl) -carbazol-3-yl) -alt-aniline represented by Formula 11 poly [bis (6- N - ( 4- (2-ethylhexyloxy) -phenyl) - carbazole-3-yl) - alt -aniline a) it was synthesized.

A schematic of the synthesis process of the compound represented by Chemical Formula 11 is shown in Scheme 3 below.

The synthesis process is summarized with reference to Scheme 3 as follows.

First, bis [6-bromo- N- (2-ethylhexyloxylphenyl) -carbazol-3-yl (hereinafter referred to as 'monomer 3') was synthesized as a monomer. As a first step, N- (2-ethylhexyloxylphenyl) -carbazole (2.9 mmol), which is the compound ( 2 ) of Scheme 2 synthesized in Example 2, was dissolved in 13 ml of chloroform, followed by FeCl ₃ (8.3 mmol). ) Was added. After stirring for 24 hours at room temperature, 13 ml of water were added. The organic layer was separated, dried over MgSO ₄ , filtered and concentrated. Pure bis [ N- (2-ethylhexyloxylphenyl) -carbazol-3-yl] (Compound ( 3 ) in Scheme 3) was obtained by column chromatography using hexane / dichloromethane eluent. (Yield 67%). ¹ H NMR (300 MHz in CDCl ₃ ): δ 8.44 (2H, Ar- H ), 8.22 (2H, Ar- H ), 7.75 (2H, Ar- H ), 7.49-7.25 (10H, Ar- H ), 7.14 (6H, Ar- H ), 4.21 (4H, -NC H _2- ), 2.05 (2H, -C H- ), 1.50-1.25 (16H, -C H _2- ), 0.91 (12H, -C H ₃ ); ¹³ C NMR (300 MHz in CDCl ₃ ): 158.7, 141.8, 140.5, 134.1, 130.1, 128.4, 125.9, 123.6, 123.3, 120.3, 119.6, 118.8, 115.6, 109.9, 70.8, 39.4, 30.5, 29.1, 23.9, 23.1 , 14.1, 11.2.

Both as a second step, the compound of the scheme 3 in THF of 70ml (3) was dissolved in bis [N - - (2- ethyl-hexyl-oxyl-phenyl) carbazol-3-yl] (2.87mmol), it was cooled to 0 ℃ . NBS (5.74 mmol) was added in small portions, and the temperature was raised to room temperature to overnight. THF was removed and the reaction was extracted with diethyl ether and water. After drying the organic layer under MgSO ₄ , Monomer 3 was obtained by column chromatography using hexane / dichloromethane eluent. (Yield 86%). ¹ H NMR (300 MHz in CDCl ₃ ): δ 8.25 (2H, Ar- H ), 7.65 (2H, Ar- H ), 7.40-7.27 (10H, Ar- H ), 7.12 (2H, Ar- H ), 7.02 (4H, Ar- H ), 4.21 (4H, -NC H _2- ), 2.05 (2H, -C H- ), 1.50-1.25 (16H, -C H _2- ), 0.91 (12H, -C H ₃ ); ¹³ C NMR (300 MHz in CDCl ₃ ): 158.8, 140.8, 140.4, 134.1, 129.4, 128.6, 128.3, 126.3, 124.9, 123.0, 122.6, 118.8, 115.6, 112.4, 111.3, 110.2, 70.7, 39.4, 30.5, 29.7 , 23.8, 23.1, 14.1, 11.2. ¹³ C-NMR spectrum of the monomer 3 is shown in FIG. 10.

Thereafter, the compound of Formula 11 was synthesized using the monomer 3. Specifically, monomer 3 (2.60 mmol) and aniline (2.60 mmol) were dissolved in 30 ml of toluene. NaO- t -Bu (7.8mmol), with _{Pd 2 (dba) 3 (0.066mmol} ) and _{P (t-Bu) 3 (} 0.4mmol) was added at room temperature. The reaction proceeded at 100 ° C. for 48 hours. After cooling to room temperature, ammonia water (50 ml) was added to stop the reaction, and the reaction was extracted with CHCl ₃ . The organic layer was concentrated and then reprecipitated with CHCl ₃ / methanol. The reaction was filtered and dried in vacuo to give a polymer of formula (11). Characterization of the polymerized compound of Formula 11 was performed and the results are summarized in Table 6 below.

division PDI T d (℃) T g (℃) λmax, UV (nm) λmax, PL (nm) Band gap (eV) HOMO (eV) LUMO (eV) Formula 11 1.1 409 121 305 433 3.32 -5.29 -1.97

The absorption spectrum and blue emission spectrum of the compound of Formula 11 are shown in FIG. 11.

Using the compound of Formula 11 as a host matrix and applying the green phosphor, Ir (ppy) ₃ as a dopant, the conditions for fabricating the PHOLED constituting the EML are summarized in Table 7 below.

Stratified Ingredients and Methods HIL PEDOT ( 1% by weight in IPA ) Spin coated for 10 minutes at 1000 rpm for 10 seconds and 2000 rpm for 10 seconds on a hot plate at 80 ° C EML Compound (11) + spin coated at 10 wt% Ir ( ppy ) ₃ ] 1200rpm in [1,1,2,2 -tetrachloroethane for 10 seconds, dried for 10 minutes on a hot plate at 100 ℃ HBL BAlq (30 nm ) thermal evaporation at 140 ° C ETL Thermal Deposition at Alq ₃ (20 nm ) 200 ℃ EIL LiF (1 nm) Cathode electrode Al  (120 nm )

Green luminescence (color coordinates x = 0.28, y = 0.39) having the highest luminescence peak at 508 nm was observed from the PHOLED manufactured under the above conditions, and blue, which was an inherent luminescence region of the compound of Formula 11, was not observed. This green emission spectrum is shown in FIG. 12. This is because the electrons and holes injected into the compound of Formula 11 can be effectively transferred to the dopant Ir (ppy) ₃ in the electrode, and thus the compound of Formula 11 has a sufficient function as a host material for phosphorescent devices.

In addition, instead of the green dopant Ir (ppy) ₃ , a red phosphorescent dopant, IR-PIQC-1, was used to fabricate a PHOLED device constituting the EML. Table 8 summarizes the fabrication conditions.

Stratified Ingredients and Methods HIL PEDOT ( 1% by weight in IPA ) Spin coated for 10 minutes at 1000 rpm for 10 seconds and 2000 rpm for 10 seconds on a hot plate at 80 ° C EML Compound of formula 11 + spin coated for 10 seconds at 10 wt% IR - PIQC -1] 1200 rpm in [1,1,2,2 -tetrachloroethane for 10 seconds, dried for 10 minutes on a hot plate at 100 ℃ HBL BAlq (30 nm ) thermal evaporation at 140 ° C ETL Thermal Deposition at Alq ₃ (20 nm ) 200 ℃ EIL LiF (1 nm) Cathode electrode Al  (120 nm )

Red luminescence having the highest luminescence peak at 624 nm and green luminescence near 500 nm originating from Alq3, which is an ETL, were simultaneously obtained from the red PHOLED fabricated under the above conditions, which is shown in FIG. 13. The green light emission is because the thickness of the ETL is so thick that excitons are formed not only in the light emitting layer but also in the ETL. The peak of the red region corresponding to 624 nm is because the electrons and holes injected into the compound of Formula 11 can be effectively transferred to the dopant IR-PIQC-1, similar to the green PHOLED, so that the compound of Formula 11 is a host material for phosphorescent devices. It was found that it functions as enough. In addition, by controlling the thickness of the ETL, it was found that the white light emission is possible by implementing red and green simultaneously.

<Example 4>

As a specific example of Formula 3, poly [ N- (4-aminophenyl) -carbazole-alt- N- (2-ethylhexyl) -3,6-carbazole] represented by Formula 12 below (poly [ N -(4-aminophenyl) -carbazole- alt - N- (2-ethylhexyl) -3,6-carbazole]) was synthesized.

A schematic of the synthesis process of the compound represented by Chemical Formula 12 is shown in Scheme 4 below.

The synthesis process with reference to Scheme 4 is as follows.

First, N- (4-aminophenyl) -carbazole (compound ( 6 ) of Scheme 4) was synthesized as a monomer, and prepared in a two-step reaction. In the first step, 4-iodonitetrobenzene (20 mmol), carbazole (15.24 mmol) and K ₃ PO ₄ (42 mmol) were added to 100 ml 1,4-dioxane at room temperature. After stirring for 30 minutes, CuI (0.4 mmol) and trans-1,2-cyclohexanediamine (2.4 mmol) were added to the reaction. The reaction was then refluxed for 24 hours. After the reaction was completed, the reaction was cooled to room temperature and filtered. After filtration, 1,4-dioxane was evaporated and ethyl acetate was added. The reaction was washed with distilled water and then dried under MgSO ₄ . Column chromatography (hexane: ethyl acetate = 9: 1) gave N- (4-nitrophenyl) -carbazole. (Yield 98%). ¹ H-NMR (300 MHz in CDCl ₃ ): δ 8.58 (1H, Ar- H ), 8.55 (1H, Ar- H ), 8.26 (1H, Ar- H ), 8.23 (1H, Ar- H ), 8.01 ( 1H, Ar- H ), 7.98 (1H, Ar- H ), 7.60 (1H, Ar- H ), 7.58 (1H, Ar- H ), 7.51-7.45 (2H, Ar- H ), 7,39-7.33 (2H, Ar- H); ¹³ C-NMR (300 MHz in CDCl ₃ ): δ 144.35, 140.70, 131.85, 127.94, 127.34, 126.36,124.82, 121.91, 121.33, 110.65; GC-MS: m / z = 288 (m +).

In the second step, N- (4-nitrophenyl) -carbazole (5 mmol) and SnCl ₂ (30.4 mmol) were added to 15 ml ethanol and heated at 70 ° C. for 4 hours. After the reaction, the reaction was cooled to room temperature, and then 1M sodium hydroxide solution was added until it became alkaline. The organic layer extracted with ethyl acetate was washed with brine solution, dried under MgSO ₄ and the solvent was evaporated. N- (4-aminophenyl) -carbazole (Compound ( 6 ) of Scheme 4) was synthesized by recrystallization from ethanol, and the result of ¹ H-NMR analysis is shown in FIG. 14. (Yield 98%). ¹ H-NMR (300 MHz in CDCl ₃ ): δ 8.15 (1H, Ar- H ), 8.12 (1H, Ar- H ), 7.42 ~ 7.22 (8H, Ar- H ) 6.87 (1H, Ar- H ), 7.84 (1H, Ar- H), 3.81 (2H, Ar-N H 2) 13 C-NMR (300MHz in CDCl 3): δ 145.89, 141.45, 128.48, 125.70, 122.92, 120.16, 119.39, 115.89, 109.75; GC-MS: m / z = 258 (m &lt; + &gt;).

In addition, N- (2-ethylhexyl) -3,6-dibromo-carbazole (hereinafter referred to as 'monomer 1') was synthesized as a comonomer. As shown in Scheme 4, 3,6-dibromocarbazole (18.46 mmol) and K ₂ CO ₃ (37 mmol) were dissolved in DMF (20 ml), and the temperature was raised to 80 ° C. under a nitrogen stream. Thereafter, 2-ethylhexyl bromide (28 mmol) was slowly added dropwise. After complete dropping, the reaction proceeded for 16 hours. After the reaction, the mixture was extracted with diethyl ether / water and the organic layer was dried with MgSO _4, and then MgSO ₄ was removed using a filter to remove the organic solvent. Pure monomer 1 was obtained by silica column chromatography using hexane as the eluent, and ¹ HNMR analysis thereof is shown in FIG. 15. (Yield 56%). ¹ HNMR (300 MHz in CDCl ₃ ): δ 8.11 (2H, Ar- H ), 7.48 (2H, Ar- H ), 7.22 (2H, Ar- H ), 4.18 (2H, -NC H _2- ), 1.23 ˜1.44 (9H, —C H −, —C H ₂ −), 0.91 (6H, —C H ₃ ).

Compound 1 was synthesized using monomer 1 and N- (4-aminophenyl) -carbazole. N- (4-aminophenyl) -carbazole (1.30 mmol), which is Compound ( 6 ) of Scheme 4, and N- (2-ethylhexyl) -3,6-dibromo-carbazole (1.30, which is monomer 1) mmol) was dissolved in 15 ml of toluene / DMF mixed solvent. NaO- t -Bu (3.9mmol), with _{Pd 2 (dba) 3 (0.033mmol} ) and _{P (t-Bu) 3 (} 0.2mmol) was added at room temperature. The reaction proceeded at 100 ° C. for 48 hours. After cooling to room temperature, ammonia water (25 ml) was added to stop the reaction, and the reaction was extracted with CHCl ₃ . The organic layer was concentrated and then reprecipitated with CHCl ₃ / methanol. The reaction was filtered and dried in vacuo to afford a polymer. Characterization of the polymerized compound of Formula 12 was carried out and the results are summarized in Table 9 below.

division PDI T d (° C) T g (° C) λmax, UV (nm) λmax, PL (nm) Band gap (eV) HOMO (eV) LUMO (eV) Formula 12 1.54 465 --- 312 453 2.97 -5.01 -2.04

An absorption spectrum and a blue emission spectrum of the compound of Formula 12 are shown in FIG. 16.

The conditions for the preparation of PHOLED constituting the EML by using the compound of Formula 12 as a host matrix and applying compound Ir (ppy) ₃ of Formula 7 as a dopant as a green phosphor as a dopant are summarized in Table 10 below.

Stratified Ingredients and Methods HIL PEDOT ( 1% by weight in IPA ) Spin coated for 10 minutes at 1000 rpm for 20 seconds at 2000 rpm for 5 minutes on a hot plate at 80 ° C EML Compound 12 of the formula + spin coating for 10 seconds at 10% by weight of Ir ( ppy ) ₃ ] 900rpm in [1,1,2,2 -tetrachloroethane , dried for 10 minutes on a hot plate at 100 ℃ HBL BAlq (30 nm ) thermal evaporation at 140 ° C ETL Thermal Deposition at Alq ₃ (20 nm ) 200 ℃ EIL LiF (1 nm) Cathode electrode Al  (120 nm )

Green light emission (color coordinates x = 0.39, y = 0.49) having a peak emission peak at 552 nm was observed from the PHOLED fabricated under the above conditions, and blue, which is an inherent emission region of the compound of Formula 12, was not observed. This green emission spectrum is shown in FIG. 17. This is because the electrons and holes injected into the compound of Formula 12 in the electrode can be effectively transferred to the dopant Ir (ppy) ₃ , whereby the compound of Formula 12 was found to have a sufficient function as a host material for phosphorescent devices.

In addition, instead of the green dopant Ir (ppy) ₃ , a red phosphorescent dopant, IR-PIQC-1, was used to fabricate a PHOLED device constituting the EML. Table 11 summarizes the manufacturing conditions.

Stratified Ingredients and Methods HIL PEDOT ( 1% by weight in IPA ) Spin coated for 10 minutes at 1000 rpm for 20 seconds at 20 rpm at 1000 rpm for 5 minutes on a hot plate at 80 ° C. EML Compound of formula 12 + spin coated for 10 seconds at 10 wt% IR - PIQC- 1] 900 rpm in [1,1,2,2 -tetrachloroethane , dried for 10 minutes on a hot plate at 100 ° C. HBL BAlq (30 nm ) thermal evaporation at 140 ° C ETL Thermal Deposition at Alq ₃ (20 nm ) 200 ℃ EIL LiF (1 nm) Cathode electrode Al  (120 nm )

Red light emission (color coordinates x = 0.63, y = 0.36) having the highest light emission peak at 620 nm was obtained from the red PHOLED manufactured under the above conditions, which is shown in FIG. 18. The peak of the red region corresponding to 620 nm is because the electrons and holes injected into the chemical formula 12 can be effectively transferred to the dopant IR-PIQC-1 as in the case of the green PHOLED. It was found to function.

<Example 5>

As another specific example of Formula 3, poly ( N- (2-ethylhexyloxylphenyl) -3,6-carbazole-alt- N- (4-aminophenyl) -carbazole) represented by Formula 13 below (Poly ( N- (2-ethylhexyloxylphenyl) -3,6-carbazole- alt - N- (4-aminophenyl) -carbazole)) was synthesized.

A schematic of the synthesis process of the compound represented by Chemical Formula 13 is shown in Scheme 5 below.

Referring to Scheme 5 to summarize the synthesis process as follows.

Formula 2 using the monomer 2 synthesized by the method shown in Scheme 2 of Example 2, and N- (4-aminophenyl) -carbazole (compound ( 6 ) of Scheme 4) synthesized in Example 4 as a comonomer 13 compound was synthesized. The monomer 2 (1.30 mmol) and N- (4-aminophenyl) -carbazole (compound ( 6 ) of Scheme 4) (1.30 mmol) were dissolved in 15 ml of toluene / DMF mixed solvent. NaO- t -Bu (3.9mmol), with _{Pd 2 (dba) 3 (0.033mmol} ) and _{P (t-Bu) 3 (} 0.2mmol) was added at room temperature. The reaction proceeded at 100 ° C. for 48 hours. After cooling to room temperature, ammonia water (25 ml) was added to stop the reaction, and the reaction was extracted with CHCl ₃ . The organic layer was concentrated and then reprecipitated with CHCl ₃ / methanol. The reaction was filtered and dried in vacuo to afford a polymer. Characterization of the polymerized formula 13 was carried out and the results are summarized in Table 12 below.

division PDI T d (° C) T g (° C) λmax, UV (nm) λmax, PL (nm) Band gap (eV) HOMO (eV) LUMO (eV) Formula 13 1.70 464 --- 320 453 540 3.25 -5.17 -1.92

Using the compound of Formula 13 as a host matrix, Ir (ppy) ₃ , a green phosphor, was applied as a dopant, and the conditions for fabricating the PHOLED constituting the EML were summarized in Table 13 below.

Stratified Ingredients and Methods HIL PEDOT ( 1% by weight in IPA ) Spin coated for 10 minutes at 1000 rpm for 10 seconds and 2000 rpm for 10 seconds on a hot plate at 80 ° C EML Spin coating at 10 wt.% Ir ( ppy ) ₃ ] 1200 rpm in 10 wt% in [1,1,2,2 -tetrachloroethane for 10 seconds and dried on a hot plate at 100 ° C. for 10 minutes. HBL BAlq (30 nm ) thermal evaporation at 140 ° C ETL Thermal Deposition at Alq ₃ (20 nm ) 200 ℃ EIL LiF (1 nm) Cathode electrode Al  (120 nm )

Green light emission (color coordinates x = 0.38, y = 0.44) having the highest emission peak at 544 nm was observed from the PHOLED manufactured under the above conditions. This green emission spectrum is shown in FIG. 19. This is because the electrons and holes injected into the compound of Formula 13 can be effectively transferred to the dopant Ir (ppy) ₃ from the electrode, and thus the compound of Formula 13 has a sufficient function as a host material for phosphorescent devices.

In addition, instead of the green dopant Ir (ppy) ₃ , a red phosphorescent dopant, IR-PIQC-1, was used to fabricate a PHOLED device constituting the EML. Table 14 summarizes the manufacturing conditions.

Stratified Ingredients and Methods HIL PEDOT ( 1% by weight in IPA ) Spin coated for 10 seconds at 1000 rpm and 20 seconds at 1000 rpm, dried for 5 minutes on a hot plate at 80 ° C. EML Compound 13 of the formula + spin coating for 10 seconds at 10% by weight of IR - PIQC -1 900rpm in [1,1,2,2 -tetrachloroethane for 10 seconds, dried for 10 minutes on a hot plate at 100 ℃ HBL BAlq (30 nm ) thermal evaporation at 140 ° C ETL Thermal Deposition at Alq ₃ (20 nm ) 200 ℃ EIL LiF (1 nm) Cathode electrode Al  (120 nm )

Red light emission (color coordinates x = 0.63, y = 0.37) having the highest light emission peak at 640 nm was obtained from the red PHOLED fabricated under the above conditions, which is shown in FIG. 20. The peak of the red region corresponding to 640 nm is because the electrons and holes injected into the compound of Formula 13 can be effectively transferred to the dopant IR-PIQC-1 as in the case of the green PHOLED. Thus, the compound of Formula 13 is a host material for phosphorescent devices. It was found that it functions as enough.

As described above, the polymer compound according to the present invention includes at least two or more amine groups having excellent hole transport characteristics as repeating units, and in particular, at least one of the two or more amine groups is a carbazole group. Excellent electron transport characteristics

The polymer compound having a phenylcarbazole group according to the present invention is a novel polymer electroluminescent device material capable of high efficiency and high color purity, and when applied to an organic electroluminescent device, it is possible to realize a full color display with high brightness and excellent color reproduction range. In addition, OLED TVs are expected to be commercialized early by contributing to the realization of large-screen OLED TVs.

As described above, although the present invention has been described with reference to limited embodiments and drawings, the present invention is not limited to the above embodiments, and those skilled in the art to which the present invention pertains various modifications and variations from such descriptions. This is possible. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the claims below but also by the equivalents of the claims.

Claims (7)

A polymer compound having a phenylcarbazole group represented by the following formula (1). [Formula 1]

(Wherein R ₁ , R ₂ and R ₃ are the same as or different from each other, hydrogen atom, halogen atom, alkyl group, alkoxy group, cyano group, nitro group, acyl group, substituted amino group, unsubstituted amino group, substituted aryl group, unsubstituted aryl group, A substituted heterocyclic group or an unsubstituted heterocyclic group, X ₁ , and X ₂ are the same or different as the linking group, and are a group selected from an alkylene group, a substituted arylene group, an unsubstituted arylene group, a substituted hetero arylene group, an unsubstituted hetero arylene group and a linking group thereof, and Y ₁ is an aryl group having 6 to 60 carbon atoms which may have a substituent, a heteroaryl group having 3 to 60 carbon atoms which may have a substituent, or a fluorene group which may have a substituent, a and b are the same or different and are 0 or 1, n is an integer from 1 to 50,000.) A polymer compound having a phenylcarbazole group represented by the following formula (2). [Formula 2]

(Wherein R ₄ , R ₅ and R ₆ are the same as or different from each other, hydrogen atom, halogen atom, alkyl group, alkoxy group, cyano group, nitro group, acyl group, substituted amino group, unsubstituted amino group, substituted aryl group, unsubstituted aryl group, A substituted heterocyclic group or an unsubstituted heterocyclic group, X ₃ , and X ₄ are the same or different as the linking group, and are a group selected from an alkylene group, a substituted arylene group, an unsubstituted arylene group, a substituted hetero arylene group, an unsubstituted hetero arylene group, and a linking group thereof, and a combination thereof Y ₂ is an aryl group having 6 to 60 carbon atoms which may have a substituent, a heteroaryl group having 3 to 60 carbon atoms which may have a substituent, or a fluorene group which may have a substituent, c and d are the same or different and are 0 or 1, m is an integer from 1 to 50,000.) A high molecular compound having a phenylcarbazole group represented by the following formula (3). [Formula 3]

(Wherein R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are the same as or different from each other, hydrogen atom, halogen atom, alkyl group, alkoxy group, cyano group, nitro group, acyl group, substituted amino group, unsubstituted amino group, substituted aryl group , An unsubstituted aryl group, a substituted heterocyclic group, or an unsubstituted heterocyclic group, Y ₃ is an aryl group having 6 to 60 carbon atoms which may have a substituent, a heteroaryl group having 3 to 60 carbon atoms which may have a substituent, a fluorene group having a substituent, or an alkyl group having 1 to 20 carbon atoms, p is an integer from 1 to 50,000.) In the polymer electroluminescent device of the form of sequentially stacking the organic material layer and the second electrode consisting of one or more layers, including the first electrode, the light emitting layer, At least one layer of the organic material layer is a polymer electroluminescent light, characterized in that it comprises at least one compound selected from the group consisting of a compound represented by the formula (1), a compound represented by the formula (2), a compound represented by the formula (3) device. [Formula 1]

(Wherein R ₁ , R ₂ and R ₃ are the same as or different from each other, hydrogen atom, halogen atom, alkyl group, alkoxy group, cyano group, nitro group, acyl group, substituted amino group, unsubstituted amino group, substituted aryl group, unsubstituted aryl group, A substituted heterocyclic group or an unsubstituted heterocyclic group, X ₁ , and X ₂ are the same or different as the linking group, and are a group selected from an alkylene group, a substituted arylene group, an unsubstituted arylene group, a substituted hetero arylene group, an unsubstituted hetero arylene group and a linking group thereof, and Y ₁ is an aryl group having 6 to 60 carbon atoms which may have a substituent, a heteroaryl group having 3 to 60 carbon atoms which may have a substituent, or a fluorene group which may have a substituent, a and b are the same or different and are 0 or 1, n is an integer from 1 to 50,000.) [Formula 2]

(Wherein R ₄ , R ₅ and R ₆ are the same as or different from each other, hydrogen atom, halogen atom, alkyl group, alkoxy group, cyano group, nitro group, acyl group, substituted amino group, unsubstituted amino group, substituted aryl group, unsubstituted aryl group, A substituted heterocyclic group or an unsubstituted heterocyclic group, X ₃ , and X ₄ are the same or different as the linking group, and are a group selected from an alkylene group, a substituted arylene group, an unsubstituted arylene group, a substituted hetero arylene group, an unsubstituted hetero arylene group, and a linking group thereof, and a combination thereof Y ₂ is an aryl group having 6 to 60 carbon atoms which may have a substituent, a heteroaryl group having 3 to 60 carbon atoms which may have a substituent, or a fluorene group which may have a substituent, c and d are the same or different and are 0 or 1, m is an integer from 1 to 50,000.) [Formula 3]

(Wherein R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are the same as or different from each other, hydrogen atom, halogen atom, alkyl group, alkoxy group, cyano group, nitro group, acyl group, substituted amino group, unsubstituted amino group, substituted aryl group , An unsubstituted aryl group, a substituted heterocyclic group, or an unsubstituted heterocyclic group, Y ₃ is an aryl group having 6 to 60 carbon atoms which may have a substituent, a heteroaryl group having 3 to 60 carbon atoms which may have a substituent, a fluorene group having a substituent, or an alkyl group having 1 to 20 carbon atoms, p is an integer from 1 to 50,000.) The method of claim 4, wherein The organic material layer includes a hole transport layer, wherein the hole transport layer is selected from the group consisting of a compound represented by Formula 1 of claim 4, a compound represented by Formula 2 of claim 4, a compound represented by Formula 3 of claim 4 Polymer electroluminescent device comprising the above compound. The method of claim 4, wherein The light emitting layer is composed of a host and a binary compound of a phosphorescent dopant or a fluorescent dopant, and the host material is represented by Formula 1 of Claim 4, Compound represented by Formula 2 of Claim 4, and Formula 3 of Claim 4. Polymer electroluminescent device, characterized in that at least one compound selected from the group consisting of compounds. The method of claim 4, wherein The organic material layer includes an electron transport layer, The electron transport layer comprises at least one compound selected from the group consisting of a compound represented by Formula 1 of claim 4, a compound represented by Formula 2 of claim 4, a compound represented by Formula 3 of claim 4 Polymer electroluminescent device.

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