KR101258701B1 - Organic electroluminescent polymer having arylamine unit containing 9'-aryl-fluoren-9'-yl group and organic electroluminescent device manufactured using the same - Google Patents

Abstract

The present invention relates to an organic electroluminescent molecule containing an arylamine unit having a 9-aryl-fluorene-9-yl group introduced therein and an electroluminescent device using the same, and more particularly, to an arylamine used as a main chain. An arylamine unit introduced with a 9-aryl-fluorene-9-yl group which can be used as an electroluminescent polymer and a host material by substituting a fluorenyl group large enough to suppress the action and the excimer It relates to an organic electroluminescent molecule containing a main chain and an electroluminescent device using the same. The electro-promoter molecules according to the present invention can be used as host materials such as blue, green and red having high solubility, high thermal stability, high glass transition temperature, excellent color purity and high quantum efficiency.

Light emitting polymer, light emitting device, blue light emitting, quantum efficiency, fluorene, fluorenyl

Description

Organic electroluminescent polymer containing an arylamine unit having a 9'-aryl-fluorene-9'-yl group introduced therein, and an electroluminescent device using the same (9'-aryl-fluoren-9'-yl) group and organic electroluminescent device manufactured using the same}

1 is a cross-sectional view showing a structure of a general organic electroluminescent device manufactured from a substrate / anode / hole transport layer / light emitting layer / electron transport layer / cathode.

2 is a view showing the monomer synthesis reaction overview of the electro-adhesive molecules represented by M1 of the present invention.

Figure 3 is a view showing the monomer synthesis reaction overview of the electro-adhesive molecules represented by M2 of the present invention.

4 is a diagram showing the current density according to the voltage of the device manufactured by the electro-molecules produced according to the third embodiment of the present invention.

5 is a view showing the luminance according to the voltage of the device produced by the electro-molecules produced according to the third embodiment of the present invention.

6 is a view showing the luminous efficiency according to the brightness of the device produced by the electro-adhesive molecules prepared according to the third embodiment of the present invention.

7 is a diagram showing the current density according to the voltage of the element produced by the electro-adhesive molecules prepared according to another embodiment 4 of the present invention.

8 is a view showing the luminance according to the voltage of the device made of the electro-adhesive molecules prepared according to the fourth embodiment of the present invention.

9 is a view showing the luminous efficiency according to the brightness of the device manufactured by the electro-adhesive molecule prepared according to another embodiment 4 of the present invention.

[Description of Reference Numerals]

11 substrate 12 anode

13 hole transport layer 14 light emitting layer

15: electron transport layer 16: cathode

The present invention relates to an organic electroluminescent molecule containing an arylamine unit introduced with a 9'-aryl-fluorene-9'-yl group and an electroluminescence device using the same, and more particularly, 9-aryl, which has excellent thermal stability and high luminous efficiency, has excellent solubility and minimizes intermolecular interaction, by substituting a fluorine substituent large enough to inhibit intermolecular interactions and excimers in the arylamine backbone. An organic electroluminescent molecule containing an arylamine unit introduced with -fluorene-9-yl group and an electroluminescent device using the same.

Recently, due to rapid growth of optical communication and multimedia field, development into a highly information-oriented society is accelerating. Accordingly, optoelectronic devices using the conversion of photons to electrons or the conversion of electrons to photons have become the core of the modern information electronics industry. Such semiconductor optoelectronic devices can be broadly classified into electroluminescent devices, light receiving devices, and devices in which they are combined.

Until now, most displays are light-receiving, while self-emissive electroluminescence displays are fast response and self-emissive, so they don't need backlighting and have excellent brightness. It is attracting attention as a display element. Such electroluminescent devices are classified into inorganic and organic light emitting devices according to materials for forming a light emitting layer.

Organic electroluminescence (EL) is a phenomenon in which when an electric field is applied to an organic material, electrons and holes are transferred from the cathode and the anode, respectively, to be combined within the material, and the energy generated is emitted as light. The electroluminescence phenomenon of such an organic material was reported by Pope et al. In 1963 and it was reported by Tang et al. In Eastmann Kodak in 1987 that alumina-quinone A light emitting device having a multi-layered structure having a quantum efficiency of 1% and a luminance of 1000 cd / m < 2 > at 10 V or less has been reported as an element fabricated from a dye having a pi-conjugated structure. They have the advantage of easy synthesis and synthesis of various types of materials and simple color tuning. However, since the processability and the thermal stability are low and the voltage is applied, joule heat is generated in the light emitting layer and the device is broken due to the rearrangement of the molecules, which causes problems in the light emitting efficiency and the lifetime of the device. Organic electroluminescent devices have been replaced.

In this regard, FIG. 1 shows a structure of a general organic electroluminescent device made of a substrate / anode / hole transport layer / light emitting layer / electron transport layer / cathode. Referring to FIG. 1, an anode 12 is formed on the substrate 11. The hole transport layer 13, the light emitting layer 14, the electron transport layer 15, and the cathode 16 are sequentially formed on the anode 12. Here, the hole transport layer 13, the light emitting layer 14, and the electron transport layer 15 are organic thin films made of an organic compound. The driving principle of the organic electroluminescent device of the above structure is as follows:

When a voltage is applied between the anode 12 and the cathode 16, holes injected from the anode 12 are transferred to the light emitting layer 14 via the hole transport layer 13. On the other hand, electrons are injected into the light emitting layer 14 from the cathode 16 via the electron transport layer 15, and carriers are recombined in the light emitting layer 14 to generate excitons. This exciton is changed from the excited state to the ground state, whereby the fluorescent molecules of the light emitting layer emit light to form an image. The organic electroluminescent device driven on the principle described above is classified into a polymer organic electroluminescent device and a low molecular organic electroluminescent device according to the molecular weight of the material for forming an organic film.

In general, in the case of using a low molecule in forming the organic film, the low molecule is easy to purify and can almost eliminate impurities, and excellent in luminescence properties. However, there is a problem that inkjet printing or spin coating is not possible and heat resistance is poor, which deteriorates or re-crystallizes due to driving heat generated when the device is driven. On the other hand, when the polymer is used to form the organic film, the energy level is separated into the conduction band and the electrical appliance diagram by the superposition of the π-electron wave function in the polymer backbone, and the band gap energy corresponding to the energy difference is used. The semiconducting properties of the polymer are determined and full color can be achieved. Such polymers are called π-conjugated polymers.

An electroluminescent device using poly (p-phenylenevinylene) (PPV), a polymer having conjugated double bonds, was first introduced in 1990 by a team of professors from RH Friend at the University of Cambridge, UK. After being announced, researches using organic polymers have been actively conducted. The polymer is superior in heat resistance to low molecular weight, and ink-jet printing and spin coating are possible, which facilitates enlargement of the display device. By introducing various suitable substituents, polyphenylenevinylene (PPV) derivatives, polythiophene (Pth) derivatives, and the like, which can improve processability and express various colors, have been reported. However, as materials such as polyphenylenevinylene derivatives and polythiophene derivatives, high efficiency red and green light emitting polymer materials can be obtained among the three primary colors of light, but high efficiency blue light emitting polymer materials can be obtained. it's difficult. In addition, polyphenylene derivatives, polyfluorene derivatives, and the like have been reported as blue light emitting polymer materials. Polyphenylene has high oxidation stability and thermal stability, but has a disadvantage of low luminous efficiency and poor solubility.

With respect to the polyfluorene derivatives, the prior art is as follows:

US Pat. No. 6,255,449 discloses 9-substituted-2,7-dihalofluorene compounds, and oligomers and polymers thereof, suitable as light emitting materials, such as light emitting layers or carrier transport layers of light emitting diodes.

US Patent Nos. 6,309,763 and 6,605,373 introduce electroluminescent copolymers containing florin groups and amine groups in repeat units. According to the '763 patent, such a copolymer is useful as a light emitting layer or a hole transporting layer of an electroluminescent device.

U.S. Patent No. 6,630,566 discloses a polymer containing N, P, S, AS or SE useful as a light emitting polymer, specifically a polymer containing repeating units of triarylamine. U.S. Patent No. 6,887,973 discloses a polymer containing anions There is disclosed a electroluminescent polymer containing a fluorene or phenylene repeating unit and a triarylamine unit such that the transferring material and the cation transferring material are present in one molecule and the first and second band gaps of different properties are present. In addition, Japanese Patent Laid-Open No. 2003-00199203 discloses an arylamine derivative having a fluorene skeleton.

As described above, researches using polyfluorene derivatives as active blue molecules have been actively conducted. However, minimization of interaction between excitons produced in one molecule and excitons in other molecules, and improvement of injection and transport properties of holes and electrons It has problems such as efficiency improvement, color purity and lifetime improvement.

Therefore, in the present invention, as a result of extensive research to solve the above problems, while having excellent thermal stability and high luminous efficiency, it has excellent solubility and can minimize the interaction between molecules, the existing polyfluorene-based PFs), the electro-advertising molecule using the new arylamine derivative introduced with 9-aryl-fluorene-9-yl group which significantly improved the hole injection and transfer properties, color purity and luminous efficiency, and electroluminescent device using the same The present invention has been completed based on this finding.

Accordingly, an object of the present invention is to minimize the intermolecular interaction, facilitate energy transfer, suppress the vibronic mode as much as possible, exhibit high luminous efficiency, and improve the injection and transfer properties of holes. The present invention is to provide an organic electroluminescent polymer required to realize high efficiency blue, green and red light emitting polymers.

Another object of the present invention is to provide an electroluminescent device manufactured using the electroluminescent polymer.

The organic electro-promoter molecule according to the present invention for achieving the above object is an organic electro-promoter molecule represented by the following formula (1) in which the fluorene-9-yl group in which the aryl group is substituted at the 9-position of fluorene is introduced into the arylamine. It features:

Wherein A ₁ and A ₂ are the same or different from each other, or an aryl group which is unsubstituted or substituted with at least one substituent selected from the group consisting of a linear or branched alkyl group having 1 to 20 carbon atoms and an alkoxy group; An aryl group substituted with at least one substituent selected from the group consisting of a linear or branched alkyl group having 1 to 20 carbon atoms and an alkoxy group having at least one hetero atom selected from the group consisting of F, S, N, O, P and Si ; Substituted with at least one substituent selected from the group consisting of a linear or branched alkyl group having 1 to 20 carbon atoms and an alkoxy group having at least one hetero atom selected from the group consisting of F, S, N, O, P and Si, An aryl group having a heterocycle of 4;

Wherein a is an integer of 1 to 2 and b is an integer of 0 to 1;

Ar is selected from the group consisting of C6-C60 substituted or unsubstituted aromatic compounds, C2-C60 substituted or unsubstituted heteroaromatic compounds, and combinations thereof; And,

x is an integer of 1-100,000, y is an integer of 0-100,000.

An electroluminescent device according to the present invention for achieving the above another object has at least one layer comprising the organic electroluminescent molecules between the anode and the cathode, wherein the layer is a hole transport layer, a light emitting layer, an electron block It is characterized in that the king (blocking) layer.

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

As described above, in the present invention, it has excellent thermal stability and high luminous efficiency, has excellent solubility and minimizes intermolecular interactions, and provides injection and delivery properties of holes, which are disadvantages of conventional polyfluorene-based (PFs), Provided are an electroluminescent molecule using a new arylamine derivative having a 9-aryl-fluorene-9-yl group introduced with improved color purity and luminous efficiency and an electroluminescent device using the same.

The organic electro-adhesive molecule according to the present invention is an aryl polymer used as a main chain as a material of a light emitting polymer having excellent thermal stability, light stability, solubility, film formability, excellent hole injection / transfer quality, excellent color purity and high quantum efficiency. By introducing a large substituent fluorenyl group into the side chain of the amine, the arylamine having a substantially planar structure is enclosed, so that intermolecular excimers and aggregation are suppressed to the maximum, and molecules of the main chain from the short-chain substituents are suppressed. Intra- or intermolecular energy transfer is possible, and rotational and vibrational modes are suppressed by substituted large fluorenyl groups, thereby greatly reducing nonradiative decay, and thus the organic electroluminescent molecules of the present invention have excellent color purity. Luminance and high efficiency of light emission.

An electroadhesive molecule containing a new arylamine derivative substituted with a 9-aryl-fluorene-9-yl group according to the present invention is represented by the following Chemical Formula 1:

Formula 1

Wherein A ₁ and A ₂ are the same or different from each other, or an aryl group which is unsubstituted or substituted with at least one substituent selected from the group consisting of a linear or branched alkyl group having 1 to 20 carbon atoms and an alkoxy group; An aryl group substituted with at least one substituent selected from the group consisting of a linear or branched alkyl group having 1 to 20 carbon atoms and an alkoxy group having at least one hetero atom selected from the group consisting of F, S, N, O, P and Si ; C 2 substituted with at least one substituent selected from the group consisting of a straight or branched chain alkyl group having 1 to 20 carbon atoms and an alkoxy group having at least one hetero atom selected from the group consisting of F, S, N, O, P and Si Aryl group having a heterocycle of ˜24;

Wherein a is an integer of 1 to 2 and b is an integer of 0 to 1;

Ar is selected from the group consisting of C6-C60 substituted or unsubstituted aromatic compounds, C2-C60 substituted or unsubstituted heteroaromatic compounds, and combinations thereof; And,

x is an integer of 1-100,000, y is an integer of 0-100,000, the weight average molecular weight of the polymer represented by General formula (1) is an integer of 800-4,000,000, and molecular weight distribution is 1-10.

When y is not 0, x: y preferably has a ratio of 5:95 to 95: 5.

Preferably, A ₁ and A ₂ may be selected from the following compounds, equal to or different from each other:

On the other hand, representative examples of the aryl group having a heterocyclic ring are as follows, and can be preferably selected therefrom:

.

.

In the above formula, R ₁ and R ₂ are selected from the group consisting of a linear or branched alkyl group having 1 to 20 carbon atoms and an alkoxy group, and preferably selected from the following compounds.

On the other hand, Ar is preferably,

(Iii) a C6 to C60 substituted or unsubstituted arylene group;

(Ii) a C2 to C60 substituted or unsubstituted heterocyclic arylene group wherein at least one hetero atom selected from the group consisting of N, S, O, P and Si is included in the aromatic ring;

(Iii) a C 6 to C 60 substituted or unsubstituted arylenevinylene group; And

(Iii) selected from the group consisting of combinations thereof

Here, Ar is a straight or branched chain alkyl or alkoxy group having 1 to 20 carbon atoms; An aryl group which is unsubstituted or substituted with at least one substituent selected from the group consisting of a linear or branched alkyl group having 1 to 20 carbon atoms and an alkoxy group; Cyano group (-CN); Or a silyl group.

More specifically,

(Iii) when Ar is a phenylene group or a fluorenyl group among the substituted or unsubstituted arylene groups of C6 to C60, representative examples of such compounds are as follows, and may be selected from:

(Ii) where Ar is a C2-C60 substituted or unsubstituted heterocyclic arylene group, representative examples of such compounds are as follows and may be selected from:

(Iii) When Ar is a C6 to C60 substituted or unsubstituted arylenevinylene group, representative examples of such compounds are as follows, and may be selected from them.

One of the methods for preparing the organic electro-molecular advertising molecule of the present invention is as follows. That is, monomers are prepared through an alkylation reaction, a bromination reaction, a Grignard reaction, a Wittig reaction or the like, and finally, an organic electroluminescence polymer is produced through a CC coupling reaction such as a Yamamoto coupling reaction or a Suzuki coupling reaction . The number average molecular weight of the polymers obtained therefrom is 800 to 4,000,000, and the molecular weight distribution is 1 to 10.

The organic electro-adhesive molecule according to the present invention described above uses new arylamine derivatives having a 9-aryl-fluorene-9-yl group introduced as a main chain, and emits light with the lowest band gap in the arylamine moiety. At this time, the 9-aryl-fluorene-9-yl group is substituted with the side chain by the arylamine group, which is a light emitting part, and has excellent thermal stability, oxidation stability and solubility, high glass transition temperature, minimizing intermolecular interaction, and energy transition. It can be easily applied to the blue, green and red light emitting hosts that exhibit high luminous efficiency by suppressing the vibration mode as much as possible.

According to the present invention, the organic electroluminescent molecule is used as a material for forming a light emitting layer, a hole transport layer or an electron blocking layer positioned between a pair of electrodes in the electroluminescent device. The organic electroluminescent device of the present invention may be configured to further include a hole transport layer and an electron transport layer as well as the most common device configuration of the anode / light emitting layer / cathode.

1 is a cross-sectional view illustrating a structure of a general organic electroluminescent device composed of a substrate / anode / hole transport layer / light emitting layer / electron transport layer / cathode. Referring to this, an example of an organic electroluminescent device to which the organic electroluminescent molecule of the present invention is applied is It can be prepared as follows.

First, a material for the anode 12 electrode is coated on the substrate 11.

Here, the substrate 11 is a substrate used in a conventional organic electroluminescent device, preferably a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproof.

As the material for the anode 12 electrode, indium tin oxide (ITO), tin oxide (SnO 2), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity may be used.

Next, the hole transport layer 13 may be formed by vacuum deposition or sputtering on the anode 11 electrode, and the light emitting layer 14 may be formed through a solution coating method such as spin coating or inkjet printing. In addition, the electron transport layer 15 is formed on the light emitting layer 14 before the cathode 16 is formed. At this time, the thickness of the light emitting layer 14 is preferably 5nm ~ 1㎛, preferably 10 ~ 500nm, the thickness of the hole transport layer and the electron transport layer is preferably 10 ~ 10,0001.

According to the present invention, a material for forming an electron transport layer may be used for the electron transport layer 15, or the compound represented by Chemical Formula 1 may be formed by vacuum deposition, sputtering, spin coating, or inkjet printing.

The hole transport layer 13 and the electron transport layer 15 serves to increase the probability of light emitting coupling in the light emitting polymer by efficiently transporting the carriers to the light emitting polymer. The hole transport layer 13 and the electron transport layer 15 which can be used in the present invention are not particularly limited but are preferably poly (styrene sulfonic acid) (PSS) PEDOT: PSS, N, N'-bis (3-methylphenyl) -N, N-diphenyl- [1,1'- biphenyl] -4, 4'-diamine (TPD) is preferable. Examples of the electron transport layer material include aluminum trihydroxyquinoline (Alq3), 1,3,4-oxadiazole derivative PBD (2- (4-biphenylyl) -5- phenyl-1,3,4-oxadiazole, quinoxaline derivatives such as TPQ (1,3,4-tris [(3-penyl-6-trifluoromethyl) quinoxaline-2-yl] benzene and triazole derivatives.

On the other hand, when the organic electro-adhesive molecule according to the present invention to form a layer through the solution coating method, by blending with polymers having conjugated double bonds, such as other fluorene-based polymers, polyphenylene vinylene-based, polyparaphenylene-based In some cases, binder resins may be mixed and used. Examples of the binder resins include polyvinylcarbazole, polycarbonate, polyester, polyarylate, polystyrene, acrylic polymer, methacryl polymer, polybutyral, polyvinyl acetal, diallyl phthalate polymer, phenol resin, epoxy resin, Silicone resins, polysulfone resins or urea resins, and the like, which may be used individually or in combination.

Optionally, a hole-blocking layer, such as lithium fluoride (LiF), is further formed by vacuum deposition or the like to limit the transfer rate of holes in the light-emitting layer 14 and to bond electron-holes. You can increase the probability.

Finally, a material for the cathode 16 electrode is coated on the electron transport layer 15.

As the cathode forming metal, lithium (Li), magnesium (Mg), calcium (Ca), aluminum (Al), Al: Li, and the like having a small work function are used.

The organic electroluminescent device according to the present invention may be manufactured in the order as described above, namely anode / hole transport layer / light emitting layer / electron transport layer / cathode, and vice versa, that is, cathode / electron transport layer / light emitting layer / hole transport layer / anode You may manufacture in order.

In addition, the organic electroluminescent molecules according to the present invention can be used not only as a polymer organic electroluminescent device but also as a photoconversion material in a photodiode or a semiconductor material in a polymer TFT (Thin Film Transistor).

As described above, the organic electroadhesive molecule according to the present invention introduces a large substituent fluorenyl group into the arylamine used as the main chain, thereby randomizing the arrangement between the main chain and the substituent by the substituent, and the intermolecular excimer by the substituent. The most inhibited properties are expressed to inhibit aggregation and / or excimer formation. In addition, the intramolecular or intermolecular energy transfer from the short-chain substituent to the main chain is possible, and the rotational and vibrational modes are suppressed by the substituted large fluorenyl group, thereby greatly reducing the non-radiative attenuation, thereby providing excellent thermal stability, light stability, Properties of solubility, film formability and high quantum efficiency. Accordingly, the organic electroluminescent molecules of the present invention and organic electroluminescent devices using the same exhibit excellent color purity, brightness and high efficiency characteristics.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto. Meanwhile, the compounds mentioned as M1 to M4 below are monomers for preparing the electroadhesive molecules of the present invention, and are represented by the following structural formulas. The following specific monomers are intended to illustrate the invention and should not be construed as limiting the invention thereto.

The following Preparation Examples 1 and 2 were carried out according to the reaction overview shown in FIG.

Production Example 1

Synthesis of Compound (1)

3.15 g of Mg is placed in a 1000 ml three-necked flask, 20 g of 2,5-dimethyl-1-bromobenzene is dissolved in 80 ml of THF, and slowly added dropwise to make a Grignard reagent. The temperature of the reactor is lowered to -40 DEG C or lower and 15.6 g of fluorenone is added under a nitrogen stream, and then the temperature is gradually raised to room temperature and stirred for 10 hours. The reaction is poured into water, extracted with diethyl ether and the solvent is evaporated with a rotary evaporator. Separation by column chromatography gave 15 g (65%) of Compound (1) in FIG.

Production Example 2

-Synthesis of monomers (M1)

10 g of Compound (1) and 14.08 g of Compound (2) were dissolved in 300 ml of dichloromethane in a 500 ml round flask, and the temperature was lowered to 0 ° C., and a solution of 3.36 g of methanesulfonic acid in 20 ml of dichloromethane was slowly stirred. Inject and stir for 2 hours. The reaction is poured into water and extracted with diethyl ether, then the solvent is blown on a rotary evaporator. Separation by column chromatography gave 16 g (68%) of compound (M1).

Preparation Example 3 was carried out according to the reaction profile shown in FIG.

Production Example 3

Synthesis of Monomer (M2)

In a 250 ml round flask, 5.0 g of the compound (1) and 5.1 g of the compound (3) were dissolved in 2500 ml of dichloromethane, and the temperature was lowered to 0 ° C., and 1.68 g of methanesulfonic acid was dissolved in 20 ml of dichloromethane while stirring. Inject slowly and stir for 2 hours. The reaction is poured into water, extracted with diethyl ether and the solvent is blown on a rotary evaporator. Separation by column chromatography gave 7.3 g (78%) of compound (M2).

Production Example 4

Synthesis of Monomer M3

The compound represented by M3 was prepared by alkylation, bromination, Grignard reaction, dehydration, or the like.

Production Example 5

Synthesis of Monomer M4

The compound represented by M4 was prepared by alkylation, bromination, Grignard reaction, dehydration, or the like.

Examples 1 and 2 and Comparative Example 1

-Synthesis of Electromolecules

Suzuki coupling reaction known as carbon-carbon coupling reaction using monomers M1, M2, M3, and M4 prepared by the methods of Preparation Examples 1 to 5 (see Chemical Reviewa, Vol. 95, 1995, p. 2457-2483) to prepare a copolymer, and its composition and molecular weight are shown in Table 1 below.

division Polymer M1
(mmol) M2
(mmol) M3
(mmol) M4
(mmol) Molecular Weight
(Mw) Molecular Weight
(Mn) PDI Comparative Example 1 Polymer 1 0.5 0.5 349000 147000 2.38 Example 1 Polymer 2 0.13 0.5 0.37 294000 110000 2.68 Example 2 Polymer 3 0.13 0.5 0.37 534000 117000 4.57

Examples 3, 4 and Comparative Example 2

-Manufacturing of electroluminescent device

After forming an indium-tin oxide (ITO) electrode on a glass substrate, spin the polymers for electroluminescent devices prepared from Examples 1, 2 and Comparative Example 1 as shown in Table 2 below the ITO electrode. The coating formed a light emitting layer having a thickness of 400-1500 Å. Al: Li was vacuum-deposited on the light emitting layer to form an aluminum-lithium electrode having a thickness of 100 to 1200 Å, to fabricate an electroluminescent device, and the light emission characteristics thereof were measured and shown in Table 2 below.

division Light emitting layer Drive start voltage
(V) Highest efficiency
(cd / A) Color coordinates
(x, y) Comparative Example 2 Polymer 1 4.0 0.64 (0.15, 0.10) Example 3 Polymer 2 3.8 1.34 (0.15, 0.11) Example 4 Polymer 3 3.4 1.51 (0.14, 0.09)

The electroluminescent polymers prepared from Examples 1 and 2 are electro-adhesive molecules that improve the delivery and injection properties by introducing the special arylamine monomers M1 and M2 developed in the present invention into the basic structure composed of M3 and M4. . In the case of the electroluminescent devices manufactured using them, as shown in Table 2, in the case of the organic electroluminescent device of Comparative Example 2 using the polymer 1 that does not use the special arylamine developed in the present invention, a driving start voltage of 4 V was obtained. In the organic electroluminescent devices of Examples 3 and 4, which are made of Polymer 2 and Polymer 3 using M1 and M2, respectively, driving start voltages of 3.8V and 3.4V, respectively, were shown. This can be seen that the effect exhibited by the arylamine developed in the present invention.

In addition, the luminous efficiency was 0.64 cd / A in Comparative Example 2, which is 1.34 cd / A and 1.51 cd / A in the case of Example 3 and Example 4 using the copolymer of M1 or M2 developed in the present invention, respectively. The color coordinates of the devices of Examples 3 and 4 were x, y = (0.15, 0.09 to 0.10), which showed the characteristics of blue light emitting material of excellent color purity close to NTSC standard blue. This is considered to be a phenomenon that occurs because the fluorenyl group, which is a large substituent, is substituted at the terminal of the arylamine having planarity and completely inhibits intermolecular interaction and excimer.

On the other hand, Figures 4 to 6 shows the current density, brightness and luminous efficiency according to the voltage of the electroluminescent device manufactured according to Example 3, Figures 7 to 9 according to the voltage of the electroluminescent device manufactured according to Example 4 Current density, brightness and luminous efficiency are shown. Referring to this, it was shown that the current density increased stably with increasing voltage, and the luminance also increased stably with increasing voltage. From these results, it can be seen that the polymers developed in the present invention have excellent characteristics such as lifetime, brightness, color purity, and efficiency, which are commercial aspects.

As described above, the electro-adhesive molecules in which the arylamine is substituted with the fluorenyl group according to the present invention improve the hole injection and transfer properties, the color purity and the luminous efficiency, so that the solubility is excellent while having excellent thermal stability and high luminous efficiency. It is excellent and can minimize the intermolecular interaction, and can be used as a host material such as blue, green and red of the organic electroluminescent device can express excellent light emission characteristics.

Claims (7)

Organic electro-adhesive molecule, characterized in that represented by the following formula (1) wherein 9-aryl-fluorene-9-yl group is introduced into the arylamine: Formula 1

Wherein A1 and A2 each have an aryl group which is unsubstituted or substituted with at least one substituent selected from the group consisting of a linear or branched alkyl group having 1 to 20 carbon atoms and an alkoxy group or different from each other; a is an integer of 1 to 2, b is an integer of 0 to 1; Ar is selected from the group consisting of C6-C60 substituted or unsubstituted aromatic compounds, C2-C60 substituted or unsubstituted heteroaromatic compounds, and combinations thereof; And, x is an integer of 1-100,000, y is an integer of 0-100,000. Organic electro-adhesive molecule, characterized in that represented by the following formula (1) wherein 9-aryl-fluorene-9-yl group is introduced into the arylamine: Formula 1

Wherein A ₁ and A ₂ are the same or different from each other and are selected from the following compounds,

a is an integer of 1 to 2, b is an integer of 0 to 1; Ar is selected from the group consisting of C6-C60 substituted or unsubstituted aromatic compounds, C2-C60 substituted or unsubstituted heteroaromatic compounds, and combinations thereof; And, x is an integer of 1-100,000, y is an integer of 0-100,000. The compound of claim 1 or 2, wherein Ar is: (Iii) a C6 to C60 substituted or unsubstituted arylene group; (Ii) a C2 to C60 substituted or unsubstituted heterocyclic arylene group wherein at least one hetero atom selected from the group consisting of N, S, O, P and Si is included in the aromatic ring; (Iii) a C 6 to C 60 substituted or unsubstituted arylenevinylene group; And (iv) selected from the group consisting of combinations thereof Here, the substituent of Ar may be a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms; An aryl group which is unsubstituted or substituted with at least one substituent selected from the group consisting of a linear or branched alkyl group having 1 to 20 carbon atoms and an alkoxy group; Cyano group (-CN); And a silyl group. ≪ RTI ID = 0.0 > 11. < / RTI > According to claim 1 or claim 2, wherein the x: y ratio of the organic electro-adhesive molecules, characterized in that 5: 5: 95 to 5. According to claim 1 or claim 2, wherein the organic electro-promoter molecules, the weight average molecular weight is an integer of 800 to 4,000,000, the molecular weight distribution is 1 to 10, characterized in that the organic electro-molecular advertising molecule. An organic electroluminescent device having at least one layer comprising an organic electroluminescent molecule according to claim 1 or 2 between an anode and a cathode, wherein said layer is a major transport layer, a light emitting layer, an electron transport layer or a hole blocking layer. The organic electroluminescent device according to claim 6, wherein the structure of the electroluminescent device is an anode / light emitting layer / cathode, an anode / hole transporting layer / light emitting layer / cathode, or an anode / hole transporting layer / light emitting layer / electron transporting layer / cathode.

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