JP2007519800A - Organic electroluminescent polymer having 9,9-di (fluorenyl) -2,7-fluorenyl unit and organic electroluminescent device produced using the same - Google Patents

Abstract

  Disclosed are an organic electroluminescent polymer having 9,9-di (fluorenyl) -2,7-fluorenyl units and an electroluminescent device using the same. In particular, the present invention provides 9,9-di (fluorenyl) -2,7-fluorenyl units that can be used as blue electroluminescent polymers and host materials by introducing a substituted fluorenyl group at the 9-position of fluorene. And an electroluminescent device using the electroluminescent polymer. The electroluminescent polymer can be used as high purity blue, green and red host materials with high solubility, high thermal stability and high quantum efficiency.

Description

  The present invention relates to an organic electroluminescent polymer having 9,9-di (fluorenyl) -2,7-fluorenyl units and an electroluminescent (EL) device produced using the same. More particularly, the present invention relates to 9,9-di (fluorenyl) -2,7-fluorenyl units that exhibit high thermal stability, high light stability, high solubility, excellent film moldability, and high quantum efficiency. And an organic electroluminescent device manufactured using the organic electroluminescent polymer.

  With the rapid progress in recent years in the fields of optical communication and multimedia, the development to an advanced information society has been accelerated. Thus, optoelectronic devices that use photon conversion to electrons or vice versa are regarded as important in the modern information electronics industry.

Semiconductor optoelectronic devices are roughly classified into electroluminescent devices, light receiving devices, and combinations thereof.
Most current displays are light-receiving, whereas electroluminescent displays have self-luminous characteristics, which results in fast response, high brightness, and no need for back light. Therefore, the electroluminescent display is regarded as the next generation display.
The electroluminescent element is classified into an inorganic light-emitting element and an organic light-emitting element depending on the type of the material of the light-emitting layer.

Organic electroluminescence (EL) means that by applying an electric field to an organic material, energy generated when electrons and holes are transferred from the cathode and anode, respectively, and combined in the organic material is emitted as light. means. The electroluminescence of such organic materials was reported in 1963 by Pope et al. In 1987, Eastman Kodak's Tan et al. Show a quantum efficiency of 1% and a luminance of 1000 cd / m ² at 10 V or less using a dye having a p-conjugated structure called alumina-quinone. Much research has been conducted since the manufacture of multilayer light emitting devices. This element is advantageous because various substances can be easily synthesized according to a simple synthesis route, and color adjustment is easy. However, the processability and thermal stability are low, and Joule heat generated in the light emitting layer upon application of voltage causes molecular rearrangement, thereby negatively affecting the light emitting efficiency or lifetime of the device. Therefore, an organic electroluminescent device having a polymer structure that alleviates the above problems is planned.
In this context, FIG. 1 shows a conventional organic electroluminescent device comprising a substrate / anode / hole transport layer / light emitting layer / electron transport layer / cathode.

  As shown in FIG. 1, the anode 12 is formed on a conventional substrate 11. A hole transport layer 13, a light emitting layer 14, an electron transport layer 15, and a 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 organic electroluminescent device having the above structure operates as follows.

  When a voltage is applied to the anode 12 and the cathode 16, holes injected from the anode 12 move to the light emitting layer 14 through the hole transport layer 13. On the other hand, electrons are injected from the cathode 16 through the electron transport layer 15 into the light emitting layer 14, and carriers recombine in the region of the light emitting layer 14 to generate excitons. This exciton changes from the excited state to the ground state, whereby the fluorescent molecules in the light emitting layer emit light and an image is formed.

The organic material used for forming the organic thin film of the EL element may be a low molecular material or a high molecular material.
When low molecular weight organic substances are used, they can be easily purified to be free of impurities, and thus have excellent light emission characteristics. However, low molecular weight materials cannot be ink-jet printed or spin-coated, and have poor heat resistance, so that they deteriorate or recrystallize due to heat generated during device driving.
On the other hand, when a high molecular weight substance (that is, a polymer) is used, the p-electron wave functions existing in the main chain of the polymer overlap each other, so that the energy level is separated into a conduction band and a temporary conduction band. Since the semiconductor characteristics of the polymer are determined by the band gap energy between the conduction band and the provisional conduction band, full color visualization becomes possible by controlling the band gap. Such a polymer is called a p-conjugated polymer.

  In 1990, R.D. H. A research team led by Professor Friend first developed an EL device based on a conjugated polymer, poly (p-phenylene vinylene) (hereinafter referred to as “PPV”), and then developed an organic polymer with semiconductor properties. There is a lot of research. In addition to being superior in heat resistance as compared to low molecular weight materials, polymer materials can be applied to large screen displays because they can be inkjet printed and spin coated. It has been reported that PPV and polythiopene (Pth) derivatives into which various functional groups are introduced have improved processability and exhibit various colors. However, such PPV and Pth derivatives are suitable for red and green light emission with high efficiency, but it is difficult to emit blue light with high efficiency. Polyphenylene derivatives and polyfluorene derivatives have been reported as blue light-emitting substances. Polyphenylene is highly stable against oxidation and heat, but has poor luminous efficiency and solubility.

Similar to the polyfluorene derivatives, the related 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, for example, light emitting layers or carrier transport layers of light emitting diodes. It is disclosed.

  U.S. Pat. Nos. 6,309,763 and 6,605,373 disclose electroluminescent copolymers containing fluorine and amine groups in repeating units. According to the '763 patent, such copolymers are useful as light emitting or hole transporting layers in electroluminescent devices.

  WO 02/77060 discloses conjugated polymers containing spirobifluorene units. According to this reference, as disclosed therein, the polymer exhibits an improved property profile as an electroluminescent material in electronic components such as PLEDs.

[Technical issues]
As mentioned above, active research has been conducted on the use of polyfluorene derivatives as blue light-emitting polymers, but it is still possible to minimize the interaction of excitons produced between adjacent molecules and to improve efficiency and lifetime. It remains a challenge to be done.

[Technical Solution]
In order to avoid the problems in the prior art, the present inventors have conducted intensive and thorough research on organic electroluminescent polymers leading to the present invention, and as a result, the electroluminescent polymers have been substituted with fluorenyl. By including a fluorene unit disubstituted at the 9-position, the electroluminescent polymer minimizes the interaction between molecules, solves the disadvantages of conventional polyfluorene systems (PFs), and has excellent thermal stability It has been discovered that it can be used as a novel host material for blue, green and red light emission, and that an electroluminescent device using the same can be produced.
Therefore, the object of the present invention is to have blue, green and red colors having high thermal and oxidative stability, small interaction between molecules, easy energy transfer, and high luminous efficiency by suppressing vibration modes. An organic electroluminescent polymer is provided as a host material necessary for realizing light emission.

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

式中、Ｒ₁、Ｒ₂、Ｒ₃およびＲ₄は、同一または異なり、それぞれ、炭素数１〜２０の直鎖または分岐鎖のアルキル基；非置換、または、炭素数１〜２０の直鎖または分岐鎖のアルキルおよびアルコキシ基よりなる群から選択される少なくとも一つの置換基で置換されたアリール基；Ｆ、Ｓ、Ｎ、Ｏ、ＰおよびＳｉよりなる群から選択される少なくとも一つのヘテロ原子を有する炭素数１〜２０の直鎖または分岐鎖のアルキル基；Ｆ、Ｓ、Ｎ、Ｏ、ＰおよびＳｉよりなる群から選択される少なくとも一つのヘテロ原子を含有する炭素数１〜２０の直鎖または分岐鎖のアルキルおよびアルコキシ基よりなる群から選択される少なくとも一つの置換基で置換されたアリール基；非置換の、または、炭素数１〜２０の直鎖または分岐鎖のアルキルおよびアルコキシ基よりなる群から選択される少なくとも一つの置換基で置換された、炭素数２〜２４のヘテロ環部分を有するアリール基；Ｆ、Ｓ、Ｎ、Ｏ、ＰおよびＳｉよりなる群から選択される少なくとも一つのヘテロ原子を含有する炭素数１〜２０の直鎖または分岐鎖のアルキルおよびアルコキシ基よりなる群から選択される少なくとも一つの置換基で置換された炭素数２〜２４のヘテロ環部分を有するアリール基；炭素数３〜４０の置換または非置換のトリアルキルシリル基；炭素数３〜４０の置換または非置換のアリールシリル基；炭素数１２〜６０の置換または非置換のカルバゾール基；炭素数６〜６０の置換または非置換のフェノチアジン基；または、炭素数６〜６０の置換または非置換のアリールアミン基であり； To achieve the above object, the present invention provides an organic electroluminescent polymer having a 9,9-di (fluorenyl) -2,7-fluorenyl unit represented by the following formula 1:

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and are each a linear or branched alkyl group having 1 to 20 carbon atoms; unsubstituted or a linear chain having 1 to 20 carbon atoms Or an aryl group substituted with at least one substituent selected from the group consisting of branched alkyl and alkoxy groups; at least one heteroatom selected from the group consisting of F, S, N, O, P and Si A linear or branched alkyl group having 1 to 20 carbon atoms and having at least one heteroatom selected from the group consisting of F, S, N, O, P and Si; An aryl group substituted with at least one substituent selected from the group consisting of a chain or branched alkyl group and an alkoxy group; an unsubstituted or linear or branched alkyl group having 1 to 20 carbon atoms; 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 an alkoxy group and an aryl group having a heterocyclic portion having 2 to 24 carbon atoms; Or a heterocycle having 2 to 24 carbon atoms substituted with at least one substituent selected from the group consisting of a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms and containing at least one heteroatom. An aryl group having a moiety; a substituted or unsubstituted trialkylsilyl group having 3 to 40 carbon atoms; a substituted or unsubstituted arylsilyl group having 3 to 40 carbon atoms; a substituted or unsubstituted carbazole group having 12 to 60 carbon atoms A substituted or unsubstituted phenothiazine group having 6 to 60 carbon atoms; or a substituted or unsubstituted arylamine group having 6 to 60 carbon atoms;

R ₅ , R ₆ , R ₇ and R ₈ are the same or different and each represents hydrogen; a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms; unsubstituted or having 1 to 20 carbon atoms An aryl group substituted with at least one substituent selected from the group consisting of linear or branched alkyl and alkoxy groups; at least one selected from the group consisting of F, S, N, O, P and Si A C1-C20 linear or branched alkyl or alkoxy group having a heteroatom; 1 carbon containing at least one heteroatom selected from the group consisting of F, S, N, O, P and Si Aryl group substituted with at least one substituent selected from the group consisting of -20 linear or branched alkyl and alkoxy groups; unsubstituted or having 1 to 1 carbon atoms An aryl group substituted with at least one substituent selected from the group consisting of 20 straight-chain or branched-chain alkyl and alkoxy groups and having a heterocyclic moiety having 2 to 24 carbon atoms; F, S, N, O Substituted with at least one substituent selected from the group consisting of straight-chain or branched alkyl and alkoxy groups having 1 to 20 carbon atoms and containing at least one heteroatom selected from the group consisting of P and Si An aryl group having a heterocyclic portion having 2 to 24 carbon atoms; a substituted or unsubstituted trialkylsilyl group having 3 to 40 carbon atoms; a substituted or unsubstituted arylsilyl group having 3 to 40 carbon atoms; A substituted or unsubstituted carbazole group having 60 carbon atoms; a substituted or unsubstituted phenothiazine group having 6 to 60 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; There in Ruamin group;

a, b, c and d are the same or different and each is an integer of 1 to 3;
Ar is selected from the group consisting of a substituted or unsubstituted aromatic moiety having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 60 carbon atoms, and combinations thereof; and
l is an integer of 1 to 100,000, m is an integer of 0 to 100,000, and n is an integer of 1 to 100,000.
Furthermore, the present invention is an organic electroluminescent polymer element having at least one layer containing the above-described polymer between an anode and a cathode,
Provided is an organic electroluminescent device, wherein the layer is a hole transport layer, a light emitting layer, an electron transport layer or a hole blocking layer.

[Advantageous effect]
The present invention provides an organic electroluminescent polymer having 9,9-di (fluorenyl) -2,7-fluorenyl units, and an organic electroluminescent device produced using the same. The electroluminescent polymer of the present invention has excellent thermal stability, high luminous efficiency and high solubility and serves to minimize molecular interactions. Furthermore, the above polymers alleviate the disadvantages of conventional polyfluorene polymers and can be used as blue, green and red light emitting host materials for electroluminescent devices, so they have excellent light emission characteristics. Presents.

[Best Mode]
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
The present invention has 9,9-di (fluorenyl) -2,7-fluorenyl units that have high solubility, high thermal stability and high quantum efficiency and can be used as high purity blue, green and red host materials An organic electroluminescent polymer containing the above and an electroluminescent device manufactured using the same are provided.
The organic electroluminescent polymer of the present invention is a substance having high thermal stability, high light stability, high solubility, high quantum efficiency, and excellent film formability, and is a bulky substituent fluorenyl group Is introduced at the 9-position of fluorene of the main chain, so that the substituent has a structure similar to that of the main chain. Therefore, the arrangement between the main chain and the substituent is random, and the excimer formation between the molecules due to the substituent is inhibited, thereby suppressing the aggregation and / or excimer formation, which are the biggest problems in the polyfluorene polymer. The Furthermore, intramolecular or intermolecular energy transfer from a substituent having a short wavelength to the main chain can be realized.
In addition, the 9-position of fluorene used as the backbone serves to control rotational and vibrational modes using bulky fluorenyl substituents, dramatically reducing non-radiative damping. Therefore, the organic electroluminescent polymer of the present invention has high color purity, high brightness and high efficiency.

式中、Ｒ₁、Ｒ₂、Ｒ₃およびＲ₄は、同一または異なり、それぞれ、炭素数１〜２０の直鎖または分岐鎖のアルキル基；非置換、または、炭素数１〜２０の直鎖または分岐鎖のアルキルおよびアルコキシ基よりなる群から選択される少なくとも一つの置換基で置換されたアリール基； Ｆ、Ｓ、Ｎ、Ｏ、ＰおよびＳｉよりなる群から選択される少なくとも一つのヘテロ原子を有する炭素数１〜２０の直鎖または分岐鎖のアルキル基；Ｆ、Ｓ、Ｎ、Ｏ、ＰおよびＳｉよりなる群から選択される少なくとも一つのヘテロ原子を含有する炭素数１〜２０の直鎖または分岐鎖のアルキルおよびアルコキシ基よりなる群から選択される少なくとも一つの置換基で置換されたアリール基；非置換の、または、炭素数１〜２０の直鎖または分岐鎖のアルキルおよびアルコキシ基よりなる群から選択される少なくとも一つの置換基で置換された、炭素数２〜２４のヘテロ環部分を有するアリール基；Ｆ、Ｓ、Ｎ、Ｏ、ＰおよびＳｉよりなる群から選択される少なくとも一つのヘテロ原子を含有する炭素数１〜２０の直鎖または分岐鎖のアルキルおよびアルコキシ基よりなる群から選択される少なくとも一つの置換基で置換された炭素数２〜２４のヘテロ環部分を有するアリール基；炭素数３〜４０の置換または非置換のトリアルキルシリル基；炭素数３〜４０の置換または非置換のアリールシリル基；炭素数１２〜６０の置換または非置換のカルバゾール基；炭素数６〜６０の置換または非置換のフェノチアジン基；または、炭素数６〜６０の置換または非置換のアリールアミン基であり； According to the present invention, an organic electroluminescent polymer having 9,9-di (fluorenyl) -2,7-fluorenyl units is represented by the following formula 1:

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and are each a linear or branched alkyl group having 1 to 20 carbon atoms; unsubstituted or a linear chain having 1 to 20 carbon atoms Or an aryl group substituted with at least one substituent selected from the group consisting of branched alkyl and alkoxy groups; at least one heteroatom selected from the group consisting of F, S, N, O, P and Si A linear or branched alkyl group having 1 to 20 carbon atoms and having at least one heteroatom selected from the group consisting of F, S, N, O, P and Si; An aryl group substituted with at least one substituent selected from the group consisting of a chain or branched alkyl group and an alkoxy group; an unsubstituted or linear or branched alkyl group having 1 to 20 carbon atoms 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 an alkoxy group and an aryl group having a heterocyclic portion having 2 to 24 carbon atoms; Or a heterocycle having 2 to 24 carbon atoms substituted with at least one substituent selected from the group consisting of a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms and containing at least one heteroatom. An aryl group having a moiety; a substituted or unsubstituted trialkylsilyl group having 3 to 40 carbon atoms; a substituted or unsubstituted arylsilyl group having 3 to 40 carbon atoms; a substituted or unsubstituted carbazole group having 12 to 60 carbon atoms A substituted or unsubstituted phenothiazine group having 6 to 60 carbon atoms; or a substituted or unsubstituted arylamine group having 6 to 60 carbon atoms;

R ₅ , R ₆ , R ₇ and R ₈ are the same or different and each represents hydrogen; a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms; unsubstituted or having 1 to 20 carbon atoms An aryl group substituted with at least one substituent selected from the group consisting of linear or branched alkyl and alkoxy groups; at least one selected from the group consisting of F, S, N, O, P and Si A C1-C20 linear or branched alkyl or alkoxy group having a heteroatom; 1 carbon containing at least one heteroatom selected from the group consisting of F, S, N, O, P and Si Aryl group substituted with at least one substituent selected from the group consisting of -20 linear or branched alkyl and alkoxy groups; unsubstituted or having 1 to 1 carbon atoms An aryl group substituted with at least one substituent selected from the group consisting of 20 straight-chain or branched-chain alkyl and alkoxy groups and having a heterocyclic moiety having 2 to 24 carbon atoms; F, S, N, O Substituted with at least one substituent selected from the group consisting of straight-chain or branched alkyl and alkoxy groups having 1 to 20 carbon atoms and containing at least one heteroatom selected from the group consisting of P and Si An aryl group having a heterocyclic portion having 2 to 24 carbon atoms; a substituted or unsubstituted trialkylsilyl group having 3 to 40 carbon atoms; a substituted or unsubstituted arylsilyl group having 3 to 40 carbon atoms; A substituted or unsubstituted carbazole group having 60 carbon atoms; a substituted or unsubstituted phenothiazine group having 6 to 60 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; There in Ruamin group;

a, b, c and d are the same or different and each is an integer of 1 to 3;
Ar is selected from the group consisting of a substituted or unsubstituted aromatic moiety having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 60 carbon atoms, and combinations thereof; and
l is an integer of 1 to 100,000, m is an integer of 0 to 100,000, and n is an integer of 1 to 100,000. Preferably, the ratio of l: m ranges from 5:95 to 95: 5.

According to the present _{invention, R 1, R 2, R} 3 and R ₄ are each preferably selected from the following group:

Further, it is preferred that R ₅ and R ₆ are each selected from the following group:

Where
(I) R ₉ and R ₁₀ are the same or different and each represents a linear or branched alkyl group having 1 to 20 carbon atoms.
The above fluorenyl may typically be selected from the following group:

(Ii) R ₁₁ is hydrogen or a linear or branched alkyl, alkoxy or trialkylsilyl group having 1 to 20 carbon atoms;
R ₁₂ and R ₁₃ are the same or different and are each a linear or branched alkyl group having 1 to 20 carbon atoms;
X is O or S;
Y and Z are N; and
a is an integer of 1 to 3.
The aryl having the above heterocyclic moiety may typically be selected from the following group:

And
(Iii) R ₁₄ , R ₁₅ and R ₁₆ are the same or different and are each a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms; or unsubstituted or having 1 to 20 carbon atoms An aryl group substituted with at least one substituent selected from the group consisting of linear or branched alkyl and alkoxy groups; and
R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ are the same or different and are each hydrogen; a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms; or an unsubstituted group; Or it is the aryl group substituted by the at least 1 substituent selected from the group which consists of a C1-C20 linear or branched alkyl and alkoxy group.
The above silyl, carbazole, phenothiazine and arylamine may typically be selected from the following group:

In addition, R ₇ and R ₈ are each preferably selected from the following group:

According to the present invention, Ar is at least selected from the group consisting of: (i) a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, (ii) N, S, O, P and Si. A substituted or unsubstituted heterocyclic arylene group having 2 to 60 carbon atoms, (iii) a substituted or unsubstituted arylene vinylene group having 6 to 60 carbon atoms, and (iv) a carbon number, wherein one heteroatom is contained in the aromatic ring Preferably selected from 6-60 substituted or unsubstituted arylamine groups, (v) substituted or unsubstituted carbazole groups having 12 to 60 carbon atoms; and (vi) combinations thereof,
Here, Ar is selected from the group consisting of a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms; an unsubstituted or linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms An aryl group substituted with at least one substituent as described above; a cyano group (—CN); or a substituent such as a silyl group.

More specifically,
(I) When Ar is a phenylene group or a fluorenylene group of a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, Ar may typically be selected from the following group:

(Ii) When Ar is a substituted or unsubstituted heterocyclic arylene group having 2 to 60 carbon atoms, Ar may typically be selected from the following group:

(Iii) When Ar is a substituted or unsubstituted arylene vinylene group having 6 to 60 carbon atoms, Ar may typically be selected from the following group:

(Iv) When Ar is a substituted or unsubstituted arylamine group having 6 to 60 carbon atoms, Ar may typically be selected from the following group:

In the formula, R ₂₃ , R ₂₄ and R ₂₅ are the same or different and are hydrogen; a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms; or unsubstituted or having 1 to 20 carbon atoms An aryl group substituted with at least one substituent selected from the group consisting of linear or branched alkyl and alkoxy groups. More preferably, Ar is selected from the following group:

And
(V) When Ar is a substituted or unsubstituted carbazole group having 12 to 60 carbon atoms, Ar may typically be selected from the following group:

In the formula, R ₂₆ is composed of a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms; or an unsubstituted or linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms. An aryl group substituted with at least one substituent selected from the group.
Further, when Ar is (iv) a substituted or unsubstituted arylamine group having 6 to 60 carbon atoms, Ar is preferably present in the electroluminescent polymer in an amount of about 5 to 15 mol%.

  For production of the organic electroluminescent polymer of the present invention, for example, a monomer is produced by alkylation, bromination, Grignard reaction, Wittig reaction, etc., and then Yamamoto coupling reaction and Suzuki coupling reaction. Production of organic electroluminescent polymers by C—C coupling reactions such as The resulting polymer has a number average molecular weight of 1,500 to 10,000,000 and a molecular weight distribution of 1 to 50.

  The organic electroluminescent polymer of the present invention can be applied as a host for blue, green and red light emission, is excellent in thermal stability, oxidation stability and solubility, has small intermolecular interaction, and is easy to transfer energy. Yes, it exhibits high luminous efficiency by suppressing the vibration mode.

According to the present invention, an organic electroluminescent polymer is used to form a light emitting layer, a hole transport layer, an electron transport layer, or a hole blocking layer positioned between a pair of electrodes in an electroluminescent device. It may be used as a substance.
The organic electroluminescent device includes a basic structure of anode / light emitting layer / cathode, and optionally further includes a hole transport layer and an electron transport layer.

FIG. 1 is a cross-sectional view showing a typical structure of an organic electroluminescent device having a substrate / anode / hole transport layer / light-emitting layer / electron transport layer / cathode. The luminescent device is manufactured, for example, using the organic electroluminescent polymer of the present invention as follows:
An electrode material for the anode 12 is coated on the substrate 11.
As the substrate 11, any substrate used for a conventional organic electroluminescent element is used. Preferably, a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling and waterproofness is useful.
In addition, examples of the electrode material for the anode 12 include indium tin oxide (ITO), tin oxide (SnO ₂ ), and zinc oxide (ZnO) which are transparent and have high conductivity.

  Next, the hole transport layer 13 may be formed on the anode 12 by vacuum deposition or sputtering, and then the light emitting layer 14 is formed by a solution coating method such as spin coating or ink jet printing. In addition, the electron transport layer 15 is formed on the light emitting layer 14 before the cathode 16 is formed. As such, the thickness of the light emitting layer 14 ranges from about 5 nm to about 1 mm, preferably from about 10 to about 500 nm. The hole transport layer and the electron transport layer are about 10 to 10,000 inches thick.

  The electron transport layer 15 is obtained by using a conventional electron transport layer forming material, or by vacuum deposition, sputtering, spin coating or ink jet printing of the compound represented by Formula 1.

  The hole transport layer 13 and the electron transport layer 15 function to efficiently transfer carriers to the luminescent polymer, thereby increasing the light emission efficiency of the luminescent polymer. Furthermore, the material for forming the hole transport layer 13 and the electron transport layer 15 is not particularly limited. For example, hole transport layer materials include PEDOT: PSS, which is poly (3,4-ethylenedioxy-thiophene) (PEDOT) doped with a poly (styrene sulfonic acid) (PSS) layer, and N, N′— Bis (3-methylphenyl) -N, N-diphenyl- [1,1′-biphenyl] -4,4′-diamine (TPD) can be mentioned, while the electron transport material is aluminum trihydroxyquinoline (Alq3 ), PBD (2- (4-biphenylyl) -5-phenyl-1,3,4-oxadiazole) which is a 1,3,4-oxadiazole derivative, TPQ (1,3,4) which is a quinoxaline derivative -Tris [(penyl-6-trifluoromethyl) quinoxalin-2-yl] benzene) and triazole derivatives.

When organic electroluminescent polymer is used in the solution coating method to form a layer, it can be mixed with polymers having conjugated double bonds such as polyphenylene vinylene and polyparaphenylene, and other fluorene polymers. Good. You may mix and use binder resin as needed. Examples of binder resins include polyvinyl carbazole, polycarbonate, polyester, polyarylate, polystyrene, acrylic polymer, methacrylic polymer, polybutyral, polyvinyl acetal, diallyl phthalate polymer, phenol resin, epoxy resin, silicone resin, polysulfone resin. Or a urea resin is mentioned. These resins may be used alone or in combination.
Optionally, a hole blocking layer made of LiF (lithium fluoride) may be further formed by, for example, vacuum deposition in order to control the hole transmission speed in the light emitting layer 14 and increase the electron-hole coupling efficiency. Form.
Finally, the electrode material for the cathode 16 is coated on the electron transport layer 15.
Examples of the cathode forming metal having a small work function include lithium (Li), magnesium (Mg), calcium (Ca), aluminum (Al), and Al: Li.

The organic electroluminescent device of the present invention comprises anode / hole transport layer / light emitting layer / electron transport layer / cathode in this order, or vice versa, that is, cathode / electron transport layer / light emitting layer / hole transport layer / anode. Are manufactured in order.
In addition, the organic electroluminescent polymer is used not only as a high molecular weight organic electroluminescent element material but also as a light conversion material for a photodiode or a semiconductor material for a polymer TFT (thin film transistor).

  According to the present invention, the organic electroluminescent polymer has a bulky fluorenyl group at the 9-position of the main-chain fluorene. Accordingly, the substituent has the same structure as the main chain, and thereby the sequence between the main chain and the substituent is random. Furthermore, intermolecular excimer formation by substituents can be inhibited, thus suppressing aggregation and / or excimer formation, which is viewed as the biggest problem in the polyfluorene-based region. In addition, intramolecular or intermolecular energy transfer from a substituent having a short wavelength to the main chain is possible. A substituted fluorenyl group introduced at the 9-position of the main-chain fluorene group controls the rotational and vibrational modes, thus dramatically reducing non-radiative damping, resulting in high thermal stability, light stability, solubility, film Exhibits formability and quantum efficiency. Therefore, the organic electroluminescent polymer of the present invention and the organic electroluminescent device manufactured using the same can exhibit excellent color purity and luminance, and high efficiency.

[Aspect of the Invention]
The invention is better understood with the aid of the following examples, which are given by way of illustration and are not intended to limit the invention.
The following Examples 1 to 4 were carried out according to the reaction shown in FIG.

Example 1
Synthesis of (9- (9,9-dihexylfluoren-2-yl) -2,7-dibromofluoren-9-ol) (1) To 5.64 g of Mg charged in a 1000 mL three-necked flask, 9, A Grignard reagent was prepared by slowly dropping 80 g of 9-dihexyl-2-bromofluorene. After the temperature of the reaction vessel was lowered to −40 ° C. or lower, 52 g of 2,7-dibromofluorenone was added to the reaction solution under a nitrogen atmosphere. The temperature was gradually raised to room temperature and stirred for 10 hours. The resulting reaction solution was poured into water and then extracted with diethyl ether. The solvent was distilled off on a rotary evaporator. Separation by column chromatography gave (9- (9,9-dihexylfluoren-2-yl) -2,7-dibromofluoren-9-ol) (1) 60 g (58%).

Example 2
Synthesis of (9,9-di (9,9-dihexylfluoren-2-yl) -2,7-dibromofluorene) (2) In a 2 L round bottom flask, 50 g of compound (1) and 9,9-dihexyl 200 g of fluorene was dissolved in 1000 mL of dichloromethane, and then the temperature was lowered to 0 ° C. A solution prepared by dissolving 10 mL of methanesulfonic acid in 100 mL of dichloromethane was slowly added to the reaction solution with stirring, and the mixture was further stirred for 2 hours. The resulting reaction solution was poured into water and then extracted with diethyl ether. The solvent was distilled off on a rotary evaporator. Separation by column chromatography gave 60 g (58%) of (9,9-di (9,9-dihexylfluoren-2-yl) -2,7-dibromofluorene) (2).

Example 3
Synthesis of (9,9-di (9,9-dihexylfluoren-2-yl) fluorene-2,7-diboronic acid) (3) In a 250 mL round bottom flask, 10 g of compound (2) was added to 60 mL of THF. The temperature was then lowered to -70 ° C. To this reaction solution, 2 equivalents of 2.5M n-butyllithium was gradually added and reacted at low temperature (−70 ° C. to −40 ° C.) for 2 hours. Moreover, 4 equivalent triethyl boronate was added at the same temperature, and the obtained reaction liquid was left still for 12 hours. The obtained reaction solution was poured into 3N-HCl aqueous solution, stirred for 4 hours, and extracted with diethyl ether. The solvent was distilled off with a rotary evaporator to obtain a solidified substance, which was washed several times with toluene, and (9,9-di (9,9-dihexylfluoren-2-yl) fluorene-2 was obtained. , 7-Diboronic acid) (3) 3.6 g (39%) was obtained.

Example 4
Synthesis of (9,9-di (9,9-dihexylfluoren-2-yl) fluorene-2,7-bisboronic acid glycol ester) (4) In a 100 mL round bottom flask attached to a Deanstark apparatus, 2 g of compound (3), 3 equivalents of ethylene glycol and 50 mL of anhydrous toluene were charged. Subsequently, the mixture was refluxed for 24 hours to remove water. The obtained substance was recrystallized from toluene to obtain 1.8 g of (9,9-di (9,9-dihexylfluoren-2-yl) fluorene-2,7-bisboronic acid glycol ester) (4). .
The following Examples 5-8 were carried out according to the reaction scheme shown in FIG.

Example 5
Synthesis of (2-bromo-9,9-di (4-hydroxyphenyl) fluorene) (5) A 500 mL round bottom flask was charged with 10 g of 2-bromofluorene, 2 equivalents of methanesulfonic acid and 100 g of phenol, and then 150 Stir for 24 hours at ° C. The reaction was cooled and then mixed with water and the solid was filtered. Next, the solid was recrystallized from toluene to obtain 12 g of (2-bromo-9,9-di (4-hydroxyphenyl) fluorene) (5).

Example 6
Synthesis of (2-bromo-9,9-di (4- (2-methyl) butyloxy) phenyl) fluorene) (6) In a 250 mL round bottom flask, 10 g of compound (5) and 2-methylbutyl p-toluenesulfonate 2.2 equivalent was dissolved in 100 mL of DMSO to obtain a reaction solution, to which 2.3 equivalent of potassium t-butoxide (t-BuOK) was slowly added. The reaction was carried out at 70 ° C. for 12 hours. The obtained reaction solution was poured into 500 mL of water, extracted with methylene chloride, and the solvent was removed with a rotary evaporator. Separation by column chromatography using a mixed solvent of hexane and ethyl acetate,
14 g of (2-bromo-9,9-di (4- (2-methyl) butyloxy) phenyl) fluorene) (6) was obtained.

Example 7
Synthesis of (4,4-dibromobiphen-2-yl-di [9,9-bis (4- (2-methyl) butyloxy) phenyl] fluoren-2-yl-methanol) (7) 250 mL 3-neck flask Inside, 18 g of compound (6) was dissolved in 300 mL of THF, and then the reactor was cooled to −40 ° C., and 2.5 M n-butyllithium was slowly added dropwise thereto, followed by stirring for 2 hours. After lowering the temperature of the reaction vessel to −40 ° C. or lower and adding 0.4 equivalent of methyl- (2-bromo-4-bromophenyl) benzoate to the reaction vessel in a nitrogen atmosphere, the temperature was gradually raised to room temperature. Stir for 10 hours. The reaction solution was poured into water and extracted with diethyl ether. The solvent was removed on a rotary evaporator. (4,4-Dibromobiphen-2-yl-di [9,9-bis (4- (2-methyl) butyloxy) phenyl] fluoren-2-yl-methanol) (7 ) 17 g was obtained.

Example 8
Synthesis of (2,7-dibromo- [9,9-bis [9,9-di (4- (2-methyl) butyloxyphenyl) fluoren-2-yl] fluorene]) (8) 250 mL round bottom flask Into this, 10 g of compound (7) and 100 mL of acetic acid were added, and 5 drops of 35% by weight hydrochloric acid were added thereto, followed by refluxing for 12 hours. The temperature of the reaction solution was lowered to room temperature, and the solid was filtered. The filtered solid is then washed with a mixture of water and methanol and recrystallized with a mixture of methyl chloride and ethanol to give (2,7-dibromo- [9,9-bis [9,9-di- (4- (2-Methyl) butyloxyphenyl) fluoren-2-yl] fluorene] (8) was obtained as a white solid.

式中、ｎ₁は、１〜１００，０００の整数である。
５００ｍＬのシュレンクフラスコ中で、６ｇ（６０７ｍｍｏＬ）の化合物（２）を窒素で脱気した６６ｍＬのトルエンに溶解し、その後、窒素雰囲気下に保管した。触媒として、Ｎｉ（ＣＯＤ）₂を３．５７６ｇ（１２．７４ｍｍｏＬ、２．１当量）、１，４−シクロオクタジエン（ＣＯＤ）１．３９２ｇ（１２．７４ｍｍｏＬ、２．１当量）、ジピリジル２．０１０ｇ（１２．７４ｍｍｏＬ、２．１当量）を、窒素下でシュレンクフラスコに加え、そこに窒素で脱化したトルエン３３ｍＬおよびＤＭＦ３３ｍＬを添加し、その後、８０℃で３０分間攪拌した。このように調製したモノマー溶液を反応器に添加し、２４時間反応させた。得られた反応液をブロモベンゼン２ｍＬと混合し、その後２４時間反応させて末端を終結させた。その後、反応液を、塩酸（３５重量％）：アセトン：エタノール＝１：１：１の溶液１５００ｍＬに添加して未反応の触媒を除去し、高分子を沈殿させた。高分子を濾過し、クロロホルムに溶解した後、セライトで濾過して残存する触媒を除去した。濃縮し、メタノールで再沈殿し、ソックスレット(Soxlet)で２４時間洗浄した。収率：６９％、分子量：Ｍｗ＝１８０，０００、Ｍｎ＝５８，０００、ＰＤＩ（多分散性）：３．１ Example 9
Synthesis of poly (9,9-di (9,9-dihexylfluoren-2-yl) -2,7-fluorenyl) (formula 2)

In the formula, n ₁ is an integer of ₁ to 100,000.
In a 500 mL Schlenk flask, 6 g (607 mmol) of compound (2) was dissolved in 66 mL of toluene degassed with nitrogen, and then stored in a nitrogen atmosphere. As catalysts, 3.576 g (12.74 mmol, 2.1 equivalents) of Ni (COD) ₂ , 1.392 g (12.74 mmol, 2.1 equivalents) of 1,4-cyclooctadiene (COD), 2. 010 g (12.74 mmol, 2.1 eq) was added to a Schlenk flask under nitrogen, to which were added 33 mL of toluene degassed with nitrogen and 33 mL of DMF, followed by stirring at 80 ° C. for 30 minutes. The monomer solution thus prepared was added to the reactor and reacted for 24 hours. The obtained reaction solution was mixed with 2 mL of bromobenzene, and then reacted for 24 hours to terminate the terminal. Thereafter, the reaction solution was added to 1500 mL of a solution of hydrochloric acid (35% by weight): acetone: ethanol = 1: 1: 1 to remove the unreacted catalyst, and the polymer was precipitated. The polymer was filtered and dissolved in chloroform, and then filtered through celite to remove the remaining catalyst. Concentrated, re-precipitated with methanol and washed with Soxlet for 24 hours. Yield: 69%, molecular weight: Mw = 180,000, Mn = 58,000, PDI (polydispersity): 3.1

4 and 5 show ¹ H-NMR spectra of the monomer represented by Compound (2) and the electroluminescent polymer represented by Formula 2, respectively. From these figures, it can be seen that the structures of the monomer and the polymer coincide with each other. FIG. 6 shows the photoluminescence (PL) spectrum of the electroluminescent polymer represented by formula 2 in a chloroform solution and on a film, respectively, where the maximum peak of the photoluminescence (PL) spectrum in the chloroform solution is shown. Is 418 nm corresponding to the blue emission region, and the shoulder peak is 442 nm. The maximum peak of the photoluminescence (PL) spectrum on the film is 427 nm corresponding to the blue emission region, and the shoulder peak is 448 nm. Furthermore, the peak due to the excimer generally observed in the vicinity of 530 nm in the photoluminescence (PL) spectrum on the fluorene-based film is not observed in the present invention. Thereby, it can confirm that the compound of this invention can be used as a substance which has high luminous efficiency.

式中、ｌ₁は１〜１００，０００の整数であり、かつｍ₁は１〜１００，０００の整数である。
この高分子は、モノマーとして化合物（２）９５％および４，４−ジブロモトリフェニルアミン５％を使用した以外は、実施例３と同様の方法で調製した。分子量：Ｍｗ＝１６５，０００、Ｍｎ＝６１，０００、ＰＤＩ（多分散性）：２．７ Example 10
Synthesis of polymer of formula 3 (l ₁ : m ₁ = 95: 5)

In the formula, l ₁ is an integer of ₁ to 100,000, and m ₁ is an integer of ₁ to 100,000.
This polymer was prepared in the same manner as in Example 3, except that 95% of compound (2) and 5% of 4,4-dibromotriphenylamine were used as monomers. Molecular weight: Mw = 165,000, Mn = 61,000, PDI (polydispersity): 2.7

Example 11
Synthesis of polymer of formula 3 (l ₁ : m ₁ = 90: 10) This polymer is an example except that 90% of compound (2) and 10% of 4,4-dibromotriphenylamine are used as monomers. 3 was prepared in the same manner as in 3. Molecular weight: Mw = 162,000, Mn = 56,000, PDI (polydispersity): 2.9

Example 12
Synthesis of polymer of formula 3 (l ₁ : m ₁ = 85: 15) This polymer is an example except that 85% of compound (2) and 15% of 4,4-dibromotriphenylamine are used as monomers. 3 was prepared in the same manner as in 3. Molecular weight: Mw = 157,000, Mn = 60,000, PDI (polydispersity): 2.6

式中、ｌ₂は１〜１００，０００の整数であり、かつｍ₂は１〜１００，０００の整数である。
化合物（８）０．５５ｇ、９，９−ビス（４−オクチルフェニル）フルオレン−２，７−ビスボロン酸グリコールエステル０．３８、およびＮ，Ｎ−ジ（４−ブロモフェニル）−Ｎ，Ｎ−ビス（４−メトキシフェニル）−［１，１−ビフェニル］−４，４−ジアミン０．０７５ｇをトルエン１０ｍＬに溶解し、そこに水２．５ｍＬ、Ｋ₃ＰＯ₄０．５５ｇ、トリカプリルイルメチルアンモニウムクロライド０．０２ｇを添加した後、窒素ガスを３０分間バブリングした。反応混合物に、テトラキストリフェニルホスフィンパラジウム（０）０．０１ｇを添加した後、８９℃で２４時間反応させた。得られた反応液を室温まで冷却し、メタノール２００ｍＬ中で沈殿させて高分子を濾過した。その後、濾過した高分子をクロロホルムに溶解し、セライトでさらに濾過して、残存する触媒を除去した。濃縮し、メタノールで再沈殿し、ソックスレット(Soxlet)で２４時間洗浄した。収率：７２％、分子量：Ｍｗ＝１５０，０００、Ｍｎ＝６３，０００、ＰＤＩ（多分散性）：２．４ Example 13
Synthesis of polymer of formula 4

In the formula, l ₂ is an integer of 1 to 100,000, and m ₂ is an integer of 1 to 100,000.
Compound (8) 0.55 g, 9,9-bis (4-octylphenyl) fluorene-2,7-bisboronic acid glycol ester 0.38, and N, N-di (4-bromophenyl) -N, N- 0.075 g of bis (4-methoxyphenyl)-[1,1-biphenyl] -4,4-diamine is dissolved in 10 mL of toluene, and 2.5 mL of water, 0.55 g of K ₃ PO _4, tricaprylylmethyl After 0.02 g of ammonium chloride was added, nitrogen gas was bubbled for 30 minutes. After adding 0.01 g of tetrakistriphenylphosphine palladium (0) to the reaction mixture, the mixture was reacted at 89 ° C. for 24 hours. The obtained reaction liquid was cooled to room temperature, precipitated in 200 mL of methanol, and the polymer was filtered. Thereafter, the filtered polymer was dissolved in chloroform and further filtered through Celite to remove the remaining catalyst. Concentrated, re-precipitated with methanol and washed with Soxlet for 24 hours. Yield: 72%, molecular weight: Mw = 150,000, Mn = 63,000, PDI (polydispersity): 2.4

  FIG. 8 shows the photoluminescence (PL) spectrum of the electroluminescent polymer represented by Formula 4 in a chloroform solution and on a film, respectively. As is clear from this figure, the maximum peak of the photoluminescence (PL) spectrum in the solution and on the film is observed at around 556 nm corresponding to the blue emission region.

Comparative Example 1
An electroluminescent polymer having the following repeating unit was synthesized by the method disclosed in WO02 / 077060 (Mw = 180,000).

Examples 14-18 and Comparative Example 2
Production of electroluminescent element An ITO (indium tin oxide) electrode was formed on a glass substrate. Thereafter, a polymer for an electroluminescent device as shown in Table 1 below was spin-coated on the ITO electrode to form a light emitting layer having a thickness of 600 to 1500 mm. Al: Li was vacuum-deposited on the light emitting layer to form an aluminum / lithium electrode having a thickness of 100 to 1200 mm, thereby producing an organic electroluminescent device, and then the light emission characteristics were measured. The results are shown in Table 1 below.

  FIG. 7 shows an electroluminescent spectrum obtained from the electroluminescent device (Example 14) using the electroluminescent polymer represented by Formula 2, and the maximum peak corresponds to the blue light emitting region. It is 426 nm and the shoulder peak is 447 nm. With such a narrow wavelength band, high color purity is obtained, and the peak due to the excimer generally observed in the vicinity of 530 nm in the electroluminescent spectrum of the polyfluorene polymer is not observed in the present invention. Thereby, it is recognized that the used polymer compound is a substance having high luminous efficiency. FIG. 9 shows an electroluminescent spectrum obtained from an electroluminescent device (Example 18) using an electroluminescent polymer represented by Formula 4, and has a maximum peak at 455 nm and is narrow. It exhibits high color purity depending on the wavelength band.

  In the above table, the result of Example 14 shows the characteristics of the electroluminescent device manufactured using the light emitting layer made of the compound of Example 9, and the characteristics of other polyfluorene polymers. It is an excellent property that cannot be predicted in light of In particular, the above elements with color coordinates x, y = 0.160, 0.080 have color coordinates that substantially match NTSC standard blue. Furthermore, the external quantum efficiency of 1.18% seems to be the highest value among the homopolyfluorene systems known so far. In Examples 15, 16, 17 and 18 using the amine-based Ar moiety of Formula 1, a decrease in drive start voltage is observed. In particular, in Example 15, a significant increase in quantum efficiency is observed. This is because the introduction of a fluorenyl group that is a bulky substituent causes the substituent to have the same structure as the main chain, and as a result, the sequence between the main chain and the substituent becomes random. In addition, aggregation and intermolecular excimer formation due to substituents are inhibited, and therefore aggregation and / or excimer formation, which appears to be the greatest problem in the region of polyfluorene-based polymers, is suppressed. Further, intramolecular or intermolecular energy transfer from a substituent having a short wavelength to the main chain can be realized. The fluorenyl group substituted at the 9-position of the main chain fluorene suppresses rotational and vibrational modes and dramatically reduces non-radiative damping. Therefore, the organic electroluminescent polymer of the present invention has high luminous efficiency, and an organic electroluminescent device using the same has high color purity, high luminance, and high efficiency. In conclusion, the electroluminescent polymer of the present invention is suitable for commercial use of electroluminescent devices.

  As described above, the present invention provides an organic electroluminescent polymer having a 9,9-di (fluorenyl) -2,7-fluorenyl unit and an organic electroluminescent device produced using the same. The electroluminescent polymer of the present invention is excellent in thermal stability, has high luminous efficiency and solubility, and plays a role in minimizing the interaction between molecules. Furthermore, the above polymer can reduce the disadvantages of the conventional polyfluorene polymer, and can be used as a blue, green and red host material of an electroluminescent device, so that it is excellent. Exhibits good luminescent properties.

  While preferred embodiments of the invention have been disclosed for purposes of illustration, those skilled in the art will recognize that various modifications, additions and alterations can be made without departing from the scope and spirit of the invention as disclosed in the appended claims. It will be understood that alternatives are possible.

The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description with reference to the accompanying drawings.
FIG. 1 is a schematic cross-sectional view showing the structure of a conventional organic electroluminescent device including a substrate / anode / hole transport layer / light emitting layer / electron transport layer / cathode. FIG. 2 is a diagram schematically showing a monomer synthesis reaction of the electroluminescent polymer represented by Formula 2 of the present invention. FIG. 3 is a diagram schematically showing a monomer synthesis reaction of the electroluminescent polymer represented by Formula 4 of the present invention. FIG. 4 is a ¹ H-NMR spectrum of the monomer represented by the compound (2) of the present invention. FIG. 5 is a ¹ H-NMR spectrum of the electroluminescent polymer represented by Formula 2 of the present invention. FIG. 6 is a photoluminescence (PL) spectrum in a chloroform solution and a film of an electroluminescent polymer represented by Formula 2 of the present invention, respectively. FIG. 7 is an electroluminescence (EL) spectrum of an electroluminescent device manufactured using the electroluminescent polymer represented by Formula 2 of the present invention. FIG. 8 is a photoluminescence (PL) spectrum in a chloroform solution and a film of the electroluminescent polymer represented by Formula 4 of the present invention, respectively. FIG. 9 is an electroluminescence (EL) spectrum of an electroluminescent device manufactured using the electroluminescent polymer represented by Formula 4 of the present invention.

Claims (12)

Organic electroluminescent polymer having 9,9-di (fluorenyl) -2,7-fluorenyl unit represented by the following formula 1:

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and are each a linear or branched alkyl group having 1 to 20 carbon atoms; unsubstituted or a linear chain having 1 to 20 carbon atoms Or an aryl group substituted with at least one substituent selected from the group consisting of branched alkyl and alkoxy groups; at least one heteroatom selected from the group consisting of F, S, N, O, P and Si A linear or branched alkyl group having 1 to 20 carbon atoms and having at least one heteroatom selected from the group consisting of F, S, N, O, P and Si; An aryl group substituted with at least one substituent selected from the group consisting of a chain or branched alkyl group and an alkoxy group; an unsubstituted or linear or branched alkyl group having 1 to 20 carbon atoms 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 an alkoxy group and an aryl group having a heterocyclic portion having 2 to 24 carbon atoms; Or a heterocycle having 2 to 24 carbon atoms substituted with at least one substituent selected from the group consisting of a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms and containing at least one heteroatom. An aryl group having a moiety; a substituted or unsubstituted trialkylsilyl group having 3 to 40 carbon atoms; a substituted or unsubstituted arylsilyl group having 3 to 40 carbon atoms; a substituted or unsubstituted carbazole group having 12 to 60 carbon atoms A substituted or unsubstituted phenothiazine group having 6 to 60 carbon atoms; or a substituted or unsubstituted arylamine group having 6 to 60 carbon atoms;
R ₅ , R ₆ , R ₇ and R ₈ are the same or different and each represents hydrogen; a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms; unsubstituted or having 1 to 20 carbon atoms An aryl group substituted with at least one substituent selected from the group consisting of linear or branched alkyl and alkoxy groups; at least one selected from the group consisting of F, S, N, O, P and Si A C1-C20 linear or branched alkyl or alkoxy group having a heteroatom; 1 carbon containing at least one heteroatom selected from the group consisting of F, S, N, O, P and Si Aryl group substituted with at least one substituent selected from the group consisting of -20 linear or branched alkyl and alkoxy groups; unsubstituted or having 1 to 1 carbon atoms An aryl group substituted with at least one substituent selected from the group consisting of 20 straight-chain or branched-chain alkyl and alkoxy groups and having a heterocyclic moiety having 2 to 24 carbon atoms; F, S, N, O Substituted with at least one substituent selected from the group consisting of straight-chain or branched alkyl and alkoxy groups having 1 to 20 carbon atoms and containing at least one heteroatom selected from the group consisting of P and Si An aryl group having a heterocyclic portion having 2 to 24 carbon atoms; a substituted or unsubstituted trialkylsilyl group having 3 to 40 carbon atoms; a substituted or unsubstituted arylsilyl group having 3 to 40 carbon atoms; Substituted or unsubstituted carbazole group having ˜60; substituted or unsubstituted phenothiazine group having 6 to 60 carbon atoms; or substituted or unsubstituted having 6 to 60 carbon atoms There reel amine groups;
a, b, c and d are the same or different and each is an integer of 1 to 3;
Ar is selected from the group consisting of a substituted or unsubstituted aromatic moiety having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 60 carbon atoms, and combinations thereof; and
l is an integer of 1 to 100,000, m is an integer of 0 to 100,000, and n is an integer of 1 to 100,000. The organic electroluminescent polymer according to claim ₁ , wherein each of R ₁ , R ₂ , R ₃ and R ₄ is selected from the following group:

The organic electroluminescent polymer according to claim 1, wherein R ₅ and R ₆ are each selected from the following group:

In the formula, R ₉ and R ₁₀ are the same or different and each represents a linear or branched alkyl group having 1 to 20 carbon atoms;
R ₁₁ is hydrogen or a linear or branched alkyl, alkoxy or trialkylsilyl group having 1 to 20 carbon atoms;
R ₁₂ and R ₁₃ are the same or different and are each a linear or branched alkyl group having 1 to 20 carbon atoms;
R ₁₄ , R ₁₅ and R ₁₆ are the same or different and each represents a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms; or an unsubstituted or straight chain having 1 to 20 carbon atoms or An aryl group substituted with at least one substituent selected from the group consisting of branched alkyl and alkoxy groups;
R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ are the same or different and are each hydrogen; a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms; or an unsubstituted group; Or an aryl group substituted with at least one substituent selected from the group consisting of a linear or branched alkyl and alkoxy group having 1 to 20 carbon atoms;
X is O or S;
Y and Z are N; and
a is an integer of 1 to 3. The organic electroluminescent polymer according to claim 1, wherein R ₇ and R ₈ are each selected from the following group:

Ar is the following group:
(I) a substituted or unsubstituted arylene group having 6 to 60 carbon atoms;
(Ii) a substituted or unsubstituted heterocyclic arylene group having 2 to 60 carbon atoms, wherein the aromatic ring contains at least one heteroatom selected from the group consisting of N, S, O, P and Si;
(Iii) a substituted or unsubstituted arylene vinylene group having 6 to 60 carbon atoms;
(Iv) a substituted or unsubstituted arylamine group having 6 to 60 carbon atoms;
The organic electroluminescent polymer according to claim 1, selected from (v) a substituted or unsubstituted carbazole group having 12 to 60 carbon atoms; and (vi) a combination thereof.
Here, Ar is selected from the group consisting of a linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms; an unsubstituted or linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms An organic electroluminescent polymer, which may include an aryl group substituted with at least one substituent selected from the group consisting of: a cyano group (—CN); and a silyl group.   The organic electroluminescent polymer according to claim 1, wherein the ratio of l: m is in the range of 5:95 to 95: 5.   The organic electroluminescence according to claim 5, wherein when Ar is a substituted or unsubstituted arylamine group having 6 to 60 carbon atoms, Ar is present in an amount of 5 to 15 mol% in the electroluminescent polymer. Nescent polymer. The organic electroluminescent polymer according to claim 1, wherein the organic electroluminescent polymer has the following formula 2.

In the formula, n ₁ is an integer of ₁ to 100,000. The organic electroluminescent polymer according to claim 1, wherein the organic electroluminescent polymer has the following formula 3.

In the formula, l ₁ is an integer of ₁ to 100,000, and m ₁ is an integer of ₁ to 100,000. The organic electroluminescent polymer according to claim 1, wherein the organic electroluminescent polymer has the following formula 4.

In the formula, l ₂ is an integer of 1 to 100,000, and m ₂ is an integer of 1 to 100,000.   An organic electroluminescent device having at least one layer containing the polymer according to claim 1 between an anode and a cathode, wherein the layer is a hole transport layer, a light emitting layer, an electron transport layer or a hole. An organic electroluminescent device which is a blocking layer.   The electroluminescent device comprises an anode / light-emitting layer / cathode, anode / hole transport layer / light-emitting layer / cathode, or anode / hole transport layer / light-emitting layer / electron transport layer / cathode structure. Item 12. The organic electroluminescent device according to Item 11.

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