KR20160074382A - Material for organic light-emitting device and orgaic organic light-emitting device including the same - Google Patents

Abstract

Disclosed are a material for an organic light-emitting device and an organic light-emitting device comprising the same. The material for an organic light-emitting device comprises a repeating unit (1), represented by chemical formula 1. The material for an organic light-emitting device has excellent electrical properties and thermal stability. The organic light-emitting device using the material for an organic light-emitting device can have high efficiency and long lifespan.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for an organic light emitting device and an organic light emitting device including the same.

A material for an organic light emitting device and an organic light emitting device including the same are presented.

An organic light-emitting device is a self-light-emitting device having a wide viewing angle, excellent contrast, fast response time, excellent luminance, driving voltage and response speed characteristics, and being able to have multiple colors .

According to an example, the organic light emitting element may include an anode, a cathode, and an organic layer interposed between the anode and the cathode and including a light emitting layer. A hole transporting region may be provided between the anode and the light emitting layer, and an electron transporting region may be provided between the light emitting layer and the cathode. The holes injected from the anode move to the light emitting layer via the hole transporting region, and electrons injected from the cathode move to the light emitting layer via the electron transporting region. The carriers such as holes and electrons recombine in the light emitting layer region to generate excitons. This exciton changes from the excited state to the ground state and light is generated.

A material for an organic light emitting device, and an organic light emitting device employing the same. Specifically, the material for the organic light emitting device includes an ethylene skeleton as a main chain and a charge transport unit as a side chain.

According to one aspect, there is provided a material for an organic light emitting device comprising a repeating unit (1) represented by the following formula (1)

≪ Formula 1 >

In Formula 1,

R ¹ is selected from the group consisting of a single bond, a phenylene group, and a group represented by any one of the following formulas a1 to a9;

Among the above formulas (a1) to (a9)

R ²² is a C ₁ -C ₆ alkyl group, and X ²¹ and X ²² are each independently selected from an oxygen atom and a sulfur atom;

A is a divalent saturated aliphatic ring group;

X ¹ is a charge transport unit.

According to another aspect, there is provided a liquid crystal display comprising: a first electrode; A second electrode; And an organic film interposed between the first electrode and the second electrode; The organic layer includes the organic light-emitting device material represented by the general formula (1).

Since the organic light emitting device material has excellent electrical characteristics and thermal stability, the organic light emitting device employing the material for the organic light emitting device can have high efficiency and long life characteristics.

1 is a schematic cross-sectional view of an organic light emitting device according to an embodiment.

In the present specification, "X to Y" representing the numerical range means "X or more and Y or less ".

Unless otherwise stated, the measurement of the operation and physical properties is carried out under the conditions of a temperature of 20 to 25 占 폚 and a humidity of 40 to 50%.

As the organic light emitting element, a variety of organic light emitting element materials including a charge transporting material such as a hole transporting material may be used. The charge transporting material not only has the ability to transport charges to the light emitting layer but also has the function of preventing the excitons formed in the light emitting layer from entering the hole transporting region and / or the electron transporting region by recombination of holes and electrons. In addition, it has been considered that the hole transporting material has high charge mobility and high triplet energy, thereby achieving high efficiency of the organic light emitting device, in particular, green and blue.

In the method of manufacturing an organic light emitting device for a coating process, a charge transporting material having a polymer structure may be used from a process viewpoint. Among the charge transport materials of the polymer structure, those having an ethylene skeleton as a main chain and a charge transport unit as a side chain are also referred to as a side chain type polymer material. For example, Japanese Patent Application Laid-Open No. 2006-237592 discloses a hole transporting side chain type polymer material containing a hole transporting unit in a side chain. The side chain type polymeric material can have high triplet energy because the charge transport units are almost separated from each other by bonding. Further, since the charge transport units are arranged in the pendent form around the main chain, the charge transport units are easy to interact with each other and can have a high charge transporting degree. In this regard, the side chain type polymer material may be advantageous as a charge transporting material for green and blue organic light emitting devices.

The material for the organic light emitting diode may include a repeating unit (1) represented by the following formula (1). The material for the organic light emitting device may be a side chain type polymer material:

≪ Formula 1 >

In Formula 1,

R ¹ is selected from the group consisting of a single bond, a phenylene group, and a group represented by any one of the following formulas a1 to a9;

Among the above formulas (a1) to (a9)

R ²² is a C ₁ -C ₆ alkyl group, and X ²¹ and X ²² are each independently selected from an oxygen atom and a sulfur atom;

A is a divalent saturated aliphatic ring group;

X ¹ is a charge transport unit.

When the organic light emitting element is driven, a heat generation due to the internal resistance of the element may occur. The generation of heat can damage the material, and thus shorten the life of the organic light emitting element. In order to realize a long-life organic light-emitting device, it is preferable that the material for the organic light-emitting device including the charge transporting material is highly heat-resistant. However, the conventional organic light emitting device material, particularly the side chain type polymer material, is not sufficiently high in heat resistance.

In addition, a material for an organic light emitting device such as a charge transporting material may affect the efficiency of the organic light emitting device. An organic light emitting device using a conventional material for an organic light emitting element may not have a sufficient luminous efficiency.

The organic light emitting device material containing the repeating unit (1) represented by the above formula (1) can provide an organic light emitting device having high heat resistance and high efficiency. Although not limiting the technical scope of the present invention, it is believed that this is due to the mechanism described below. That is, the side chain type polymer material containing the repeating unit (1) represented by the above formula (1) includes a saturated aliphatic cyclic group A such as an adamantylene group in the side chain. Saturated aliphatic cyclic groups such as adamantylene groups provide a rigid structure, which can provide high heat resistance. Therefore, materials for an organic light emitting device having a saturated aliphatic cyclic group such as an adamantylene group are expected to have a high decomposition temperature (Td) and high heat resistance. In addition, the material for an organic light emitting diode including the repeating unit (1) represented by the formula (1) is expected to have a relatively high glass transition temperature (Tg) and high heat resistance. Therefore, the organic light emitting device including the organic light emitting element can suppress the denaturation or the change of the material and / or the organic film due to the heat generated by the driving, and thus can have a long life characteristic.

In the above formula (1), R ¹ may be selected from the group consisting of a single bond, a phenylene group and any one of the following formulas (a1) to (a9)

Among the above formulas (a1) to (a9)

R ²² is a C ₁ -C ₆ alkyl group, and X ²¹ and X ²² are independently selected from an oxygen atom and a sulfur atom.

For example, in the above formula (1), R ¹ may be selected from a phenylene group and a group represented by any one of the above formulas (a1) to (a9), but is not limited thereto.

As another example, in the above formula (1), R ¹ may be selected from a phenylene group and the above formula (a1), but is not limited thereto.

As another example, in the above formula (1), R ¹ may be a phenylene group, but is not limited thereto. In the above formula (1), R ¹ is preferably a phenylene group in view of easy radical polymerization reaction.

For example, in the formula (a1), R ²² may be a C ₁ -C ₃ alkyl group, but is not limited thereto.

In Formula 1, A may be a divalent saturated aliphatic cyclic group.

For example, in Formula 1, A is an adamantylene group, a diamantylene group, a triamantylene group, a tetramantylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, [2.1.0] pentyl group, a bicyclo [3.1.0] hexyl group, a bicyclo [2.1.1] hexyl group, a bicyclo [4.1.0] heptyl group, a bicyclo [2.2.1] heptyl group and a cuvanyl group It may be selected from ^{(cubanyl group, pentacyclo [4.2.0.0 2} , 5 .0 3, 8 .0 4, 7] octanyl group), but is not limited to such.

As another example, in the above formula (1), A may be selected from among adamantylene group, diamantylene group, triamantylene group and tetramantylene group, but is not limited thereto. In the above formula (1), if A is selected from an adamantylene group, a diamantylene group, a triamantylene group and a tetramantylene group, it may be preferable from the viewpoint of providing high heat resistance.

As another example, in the above formula (1), A may be an adamantylene group, but is not limited thereto.

In Formula 1, X ¹ may be a charge transport unit. The material for an organic light emitting diode according to an embodiment of the present invention is excellent in high heat resistance and light emitting efficiency and thus may be suitable as a hole transporting material, a hole injecting material, an electron transporting material, and / or an electron injecting material. Therefore, the charge transporting unit may be a hole transporting unit or an electron transporting unit, but the material for an organic light emitting device according to an embodiment of the present invention is particularly suitable for the hole injection layer or the hole transporting layer in terms of ionization potential and charge mobility. can do. Accordingly, in Formula 1, X ¹ may be a hole transport unit.

Since the material for an organic light emitting diode according to the present invention is excellent in high temperature durability and device luminous efficiency, it is suitably used as a hole transporting material or a hole injecting material, or as an electron transporting material or an electron injecting material. Thus, the charge transporting unit may be any of a hole transporting unit or an electron transporting unit, but the material for an organic light emitting device according to the present invention is particularly suitably used for a hole injection layer or a hole transporting layer in view of ionization potential and charge mobility. Therefore, X ¹ is preferably a hole transport unit.

For example, in the above formula (1), X ¹ represents a hole transporting unit such as an arylamine skeleton, a fluorene skeleton, a carbazole skeleton, a dibenzofuranyl skeleton, a dibenzothienyl skeleton, a fused ring thereof, ; And at least one of fluorenone skeleton, quinone skeleton, anthraquinone skeleton, diphenylquinone skeleton, thiopyran dioxide skeleton, oxazole skeleton, oxazole skeleton, triazole skeleton, imidazole skeleton, anthrone skeleton, bipyridine skeleton, And electron transport units such as a skeleton. However, the present invention is not limited thereto.

As another example, X ¹ in the above formula (1) may be a group represented by any one of the following formulas (b1) to (b13), but is not limited thereto:

Among the above-mentioned formulas b1 to b13,

^{R 311, R 312, R 313} , R 321, R 322, R 331, R 341, R 351, R 352, R 361, R 362, R 363, R 371, R 372, R 381, R 391, R 3101 , R ³¹¹¹ , R ³¹¹² , R ³¹¹³ , R ³¹²¹ , R ³¹²² , R ³¹²³ , R ³¹²⁴ , R ³¹²⁵ , R ³¹³¹ and R ³¹³² independently represent a hydrogen atom C ₁ -C ₆ alkyl group and a group represented by the following formulas c1 to c16 A group selected from any one of the groups;

Among the above formulas c1 to c16,

p is 0 or 1;

^{Z 11, Z 12, Z 21} , Z 31, Z 41, Z 42, Z 51, Z 52, Z 53, Z 61, Z 62, Z 71, Z 72, Z 81, Z 82, Z 91 and Z ⁹² Are independently selected from the group consisting of a C ₁ -C ₆ alkyl group, a methoxy group and any one of the following formulas d1 to d7;

Among the above-mentioned formulas d1 to d7,

alkyl is a C ₁ -C ₆ alkyl group;

Y ¹¹ , Y ¹² , Y ²¹ , Y ³¹ , Y ⁴¹ , Y ⁴² , Y ⁵¹ , Y ⁵² , Y ⁶¹ , Y ⁶² and Y ⁶³ are each independently a group represented by any one of the following formulas e1 to e11;

Among the above-mentioned formulas e1 to e11,

R ⁴¹¹ , R ⁴¹² , R ⁴²¹ , R ⁴³¹ , R ⁴⁴¹ , R ⁴⁴² , R ⁴⁵¹ , R ⁴⁵² , R ⁴⁶¹ and R ⁴⁶² are independently selected from a hydrogen atom, a C ₁ -C ₆ alkyl group, a phenyl group and a tolyl group do.

As another example, X ¹ in the above formula (1) may be represented by any one of the above-mentioned formulas b ¹ to b 5, b 8 and b 11, but is not limited thereto.

As another example, X ¹ in the formula ( ¹⁾ may be a group represented by any one of the formulas (b1) and (b11), but is not limited thereto.

For example, the formula b6 may be represented by the following formula b6-1, the formula b7 may be represented by the following formula b7-1 or b7-2, and the formula b8 may be represented by the formula b8-1 or b8-1, 2, the formula b9 may be represented by the following formula (b9-1), the formula (b10) may be represented by the formula (b10-1), and the formula (b12) may be represented by the formula And the formula b13 may be represented by the following formula b13-1:

For example, the formula c2 may be represented by the following formula c2-1 or c2-2, the formula c3 may be represented by the following formula c3-1, and the formula c4 may be represented by the formula c4-1 The formula c5 may be represented by the following formula c5-1 or c5-2, the formula c6 may be represented by the following formula c6-1 or c6-2, and the formula c7 may be represented by the following formula c7-1 Or c7-2, the formula c8 may be represented by the following formula c8-1, the formula c9 may be represented by the formula c9-1, and the formula c11 may be represented by the formula c11-1 or c11-2, wherein the formula c12 may be represented by the following formula c12-1 or c12-2, the formula c13 may be represented by the following formula c13-1, and the formula c14 may be represented by the formula c14 -1, and the formula c15 may be represented by the following formula c15-1 have:

For example, In the formula, c5, c5-1 and c5-2, Z ¹¹ and Z ¹² may be a independently, C ₁ -C ₆ alkyl group with each other, and the like.

For one example, the formula c6, c6-1 and c6-2, Z ²¹ is not however be group represented by any of the formula d1 to d3, like.

For example, Z ³¹ , Z ⁴¹ , Z ⁴² , Z ⁵¹ , Z ⁵² and Z ⁵³ in the above formulas c7 to c9, c7-1, c7-2, c8-1 and c9-1 independently of one another are C ₁ -C ₆ alkyl group, a methoxy group and may be selected from a group represented by any one of the d1 and d2, but is not limited to such.

For example, in the above formulas c13 and c13-1, Z ⁷¹ and Z ⁷² may be independently selected from the groups represented by any one of the above formulas d1 to d5, but are not limited thereto.

For example, Z ⁸¹ , Z ⁸² , Z ⁹ 1, and Z ⁹² in the above formulas c14, c15, c14-1, and c15-1 may independently be groups represented by the above formula d1 or d6, It is not.

For example, the formula d2 may be represented by the following formula d2-1 or d2-2, the formula d3 may be represented by the following formula d3-1, and the formula d4 may be represented by the formula D5 may be represented by the following formula d5-1, d6 may be represented by the following formula d6-1, and d7 may be represented by the following formula d7-1:

For example, the formula e1 may be represented by the following formula e1-1, the formula e2 may be represented by e2-1 or e2-2, the formula e3 may be represented by the following formula e3-1 , The formula e4 may be represented by the following formula e4-1, the formula e5 may be represented by the following formula e5-1, the formula e6 may be represented by the following formula e6-1, The formula e8 may be represented by the following formula e8-1, the formula e9 may be represented by the following formula e9-1, and the formula e10 may be represented by the following formula e10-1 And the formula e11 may be represented by the following formula: e11-1:

For example, the e1 to e11, e1-1, e2-1, e2-2, e3-1, e4-1, e5-1, e6-1, e7-1, e8-1, e9-1, e10 of 1 and ^{e11-1, R 411, R 412,} R 421, R 431, R 441, R 442, R 451, R 452, R 461 and R ⁴⁶² are independently a hydrogen atom, C ₁ -C ₆ together An alkyl group, a phenyl group, and a tolyl group, but the present invention is not limited thereto.

As another example, among the above-mentioned formulas e2, e2-1 and e2-2, R ⁴¹¹ and R ⁴¹² independently of each other may be a C ₁ -C ₆ alkyl group, but are not limited thereto.

As another example, in the above formulas e5 and e5-1, R ⁴²¹ may be selected from a phenyl group and a tolyl group, but is not limited thereto.

R ⁴³¹ , R ⁴⁴¹ , R ⁴⁴² , R ⁴⁵¹ , R ⁴⁵² , R ⁴⁶¹ and R ⁴⁶² in the above formulas e8 to e11, e8-1, e9-1, e10-1 and e11-1 are independently Which may be, but not limited to, a C ₁ -C ₆ alkyl group.

For example, in the above formulas b1 to b13, R ³¹¹ , R ³¹² , R ³¹³ , R ³²¹ , R ³²² , R ³³¹ , R ³⁴¹ , R ³⁵¹ , R ³⁵² , R ³⁶¹ , R ³⁶² , R ³⁶³ , R ³⁷¹ , R ³⁷² , R ³⁸¹ , R ³⁹¹ , R ³¹⁰¹ , R ³¹¹¹ , R ³¹¹² , R ³¹¹³ , R ³¹¹² , R 3122, R ³¹²³ , R ³¹²⁴ , R ³¹²⁵ , R ³¹³¹ and R ³¹³² are independently of each other, Z ¹¹ , Z ¹² , Z ²¹ , Z ³¹ , Z ⁴¹ , Z ⁴² , Z ⁵¹ , Z ⁵² , Z ⁵³ , Z ⁶¹ , Z ⁶² , Z ⁷¹ , Z ⁷² , Z ⁸¹ , Z ^82, Z ⁹¹ and Z ⁹² are, each independently, may be selected from the group represented by any of the hydrogen atoms, C ₁ -C ₆ alkyl group, a methoxy group and the formula d1 to d7 to one, Y ^11, Y ^12, Y to each other ²¹ , Y ³¹ , Y ⁴¹ , Y ⁴² , Y ⁵¹ , Y ⁵² , Y ⁶¹ , Y ⁶² and Y ⁶³ may be phenylene groups, but are not limited thereto.

In one embodiment, in Formula 1, R ¹ is a phenylene group or a group represented by the general formula a1, and A is selected from an adamantylene group, a diadamantylene group, a triadamantylene group, and a tetramantylene group , And X ¹ is a group represented by any one of the above formulas b1 to b5, b8, and b11, but is not limited thereto.

In another embodiment, in Formula 1, R ¹ is a phenylene group and A is an adamantylene group, but is not limited thereto.

In another embodiment, the repeating unit (1) represented by the formula (1) may be represented by the following formula (1a), but is not limited thereto:

<Formula 1a>

In the formula (1a)

X ¹ refers to the description of the formula (I).

The material for the organic light emitting diode may include n repeating units (1) represented by the formula (1).

In one embodiment, the organic light emitting device material containing n repeating units (1) represented by the formula (1) may be represented by the following formula (1-1), but is not limited thereto:

&Lt; Formula 1-1 >

In Formula 1-1, n may be an integer of 20 to 500. If n is less than 20, the film-forming property may be deteriorated and it may be undesirable. If n exceeds 500, the material may be undesirably embrittlement.

For example, in Formula 1-1, n may be an integer of 100 to 300, but is not limited thereto.

For example, the total number of repeating units of the organic light emitting device material may be 20 to 500, but is not limited thereto.

For example, the material for the organic light emitting diode may include 10 to 100 mol% of the repeating unit (1) represented by the formula (1) among all the structural units, but is not limited thereto. When the content of the repeating unit (1) represented by the above formula (1) in the total constitutional units is 10 mol% or more, the heat resistance can be increased.

As another example, the material for the organic light emitting diode may include 30 to 100 mol% of the repeating unit (1) represented by the formula (1) among all the structural units, but is not limited thereto. When the above range is satisfied, the Td and Tg of the material for an organic light emitting device can be improved.

As another example, the material for the organic light emitting diode may include 60 to 100 mol% of the repeating unit (1) represented by the formula (1) among all the structural units, but is not limited thereto.

(1) represented by the general formula (1) is less than 100 mol%, that is, when the material for an organic light emitting device is a mixture of the repeating unit (1) represented by the general formula (1) In the case of a copolymer containing a repeating unit derived from an ethylenically unsaturated monomer (hereinafter, the "repeating unit derived from another ethylenically unsaturated monomer" is referred to as "remaining repeating unit"), the remaining repeating unit is particularly limited It is not.

The ratio of each repeating unit can be arbitrarily adjusted by changing the ratio of the monomer used in polymerizing the material for an organic light emitting element. The proportion of each repeating unit contained in the total constituent units can be measured by NMR.

For example, the remaining repeating unit may be a repeating unit (2) represented by the following general formula (2), but is not limited thereto. The material for an organic light emitting diode according to an embodiment of the present invention may be a copolymer including a repeating unit (1) represented by the formula (1) and a repeating unit (2) represented by the following formula (2) Not:

(2)

In Formula 2,

R ¹⁰ refers to the description of R ¹ in the above formula (1);

X ¹⁰ refers to the description of X ¹ in the above formula (1);

q is 0 or 1;

For example, in formula (2), when q is 0, (X ¹⁰ ) _q may represent a hydrogen atom.

For example, the other ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, methylstyrene, methoxystyrene, ethylstyrene, butylstyrene, hexylstyrene, octylstyrene, chlorostyrene, phenylstyrene, vinyltoluene, vinylbenzylmethylether (Meth) acrylic acid; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, (Meth) acrylate, 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate Acrylic compounds and derivatives thereof; Carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl propionate and vinyl benzoate; A vinyl cyanide compound such as (meth) acrylonitrile; Vinyl ether compounds such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether and vinyl phenyl ether; And olefin compounds such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene, butadiene, isoprene and chloroprene.

The other ethylenically unsaturated monomer may include one kind or two or more kinds of different kinds, but is not limited thereto.

When the material for the organic light emitting element is a copolymer, the bonding method is not particularly limited. For example, the material for the organic light emitting diode may be any one of a random copolymer, an alternating copolymer, a periodic copolymer and a block copolymer, but is not limited thereto.

In one embodiment, the material for the organic light emitting diode may be represented by the following formula (3), but is not limited thereto:

(3)

In Formula 3,

R ¹ and R ¹⁰ independently of one another refer to the definition of R ¹ in formula (1) above;

A refers to the definition of A in the above formula (1);

X ¹ and X ¹⁰ independently of one another refer to the definition of X ^{1 in} the above formula (1);

q refers to the definition of q in Formula 2 above;

n is an integer from 20 to 500;

m is an integer of 1 to 180;

For example, in Formula 3, when q is 0, (X ¹⁰ ) _q may represent a hydrogen atom. For example, in Formula 3, q may be 1, but is not limited thereto. When q in Formula 3 is 1, the luminous efficiency can be improved.

For example, in Formula 3, n and m may satisfy 0.1? N / (n + m)? 1, but are not limited thereto. That is, the material for the organic light emitting diode represented by Formula 3 may be composed of 10 to 100 mol% of the repeating units (1) and the remaining repeating units (2).

As another example, in Formula 3, 0.3? N / (n + m)? 1 may be satisfied, but is not limited thereto. That is, the material for the organic light emitting diode represented by Formula 3 may be composed of 30 to 100 mol% of the repeating unit (1) and the remaining repeating unit (2). When the above range is satisfied, the Td and Tg of the material for the organic light emitting diode can be improved.

As another example, in Formula 3, 0.6? N / (n + m)? 1 may be satisfied, but is not limited thereto. That is, the material for the organic light emitting diode represented by Formula 3 may be composed of 60 to 100 mol% of the repeating units (1) and the remaining repeating units (2).

For example, in Formula 3, n and m may satisfy 20? N + m? 500, but are not limited thereto.

The terminal of the material for the organic light emitting diode is not particularly limited and may be appropriately selected depending on the kind of the monomer to be used, but may be generally a hydrogen atom.

The structure of each repeating unit contained in the material for an organic light emitting device may be the same or different.

The number-average molecular weight (Mn) of the material for the organic light-emitting device is not particularly limited, but may be, for example, 5000 to 100. Specifically, it may be 6,000 to 10. When the number average molecular weight is 5000 or more, there is an advantage that the film formed by using it has no brittleness. On the other hand, when the number average molecular weight is less than 1 million, there is an advantage that the material for an organic light emitting diode is not brittle when a film is formed using the material.

The number average molecular weight and the degree of dispersion (Mw / Mn) of the polymer were measured by size exclusion chromatography using polystyrene as a standard material.

The material for the organic light-emitting device was evaluated by a 5% weight reduction temperature (decomposition temperature Td) (占 폚) measured by the method described in Examples, and the high heat resistance was high heat resistance. The Td of the material for the organic light emitting device may be 410 캜 or higher, specifically 420 캜 or higher, and more specifically 430 캜 or higher. If Td is less than 410 占 폚, it may be difficult to drive the organic light emitting element for a long time by decomposition and / or deterioration of the material. The upper limit of Td is not particularly limited, but may be 550 캜, for example.

The material for the organic light emitting device is excellent in luminous efficiency. The glass transition temperature (Tg) (占 폚) of the material for the organic light emitting diode may be 145 占 폚 or higher, specifically 155 占 폚 or higher, but is not limited thereto . The upper limit of the Tg is not particularly limited, but may be, for example, 230 deg. The Tg can be measured by the method described in the examples.

Both Tg and Td satisfy the above range, which may be particularly preferable for providing an organic light emitting device having high heat resistance and high efficiency.

A high charge mobility can be achieved as the material for the organic light emitting device. If the charge carrier mobility is measured using impedance spectroscopy, it can be greater than or equal to ^{1 × 10 -6 (cm 2 /} Vs), and more specifically may be at least ^{1 × 10 -4 (cm 2 /} Vs).

The material for an organic light emitting diode comprising the repeating unit (1) represented by the above formula (1) can be produced by polymerizing an ethylenically unsaturated monomer represented by the following formula (I)

(I)

In one embodiment, the material for the organic light emitting diode may be prepared by a styrene derivative represented by the following formula (Ia), but is not limited thereto:

<Formula Ia>

In the above formulas (I) and (Ia), R ¹ , A and X are described with reference to the description in the above formula (1).

The styrene derivative that can be used in the production of the organic light emitting device material may be any of the following exemplary monomers 1 to 170, but is not limited thereto:

When the material for the organic light emitting device is a copolymer, it may be formed by polymerizing an ethylenically unsaturated monomer constituting the remaining repeating unit in any one or more of the above Exemplary Monomers 1 to 170. Or the above exemplified monomers 1 to 170 may be used alone or in combination of two or more.

The monomer used for the material for the organic light emitting device can be synthesized by using a known synthesizing method, and the structure of the monomer can also be confirmed by using NMR and LC-MS.

The polymerization method of the material for the organic light emitting element is not particularly limited, and for example, a known polymerization method such as a radical polymerization reaction, an anionic polymerization, and a cationic polymerization reaction can be used.

Examples of the solvent used in the polymerization of the material for the organic light emitting device include toluene, xylene, diethyl ether, chloroform, ethyl acetate, methylene chloride, tetrahydrofuran, acetone, acetonitrile, N, Sulfoxide, and the like. As another example, the solvent may be toluene. The solvent may be used alone, or two or more solvents may be used together.

The monomer concentration in the solvent (total monomer when a plurality of monomers are used) may be 10 to 90 wt% with respect to the whole reaction solution. Specifically, the monomer concentration in the solvent may be 15 to 80% by weight, but is not limited thereto.

The polymerization temperature may be 40 to 100 DEG C from the viewpoint of molecular weight control, but is not limited thereto.

The polymerization reaction may be conducted for 30 minutes to 24 hours, but is not limited thereto.

The solvent to which the monomer is added may be degassed before addition of the polymerization initiator. For example, the degassing process may be freeze deaeration, degassing using an inert gas such as nitrogen gas, but is not limited thereto.

As the polymerization initiator, known ones can be used, for example, but not limited to, benzophenone, benzoyl peroxide, acetyl peroxide, lauroyl peroxide and azobisisobutyronitrile. The amount of the polymerization initiator to be added may be, for example, from 0.0001 to 1 mole based on 1 mole of the total monomers used in the production of the material for an organic light emitting device, but is not limited thereto.

A method of synthesizing a material for an organic light emitting device comprising the repeating unit (1) represented by the above formula (1) can be easily recognized by those skilled in the art with reference to the following synthesis examples.

The material for the organic light emitting diode may be used for an organic light emitting diode. A first electrode; A second electrode; And an organic film interposed between the first electrode and the second electrode; The organic layer may include an organic light emitting diode. From the viewpoint of longevity and high efficiency of the organic light emitting device, the material for the organic light emitting device may be included in the hole injecting layer and / or the hole transporting layer.

1 is a cross-sectional view of an organic light emitting diode 100 according to an embodiment of the present invention.

1 is a plan view of an organic light emitting device 100 according to an embodiment of the present invention. Referring to FIG. 1, the organic light emitting device 100 includes a first electrode 120, a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, Electrode 180. However, the present invention is not limited to this structure. The organic light emitting device includes a single layer / light emitting layer / electron transport layer / second electrode having a first electrode / hole injecting function and a hole transporting function or a single layer / light emitting layer / electron transporting layer / Electron injecting layer / second electrode.

The organic light emitting element may be a top emission type or a back emission type.

Hereinafter, an organic light emitting device according to an embodiment of the present invention will be described with reference to FIG.

The organic light emitting device 100 includes a substrate 110, a first electrode 120 disposed on the substrate 110, a hole injection layer 130 disposed on the first electrode 120, a hole injection layer 130, A light emitting layer 150 disposed on the hole transporting layer 140, an electron transporting layer 160 disposed on the light emitting layer 150, an electron injection layer 160 disposed on the electron transporting layer 160, And a second electrode 180 disposed on the electron injection layer 170 and the electron injection layer 170.

The substrate 110 may be a substrate used as a typical organic light emitting device. For example, the substrate 110 may be a glass substrate, a semiconductor substrate, or a transparent plastic substrate.

The first electrode 120 is, for example, an anode, and may be formed on the substrate 110 using a deposition method, a sputtering method, or the like. Specifically, the first electrode 120 may be formed as a transmissive electrode by a metal, an alloy, a conductive compound, or the like having a large work function. The first electrode 120 may be formed of indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) or the like which is transparent and excellent in conductivity. Also, the first electrode 120 may be formed as a reflective electrode using magnesium (Mg), aluminum (Al), or the like.

The hole injection layer 130 is a layer having a function of facilitating the injection of holes from the first electrode 120. The hole injection layer 130 is formed by a vacuum deposition method, a spin coating method, an ink jet method, 1 electrode 120, as shown in FIG. In addition, the hole injection layer 130 may be formed specifically at a thickness of from about 10 nm to about 1,000 nm, more specifically, from about 10 nm to about 100 nm.

The hole injection layer 130 can be formed using a known material in addition to the organic light emitting element material containing the repeating unit (1) represented by the above formula (1). For example, N, N'-di Phthalocyanine compounds such as phenyl-N, N'-bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl 4,4'- diamine (DNTPD), copper phthalocyanine, N, N'-diphenylbenzidine (NPB), 4,4 '- tris (3-methylphenylphenylamino) triphenylamine (m-MTDATA) , 4 "-tris {N, N-diphenylamino} triphenylamine (TDATA), 4,4 ' , PANI / DBSA (polyaniline / dodecylbenzenesulfonic acid), PEDOT / PSS (poly (3,4-ethylenedioxythiophene) / poly Poly (4-styrenesulfonate), PANI / CSA (polyaniline / camphor sulfonic acid), PANI / PSS (polyaniline) 4-styrenesulfonate): polyaniline) / poly (4-styrenesulfonate)).

When the material for the organic light emitting diode is used in the hole injection layer, the content of the organic light emitting material may be 50 to 100% by weight (dry weight), specifically 90 to 100% by weight (dry weight).

The hole transport layer 140 is a layer including a hole transport material having a function of transporting holes and may be formed on the hole injection layer 130 by using a vacuum deposition method, a spin coating method, an inkjet method, or the like. In addition, the hole transporting layer 140 can be formed specifically at a thickness of about 5 nm to about 500 nm, more specifically about 100 nm to about 250 nm. The hole transport layer 140 can be formed using a known material in addition to the organic light emitting element material containing the repeating unit (1) represented by the above formula (1), for example, N-phenylcarbazole, poly Carbazole derivatives such as vinyl carbazole, TPD (N, N'-bis (3-methylphenyl) -N, N'- diphenyl- [1,1-biphenyl] -4,4'- N, N'-diphenyl- [1,1-biphenyl] -4,4'-diamine), TCTA (4,4 ', 4 "-tris (N-carbazolyl) triphenylamine, 4,4 ', 4 "-tris (N-carbazolyl) triphenylamine), NPB (N, N'-bis (naphthalen- N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -benzidine).

When the material for the organic light emitting diode is used in the hole injection layer, the content of the organic light emitting material may be 50 to 100% by weight (dry weight), specifically 90 to 100% by weight (dry weight).

The light emitting layer 150 is a layer that emits light such as phosphorescence or fluorescence light and may be formed on the hole transport layer 140 by using a vacuum deposition method, a spin coating method, an inkjet method, or the like. The light emitting layer 150 may include a host material and a dopant material, or may include a material for an organic light emitting device including the repeating unit (1) represented by the formula (1). The light emitting layer 150 may be specifically formed to a thickness of about 10 nm to about 100 nm, more specifically about 20 nm to about 60 nm.

Further, the light emitting layer 150 may include a different host material, e.g., Alq ₃ (tris (8-quinolinolato) aluminum), CBP (4,4'-N, N'-dicabazole-biphenyl, N-vinylcarbazole), ADN (9,10-di (naphthalene-2-yl) anthracene, 9,10-di (naphthalen-2-yl) anthracene), TCTA, TPBI (1,3,5-tris (N-phenylbenzimidazole- Benzimidazol-2-yl) benzene), TBADN (3-tert-butyl-9,10-di (naphth-2-yl) anthracene, Bis (9-carbazole) -2,2'-dimethylbiphenyl, 4,4'-bis (9-carbazole) -2,2'-dimethylbiphenyl, dithiarylene, distyrylarylene, distyrylarylene) Dimethyl biphenyl), 2,4,6-tris (diphenylamino) -1,3,5-triazine, and the like.

The light emitting layer 150 may be formed as a light emitting layer that emits light of a specific color. For example, the light emitting layer 150 may be formed as a red light emitting layer, a green light emitting layer, and a blue light emitting layer.

When the light emitting layer 150 is a blue light emitting layer, known materials can be used as the blue dopant. For example, perylene and its derivatives, bis [2- (4,6-difluorophenyl) pyridinate ] Iridium (Ir) complexes such as picolinate iridium (III) (FIrpic) and the like can be used.

When the light emitting layer 150 is a red light emitting layer, known materials can be used as the red dopant. For example, rubrene and its derivatives, DCM (4- (Dicyanomethylene) -2-methyl-6- [ pyran) and its derivatives, Ir (piq) ₂ (p-dimethylamino) styryl] -4H-pyran, 4- (dicyanomethylene) an iridium complex such as acac (bis (1-phenylisoquinoline) (acetylacetonate) iridium (III)), an osmium (Os) complex or a platinum complex.

For example, coumarin and its derivatives, tris (2-phenylpyridine) iridium (III) (Ir (ppy) ₃ ) And the like can be used.

When the material for the organic light emitting diode is used for the light emitting layer, the content of the organic light emitting material may be 50 to 100% by weight (dry weight), specifically 90 to 100% by weight (dry weight).

The electron transporting layer 160 is a layer containing an electron transporting material having a function of transporting electrons and may be formed on the light emitting layer 150 by using a vacuum deposition method, a spin coating method, an inkjet method, or the like. Further, the electron transporting layer 160 can be formed specifically at a thickness of from about 10 nm to about 100 nm, more specifically, from about 15 nm to about 50 nm. The electron transporting layer 160 can be formed using a known electron transporting material in addition to the organic light emitting device material containing the recurring unit (1) represented by the above formula (1). For example, lithium quinolate (LiQ) Quinoline derivatives such as tris (8-quinolinato) aluminum (Alq ₃ ), 1,2,4-triazole derivatives (TAZ), bis (2-methyl-8- quinolinolato (P-phenylphenolato) -aluminum (BAlq), beryllium bis (benzoquinoline 10-orate) (BeBq ₂ ), and the like.

When the organic light emitting device material is used in an electron transporting layer, the content of the organic layer may be 50 to 100% by weight (dry weight), and more preferably 90 to 100% by weight (dry weight).

The electron injection layer 170 is a layer having a function of facilitating injection of electrons from the second electrode 180, and may be formed on the electron transport layer 160 using a vacuum deposition method or the like. In addition, the electron injection layer 170 can be formed specifically at a thickness of about 0.1 nm to about 10 nm, more specifically, about 0.3 nm to about 9 nm. The electron injection layer 170 can be formed using a known electron transporting material in addition to the material for the organic light emitting diode including the recurring unit (1) represented by the formula (1). For example, lithium fluoride (LiF) , Sodium chloride (NaCl), cesium fluoride (CsF), lithium oxide (Li ₂ O), barium oxide (BaO), or the like.

When the material for the organic light emitting diode is used for the electron injection layer, the content of the whole layer may be 50 to 100% by weight (dry weight), and specifically 90 to 100% by weight (dry weight).

The second electrode 180 is, for example, a cathode and may be formed on the electron injection layer 170 using a deposition method, a sputtering method, or the like. Specifically, the second electrode 180 may be formed as a reflective electrode with a metal, an alloy, a conductive compound, or the like having a small work function. The second electrode 180 may be formed of, for example, Li, Mg, Al, Al-Li, Ca, Mg-Mg, - silver (Mg-Ag) or the like. The second electrode 180 may be formed as a transmissive electrode using indium tin oxide (ITO), indium zinc oxide (IZO), or the like.

Although the structure of the organic light emitting device 100 according to the embodiment of the present invention has been described above, the structure of the organic light emitting device 100 according to one embodiment of the present invention is not limited to the above example . The organic light emitting device 100 according to an embodiment of the present invention may be formed using various structures of known organic light emitting devices. For example, the organic light emitting device 100 may not have one or more layers of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, and the electron injection layer 170. Each layer of the organic light emitting diode 100 may be formed as a single layer or a plurality of layers.

The organic light emitting diode 100 may include a hole blocking layer between the hole transport layer 140 and the light emitting layer 150 to prevent triplet excitons or holes from diffusing into the electron transport layer 160. The hole blocking layer can be formed, for example, by an oxadiazole derivative, a triazole derivative, a phenanthroline derivative or the like.

In the present specification, a C ₁ -C ₆ alkyl group means a linear, branched or cyclic aliphatic hydrocarbon monovalent group having 1 to 6 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, Propyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec- A hexyl group, an isohexyl group, and a cyclohexyl group.

Hereinafter, a material for an organic light emitting diode and an organic light emitting diode according to an embodiment of the present invention will be described in more detail with reference to the following Synthesis Examples and Examples, but the present invention is not limited to the following Synthesis Examples and Examples .

[Example]

Various analyzes were conducted according to the methods described below in the following Synthesis Examples.

(1) Number average molecular weight and weight average molecular weight measurement

Polystyrene reduced number average molecular weight (Mn) and dispersion degree

GPC (product name: LC-20AD, manufactured by Shimadzu Corporation) was used as the dispersion degree (Mw / Mn). At this time, 20 μL of a solution in which the polymer to be measured was dissolved in tetrahydrofuran (THF) to a concentration of about 0.05% by weight was injected into GPC. THF was used as the mobile phase of GPC and flowed at a flow rate of 1.0 mL / min. The column was PLgel MIXED-B (manufactured by Polymer Laboratories). A UV-VIS detector (product name: SPD-10AV, manufactured by Shimadzu Corporation) was used for the detector.

(2) NMR measurement

NMR measurement was carried out by dissolving 5 to 20 mg of a sample to be measured in about 0.5 mL of deuterated chloroform and using NMR (trade name: AVANCE III 300, manufactured by BRUKER, Inc.).

(3) Measurement of LC-MS

LC-MS (trade name: Agilent 6130B, manufactured by Agilent Technologies) was used for molecular weight measurement. The mobile phase was used in a ratio of MeOH: water: THF: = 70: 5: 25 (volume ratio). The dry gas temperature was 280 DEG C and the dry gas flow rate was 6.0 L / min. Ionization in the APCI method.

(4) Glass transition temperature measurement

The glass transition temperature (占 폚) was measured by DSC (trade name: DSC6000, manufactured by Seiko Instruments Inc.). Each of the polymers was heated from 30 占 폚 to 250 占 폚 at a heating rate of 10 占 폚 / minute under an argon atmosphere, followed by quenching to 50 占 폚. Then, the temperature was measured up to 250 DEG C at a heating rate of 10 DEG C per minute.

(5) 5% weight reduction Temperature measurement

TG / DTA (trade name: TG / DTA6000, manufactured by Seiko Instruments Inc.) was used to measure the 5% weight loss temperature (Td). Each of the polymers was measured at a temperature elevation rate of 10 DEG C per minute at 30 DEG C under an argon atmosphere up to 500 DEG C. [

Synthesis Example 1: Synthesis of Monomer A

The following scheme illustrates a method of synthesizing monomer A (another ethylenically unsaturated monomer 1)

4-Bromo-4 ', 4 "-dimethyltriphenylamine (10.0 g), 4-butylaniline (4.66 g) and [1,1'-bis (diphenylphosphino) (1.16 g), sodium tert-butoxide (3.00 g) and toluene (330 mL) were added and heated at 110 ° C for 2 hours. After cooling to room temperature, the insoluble material was passed through celite N ', N'-di- (p-tolyl) benzene-1,4-diamine (7.56 g) was added to the filtrate, and the solvent was distilled off under reduced pressure and purified by column chromatography. &Lt; / RTI &gt;

N, N'-di- (p-tolyl) benzene-1,4-diamine (2.00 g) and 4-bromostyrene (0.900 g ), Bis (tri-tert-butylphosphine) palladium (0.121 g), sodium tert-butoxide (0.914 g) and toluene (100 mL) were added and heated at 110 ° C for 6 hours. After cooling to room temperature, the insoluble material was filtered through celite. The solvent was distilled off from the filtrate under reduced pressure, and the residue was purified by column chromatography and recrystallization to obtain 1.76 g of Monomer A.

The structural analysis results of monomer A are shown below:

^{1 H-NMR (300MHz / CDCl} 3, δ (ppm): 7.29 ~ 6.95 (m, 24H), 6.66 (dd, 1H) 5.62 (d, 1H) 5.14 (d, 1H) 2.58 (t, 2H) 2.32 ( s, 6H), 1.64-1.59 (m, 2H), 1.42-1.35 (m, 2H) 0.98 (t,

LC-MS (APCI-Positive, m / z): [M + H] &lt; + &gt;

Synthesis Example 2: Synthesis of monomer B

The following scheme illustrates a method of synthesizing monomer B (another ethylenically unsaturated monomer 2)

A solution of aniline (2.79 g), 4-bromobenzocyclobutene (11.5 g), tris (dibenzylideneacetone) dipalladium (0.549 g) and tri-tert-butylphosphonium bromide tetrafluoro (0.696 g), sodium tert-butoxide (8.55 g) and toluene (150 mL), and the mixture was heated at 110 DEG C for 2 hours. After cooling to room temperature, the insoluble material was filtered through celite. The solvent was distilled off from the filtrate under reduced pressure, and the residue was purified by column chromatography to give N- (bicyclo [4.2.0] octa-1,3,5-triene-3-yl) ] Octa-1 (6), 2,4-triene-3-amine (9.16 g).

In a four-necked-flask, a solution of N- (bicyclo [4.2.0] octa-1,3,5-trien-3-yl) ), 2,4-triene-3-amine (6.12 g) and DMF (41.2 mL) were added followed by cooling with ice water. N-Bromosuccinimido (3.67 g) dissolved in DMF (20.6 mL) was added dropwise and stirred for 2 hours. Toluene (150 mL) was added, washed with water and dried over magnesium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by column chromatography to give N- (bicyclo [4.2.0] octa-1,3,5-trien-3-yl) -N- (4- bromophenyl) bicyclo [ 4.2.0] octa-1 (6) and 2,4-triene-3-amine (7.08 g).

(4.2.0) octa-1,3,5-trien-3-yl) -N- (4-bromophenyl) bicyclo [4.2.0] octane- Octane-1 (6), 2,4-triene-3-amine (4.88 g), 4-butylaniline (2.12 g), [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium g), sodium tert-butoxide (2.50 g) and toluene (70 mL) were added, and the mixture was heated at 120 DEG C for 6 hours. After cooling to room temperature, the insoluble material was filtered through celite. The solvent was distilled under reduced pressure from the filtrate and the residue was purified by column chromatography and recrystallization to give bicyclo [4.2.0] octa-1 (6), 2,4-trien-3-yl) N1-bicyclo [4.2.0] Octane-1,3,5-triene-3-yl) -N4- (4-butylphenyl) benzene-1,4-diamine (2.98 g).

(4.2.0) octa-1 (6), 2,4-trien-3-yl) N1-bicyclo [4.2.0] octa- 3-yl) -N4- (4-butylphenyl) benzene-1,4-diamine (2.00 g), 4- bromostyrene (0.640 mL), bis (tri- tert-butylphosphine) palladium 0.0476 g), sodium tert-butoxide (0.850 g) and toluene (23 mL), and the mixture was heated at 110 DEG C for 6 hours. After cooling to room temperature, the insoluble material was filtered through celite. The solvent was distilled off the filtrate under reduced pressure, and the residue was purified by column chromatography and recrystallization to obtain 2.14 g of monomer B.

The structural analysis results of monomer B are shown below:

^{1 H-NMR (300MHz / CDCl} 3, δ (ppm): 7.6 ~ 6.7 (br, 24H), 6.67 (dd, 1H) 5.61 (d, 1H) 5.10 (d, 1H) 3.09 (s, 8H) 2.8 ~ 2H), 1.61-1.56 (m, 2H), 1.36 (q, 2H) 0.93 (t, 3H)

LC-MS (APCI-Positive, m / z): [M] + 546,547,548,549.

Synthesis Example 3: Synthesis of monomer C

The following scheme illustrates a method of synthesizing monomer C (other ethylenically unsaturated monomer 3)

A solution of 4-dibromobenzene (66.1 g), 4-methylaniline (90.3 g), bisdiphenylphosphinylpellocene (15.7 g), palladium acetate (3.20 g), sodium tert- The side (80.7 g) and toluene (680 mL) were added and heated at 110 [deg.] C for 15 hours. After cooling to room temperature, a saturated aqueous ammonium chloride solution (1000 mL) was added, extracted with ethyl acetate, washed with brine, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting solid was washed with hexane and purified by column chromatography. The undissolved material was filtered through celite. The solvent was distilled under reduced pressure from the filtrate and purified by column chromatography to obtain N, N'-bis (4-methylphenyl) -1,4-phenylenediamine (50.6 g).

(4-methylphenyl) -1,4-phenylenediamine (2.50 g), 4-bromobenzocyclobutene (1.59 g), bis (tri-tert- Butylphosphine) palladium (0.0890 g), sodium tert-butoxide (1.67 g) and toluene (43 mL) were added and heated at 110 ° C for 6 hours. After cooling to room temperature, the insoluble material was filtered through celite. The solvent was distilled off from the filtrate under reduced pressure, and the residue was purified by column chromatography and recrystallization to obtain N1- (bicyclo [4.2.0] octa- (6), 2,4-trien-3-yl) -N1, N4- -4-trilbenzene-1,4-diamine (1.35 g).

In a four-necked-flask, a solution of N1- (bicyclo [4.2.0] octa-1 (6), 2,4-trien-3-yl) -N1, N4- 4-Bromostyrene (0.44 mL), bis (tri-tert-butylphosphine) palladium (0.0349 g), sodium tert-butoxide (0.649 g) and toluene And heated at 110 DEG C for 5 hours. After cooling to room temperature, the insoluble material was filtered through celite. The solvent was distilled off from the filtrate under reduced pressure, and purified by column chromatography and recrystallization to obtain monomer C (0.500 g).

The structural analysis results of monomer C are shown below:

^{1 H-NMR (300MHz / CDCl} 3, δ (ppm): 7.6 ~ 6.7 (br, 19H), 6.64 (dd, 1H) 5.60 (d, 1H) 5.11 (d, 1H) 3.10 (s, 4H) 2.31 ( s, 6H)

LC-MS (APCI-Positive, m / z): [M] &lt;

Synthesis Example 4: Synthesis of monomer D

The following scheme illustrates a method of synthesizing monomer D (another ethylenically unsaturated monomer 4)

(5.00 g), 4-vinylphenylboronic acid (2.24 g), tetrakis (triphenylporphine) palladium ( 0.730 g), potassium carbonate (3.50 g), THF (50 mL) and (13 mL), and the mixture was heated at 65 ° C for 8 hours. After cooling to room temperature, the insoluble material was filtered through celite. The solvent was distilled under reduced pressure from the filtrate and purified by column chromatography to obtain monomer D (4.45 g).

The structural analysis results of monomer D are shown below:

^{1 H-NMR (300MHz / CDCl} 3, δ (ppm): 7.94 ~ 7.81 (m, 4H), 7.67 ~ 7.63 (m, 1H), 7.43 ~ 7.37 (m, 6H), 7,17 ~ 7.11 (m, (M, 2H), 5.73 (d, 1H), 5.34 (d,

LC-MS (APCI-Positive, m / z): [M] + 418, 419, 420, 421.

Synthesis Example 5: Synthesis of Exemplary Monomer 28

The following scheme illustrates a method of synthesizing Exemplary Monomer 28:

In a four-necked flask, iron (III) chloride (450 mg) and bromobenzene (108 g) were added under an argon atmosphere and heated at 60 ° C for 10 minutes. A solution prepared by dissolving 1,3-dibromoadamantane (40.2 g) in bromobenzene (215 g) was added dropwise thereto, followed by stirring at 60 ° C for 4 hours. After cooling to room temperature, water (300 mL) was added, extracted with toluene, and the organic layer was washed with saturated brine. Dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was recrystallized to obtain 1,3-bis (4'-bromophenyl) adamantane (32.3 g).

(4'-bromophenyl) adamantane (3 g), potassium trifluorovinylborate (0.901 g), bis (tri-tert-butylphosphine) palladium (0.220 g), triethylamine (0.680 g), 1-propanol (20 mL) and toluene (80 mL) were added and heated at 110 ° C for 6 hours. After cooling to room temperature, the insoluble material was filtered through celite. The solvent was distilled off the filtrate under reduced pressure to obtain 1- (4'-bromophenyl) -3- (4'-vinylphenyl) -adamantane (1.25 g).

N, N'-di-p-tolylbenzene) 1,4-diamine (1.50 g) and 1- (4'-bromophenyl) - (1.25 g), bis (tri-tert-butylphosphine) palladium (0.0680 g), sodium tert-butoxide (0.512 g) and toluene And heated at 110 DEG C for 6 hours. After cooling to room temperature, the insoluble material was filtered through celite. The solvent was distilled off the filtrate under reduced pressure, and the residue was purified by column chromatography and recrystallization to obtain 0.6 g of an exemplary monomer 28. [

The structural analysis results of Exemplary Monomer 28 are shown below:

^{1 H-NMR (300MHz / CDCl} 3, δ (ppm): 7.36 ~ 6.91 (m, 24H), 6.53 (dd, 1H) 5.71 (d, 1H) 5.19 (d, 1H) 2.57 ~ 2.52 (m, 2H) (M, 2H), 1.37 (m, 2H), 1.21 (d, 2H) 0.93 (t, 3H)

LC-MS (APCI-Positive, m / z): [M + H] +733, 734, 735.

Synthesis Example 6: Synthesis of Exemplary Monomer 126

The following chemical reaction formula illustrates the synthesis of Exemplary Monomer 126:

(4'-bromophenyl) -3- (4'-vinylphenyl) - (4'-fluorophenyl) Adamantane (1.00 g), tetrakis (triphenylphosphine) palladium (0.0294 g), 2 M sodium carbonate aqueous solution (10 mL) and xylene (30 mL) were added and heated at 110 ° C for 3 hours and cooled to room temperature. The mixture was extracted with toluene, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was recrystallized in THF to obtain an exemplary monomer 126 (0.500 g).

The structural analysis results of Exemplary Monomer 126 are shown below:

^{1 H-NMR (300MHz / CDCl} 3, δ (ppm): 7.89 ~ 6.62 (m, 24H) 5.70 (d, 1H) 5.19 (d, 1H) 2.33 ~ 2.24 (br, 2H) 2.01 ~ 1.96 (br, 2H ), 1.96-1.85 (br, 8H), 1.80-1.74 (br, 2H)

LC-MS (APCI-Positive, m / z): [M] + 628,629,630,631.

Example 1: Synthesis of Polymer 1

Example monomer 28 (0.450 g), azobisisobutyronitrile (1.09 쨉 g) and toluene (0.575 g) were added to a Schlenk tube, and freeze-thawing was performed three times. Then, it was heated at 70 DEG C for 6 hours. The reaction mixture was cooled to room temperature and then reprecipitated five times using THF as a good solvent and an excessive amount of acetone / methanol (1/1, v / v) as a bad solvent. And dried to obtain Polymer 1 (0.200 g). The number average molecular weight and the degree of dispersion of Polymer 1 were Mn = 68,600 and Mw / Mn = 2.79, respectively. The glass transition temperature and 5% weight reduction temperature of polymer 1 were Tg = 173 캜 and Td = 436 캜, respectively.

Example 2: Synthesis of Polymer 2

(0.650 g), monomer C (0.0526 g), azobisisobutyronitrile (1.70 쨉 g) and toluene (0.937 g) were added to a Schlenk tube, and freeze-degasification was performed three times. At this time, exemplary monomer 28: monomer C = 90: 10 (molar ratio). Then, it was heated at 70 DEG C for 6 hours. After cooling to room temperature, the mixture was reprecipitated five times using THF as a good solvent and an excess of acetone / methanol (1/1, v / v) as a poor solvent, and the resulting material was vacuum dried to obtain Polymer 2 (0.340 g) (Containing 90 mol% of the above-mentioned repeating unit (1) in all the constitutional units). The number average molecular weight and the degree of dispersion of polymer 2 were Mn = 43,500 and Mw / Mn = 3.21, respectively. The glass transition temperature and 5% weight reduction temperature of polymer 2 were Tg = 152 캜 and Td = 433 캜, respectively.

Example 3: Synthesis of Polymer 3

(1.40 g), Monomer A (0.448 g), Monomer D (0.293 g), Monomer B (0.785 g), Azobisisobutyronitrile (0.0351 g) and Toluene (7.78 g) were added to a Schlenk tube Followed by freeze-thawing three times. Then, it was heated at 70 DEG C for 6 hours. After cooling to room temperature, THF was reprecipitated five times with a small amount of acetone / methanol (1/1, v / v) as a poor solvent, and the resulting material was vacuum dried to obtain Polymer 3 (2.10 g) (Containing 50 mol% of the above-mentioned repeating unit (1) in all the constitutional units). The number average molecular weight and the degree of dispersion of polymer 3 were Mn = 17,800 and Mw / Mn = 2.15, respectively. The glass transition temperature and 5% weight reduction temperature of polymer 3 were Tg = 150 캜 and Td = 411 캜, respectively.

Example 4: Synthesis of Polymer 4

Example monomer (126) (0.600 g), azobisisobutyronitrile (6.52 μg) and toluene (1.09 g) were added to a Schlenk tube, and freeze-degasification was performed three times. Then, it was heated at 70 DEG C for 6 hours. After cooling to room temperature, THF was reprecipitated 5 times with a small amount of acetone / methanol (1/1, v / v) as a poor solvent, and the resulting material was vacuum dried to obtain Polymer 4 (0.288 g) . The number average molecular weight and the degree of dispersion of polymer 4 were Mn = 6,300 and Mw / Mn = 2.48, respectively. The glass transition temperature and 5% weight reduction temperature of polymer 4 were Tg = 164 ° C and Td = 423 ° C, respectively.

Example 5: Synthesis of Polymer 9

Polymer 9 was obtained in the same manner as in Example 3, except that monomer 126 (0.435 g) was used instead of monomer D. [ The number average molecular weight and the degree of dispersion of Polymer 9 were Mn = 20,800 and Mw / Mn = 2.25, respectively. The glass transition temperature and 5% weight reduction temperature of polymer 9 were Tg = 159 ° C and Td = 421 ° C, respectively.

Comparative Example 1: Synthesis of Polymer 5

Monomer A (0.700 g), azobisisobutyronitrile (2.19 mu g) and toluene (1.29 g) were added to the Schlenk tube, and freeze-degasification was performed three times. Then, it was heated at 70 DEG C for 6 hours. The reaction mixture was cooled to room temperature and then reprecipitated 5 times using THF as an excess solvent and an excess amount of acetone / methanol (1/1, v / v) as a good solvent. The resulting material was vacuum dried to obtain Polymer 5 (0.510 g) . The number average molecular weight and the degree of dispersion of polymer 5 were Mn = 4,100 and Mw / Mn = 2.46, respectively. The glass transition temperature and 5% weight reduction temperature of polymer 5 were Tg = 152 캜 and Td = 402 캜, respectively.

Comparative Example 2: Synthesis of Polymer 6

Monomer A (0.65 g), monomer C (0.0613 g), azobisisobutyronitrile (2.94 g) and toluene (1.33 g) were added to the Schlenk tube, and freeze-degasification was performed three times. At this time, monomer A: monomer C = 91: 9 (molar ratio) was obtained. Then, it was heated at 70 DEG C for 6 hours. After cooling to room temperature, THF was reprecipitated 5 times with acetone / methanol (1/1, v / v) with a poor solvent as a good solvent, and the resulting material was vacuum dried to obtain Polymer 6 (0.501 g) &Lt; / RTI &gt; The number average molecular weight and the degree of dispersion of polymer 6 were Mn = 39,200 and Mw / Mn = 2.27, respectively. The glass transition temperature and 5% weight reduction temperature of polymer 6 were Tg = 131 캜 and Td = 409 캜, respectively.

Comparative Example 3: Synthesis of Polymer 7

Monomer A (0.650 g), monomer D (8.93 mg), monomer B (0.0467 g), azobisisobutyronitrile (8.76 mg) and toluene (1.42 g) were added to a Schlenk tube, Three times. At this time, monomer A: monomer D: monomer B = 90: 2: 8 (molar ratio). Then, it was heated at 70 DEG C for 6 hours. After cooling to room temperature, THF was reprecipitated five times with THF as an excess of acetone / methanol (1/1, v / v) as a poor solvent, and the resulting material was vacuum dried to obtain polymer 7 (0.58 g). The number average molecular weight and the degree of dispersion of polymer 7 were Mn = 55,000 and Mw / Mn = 3.04, respectively. The glass transition temperature and the 5% weight reduction temperature of polymer 7 were Tg = 129 캜 and Td = 399 캜, respectively.

Comparative Example 4: Synthesis of Polymer 8

Monomer D (0.700 g), azobisisobutyronitrile (13.7 μg) and THF (5.99 g) were added to a Schlenk tube, and freeze-degasification was performed three times. Then, it was heated at 70 DEG C for 6 hours. After cooling to room temperature, THF was reprecipitated five times using THF as an excess of a good solvent and acetone / methanol (1/1, v / v) excess solvent as a poor solvent, and the resulting material was vacuum dried to obtain Polymer 8 (0.420 g). The number average molecular weight and the degree of dispersion of Polymer 8 were Mn = 5,800 and Mw / Mn = 2.24, respectively. The glass transition temperature and 5% weight reduction temperature of polymer 8 were Tg = 139 캜 and Td = 402 캜, respectively.

polymer The number (n) of repeating units (1) Number average molecular weight
(Mn) Dispersion degree
(Mw / Mn) Glass transition temperature (캜) 5% weight reduction temperature (℃) Example 1 Polymer 1 261 68,600 2.79 173 436 Comparative Example 1 Polymer 5 19 4,100 2.46 152 402 Example 2 Polymer 2 177 43,500 3.21 152 433 Comparative Example 2 Polymer 6 154 39,200 2.27 131 409 Example 3 Polymer 3 31 17,800 2.15 150 411 Comparative Example 3 Polymer 7 293 55,000 3.04 129 399 Example 4 Polymer 4 24 6,300 2.48 164 423 Comparative Example 4 Polymer 8 31 5,800 2.24 139 402 Example 5 Polymer 9 31 20,800 2.25 159 421

Polymer 1, Polymer 2, Polymer 3, Polymer 4 and Polymer 9 comprising the recurring unit (1) represented by the above formula (1) have higher decomposition temperatures than conventional Polymer 5, Polymer 6, Polymer 7 and Polymer 8, And is promising as a material for a light emitting device, particularly as a hole transporting material. Polymer 1, Polymer 2, Polymer 3, Polymer 4 and Polymer 9 containing the repeating unit (1) represented by the above formula (1) have both a high decomposition temperature and a high glass transition temperature.

Example 6

The organic light emitting device shown in Fig. 1 was produced by the following method.

On the ITO glass substrate on which the stripe-shaped ITO (thickness: 150 nm) was disposed, a hole injection layer was formed with PEDOT / PSS (Sigma-Aldrich). Specifically, a solution obtained by filtering the suspension of PEDOT / PSS with a 0.2 μm membrane filter was used, and the solution was spin-coated to a thickness of 30 nm to form a thin film. Then, the thin film was formed on a hot plate at 200 ° C. for 10 minutes And dried to form a hole injection layer having a thickness of 30 nm.

 Next, Polymer 2 (3 wt% xylene solution) was spin-coated on the hole injection layer in a nitrogen atmosphere, and then heat-treated on a hot plate at 230 캜 for 1 hour to form a hole transporting layer having a thickness of 110 nm.

Then, a xylene solution containing the following compounds PH-1 and PH-2 (mixed in a weight ratio of 3: 7) as a host and containing the following compound PD-1 (10% by weight based on the host) as a dopant : 3% by weight) was spin-coated on the hole injection layer, and then heat-treated on a hot plate at 100 캜 for 30 minutes to form a light emitting layer with a thickness of 30 nm.

Subsequently, a substrate formed up to the light emitting layer was introduced into a vacuum evaporator, Alq ₃ was vapor-deposited to a thickness of 36 nm to form an electron transport layer, and LiF was deposited to a thickness of 0.8 nm to form an electron injection layer.

Subsequently, aluminum was deposited on the electron injection layer to form a cathode (cathode) having a thickness of 100 nm, thereby manufacturing an organic light emitting device.

By applying a voltage to the obtained organic luminescent element, green luminescence due to the iridium complex was observed.

Example 7

An organic light emitting device was fabricated in the same manner as in Example 6, except that Polymer 9 was used instead of Polymer 2.

Comparative Example 5

An organic light emitting device was fabricated in the same manner as in Example 6, except that Polymer 6 was used instead of Polymer 2.

Evaluation Example 1: Evaluation of organic light emitting device

The characteristics and the initial luminance of the organic light emitting diode fabricated in Examples 6 and 7 and Comparative Example 5 were tested in a DC driving test at 1000 cd / m ^{2 and} are shown in Table 2 below. The time (driving lifetime) until the initial luminance decreased to 5% is shown in Table 2, and the luminance was measured with a luminance measuring apparatus (for example, SR-3: Topcon Co.). The current efficiency (cd / A) was calculated by calculating the current value (current density) per unit area in the area of the device and dividing the luminance (cd / m ² ) by the current value (current density). The power efficiency was measured using an external quantum efficiency measuring device "C9920-12" (manufactured by Hamamatsu Photonics KK).

polymer The relative value (1000 cd / m ² ) calculated from Comparative Example 5 as 1, Current efficiency Power efficiency Drive life Example 6 Polymer 2 1.2 1.2 1.8 Example 7 Polymer 9 1.3 1.3 2.1 Comparative Example 5 Polymer 6 One One One

100: organic light emitting device,
110: substrate
120: first electrode
130: Hole injection layer
140: hole transport layer
150: light emitting layer
160: electron transport layer
170: electron injection layer
180: second electrode

Claims (20)

1. A material for an organic electroluminescent device comprising a repeating unit (1) represented by the following formula (1)
&Lt; Formula 1 >

In Formula 1,
R ¹ is selected from the group consisting of a single bond, a phenylene group, and a group represented by any one of the following formulas a1 to a9;

Among the above formulas (a1) to (a9)
R ²² is a C ₁ -C ₆ alkyl group, and X ²¹ and X ²² are each independently selected from an oxygen atom and a sulfur atom;
A is a divalent saturated aliphatic ring group;
X ¹ is a charge transport unit. The method according to claim 1,
R ¹ is selected from the group consisting of a phenylene group and a group represented by any one of the above formulas (a1) to (a9). The method according to claim 1,
And R &lt; ¹ &gt; is selected from a phenylene group and the above formula (a1). The method according to claim 1,
And R &lt; ¹ &gt; is a phenylene group. The method according to claim 1,
A is a group selected from an adamantylene group, a diamantylene group, a triamantylene group, a tetramantylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a bicyclo [2.1.0] pentyl group, Cyclo [3.1.0] hexyl group, a bicyclo [2.1.1] hexyl group, a bicyclo [4.1.0] heptyl group, a bicyclo [2.2.1] heptyl group and a cubanyl group, pentacyclo [4.2.0.0 The material for an organic light emitting device is selected from ^{2, 5 .0 3, 8 .0} 4, 7] octanyl group). The method according to claim 1,
And A is selected from an adamantylene group, a diamantylene group, a triamantylene group and a tetramantylene group. The method according to claim 1,
X ¹ is an arylamine skeleton, a fluorene skeleton, a carbazole skeleton, a dibenzofuranyl skeleton, a dibenzothienyl skeleton and condensed rings thereof, or a spiro ring thereof; And at least one of fluorenone skeleton, quinone skeleton, anthraquinone skeleton, diphenylquinone skeleton, thiopyran dioxide skeleton, oxazole skeleton, oxazole skeleton, triazole skeleton, imidazole skeleton, anthrone skeleton, bipyridine skeleton, Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; The method according to claim 1,
And X &lt; ¹ &gt; is a group represented by any one of the following formulas (b1) to (b13)

Among the above-mentioned formulas b1 to b13,
^{R 311, R 312, R 313} , R 321, R 322, R 331, R 341, R 351, R 352, R 361, R 362, R 363, R 371, R 372, R 381, R 391, R 3101 , R ³¹¹¹ , R ³¹¹² , R ³¹¹³ , R ³¹²¹ , R ³¹²² , R ³¹²³ , R ³¹²⁴ , R ³¹²⁵ , R ³¹³¹ and R ³¹³² independently represent a hydrogen atom C ₁ -C ₆ alkyl group and a group represented by the following formulas c1 to c16 A group selected from any one of the groups;

Among the above formulas c1 to c16,
p is 0 or 1;
^{Z 11, Z 12, Z 21} , Z 31, Z 41, Z 42, Z 51, Z 52, Z 53, Z 61, Z 62, Z 71, Z 72, Z 81, Z 82, Z 91 and Z ⁹² Are independently selected from the group consisting of a C ₁ -C ₆ alkyl group, a methoxy group and any one of the following formulas d1 to d7;

Among the above-mentioned formulas d1 to d7,
alkyl is a C ₁ -C ₆ alkyl group;
Y ¹¹ , Y ¹² , Y ²¹ , Y ³¹ , Y ⁴¹ , Y ⁴² , Y ⁵¹ , Y ⁵² , Y ⁶¹ , Y ⁶² and Y ⁶³ are each independently a group represented by any one of the following formulas e1 to e11;

Among the above-mentioned formulas e1 to e11,
R ⁴¹¹ , R ⁴¹² , R ⁴²¹ , R ⁴³¹ , R ⁴⁴¹ , R ⁴⁴² , R ⁴⁵¹ , R ⁴⁵² , R ⁴⁶¹ and R ⁴⁶² are independently selected from a hydrogen atom, a C ₁ -C ₆ alkyl group, a phenyl group and a tolyl group do. 9. The method of claim 8,
X ¹ is a group represented by any one of the formulas (b1) to (b5), (b8) and (b11). 9. The method of claim 8,
X ¹ is a group represented by any one of the formulas (b1) and (b11). The method according to claim 1,
Wherein the repeating unit (1) represented by the formula (1) is represented by the following formula (1a):
<Formula 1a>

In the formula (1a)
X ¹ is defined in reference to Formula 1. The method according to claim 1,
Wherein the total number of repeating units in the material for the organic light emitting device is from 20 to 500. The method according to claim 1,
Wherein the content of the repeating unit (1) represented by the formula (1) is 10 to 100 mol%. The method according to claim 1,
Wherein the content of the repeating unit (1) represented by the formula (1) is 30 to 100 mol%. The method according to claim 1,
1. A material for an organic light emitting device, which further comprises a repeating unit (2) represented by the following formula (2)
(2)

In Formula 2,
R ¹⁰ refers to the definition of R ¹ in Formula 1 above;
X ¹⁰ refers to the definition of X ^{1 in} the above formula (1);
q is 0 or 1; The method according to claim 1,
Wherein the material for the organic light emitting element is represented by the following Chemical Formula 3:
(3)

In Formula 3,
R ¹ and R ¹⁰ independently of one another refer to the definition of R ¹ in formula (1) above;
A refers to the definition of A in the above formula (1);
X ¹ and X ¹⁰ independently of one another refer to the definition of X ^{1 in} the above formula (1);
q is 0 or 1;
n is an integer from 20 to 500;
m is an integer of 1 to 180; 17. The method of claim 16,
n and m satisfies 0.1? n / (n + m)? 1. 17. The method of claim 16,
and n and m satisfy 20? n + m? 500. A first electrode; A second electrode; And an organic film interposed between the first electrode and the second electrode;
Wherein the organic film comprises the material for an organic light emitting device according to any one of claims 1 to 18. 20. The method of claim 19,
Wherein the organic film comprises a hole injection layer and / or a hole transport layer;
Wherein the organic light emitting device material is contained in the hole injection layer and / or the hole transport layer.

Images