KR102639370B1 - Novel heterocyclic compounds and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a heterocyclic compound represented by the following [Formula A] and an organic light-emitting device containing the same, wherein Ar1 to Ar3 are each as defined in the detailed description of the invention.
[Formula A]

Description

Novel heterocyclic compounds and organic light-emitting diode including the same}

The present invention relates to a novel heterocyclic compound that can be used in a light-emitting layer in an organic light-emitting device and an organic light-emitting device containing the same.

Organic light-emitting devices that utilize the organic light-emitting phenomenon that converts electrical energy into light energy using organic materials usually have a structure that includes an anode, a cathode, and an organic material layer between them.

Here, the organic material layer is often composed of a multi-layer structure composed of different materials to increase the efficiency and stability of the organic light-emitting device, and may be composed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode into the organic material layer. When the injected holes and electrons meet, an exciton is formed, and this exciton is When it falls back to the ground state, it glows. These organic light-emitting devices are known to have characteristics such as self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

In organic light-emitting devices, light-emitting materials can be classified into fluorescent materials derived from the singlet excited state of electrons and phosphorescent materials derived from the triplet excited state of electrons, depending on the emission mechanism.

On the other hand, when only one substance is used as a light-emitting material, the maximum emission wavelength moves to a longer wavelength due to intermolecular interactions, and problems arise such as color purity being reduced or the efficiency of the device being reduced due to the emission attenuation effect. Therefore, color purity is increased and energy is reduced. A host-dopant system can be used as a light-emitting material to increase light-emitting efficiency through transition.

The principle is that when a small amount of a dopant with a smaller energy band gap than the host forming the light-emitting layer is mixed into the light-emitting layer, excitons generated in the light-emitting layer are transported to the dopant, producing highly efficient light. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of the desired wavelength can be obtained depending on the type of dopant used.

In order for the organic light-emitting device to fully demonstrate the above-mentioned excellent characteristics, the materials forming the organic layer within the device, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, and electron injection materials, must be supported by stable and efficient materials. must come first.

When a current is applied to an organic light-emitting device, holes and electrons are injected from the anode and cathode, respectively, and the injected holes and electrons recombine in the light-emitting layer through each hole transport layer and electron transport layer to form a light-emitting exciton. The luminescent excitons formed in this way transition to the ground state and emit light. The light can be divided into fluorescence using singlet excitons and phosphorescence using triplet excitons depending on the emission mechanism, and the fluorescence and phosphorescence can be used as light emission sources of organic light-emitting devices.

On the other hand, fluorescence using only singlet excitons has a 25% probability of singlet exciton occurrence, which limits the luminous efficiency, whereas phosphorescence, which can use triplet excitons, has a luminous efficiency far superior to that of fluorescence, leading to many studies. is continuing.

However, devices using existing phosphorescent materials have higher efficiency than devices using fluorescent materials, but in the case of conventional materials such as BAlq or CBP used as hosts for phosphorescent materials, the driving voltage is lower than that of devices using fluorescent materials. Because it is high, there is no significant advantage in terms of power efficiency (lm/w), and it also has the disadvantage of being unsatisfactory in terms of lifespan. In addition, in order to use such a phosphorescent material as a light-emitting device, in Patent Publication No. 10-2011-0013220 (2011.02.09), an aromatic hetero ring is added to the skeleton of a 6-membered aromatic ring or 6-membered hetero-aromatic ring. The introduced organic compounds are described, and Japanese Patent Application Laid-Open No. 2010-166070 (July 29, 2010) describes organic compounds in which an aryl or heteroaryl ring is bonded to a substituted or unsubstituted pyrimidine or quinazoline skeleton. It is done.

However, despite efforts to manufacture light-emitting materials for organic light-emitting devices as described above, it cannot be said that sufficient development of materials for low driving voltage or high light-emitting efficiency has been achieved. The need for development of this excellent light-emitting material or material for the electron transport layer continues to be required.

Public Patent Publication No. 10-2011-0013220 (2011.02.09)

Japanese Patent Laid-Open No. 2010-166070 (July 29, 2010)

Therefore, the first technical task to be achieved by the present invention is to provide a novel heterocyclic compound that can be used in the light-emitting layer of an organic light-emitting device, has long lifespan, low voltage driving characteristics, and has excellent luminous efficiency.

The second technical problem to be achieved by the present invention is to provide an organic light-emitting device containing the organic compound.

In order to achieve the first technical problem, the present invention provides a heterocyclic compound represented by the following [Chemical Formula A].

[Formula A]

In Formula A,

Ar1 to Ar3 are each the same or different and independently of each other hydrogen, deuterium, a substituted or unsubstituted alkyl group with 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 30 carbon atoms, or a substituted or unsubstituted carbon number of 2 to 30. 30 alkynyl group, substituted or unsubstituted cycloalkyl group with 3 to 30 carbon atoms, substituted or unsubstituted heterocycloalkyl group with 2 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl group with 5 to 30 carbon atoms, substituted or unsubstituted an alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthoxy group having 6 to 30 carbon atoms , a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryl group having 2 to 50 carbon atoms, Heteroaryl group of 50, substituted or unsubstituted silyl group of 1 to 30 carbon atoms, substituted or unsubstituted carboxyl group of 1 to 30 carbon atoms, thiol group, cyano group, hydroxy group, nitro group, halogen group, selenium group, tellurium group , an amino group, a substituted or unsubstituted ester group having 1 to 30 carbon atoms, or a substituent represented by the structural formula A below,

At least one of Ar1 to Ar3 is a substituent represented by the structural formula A below,

When two or more of Ar1 to Ar3 are substituents represented by structural formula A below, each substituent represented by structural formula A is the same or different from each other.

[Structural Formula A]

In structural formula A,

W is any one selected from O, S, or CR1R2;

The substituents R1, R2, R11 and R12 are each the same or different, and independently of each other

Hydrogen, deuterium, substituted or unsubstituted alkyl group with 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group with 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group with 2 to 30 carbon atoms, substituted or unsubstituted alkyl group with 3 to 30 carbon atoms 30 cycloalkyl group, substituted or unsubstituted heterocycloalkyl group with 2 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl group with 5 to 30 carbon atoms, substituted or unsubstituted alkoxy group with 1 to 30 carbon atoms, substituted or unsubstituted Aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthioxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine having 1 to 30 carbon atoms group, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted carbon number of 1 Silyl group of 1 to 30 carbon atoms, substituted or unsubstituted carboxyl group of 1 to 30 carbon atoms, thiol group, cyano group, hydroxyl group, nitro group, halogen group, selenium group, tellurium group, amino group, substituted or unsubstituted group of 1 to 30 carbon atoms A substituent selected from ester groups, which may be connected to adjacent functional groups to form an alicyclic or aromatic monocyclic or polycyclic ring;

The linking group L is a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, substituted or unsubstituted. A substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms. selected from arylene groups;

m is 1 or 2,

p is an integer from 1 to 4, but when p is 2 or more, each R11 is the same or different from each other,

q is an integer from 1 to 3, but when q is 2 or more, each R12 is the same or different from each other,

n is an integer from 1 to 3, but when n is 2 or more, each L is the same as or different from each other;

'-**' is bonded to the carbon atom of the triazine ring in Formula A,

When the substituents of R11 or R12 are not bonded to the carbon atoms in the aromatic 6-membered ring on both sides of the structural formula A, hydrogen or deuterium is bonded to them.

In addition, in order to achieve the second object, the present invention includes a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer is An organic light-emitting device containing one or more types of heterocyclic compounds of the invention is provided.

When used as a phosphorescent host material, the heterocyclic compound according to the present invention has long lifespan, low voltage driving characteristics, and excellent luminous efficiency, so it can be used to manufacture excellent organic light-emitting devices.

1 is a schematic diagram of an organic light-emitting device according to an embodiment of the present invention.

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

The present invention provides a compound represented by the following [Chemical Formula A] as a heterocyclic compound that can be used in the light-emitting layer of an organic light-emitting device.

[Formula A]

In Formula A,

Ar1 to Ar3 are each the same or different and independently of each other hydrogen, deuterium, a substituted or unsubstituted alkyl group with 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 30 carbon atoms, or a substituted or unsubstituted carbon number of 2 to 30. 30 alkynyl group, substituted or unsubstituted cycloalkyl group with 3 to 30 carbon atoms, substituted or unsubstituted heterocycloalkyl group with 2 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl group with 5 to 30 carbon atoms, substituted or unsubstituted an alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthoxy group having 6 to 30 carbon atoms , a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryl group having 2 to 50 carbon atoms, Heteroaryl group of 50, substituted or unsubstituted silyl group of 1 to 30 carbon atoms, substituted or unsubstituted carboxyl group of 1 to 30 carbon atoms, thiol group, cyano group, hydroxy group, nitro group, halogen group, selenium group, tellurium group , an amino group, a substituted or unsubstituted ester group having 1 to 30 carbon atoms, or a substituent represented by the structural formula A below,

At least one of Ar1 to Ar3 is a substituent represented by the structural formula A below,

When two or more of Ar1 to Ar3 are substituents represented by structural formula A below, each substituent represented by structural formula A is the same or different from each other.

[Structural Formula A]

In structural formula A,

W is any one selected from O, S, or CR1R2;

The substituents R1, R2, R11 and R12 are each the same or different, and independently of each other

Hydrogen, deuterium, substituted or unsubstituted alkyl group with 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group with 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group with 2 to 30 carbon atoms, substituted or unsubstituted alkyl group with 3 to 30 carbon atoms 30 cycloalkyl group, substituted or unsubstituted heterocycloalkyl group with 2 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl group with 5 to 30 carbon atoms, substituted or unsubstituted alkoxy group with 1 to 30 carbon atoms, substituted or unsubstituted Aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthioxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine having 1 to 30 carbon atoms group, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted carbon number of 1 Silyl group of 1 to 30 carbon atoms, substituted or unsubstituted carboxyl group of 1 to 30 carbon atoms, thiol group, cyano group, hydroxyl group, nitro group, halogen group, selenium group, tellurium group, amino group, substituted or unsubstituted group of 1 to 30 carbon atoms A substituent selected from ester groups, which may be connected to adjacent functional groups to form an alicyclic or aromatic monocyclic or polycyclic ring;

The linking group L is a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, substituted or unsubstituted. A substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms. selected from arylene groups;

m is 1 or 2,

p is an integer from 1 to 4, but when p is 2 or more, each R11 is the same or different from each other,

q is an integer from 1 to 3, but when q is 2 or more, each R12 is the same or different from each other,

n is an integer from 1 to 3, but when n is 2 or more, each L is the same as or different from each other;

'-**' is bonded to the carbon atom of the triazine ring in Formula A,

When the substituents of R11 or R12 are not bonded to the carbon atoms in the aromatic 6-membered ring on both sides of the structural formula A, hydrogen or deuterium is bonded to them;

'Substitution' in 'substituted or unsubstituted' refers to deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group with 1 to 24 carbon atoms, halogenated alkyl group with 1 to 24 carbon atoms, alkenyl group with 2 to 24 carbon atoms. , an alkynyl group with 2 to 24 carbon atoms, a heteroalkyl group with 2 to 24 carbon atoms, an aryl group with 6 to 24 carbon atoms, an arylalkyl group with 7 to 24 carbon atoms, a heteroaryl group with 2 to 24 carbon atoms, or a heteroarylalkyl group with 2 to 24 carbon atoms. , alkoxy group of 1 to 24 carbon atoms, alkylamino group of 1 to 24 carbon atoms, arylamino group of 6 to 24 carbon atoms, heteroarylamino group of 2 to 24 carbon atoms, alkylsilyl group of 1 to 24 carbon atoms, arylsilyl of 6 to 24 carbon atoms. It means being substituted with one or more substituents selected from the group consisting of aryloxy groups having 6 to 24 carbon atoms.

Meanwhile, considering the range of the alkyl group or aryl group in the “substituted or unsubstituted alkyl group having 1 to 30 carbon atoms” and “substituted or unsubstituted aryl group having 5 to 50 carbon atoms” in the present invention, the The range of the carbon number of the alkyl group having 1 to 30 carbon atoms and the aryl group having 5 to 50 carbon atoms means the total number of carbon atoms constituting the alkyl portion or aryl portion when the substituent is regarded as unsubstituted without considering the substituted portion, respectively. will be. For example, a phenyl group substituted with a butyl group at the para position should be viewed as corresponding to an aryl group with 6 carbon atoms substituted with a butyl group with 4 carbon atoms.

In addition, the aryl group used in the compound of the present invention is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and contains a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members, Additionally, if the aryl group has a substituent, it may be fused with neighboring substituents to further form a ring.

Specific examples of the aryl include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, and fluoran. Including, but not limited to, Tenil, etc.

One or more hydrogen atoms of the aryl group may be a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group (-NH2, -NH(R), -N(R')(R''), R ' and R" are independently alkyl groups having 1 to 10 carbon atoms, in this case referred to as "alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, alkyl group having 1 to 24 carbon atoms, carbon number Halogenated alkyl group of 1 to 24 carbon atoms, alkenyl group of 1 to 24 carbon atoms, alkynyl group of 1 to 24 carbon atoms, heteroalkyl group of 1 to 24 carbon atoms, aryl group of 6 to 24 carbon atoms, arylalkyl group of 6 to 24 carbon atoms, carbon number It may be substituted with a heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms.

The heteroaryl group, which is a substituent used in the compound of the present invention, has 2 carbon atoms and may contain 1 to 4 heteroatoms selected from N, O, P, Se, Te, Si, Ge or S in each ring of the aryl group. It refers to a heteroaromatic organic radical of 24 to 24, and the rings can be fused to form a ring. And one or more hydrogen atoms of the heteroaryl group may be replaced with the same substituent as that of the aryl group.

Specific examples of the alkyl group as a substituent used in the present invention include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, etc., and one or more of the alkyl groups The hydrogen atom can be substituted with the same substituent as in the case of the aryl group.

Specific examples of the alkoxy group as a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, etc., One or more hydrogen atoms of the alkoxy group may be replaced with the same substituent as that of the aryl group.

Specific examples of the silyl group as a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, and methylcyclo. Examples include butylsilyl, dimethylfurylsilyl, and the like, and one or more hydrogen atoms of the silyl group can be replaced with the same substituent as that of the aryl group.

The present invention relates to a heterocyclic compound represented by the formula A, wherein at least one of the substituents Ar1 to Ar3 in the heterocyclic compound is a substituent represented by the structural formula A, and the structural formula A is a 6-membered ring on both sides condensed with a 5-membered ring containing W. Its technical characteristic is that it has a structure in which a linking group L is bonded to one of the six-membered rings.

In the case of a heterocyclic compound having this structure in the present invention, it can be used as a phosphorescent host in a light-emitting layer.

As an example, the linking group L in Formula A of the present invention is the same or different, and may independently be a single bond or any one selected from Structural Formulas 1 to 9 below.

[Structural Formula 1] [Structural Formula 2] [Structural Formula 3] [Structural Formula 4]

[Structural Formula 5] [Structural Formula 6] [Structural Formula 7] [Structural Formula 8]

[Structural Formula 9]

Here, hydrogen or deuterium may be bonded to the carbon site of the aromatic ring in Structural Formulas 1 to 9.

As an example, in the present invention, the substituents R1, R2, R11, and R12 of Formula A are each the same or different, and are independently hydrogen, deuterium, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

Additionally, in the present invention, B1 to B4 in [Formula A] may not all be nitrogen atoms. That is, the aromatic ring forming the hexagonal ring in structural formula Q may be composed of only hydrocarbons.

As an example, in the present invention, m in [Formula A] may be 1 or 2, and preferably may be 1.

As an example, only one of the substituents Ar1 to Ar3 in the triazine ring in [Formula A] may be a substituent represented by structural formula A, or two may be substituents represented by structural formula A, preferably only one. It may be a substituent represented by structural formula A. In this case, the substituents other than those represented by structural formula A among Ar1 to Ar3 may be the same or different from each other and may be substituted or unsubstituted aryl groups having 6 to 20 carbon atoms.

A more specific example of the heterocyclic compound represented by Formula A in the present invention may be any one compound selected from [Compound 1] to [Compound 120] below.

<Compound 1> <Compound 2> <Compound 3> <Compound 4>

<Compound 5> <Compound 6> <Compound 7> <Compound 8>

<Compound 9> <Compound 10> <Compound 11> <Compound 12>

<Compound 13> <Compound 14> <Compound 15> <Compound 16>

<Compound 17> <Compound 18> <Compound 19> <Compound 20>

<Compound 21> <Compound 22> <Compound 23> <Compound 24>

<Compound 25> <Compound 26> <Compound 27> <Compound 28>

<Compound 29> <Compound 30> <Compound 31> <Compound 32>

<Compound 33> <Compound 34> <Compound 35> <Compound 36>

<Compound 37> <Compound 38> <Compound 39> <Compound 40>

<Compound 41> <Compound 42> <Compound 43> <Compound 44>

<Compound 45> <Compound 46> <Compound 47> <Compound 48>

<Compound 49> <Compound 50> <Compound 51> <Compound 52>

<Compound 53> <Compound 54> <Compound 55> <Compound 56>

<Compound 57> <Compound 58> <Compound 59> <Compound 60>

<Compound 61> <Compound 62> <Compound 63> <Compound 64>

<Compound 65> <Compound 66> <Compound 67> <Compound 68>

<Compound 69> <Compound 70> <Compound 71> <Compound 72>

<Compound 73> <Compound 74> <Compound 75> <Compound 76>

<Compound 77> <Compound 78> <Compound 79> <Compound 80>

<Compound 81> <Compound 82> <Compound 83> <Compound 84>

<Compound 85> <Compound 86> <Compound 87> <Compound 88>

<Compound 89> <Compound 90> <Compound 91> <Compound 92>

<Compound 93> <Compound 94> <Compound 95> <Compound 96>

<Compound 97> <Compound 98> <Compound 99> <Compound 100>

<Compound 101> <Compound 102> <Compound 103> <Compound 104>

<Compound 105> <Compound 106> <Compound 107> <Compound 108>

<Compound 109> <Compound 110> <Compound 111> <Compound 112>

<Compound 113> <Compound 114> <Compound 115> <Compound 116>

<Compound 117> <Compound 118> <Compound 119> <Compound 120>

Additionally, the present invention can provide a composition for a light-emitting layer of an organic light-emitting device containing the heterocyclic compound. Here, the composition includes a first host material and a second host material, and the first host material uses the heterocyclic compound of the present invention. At this time, the weight ratio of the first host material and the second host material may be in the range of 1:99 to 99:1, and the second host material may be any known phosphorescent host, but may be any of the following Chemical Formulas 3 to 6: It may be one or more compounds selected from the following.

<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

In Formulas 3 to 6,

A is hydrogen, deuterium, a substituted or unsubstituted alkyl group with 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group with 2 to 30 carbon atoms, and a substituted or unsubstituted carbon number. 3 to 30 cycloalkyl group, substituted or unsubstituted heterocycloalkyl group with 2 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl group with 5 to 30 carbon atoms, substituted or unsubstituted alkoxy group with 1 to 30 carbon atoms, substituted or Unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthioxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms Alkylamine group, substituted or unsubstituted arylamine group with 6 to 30 carbon atoms, substituted or unsubstituted aryl group with 6 to 50 carbon atoms, substituted or unsubstituted heteroaryl group with 2 to 50 carbon atoms, substituted or unsubstituted Silyl group of 1 to 30 carbon atoms, substituted or unsubstituted carboxyl group of 1 to 30 carbon atoms, thiol group, cyano group, hydroxy group, nitro group, halogen group, selenium group, tellurium group, amino group, substituted or unsubstituted carbon number of 1 to 30 It is a substituent selected from 30 ester groups;

The linking group L is the same as L described previously,

n1 is an integer from 1 to 3, but when n1 is 2 or more, each L is the same as or different from each other;

Substituent R31 is the same as R1 and R2 described above,

n2 is an integer from 1 to 5, but when n2 is 2 or more, each R31 is the same or different;

In Formula 3, n3 is an integer from 1 to 6, and when n3 is 2 or more, each [(L)n1-(R31)n2] is the same or different from each other,

In Formula 4, n3 is an integer from 1 to 8, and when n3 is 2 or more, each [(L)n1-(R31)n2] is the same or different from each other,

In Formula 5, n3 is an integer from 1 to 14, and when n3 is 2 or more, each [(L)n1-(R31)n2] is the same or different from each other , and the ring containing the nitrogen atom forms a 5-membered ring. ,

In Formula 6, Y is any one selected from NR ₃ , CR ₄ R ₅ , SiR ₆ R ₇ , GeR ₈ R ₉ , O, S and Se, and the ring containing Y forms a 5-membered ring,

n3 is an integer from 1 to 10, and when n3 is 2 or more, each [(L)n1-(R31)n2] is the same or different from each other,

At this time, R3 to R9 may be defined in the same way as R1 and R2 described above.

Specifically, preferred examples of the second host material are as follows.

In addition, the present invention includes a first electrode; a second electrode opposite the first electrode; and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer contains one or more of the heterocyclic compounds of the present invention; Or, comprising a composition for a light-emitting layer of an organic light-emitting device containing the heterocyclic compound; can provide an organic light-emitting device.

In the present invention, “(the organic layer) includes one or more organic compounds” means “(the organic layer) contains one type of organic compound within the scope of the present invention or two or more different types of compounds within the scope of the organic compounds. It can be interpreted as “may include.”

Additionally, the organic layer may include at least one of a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a light emitting layer, an electron transport layer, and an electron injection layer. At this time, the organic layer interposed between the first electrode and the second electrode includes a light-emitting layer, and the light-emitting layer is composed of a host and a dopant, and the heterocyclic compound in the present invention may be used as a host.

Meanwhile, in the present invention, a dopant material may be used in the light emitting layer in addition to a host. When the light-emitting layer includes a host and a dopant, the content of the dopant may typically be selected in the range of about 0.01 to about 20 parts by weight based on about 100 parts by weight of the host, but is not limited thereto.

Meanwhile, when the heterocyclic compound in the present invention is used as a host, the organic layer may additionally include a hole blocking layer or an electron blocking layer.

Meanwhile, in the present invention, known electron transport materials that function to stably transport electrons injected from an electron injection electrode (cathode) can be used as the electron transport layer material of the organic light emitting device. Examples of known electron transport materials include quinoline derivatives, especially tris(8-quinolinolate) aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10- olate: Bebq2), ADN, Compound 201, Compound 202, oxadiazole derivatives PBD, BMD, BND, etc. may be used, but are not limited thereto.

TAZ BAlq

<Compound 201> <Compound 202> BCP

Additionally, the electron transport layer used in the present invention may be an organometallic compound represented by Chemical Formula C, used alone or in a mixture with the electron transport layer material.

[Formula C]

In [Formula C] above,

Y is a portion selected from C, N, O, and S that is directly bonded to the M to form a single bond, and a portion selected from C, N, O, and S that forms a coordination bond to the M. It is a ligand chelated by the single bond and coordination bond.

The M is an alkali metal, alkaline earth metal, aluminum (Al) or boron (B) atom, and the OA is a monovalent ligand capable of single bonding or coordinating with the M,

O is oxygen,

A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms. Alkynyl group, substituted or unsubstituted cycloalkyl group with 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl group with 5 to 30 carbon atoms, and substituted or unsubstituted hetero atom with 2 to 50 carbon atoms having O, N or S as a heteroatom. Any one selected from the aryl group,

When M is a metal selected from alkali metals, m = 1, n = 0,

When M is a metal selected from alkaline earth metals, m = 1, n = 1, or m = 2, n = 0,

When M is boron or aluminum, m = any one of 1 to 3, n is any one of 0 to 2 and satisfies m + n = 3;

'Substitution' in 'substituted or unsubstituted' means deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, heteroarylamino group, alkylsilyl group, arylsilyl group, It means being substituted with one or more substituents selected from the group consisting of aryloxy group, aryl group, heteroaryl group, germanium, phosphorus, and boron.

In the present invention, Y may be the same or different, and may be independently selected from [Structural Formula C1] to [Structural Formula C39] below, but is not limited thereto.

[Structural Formula C1][Structural Formula C2][Structural Formula C3]

[Structural Formula C4][Structural Formula C5][Structural Formula C6]

[Structural Formula C7][Structural Formula C8][Structural Formula C9][Structural Formula C10]

[Structural Formula C11] [Structural Formula C12] [Structural Formula C13]

[Structural Formula C14][Structural Formula C15][Structural Formula C16]

[Structural Formula C17][Structural Formula C18][Structural Formula C19][Structural Formula C20]

[Structural Formula C21] [Structural Formula C22] [Structural Formula C23]

[Structural Formula C24][Structural Formula C25][Structural Formula C26]

[Structural Formula C27][Structural Formula C28][Structural Formula C29][Structural Formula C30]

[Structural Formula C31] [Structural Formula C32] [Structural Formula C33]

[Structural Formula C34][Structural Formula C35][Structural Formula C36]

[Structural Formula C37][Structural Formula C38][Structural Formula C39]

In the above [structural formula C1] to [structural formula C39],

R are the same or different from each other, and are each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted Heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or An unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms. It may be selected from the group and connected to adjacent substituents with alkylene or alkenylene to form a spiro ring or fused ring.

Hereinafter, the organic light-emitting device of the present invention will be described with reference to FIG. 1.

1 is a cross-sectional view showing the structure of an organic light-emitting device of the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60, and a cathode 80, and, if necessary, a hole injection layer 30 and an electron It may further include an injection layer 70, and in addition to that, it is also possible to form an intermediate layer of one or two layers, and a hole blocking layer or an electron blocking layer can also be formed.

With reference to Figure 1, the organic light emitting device of the present invention and its manufacturing method will be examined as follows.

First, the anode 20 is formed by coating the anode electrode material on the substrate 10. Here, as the substrate 10, a substrate used in a typical organic EL device is used, and an organic substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness is preferable. In addition, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), and zinc oxide (ZnO), which are transparent and have excellent conductivity, are used as materials for the anode electrode.

The hole injection layer 30 is formed by vacuum thermal deposition or spin coating of a hole injection layer material on the top of the anode 20 electrode. Next, a hole transport layer 40 is formed on the top of the hole injection layer 30 by vacuum thermal evaporation or spin coating of a hole transport layer material.

The hole injection layer material can be used without particular restrictions as long as it is commonly used in the industry, for example, 2-TNATA [4,4',4"-tris(2-naphthylphenyl-phenylamino)-triphenylamine] , NPD[N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine)], TPD[N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'- biphenyl-4,4'-diamine], DNTPD[N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine ] can be used, etc. However, the present invention is not necessarily limited to this.

Additionally, the material of the hole transport layer is not particularly limited as long as it is commonly used in the art, for example, N,N'-bis(3-methylphenyl)-N,N'-diphenyl -[1,1- Biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthalen-1-yl)-N,N'-diphenylbenzidine (a-NPD) can be used. However, the present invention is not necessarily limited thereto.

Next, an organic light-emitting layer 50 is stacked on top of the hole transport layer 40, and a hole-blocking layer (not shown) is selectively formed on top of the organic light-emitting layer 50 by vacuum deposition or spin coating. can be formed.

The hole blocking layer serves to prevent this problem by using a material with a very low HOMO (Highest Occupied Molecular Orbital) level because the lifespan and efficiency of the device are reduced when holes pass through the organic light-emitting layer and flow into the cathode. . At this time, the hole blocking material used is not particularly limited, but must have an electron transport ability and a higher ionization potential than the light-emitting compound. Representative examples include BAlq, BCP, and TPBI.

As a material used in the hole blocking layer, any one selected from BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq and Formulas 1001 to 1007 may be used, but is not limited thereto. .

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

Formula 1001 Formula 1002 Formula 1003

Formula 1004 Formula 1005 Formula 1006

Chemical formula 1007

After depositing the electron transport layer 60 on this hole blocking layer through a vacuum deposition method or spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is vacuum heated on top of the electron injection layer 70. The organic EL device is completed by depositing to form the cathode 80 electrode. Here, the metals for forming the cathode include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver ( Mg-Ag), etc. can be used, and to obtain a top-emitting device, a transmissive cathode using ITO or IZO can be used.

Additionally, the light emitting layer may be composed of a host and a dopant.

Additionally, according to a specific example of the present invention, the thickness of the light-emitting layer is preferably 50 to 2,000 Å.

At this time, the phosphorescent dopant used when the light-emitting layer utilizes phosphorescence may be one or more compounds selected from compounds represented by the following general formulas (A-1) to (J-1).

[General formula A-1]

The M is selected from the group consisting of metals of Groups 7, 8, 9, 10, 11, 13, 14, 15 and 16, preferably Ir, Pt, Pd, Rh and Re. , Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag. In addition, L ₁ , L ₂ and L ₃ may be the same as or different from each other as ligands and may each independently be selected from the structural formula D below, but are not limited thereto.

In addition, “*” in the structural formula D below represents a site that coordinates with the metal ion M.

[Structural Formula D]

In the structural formula D, the R are different from or the same as each other and are each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group with 1 to 30 carbon atoms, substituted or unsubstituted aryl group with 6 to 50 carbon atoms, substituted or an unsubstituted heteroaryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted alkene having 2 to 30 carbon atoms. Nyl group, substituted or unsubstituted alkylamino group with 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group with 1 to 30 carbon atoms, substituted or unsubstituted arylamino group with 6 to 30 carbon atoms, and substituted or unsubstituted 6 to 30 carbon atoms. It may be any one selected from 30 arylsilyl groups;

The R is each independently selected from an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 40 carbon atoms, a heteroaryl group with 3 to 20 carbon atoms, a cyano group, a halogen group, deuterium and hydrogen. may be further substituted with one or more substituents;

In addition, R may be connected to each adjacent substituent with alkylene or alkenylene to form a cyclic ring and a monocyclic or polycyclic aromatic ring;

The L may be connected to an adjacent substituent with alkylene or alkenylene to form a spiro ring or fused ring.

As an example, the dopant represented by [General Formula A-1] may be any one selected from the following compounds.

[General formula B-1]

In the general formula B-1,

M ^A1 represents the same metal ion as defined in general formula (A-1), and Y ^A11 , Y ^A14 , Y ^A15 , and Y ^A18 each independently represent a carbon atom or a nitrogen atom, Y ^A12 , Y ^A13 , Y ^A16 and Y ^A17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, and a sulfur atom, and L ^A11 , L ^A12 , L ^A13 , and L ^A14 are each a linking group as previously defined. , and Q ^A11 and Q ^A12 represent partial structures containing atoms bonded to M ^A1 .

An exemplary structure of the compound represented by the general formula B-1 is as follows, but is not limited thereto.

[General formula C-1]

In the general formula C-1,

M ^B1 represents the same metal ion as defined in General Formula A-1, Y ^B11 , Y ^B14 , Y ^B15 and Y ^B18 each independently represent a carbon atom or a nitrogen atom, Y ^B12 , Y ^B13 , Y ^B16 and Y ^B17 each independently represents a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, and a sulfur atom, L ^B11 , L ^B12 , L ^B13 , L ^B14 represent a linking group, and Q ^B11 and Q ^B12 represent M It represents the partial structure containing the atom bonded to ^B1 .

An exemplary structure of the compound represented by the general formula C-1 is as follows, but is not limited thereto.

[General formula D-1]

In the general formula D-1,

M ^C1 represents the same metal ion as defined in General Formula A-1, and R ^C11 and R ^C12 each independently represent a hydrogen atom, a substituent that connects to each other to form a 5-ring ring, and a substituent that does not connect to each other. R ^C13 and R ^C14 each independently represent a hydrogen atom, a substituent connected to each other to form a 5-ring ring, and a substituent not connected to each other, and G ^C11 and G ^C12 each independently represent a nitrogen atom, a substituted or unsubstituted group. It represents a carbon atom, L ^C11 and L ^C12 represent a linking group, and Q ^C11 and Q ^C12 represent a partial structure containing an atom bonded to M ^C1 .

An exemplary structure of the compound represented by the general formula D-1 is as follows, but is not limited thereto.

[General formula E-1]

In the general formula E-1,

M ^D1 represents the same metal ion as defined in general formula (A-1), G ^D11 and G ^D12 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, J ^D11 , J ^D12 , J ^D13 and J ^D14 each independently represents an atom group necessary to form a five-membered ring, and L ^D11 and L ^D12 represent a linking group.

An exemplary structure of the compound represented by the general formula E-1 is as follows, but is not limited thereto.

[General formula F-1]

In the general formula F-1,

M ^E1 represents the same metal ion as defined in General Formula A-1, J ^E11 and J ^E12 each independently represent the atomic group required to form a five-membered ring, and G ^E11 , G ^E12 , G ^E13 and G ^E14 are each Independently represents a nitrogen atom or a substituted or unsubstituted carbon atom, and Y ^E11 , Y ^E12 , Y ^E13 and Y ^E14 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.

An exemplary structure of the compound represented by the general formula F-1 is as follows, but is not limited thereto.

[General formula G-1]

In the general formula G-1,

M ^F1 represents the same metal ion as defined in General Formula A-1,

L ^F11 , L ^F12 and L ^F13 represent a linking group, R ^F11 , R ^F12 , R ^F13 and R ^F14 represent a substituent, R ^F11 and R ^F12 , R F12 and R ^F13 , ^{R F13 and} R ^F14 are connected to each other A ring can be formed, and in this case, the ring formed by R ^F1 , R ^F12 , R ^F13 , and R ^F14 is a 5-membered ring. Additionally, Q ^F11 and Q ^F12 represent partial structures containing atoms bonded to M ^F1 .

An exemplary structure of the compound represented by the general formula G-1 is as follows, but is not limited thereto.

[General formula H-1] [General formula H-2] [General formula H-3]

In the general formula H-1,

R ¹¹ , R ¹² are substituents of alkyl, aryl or heteroaryl; In addition, a fused ring can be formed with substituents adjacent to each other, and q11 and q12 are integers from 0 to 4, preferably 0 to 2.

In addition, when q11 and q12 are 2 to 4, a plurality of R11 and R12 are the same or different, respectively,

L ¹ is a ligand that binds to platinum, and is preferably a ligand capable of forming an ortho metal platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, or a halogen ligand, and more preferably an ortho metal (ortho metal) platinum complex. metal) It is a ligand that forms a white gold complex, a bipyridyl ligand, or a phenanthroline ligand.

n ¹ is an integer from 0 to 3, preferably 0, and m ¹ is 1 or 2, preferably 2.

In addition, it is preferable that n ¹ and m ¹ make the metal complex represented by the general formula H-1 a neutral complex.

In the general formula H-2, R ²¹ ,R ²² ,n ² ,m ² ,q ²² ,L ² are the same as R ¹¹ ,R ¹² ,n ¹ ,m ¹ ,q ¹² ,L ¹ respectively, and q ²¹ is an integer from 0 to 2, and 0 is preferable.

In the general formula H-3, R ³¹ , n ³ , m ³ , L ³ are the same as R ¹¹ , n ¹ , m ¹ , L ¹ respectively, and q ³¹ represents an integer from 0 to 8, and 0 to 2 is preferable, and 0 is more preferable.

Specific examples of compounds of the general formulas H-1 to H-3 are as follows, but are not limited thereto.

[General formula I-1]

In the general formula I-1,

Ring A, Ring B, Ring C, and Ring D represent nitrogen-containing heterocycles in which any two rings of rings A to D may have a substituent, and the remaining two rings represent an aryl ring or heteroaryl ring that may have a substituent. It represents a ring, and a condensed ring can be formed with ring A and ring B, ring A and ring C, and/or ring B and ring D. Any two ^{of X 1 ,} Q ¹ , Q ² and Q ³ each independently represent a divalent atom (single) or a bond, but Q ¹ , Q ² and Q ³ do not represent a bond at the same time. Any two of Z ¹ , Z ² , Z ³ and Z ⁴ represent a coordination bond, and the remaining two represent a covalent bond, an oxygen atom, or a sulfur atom.

Specific examples of compounds of the general formula I-1 are as follows, but are not limited thereto.

[General formula J-1]

In the general formula J-1,

M represents the same metal ion as defined in General Formula A-1, Ar1 represents a substituted or unsubstituted ring structure, and in the two azomethine bonds (-C=N-) bonded to M, , The nitrogen atom (N) is each bonded to the M, and as a whole forms a tridentate ligand bonded to the M at the 3rd position.

Additionally, in Ar1, C represents a carbon atom constituting the ring structure represented by Ar1. In addition, R1 and R2 may be the same or different from each other, and each represents a substituted or unsubstituted alkyl group or aryl group, and L represents a single-dentate ligand.

In the general formula J-1, M is preferably Pt. In addition, Ar1 is preferably selected from 5-membered rings, 6-membered rings, and condensed ring groups thereof.

Specific examples of compounds of the general formula J-1 are as follows, but are not limited thereto.

Additionally, the light emitting layer may further include various hosts and various dopant materials in addition to the dopant and host.

Additionally, in the present invention, one or more layers selected from the hole injection layer, hole transport layer, electron blocking layer, light-emitting layer, hole blocking layer, electron transport layer, and electron injection layer may be formed by a single molecule deposition method or a solution process. Here, the deposition method refers to a method of forming a thin film by evaporating the material used as a material for forming each layer through heating in a vacuum or low pressure state, and the solution process is used to form each layer. This refers to a method of mixing a substance used as a material with a solvent and forming a thin film through methods such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, and spin coating.

Additionally, the organic light emitting device in the present invention may include a flat panel display device; flexible display device; Devices for monochromatic or white flat panel lighting; and a monochromatic or white flexible lighting device.

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

(Example)

Synthesis Example 1: Synthesis of Compound 1

Synthesis Example 1-(1): Synthesis of Intermediate 1-a

According to Scheme 1 below, intermediate 1-a was synthesized.

<Scheme 1>

[Intermediate 1-a]

In a 2L reactor, 1,3,5-tribromobenzene (50 g, 159 mmol), 4-dibenzofuran boronic acid (67 g, 318 mmol), tetrakis(triphenylphosphine)palladium (3.7 g, 3.17 mmol), potassium carbonate (65.7 g, 476 mmol), 700 mL of toluene, and 200 mL of distilled water were added and stirred at 100°C for 12 hours. After cooling to room temperature, the organic layer was extracted using ethyl acetate. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain [Intermediate 1-a]. (33g, 43%)

Synthesis Example 1-(2): Synthesis of Intermediate 1-b

Intermediate 1-b was synthesized according to Scheme 2 below.

<Scheme 2>

[Intermediate 1-a] [Intermediate 1-b]

500 mL of tetrahydrofuran and [Intermediate 1-a] (33 g, 72.6 mmol) obtained in Synthesis Example 1-(1) were added to a 1L reaction vessel, and the temperature was cooled to -78°C under a nitrogen atmosphere. After 30 minutes, 1.6M n-butyllithium (50 mL, 80 mmol) was slowly added dropwise and stirred at -78°C for 1 hour. Trimethyl borate (9.05 g, 87.1 mmol) was slowly added dropwise at -78°C, and the temperature was raised to room temperature. After stirring for 2 hours, an aqueous hydrochloric acid solution was added to terminate the reaction, and the organic layer was extracted and distilled under reduced pressure. The solid produced by recrystallization from hexane was filtered and dried to obtain [Intermediate 1-b]. (27 g, 88%)

Synthesis Example 1-(3): Synthesis of Compound 1

Compound 1 was synthesized according to Scheme 3 below.

<Scheme 3>

[Intermediate 1-b] [Compound 1]

Instead of 1,3,5-tribromobenzene used in Synthesis Example 1-(1), 2-chloro-4,6-diphenyl-1,3,5-triazine was used, and 4-dibenzofuran was used instead of boronic acid. [Compound 1] was obtained by synthesis in the same manner except that [Intermediate 1-b] was used. (8.3 g, 54%)

MS (MALDI-TOF): m/z 641.21 [M ⁺ ]

Synthesis Example 2: Synthesis of Compound 11

Synthesis Example 2-(1): Synthesis of Intermediate 2-a

According to Scheme 4 below, intermediate 2-a was synthesized.

<Scheme 4>

[Intermediate 2-a]

Except that 3-bromoiodobenzene was used instead of 1,3,5-tribromobenzene used in Synthesis Example 1-(1), and 4-dibenzothiophene boronic acid was used instead of 4-dibenzofuran boronic acid. Then, it was synthesized in the same manner to obtain [Intermediate 2-a]. (29 g, 59%)

Synthesis Example 2-(2): Synthesis of Intermediate 2-b

According to Scheme 5 below, intermediate 2-b was synthesized.

<Scheme 5>

[Intermediate 2-a] [Intermediate 2-b]

[Intermediate 2-b] was obtained by synthesis in the same manner, except that [Intermediate 2-a] was used instead of [Intermediate 1-a] used in Synthesis Example 1-(2). (22 g, 79%)

Synthesis Example 2-(3): Synthesis of Compound 11

Compound 11 was synthesized according to Scheme 6 below.

<Scheme 6>

[Intermediate 2-b] [Compound 11]

Instead of 1,3,5-tribromobenzene used in Synthesis Example 1-(1), 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine was used and 4- [Compound 11] was obtained by synthesizing in the same manner, except that [Intermediate 2-b] was used instead of dibenzofuran boronic acid. (17 g, 61%)

MS (MALDI-TOF): m/z 567.18 [M ⁺ ]

Synthesis Example 3: Synthesis of Compound 23

Synthesis Example 3-(1): Synthesis of Intermediate 3-a

Intermediate 3-a was synthesized according to Scheme 7 below.

<Scheme 7>

[Intermediate 3-a]

[Intermediate 3-a] was obtained by synthesis in the same manner, except that 2-bromo-9-9-dimethylfluorene was used instead of [Intermediate 1-a] used in Synthesis Example 1-(2). (23) g, 82%)

Synthesis Example 3-(2): Synthesis of Intermediate 3-b

Intermediate 3-b was synthesized according to Scheme 8 below.

<Scheme 8>

[Intermediate 3-a] [Intermediate 3-b]

[Intermediate 3-b] was obtained by synthesis in the same manner, except that [Intermediate 3-a] was used instead of 4-dibenzothiophene boronic acid used in Synthesis Example 2-(1). (21 g, 74%) )

Synthesis Example 3-(3): Synthesis of intermediate 3-c

According to Scheme 9 below, intermediate 3-c was synthesized.

<Scheme 9>

[Intermediate 3-b] [Intermediate 3-c]

[Intermediate 3-c] was obtained by synthesis in the same manner, except that [Intermediate 3-b] was used instead of [Intermediate 1-a] used in Synthesis Example 1-(2). (17 g, 81%)

Synthesis Example 3-(4): Synthesis of Compound 23

Compound 23 was synthesized according to Scheme 10 below.

<Scheme 10>

[Intermediate 3-c] [Compound 23]

[Compound 23] was obtained by synthesis in the same manner except that [Intermediate 3-c] was used instead of [Intermediate 2-b] used in Synthesis Example 2-(3). (14 g, 64%)

MS (MALDI-TOF): m/z 577.25 [M ⁺ ]

Synthesis Example 4: Synthesis of Compound 42

Synthesis Example 4-(1): Synthesis of Intermediate 4-a

According to Scheme 11 below, intermediate 4-a was synthesized.

<Scheme 11>

[Intermediate 4-a]

[Intermediate 4-a] was obtained by synthesis in the same manner, except that 2-bromo dibenzofuran was used instead of [Intermediate 1-a] used in Synthesis Example 1-(2). (26 g, 79%)

Synthesis Example 4-(2): Synthesis of Intermediate 4-b

According to Scheme 12 below, intermediate 4-b was synthesized.

<Scheme 12>

[Intermediate 4-a] [Intermediate 4-b]

[Intermediate 4-b] was obtained by synthesis in the same manner, except that [Intermediate 4-a] was used instead of 4-dibenzothiophene boronic acid used in Synthesis Example 2-(1). (21 g, 71%) )

Synthesis Example 4-(3): Synthesis of Intermediate 4-c

According to Scheme 13 below, intermediate 4-c was synthesized.

<Scheme 13>

[Intermediate 4-b] [Intermediate 4-c]

[Intermediate 4-c] was obtained by synthesis in the same manner, except that [Intermediate 4-b] was used instead of [Intermediate 1-a] used in Synthesis Example 1-(2). (16 g, 83%)

Synthesis Example 4-(4): Synthesis of Compound 42

Compound 42 was synthesized according to Scheme 14 below.

<Scheme 14>

[Intermediate 4-c] [Compound 42]

[Compound 42] was obtained by synthesis in the same manner except that [Intermediate 4-c] was used instead of [Intermediate 2-b] used in Synthesis Example 2-(3). (11 g, 58%)

MS (MALDI-TOF): m/z 551.20 [M ⁺ ]

Synthesis Example 5: Synthesis of Compound 68

Synthesis Example 5-(1): Synthesis of Intermediate 5-a

According to Scheme 15 below, intermediate 5-a was synthesized.

<Scheme 15>

[Intermediate 5-a]

[Intermediate 5-a] was obtained by synthesis in the same manner, except that 2-bromo dibenzothiophene was used instead of [Intermediate 1-a] used in Synthesis Example 1-(2). (26 g, 79%) )

Synthesis Example 5-(2): Synthesis of Intermediate 5-b

Intermediate 5-b was synthesized according to Scheme 16 below.

<Scheme 16>

[Intermediate 5-a] [Intermediate 5-b]

[Intermediate 5-b] was obtained by synthesis in the same manner, except that [Intermediate 5-a] was used instead of 4-dibenzothiophene boronic acid used in Synthesis Example 2-(1). (22 g, 74%) )

Synthesis Example 5-(3): Synthesis of intermediate 5-c

According to Scheme 17 below, intermediate 5-c was synthesized.

<Scheme 17>

[Intermediate 5-b] [Intermediate 5-c]

[Intermediate 5-c] was obtained by synthesis in the same manner, except that [Intermediate 5-b] was used instead of [Intermediate 1-a] used in Synthesis Example 1-(2). (16 g, 77%)

Synthesis Example 5-(4): Synthesis of Compound 68

Compound 68 was synthesized according to Scheme 18 below.

<Scheme 18>

[Intermediate 5-c] [Compound 68]

Instead of 1,3,5-tribromobenzene used in Synthesis Example 1-(1), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine was used and 4- [Compound 68] was obtained by synthesizing in the same manner except that [Intermediate 5-c] was used instead of dibenzofuran boronic acid. (13 g, 52%)

MS (MALDI-TOF): m/z 567.18 [M ⁺ ]

Synthesis Example 6: Synthesis of Compound 75

Synthesis Example 6-(1): Synthesis of Intermediate 6-a

According to Scheme 19 below, intermediate 6-a was synthesized.

<Scheme 19>

[Intermediate 6-a]

[Intermediate 6-a] was obtained by synthesizing in the same manner except that 4-dibenzofuran boronic acid was used instead of 4-dibenzothiophene boronic acid used in Synthesis Example 2-(1). (31 g, 76 %)

Synthesis Example 6-(2): Synthesis of Intermediate 6-b

According to Scheme 20 below, intermediate 6-b was synthesized.

<Scheme 20>

[Intermediate 6-a] [Intermediate 6-b]

[Intermediate 6-c] was obtained by synthesis in the same manner, except that [Intermediate 6-a] was used instead of [Intermediate 1-a] used in Synthesis Example 1-(2). (26 g, 72%)

Synthesis Example 6-(3): Synthesis of Compound 75

Compound 75 was synthesized according to Scheme 21 below.

<Scheme 21>

[Intermediate 6-b] [Compound 75]

[Compound 75] was obtained by synthesis in the same manner, except that [Intermediate 6-b] was used instead of [Intermediate 2-b] used in Synthesis Example 2-(3). (18 g, 58 %)

MS (MALDI-TOF): m/z 551.20 [M ⁺ ]

Synthesis Example 7: Synthesis of Compound 89

Synthesis Example 7-(1): Synthesis of Compound 89

Compound 89 was synthesized according to Scheme 22 below.

<Scheme 22>

[Intermediate 3-c] [Compound 89]

[Compound 89] was obtained by synthesis in the same manner, except that [Intermediate 3-c] was used instead of [Intermediate 5-c] used in Synthesis Example 5-(4). (12 g, 49%)

MS (MALDI-TOF): m/z 577.25 [M ⁺ ]

Synthesis Example 8: Synthesis of Compound 108

Synthesis Example 8-(1): Synthesis of Intermediate 8-a

According to Scheme 23 below, intermediate 8-a was synthesized.

<Scheme 23>

[Intermediate 8-a]

[Intermediate 8- a] was obtained (19 g, 41%).

Synthesis Example 8-(2): Synthesis of intermediate 8-b

According to Scheme 24 below, intermediate 8-b was synthesized.

<Scheme 24>

[Intermediate 8-a] [Intermediate 8-b]

[Intermediate 8-b] was obtained by synthesis in the same manner, except that [Intermediate 8-a] was used instead of [Intermediate 1-a] used in Synthesis Example 1-(2). (15 g, 84%)

Synthesis Example 8-(3): Synthesis of Compound 108

Compound 108 was synthesized according to Scheme 25 below.

<Scheme 25>

[Intermediate 8-b] [Compound 108]

[Compound 108] was obtained by synthesis in the same manner, except that [Intermediate 8-b] was used instead of [Intermediate 1-b] used in Synthesis Example 1-(3). (9.1 g, 62%)

MS (MALDI-TOF): m/z 693.31 [M ⁺ ]

Synthesis Example 9: Synthesis of Compound 115

Synthesis Example 9-(1): Synthesis of Compound 115

Compound 115 was synthesized according to Scheme 26 below.

<Scheme 26>

[Intermediate 3-c] [Compound 115]

Instead of 1,3,5-tribromobenzene used in Synthesis Example 1-(1), 2-4-dichloro-6-phenyl-1,3,5-triazine was used, and [Intermediate 1-b] was used instead of [Intermediate 1-b]. [Compound 115] was obtained by synthesis in the same manner except that [3-c] was used. (6.7 g, 43%)

MS (MALDI-TOF): m/z 551.20 [M+]

Examples 1 to 15 (Manufacture of organic light emitting device)

The ITO glass was patterned so that the light emitting area was 2 mm x 2 mm in size and then cleaned. After mounting the substrate in a vacuum chamber, the base pressure was set to 1x10 ^-6 torr, and organic materials such as HATCN (50 Å), NPD (900 Å), and the compounds prepared according to the present invention listed in Table 1 below were added to the ITO. Green phosphorescent dopant (GD) was used and doped at 7% to form a light emitting layer with a thickness of 300 Å. Afterwards, films were formed in the following order: ET: Liq = 1:1 (300 Å), Liq (10 Å), and Al (1,000 Å), and measurements were made at 0.4 mA.

[HATCN] [NPD]

[ET] [Liq] [GD]

Comparative example

The organic light emitting device for the comparative example was manufactured in the same manner as the device structures of Examples 1 to 15 except that CBP, which is commonly used as a phosphorescent host material, was used instead of the compound manufactured by the invention, and the structure of the CBP was It is as follows.

<CBP>

For the organic light-emitting devices manufactured according to Examples 1 to 15 and Comparative Example, voltage, luminance, color coordinates, and lifespan were measured, and the results are shown in Table 1 below. T ₉₅ means the time it takes for the luminance to decrease from the initial luminance (6000 cd/m ² ) to 95%.

host driving voltage
(V) Luminous efficiency (cd/A) CIEx CIey T95
6000nit(h) Example 1 Compound 1 3.4 55 0.335 0.627 60 Example 2 Compound 11 3.4 48 0.339 0.631 50 Example 3 Compound 24 3.6 53 0.331 0.627 55 Example 4 Compound 34 3.7 52 0.324 0.636 70 Example 5 Compound 37 3.5 56 0.333 0.628 50 Example 6 Compound 42 3.4 48 0.334 0.629 60 Example 7 Compound 50 3.6 58 0.336 0.627 65 Example 8 Compound 61 3.5 52 0.328 0.632 65 Example 9 Compound 68 3.5 54 0.327 0.632 50 Example 10 Compound 70 3.8 55 0.328 0.633 70 Example 11 Compound 75 3.7 60 0.330 0.632 75 Example 12 Compound 89 3.6 58 0.338 0.626 50 Example 13 Compound 101 3.4 51 0.330 0.632 50 Example 14 Compound 108 3.7 49 0.326 0.634 65 Example 15 Compound 115 3.5 55 0.330 0.631 55 Comparative example CBP 6.9 36 0.335 0.628 8

As shown in Table 1, it can be seen that the organic light-emitting device using the organic compound according to the present invention has higher efficiency, lower driving voltage, and longer lifespan than the organic light-emitting device according to the comparative example.

Claims (14)

A heterocyclic compound represented by the following [Formula A].
[Formula A]

In Formula A,
Ar1 to Ar3 are each the same or different and are independently selected from a substituted or unsubstituted aryl group having 6 to 50 carbon atoms or a substituent represented by the structural formula A below,
Among Ar1 to Ar3, two are substituents represented by the structural formula A below,
When two or more of Ar1 to Ar3 are substituents represented by structural formula A below, each substituent represented by structural formula A is the same or different from each other.
[Structural Formula A]

In structural formula A,
W is any one selected from O, S, or CR1R2;
The substituents R1, R2, R11 and R12 are each the same or different, and are independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or A substituent selected from an unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group, and is connected to an adjacent functional group to form an alicyclic or aromatic group. May form a monocyclic or polycyclic ring;
The linking group L is a substituted or unsubstituted arylene group having 6 to 60 carbon atoms;
The m is 1,
Except in the case where W in each structural formula A above is all oxygen atoms, all sulfur atoms, or all CR1R2,
p is an integer from 1 to 4, but when p is 2 or more, each R11 is the same or different from each other,
q is an integer from 1 to 3, but when q is 2 or more, each R12 is the same or different from each other,
n is an integer from 1 to 3, but when n is 2 or more, each L is the same as or different from each other;
'-**' is bonded to the carbon atom of the triazine ring in Formula A,
When the substituents of R11 or R12 are not bonded to the carbon atoms in the aromatic 6-membered ring on both sides of the structural formula A, hydrogen or deuterium is bonded to them;
'Substitution' in 'substituted or unsubstituted' means deuterium, cyano group, halogen group, nitro group, alkyl group with 1 to 24 carbon atoms, halogenated alkyl group with 1 to 24 carbon atoms, aryl group with 6 to 24 carbon atoms, carbon number. It means being substituted with one or more substituents selected from the group consisting of an arylalkyl group with 7 to 24 carbon atoms, an alkylsilyl group with 1 to 24 carbon atoms, and an arylsilyl group with 6 to 24 carbon atoms.
However, the following compounds A-21 to A-24 and D-1 to D-4 are excluded.

According to claim 1,
The linking group L is the same or different, and is independently selected from the following structural formulas 1, 2, 4, 6, 7, and 9.
[Structural Formula 1] [Structural Formula 2] [Structural Formula 4]

[Structural Formula 6] [Structural Formula 7]

[Structural Formula 9]

In Structural Formula 1, Structural Formula 2, Structural Formula 4, Structural Formula 6, Structural Formula 7, and Structural Formula 9, hydrogen or deuterium is bonded to the carbon site of the aromatic ring. According to claim 1,
The substituents R1, R2, R11, and R12 of [Formula A] are each the same or different, and are independently hydrogen, deuterium, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; A heterocyclic compound selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. delete delete According to claim 1,
A heterocyclic compound, wherein the substituent other than the substituent represented by structural formula A among Ar1 to Ar3 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. According to claim 1,
A heterocyclic compound represented by <Compound 62> or <Compound 63> below.
<Compound 62><Compound63>
A composition for an organic light-emitting device comprising a first host material and a second host material,
The first host material is a heterocyclic compound selected from claims 1 to 3, 6, and 7, and the second host material is a heterocyclic compound selected from the compounds of formulas 3 to 6 below. A composition for an organic light-emitting device, characterized in that it contains at least one composition.
<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

In Formulas 3 to 6,
A is hydrogen, deuterium, a substituted or unsubstituted alkyl group with 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 to 30 carbon atoms, and a substituted or unsubstituted aryl group with 6 to 50 carbon atoms;
Connector L is the same as L in claim 1,
n1 is an integer from 1 to 3, but when n1 is 2 or more, each L is the same as or different from each other;
Substituent R31 is the same as R1 and R2 in claim 1,
n2 is an integer from 1 to 5, but when n2 is 2 or more, each R31 is the same or different;
In Formula 3, n3 is an integer from 1 to 6, and when n3 is 2 or more, each [(L)n1-(R31)n2] is the same or different from each other,
In Formula 4, n3 is an integer from 1 to 8, and when n3 is 2 or more, each [(L)n1-(R31)n2] is the same or different from each other,
In Formula 5, n3 is an integer from 1 to 14, and when n3 is 2 or more, each [(L)n1-(R31)n2] is the same or different from each other, and the ring containing the nitrogen atom forms a 5-membered ring. ,
In Formula 6, Y is any one selected from NR ₃ , CR ₄ R ₅ , SiR ₆ R ₇ , O and S, and the ring containing Y forms a 5-membered ring,
n3 is an integer from 1 to 10, and when n3 is 2 or more, each [(L)n1-(R31)n2] is the same or different from each other,
At this time, R3 to R7 may be defined in the same way as R1 and R2 described above. first electrode;
a second electrode opposite the first electrode; and
An organic layer interposed between the first electrode and the second electrode, wherein the organic layer contains at least one heterocyclic compound selected from claims 1 to 3, 6, and 7. An organic light emitting device containing. According to clause 9,
The organic layer is an organic light-emitting device comprising at least one of a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a light emitting layer, an electron transport layer, and an electron injection layer. According to claim 10,
An organic layer interposed between the first electrode and the second electrode includes a light emitting layer,
The light-emitting layer is composed of a host and a dopant, and the heterocyclic compound is used as a host. According to claim 11,
An organic light-emitting device, wherein the organic layer further includes a hole blocking layer or an electron blocking layer. According to clause 10,
An organic light emitting device, wherein one or more layers selected from among the above layers are formed by a deposition process or a solution process. According to clause 9,
The organic light emitting device may include a flat panel display device; flexible display device; Devices for monochromatic or white flat panel lighting; and, a monochromatic or white flexible lighting device.