KR102130214B1 - Anthracene derivative and organic light emitting device comprising the same - Google Patents

Abstract

The present specification relates to an anthracene derivative represented by Chemical Formula 1 and an organic light emitting device including the same.

Description

An anthracene derivative and an organic light emitting device containing the same ANTANTRACENE DERIVATIVE AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME

This application claims the benefit of the filing date of Korean Patent Application No. 10-2017-0133986 filed with the Korean Intellectual Property Office on October 16, 2017, the entire contents of which are incorporated herein.

The present specification relates to an anthracene derivative and an organic light emitting device including the same.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, for example, may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it will shine.

The development of new materials for such organic light-emitting devices continues to be required.

US Patent Application Publication No. 2004-0251816

The present specification provides an anthracene derivative and an organic light emitting device including the same.

According to an exemplary embodiment of the present specification provides an anthracene derivative represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

X1 is O; S; Or CRR',

R, R', R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitrile group; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or adjacent substituents combine with each other to form a substituted or unsubstituted ring,

L1 and L2 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

n and m are each an integer of 1 or 2,

When n is an integer of 2, L1 is the same as or different from each other,

When m is an integer of 2, L2 is the same as or different from each other,

Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

a is an integer from 0 to 9,

b is an integer from 0 to 7,

When a is an integer of 2 or more, R1 is the same as or different from each other,

When b is an integer of 2 or more, R2 is the same as or different from each other.

In addition, according to an exemplary embodiment of the present specification, the first electrode; A second electrode provided opposite to the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes an anthracene derivative represented by the formula (1). to provide.

The anthracene derivative according to an exemplary embodiment of the present specification may be used as a material of an organic material layer of an organic light emitting device, and by using this, it is possible to improve efficiency, improve low driving voltage and/or lifespan characteristics in the organic light emitting device.

1 shows an organic light emitting device 10 according to an exemplary embodiment of the present specification.
2 shows an organic light emitting diode 11 according to another exemplary embodiment of the present specification.

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

The present specification provides an anthracene derivative represented by Chemical Formula 1 above.

The anthracene derivative represented by Chemical Formula 1 has a substituent on carbons 1, 8, and 10 to increase the conjugate length of the anthracene host, resulting in an increase in the HOMO (High Occupied Molecular Orbital) level. For this reason, compared to the anthracene derivatives which are divalently substituted on carbons 9 and 10, injection of holes is increased to improve device performance of the organic light emitting device.

In the present specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

In the present specification, when a member is said to be positioned “on” another member, this includes not only the case where one member is in contact with the other member but also another member between the two members.

Examples of substituents in the present specification are described below, but are not limited thereto.

The term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and when two or more are substituted , 2 or more substituents may be the same or different from each other.

The term "substituted or unsubstituted" in this specification is deuterium; Nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; And substituted or unsubstituted heteroaryl groups, substituted with 1 or 2 or more substituents, or substituted with 2 or more substituents among the exemplified substituents, or having no substituents. For example, the "substituent in which two or more substituents are connected" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heteroaryl group substituted with an aryl group, an aryl group substituted with an alkyl group, or the like.

According to an exemplary embodiment of the present specification, the term "substituted or unsubstituted" is deuterium; Nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; And 1 or 2 or more substituents selected from the group consisting of substituted or unsubstituted heteroaryl groups.

In the present specification, the alkyl group may be a straight chain or a branched chain, and carbon number is not particularly limited, but is preferably 1 to 30. Specifically, it is preferable to have 1 to 20 carbon atoms. More specifically, it is preferable to have 1 to 10 carbon atoms. Specific examples include methyl groups; Ethyl group; Propyl group; n-propyl group; Isopropyl group; Butyl group; n-butyl group; Isobutyl group; tert-butyl group; sec-butyl group; 1-methylbutyl group; 1-ethyl butyl group; Pentyl group; n-pentyl group; Isopentyl group; Neopentyl group; tert-pentyl group; Hexyl group; n-hexyl group; 1-methylpentyl group; 2-methylpentyl group; 3,3-dimethylbutyl group; 2-ethylbutyl group; Heptyl group; n-heptyl group; 1-methylhexyl group; Cyclopentyl methyl group; Cyclohexylmethyl group; Octyl group; n-octyl group; tert-octyl group; 1-methylheptyl group; 2-ethylhexyl group; 2-propylpentyl group; n-nonyl group; 2,2-dimethylheptyl group; 1-ethylpropyl group; 1,1-dimethylpropyl group; Isohexyl group; 2-methylpentyl group; 4-methylhexyl group; 5-methylhexyl group, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms. Specifically, a cyclopropyl group; Cyclobutyl group; Cyclopentyl group; 3-methylcyclopentyl group; 2,3-dimethylcyclopentyl group; Cyclohexyl group; 3-methylcyclohexyl group; 4-methylcyclohexyl group; 2,3-dimethylcyclohexyl group; 3,4,5-trimethylcyclohexyl group; 4-tert-butylcyclohexyl group; Cycloheptyl group; Cyclooctyl group, and the like, but is not limited thereto.

In the present specification, the silyl group may be represented by the formula of -SiRaRbRc, wherein Ra, Rb and Rc are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The silyl group is specifically a trimethylsilyl group; Triethylsilyl group; t-butyldimethylsilyl group; Vinyl dimethyl silyl group; Propyl dimethyl silyl group; Triphenylsilyl group; Diphenylsilyl group; Phenylsilyl group, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 30 carbon atoms, and more preferably 6 to 20 carbon atoms. The aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. Specifically, as the monocyclic aryl group, a phenyl group; Biphenyl group; It may be a terphenyl group, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it has 10 to 30 carbon atoms. Specifically, a polycyclic aryl group is a naphthyl group; Anthracenyl group; Phenanthryl group; Triphenyl group; Pyrenyl group; Phenenyl group; Perylenyl group; Chrysenyl group; It may be a fluorenyl group and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.

,

,

,

,

, 및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다. When the fluorenyl group is substituted,

,

,

,

,

, And

It can be back. However, it is not limited thereto.

In the present specification, the heteroaryl group includes one or more non-carbon atoms and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, and S. The number of carbon atoms is not particularly limited, and preferably 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. The heteroaryl group may be monocyclic or polycyclic, and may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and examples of the aromatic heteroaryl group include thiophene group, furanyl group, pyrrol group, imidazolyl group, and thiazolyl group. , Oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, triazolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, Quinoxalinyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzo Thiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, phenanthroline group, isooxazolyl group, thiadiazolyl group, phenothiazinyl group and dibenzofura Neil group, and the like, but is not limited thereto.

In the present specification, the description of the aryl group described above may be applied, except that the arylene group is a divalent group.

In the present specification, the description of the heteroaryl group described above may be applied, except that the heteroarylene group is a divalent group.

In the present specification, in a substituted or unsubstituted ring formed by bonding adjacent groups to each other, "ring" is a substituted or unsubstituted hydrocarbon ring; Or substituted or unsubstituted heterocyclic ring.

In the present specification, the hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the cycloalkyl group or aryl group except for non-monovalent.

In the present specification, the aromatic ring may be monocyclic or polycyclic, and may be selected from examples of the aryl group, except that it is not monovalent.

In the present specification, the heterocycle is a non-carbon atom, and contains at least one heteroatom, specifically, the heteroatom may include at least one atom selected from the group consisting of O, N, and S. The heterocycle may be monocyclic or polycyclic, may be aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the heteroaryl group except for non-monovalent.

In Formula 1, a 5-membered ring containing O is connected to carbon 10 of anthracene.

According to an exemplary embodiment of the present specification, X1 is O; Or CRR'.

According to an exemplary embodiment of the present specification, the R and R'are the same as or different from each other, and each independently substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group, or R and R'may combine with each other to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, the R and R'are the same as or different from each other, and each independently substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or R and R'may combine with each other to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, R and R'are the same as or different from each other, and each independently a substituted or unsubstituted methyl group; A substituted or unsubstituted ethyl group; A substituted or unsubstituted propyl group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted naphthyl group, or R and R'may combine with each other to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, the R and R'are the same as or different from each other, and each independently a methyl group; Ethyl group; Propyl group; Phenyl group; Biphenyl group; Or a naphthyl group, or R and R'may combine with each other to form a ring,

The methyl group, ethyl group, propyl group, phenyl group, biphenyl group, naphthyl group or ring is a nitrile group; An alkyl group having 1 to 10 carbon atoms; An aryl group having 6 to 13 carbon atoms; Or it is substituted or unsubstituted with a heteroaryl group having 2 to 13 carbon atoms.

According to an exemplary embodiment of the present specification, the R and R'are the same as or different from each other, and each independently a methyl group; Or it may be a phenyl group, or R and R'may combine with each other to form a fluorene ring.

According to an exemplary embodiment of the present specification, the R and R'are the same as or different from each other, or each independently a methyl group, or R and R'may combine with each other to form a fluorene ring.

According to one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms.

According to one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted terphenylene group; A substituted or unsubstituted naphthylene group; A substituted or unsubstituted phenanthrenylene group; A substituted or unsubstituted anthracenyl group; A substituted or unsubstituted triphenylenylene group; A substituted or unsubstituted fluorenylene group; A substituted or unsubstituted divalent thiophene group; A substituted or unsubstituted furanylene group; A substituted or unsubstituted divalent dibenzothiophene group; A substituted or unsubstituted dibenzofuranylene group; A substituted or unsubstituted carbazolylene group; Or a substituted or unsubstituted pyrrole group.

According to one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; Phenylene group; Biphenylene group; Terphenylene group; Naphthylene group; Phenanthrenylene group; Anthracenyl group; Triphenylenylene group; A fluorenylene group unsubstituted or substituted with an alkyl group or an aryl group; Divalent thiophene group; Furanylene group; Divalent dibenzothiophene group; Dibenzofuranylene group; A carbazolylene group unsubstituted or substituted with an alkyl group or an aryl group; Or a pyrrolene group unsubstituted or substituted with an alkyl group or an aryl group.

According to one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; Phenylene group; Biphenylene group; Terphenylene group; Naphthylene group; Phenanthrenylene group; Anthracenyl group; Triphenylenylene group; A fluorenylene group unsubstituted or substituted with a methyl group, an ethyl group, or a phenyl group; Divalent thiophene group; Furanylene group; Divalent dibenzothiophene group; Dibenzofuranylene group; A carbazolylene group unsubstituted or substituted with a methyl group, an ethyl group, or a phenyl group; Or a pyrrolene group unsubstituted or substituted with a methyl group, an ethyl group, or a phenyl group.

According to one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; Or a substituted or unsubstituted naphthylene group.

According to one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; Phenylene group; Biphenylene group; Or a naphthylene group.

According to one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; Or a phenylene group.

According to an exemplary embodiment of the present specification, each of n and m is 1.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic to 4 ring aryl group; Or a substituted or unsubstituted monocyclic to 4 ring heteroaryl group.

According to the exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted anthracenyl group; A substituted or unsubstituted phenanthrenyl group; A substituted or unsubstituted perenyl group; A substituted or unsubstituted fluoranthenyl group; A substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted phenenyl group; A substituted or unsubstituted pyrenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted pyridyl group; A substituted or unsubstituted pyrimidinyl group; A substituted or unsubstituted pyridazinyl group; A substituted or unsubstituted isoquinolinyl group; A substituted or unsubstituted quinolyl group; A substituted or unsubstituted quinazolinyl group; A substituted or unsubstituted quinoxalinyl group; A substituted or unsubstituted acridinyl group; A substituted or unsubstituted diazanaphthalenyl group; A substituted or unsubstituted indole group; A substituted or unsubstituted benzothiazolyl group; A substituted or unsubstituted benzooxazolyl group; A substituted or unsubstituted benzimidazole group; A substituted or unsubstituted benzothiophene group; A substituted or unsubstituted benzofuranyl group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted dibenzofuranyl group; A substituted or unsubstituted carbazolyl group; A substituted or unsubstituted benzocarbazolyl group; A substituted or unsubstituted naphthobenzothiophene group; Or a substituted or unsubstituted naphthobenzofuranyl group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently an aryl group or a heteroaryl group-substituted or unsubstituted phenyl group; A biphenyl group unsubstituted or substituted with an aryl group or a heteroaryl group; A terphenyl group unsubstituted or substituted with an aryl group or a heteroaryl group; A naphthyl group unsubstituted or substituted with an aryl group or a heteroaryl group; Anthracenyl group; Phenanthrenyl group; Perylenyl group; Fluoranthenyl group; Triphenylenyl group; Phenenyl group; Pyrenyl group; A fluorenyl group unsubstituted or substituted with an alkyl group or an aryl group; Pyridyl group; Pyrimidinyl group; Pyridazinyl group; Isoquinolinyl group; Quinolyl group; Quinazolinyl group; Quinoxalinyl group; Acridinyl group; Diazanaphthalenyl group; Indolescence; Benzothiazolyl group; Benzooxazolyl group; Benzimidazole group; Benzothiophene group; Benzofuranyl group; Dibenzothiophene group; Dibenzofuranyl group; A carbazolyl group unsubstituted or substituted with an alkyl group, an aryl group, or a heteroaryl group; A benzocarbazolyl group unsubstituted or substituted with an alkyl group, an aryl group, or a heteroaryl group; Naphthobenzothiophene group; Or a naphthobenzofuranyl group.

According to one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group, a naphthyl group, or a dibenzothiophene group. Or a phenyl group unsubstituted or substituted with a dibenzofuran group; Phenyl group, naphthyl group, dibenzothiophene group. Or a biphenyl group unsubstituted or substituted with a dibenzofuran group; Phenyl group, naphthyl group, dibenzothiophene group. Or a terphenyl group unsubstituted or substituted with a dibenzofuran group; Phenyl group, naphthyl group, dibenzothiophene group. Or a naphthyl group unsubstituted or substituted with a dibenzofuran group; Anthracenyl group; Phenanthrenyl group; Perylenyl group; Fluoranthenyl group; Triphenylenyl group; Phenenyl group; Pyrenyl group; A fluorenyl group unsubstituted or substituted with a methyl group, an ethyl group, or a phenyl group; Pyridyl group; Pyrimidinyl group; Pyridazinyl group; Isoquinolinyl group; Quinolyl group; Quinazolinyl group; Quinoxalinyl group; Acridinyl group; Diazanaphthalenyl group; Indolescence; Benzothiazolyl group; Benzooxazolyl group; Benzimidazole group; Benzothiophene group; Benzofuranyl group; Dibenzothiophene group; Dibenzofuranyl group; A carbazolyl group unsubstituted or substituted with a methyl group, an ethyl group, a t-butyl group, or a phenyl group; A benzocarbazolyl group unsubstituted or substituted with a methyl group, an ethyl group, a t-butyl group, or a phenyl group; Naphthobenzothiophene group; Or a naphthobenzofuranyl group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently an aryl group or a heteroaryl group-substituted or unsubstituted phenyl group; A biphenyl group unsubstituted or substituted with an aryl group or a heteroaryl group; A terphenyl group unsubstituted or substituted with an aryl group or a heteroaryl group; A naphthyl group unsubstituted or substituted with an aryl group or a heteroaryl group; Anthracenyl group; Phenanthrenyl group; Perylenyl group; Fluoranthenyl group; Triphenylenyl group; Phenenyl group; Pyrenyl group; A fluorenyl group unsubstituted or substituted with an alkyl group or an aryl group; Pyridyl group; Pyrimidinyl group; Pyridazinyl group; Isoquinolinyl group; Quinolyl group; Quinazolinyl group; Quinoxalinyl group; Acridinyl group; Diazanaphthalenyl group; Indolescence; Benzothiazolyl group; Benzooxazolyl group; Benzimidazole group; Benzothiophene group; Benzofuranyl group; Dibenzothiophene group; Dibenzofuranyl group; A carbazolyl group unsubstituted or substituted with an alkyl group, an aryl group, or a heteroaryl group; A benzocarbazolyl group unsubstituted or substituted with an alkyl group, an aryl group, or a heteroaryl group; Naphthobenzothiophene group; Or a naphthobenzofuranyl group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group; Biphenyl group; Naphthyl group; Fluorenyl group; Dibenzothiophene group; Or a dibenzofuranyl group,

The phenyl group, biphenyl group, naphthyl group, fluorenyl group, dibenzothiophene group, or dibenzofuranyl group has an aryl group having 6 to 13 carbon atoms; Or it is substituted or unsubstituted with a heteroaryl group having 2 to 13 carbon atoms.

According to one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group, a naphthyl group, or a dibenzothiophene group. Or a phenyl group unsubstituted or substituted with dibenzofuranyl group; A biphenyl group unsubstituted or substituted with a phenyl group, a naphthyl group, a dibenzothiophene group, or a dibenzofuranyl group; A naphthyl group unsubstituted or substituted with a phenyl group, a naphthyl group, a dibenzothiophene group, or a dibenzofuranyl group; A dibenzothiophene group unsubstituted or substituted with a phenyl group; Or a dibenzofuranyl group unsubstituted or substituted with a phenyl group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group; Biphenyl group; Naphthyl group; Dibenzothiophene group; Or a dibenzofuranyl group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group; Biphenyl group; Dibenzothiophene group; Or a dibenzofuranyl group.

According to one embodiment of the present specification, R1 and R2 are hydrogen.

According to an exemplary embodiment of the present specification, a is 0.

According to an exemplary embodiment of the present specification, a is 9.

According to an exemplary embodiment of the present specification. B is 0.

According to an exemplary embodiment of the present specification, b is 7.

According to one embodiment of the present specification, Chemical Formula 1 may be represented by one selected from Chemical Formulas 1-1 to 1-4 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Chemical Formulas 1-1 to 1-4,

The definitions of X1, R1, R2, L1, L2, Ar1, Ar2, n, m, a and b are as defined in Formula 1.

According to another exemplary embodiment of the present specification, the anthracene derivative of Formula 1 may be represented by the following structural formulas.

According to an exemplary embodiment of the present specification, the anthracene derivative of Formula 1 may be prepared according to the following general formula, but is not limited thereto. In the following scheme, the type and number of substituents can be determined by appropriately selecting a starting material known by a person skilled in the art. Reaction types and reaction conditions may be those known in the art.

[general meal]

In the above general formula, Ar ₁ corresponds to Ar ₁ and Ar ₂ in Formula 1, and HAr corresponds to a 5-ring ring in Formula 1. Although other substituents are not indicated in the general formula, substituents in which L1, L2, R1 and R2 are substituted may be used, or the product produced by the general formula may be substituted with a substituent known in the art.

The anthracene derivatives described in the present specification can all be prepared by appropriately combining the preparation formulas described in the examples of the present specification and the intermediates based on common technical knowledge.

According to an exemplary embodiment of the present specification, the first electrode; A second electrode provided opposite to the first electrode; And an organic light emitting device including at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the anthracene derivative described above.

In addition, according to an exemplary embodiment of the present specification, the first electrode; A second electrode provided opposite to the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the anthracene derivative described above. to provide.

According to the exemplary embodiment of the present specification, the organic material layer of the organic light emitting device of the present specification may have a single layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include fewer or more organic material layers.

For example, the structure of the organic light emitting device of the present specification may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.

In FIG. 1, the structure of the organic light emitting device 10 in which the first electrode 30, the light emitting layer 40, and the second electrode 50 are sequentially stacked on the substrate 20 is illustrated. 1 is an exemplary structure of an organic light emitting device according to an exemplary embodiment of the present specification, may further include another organic material layer. According to an exemplary embodiment of the present invention, the light emitting layer 40 includes an anthracene derivative represented by Chemical Formula 1.

2, the first electrode 30, the hole injection layer 60, the hole transport layer 70, the light emitting layer 40, the electron transport layer 80, the electron injection layer 90 and the second electrode on the substrate 20 ( The structure of the organic light emitting element 11 in which 50) is sequentially stacked is illustrated. 2 is an exemplary structure according to an exemplary embodiment of the present specification, and may further include another organic material layer. According to an exemplary embodiment of the present invention, at least one of the hole injection layer 60, the hole transport layer 70, the light emitting layer 40, the electron transport layer 80 and the electron injection layer 90 is represented by Formula 1 Anthracene derivatives.

According to one embodiment of the present specification, the organic material layer includes a hole injection layer, a hole transport layer, or an electron blocking layer, and the hole injection layer, a hole transport layer, or an electron blocking layer includes the anthracene derivative.

According to the exemplary embodiment of the present specification, the organic material layer includes a hole blocking layer, an electron transport layer, or an electron injection layer, and the hole blocking layer, an electron transport layer, or an electron injection layer includes the anthracene derivative.

According to an exemplary embodiment of the present specification, the first electrode; A second electrode provided opposite to the first electrode; And an organic material layer included between the first electrode and the second electrode, and includes a hole injection layer, a hole transport layer, a light emitting layer including the anthracene derivative, and a layer simultaneously performing electron injection and electron transport.

The organic light emitting diode according to the exemplary embodiment of the present specification includes a first electrode, a hole injection layer, a hole transport layer, a light emitting layer containing the anthracene derivative, a layer simultaneously performing electron injection and electron transport, and a second electrode in sequence do.

According to the exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes the anthracene derivative.

According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the anthracene derivative as a host of the light emitting layer.

According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, the anthracene derivative as a host of the light emitting layer, the light emitting layer further comprises a dopant of the light emitting layer. In this case, based on the host weight included in the light-emitting layer, the dopant of the light-emitting layer may be included 0.1% to 15% by weight, more preferably 0.1% to 10% by weight, more preferably 1% to 6% by weight It may be weight percent.

According to an exemplary embodiment of the present specification, when the anthracene derivative is included as a host of the light emitting layer, the dopant of the light emitting layer may include an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, a metal complex, etc. . Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamine group, and includes pyrene, anthracene, chrysene, periplanene, etc. having an arylamine group, and substituted or unsubstituted as a styrylamine compound. As a compound in which at least one arylvinyl group is substituted in the substituted arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamine group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes, platinum complexes, and the like.

According to the exemplary embodiment of the present specification, the organic material layer may include a light emitting layer, the anthracene derivative as a host of the light emitting layer, and a diamine-based compound as an aromatic amine derivative as a dopant in the light emitting layer.

According to the exemplary embodiment of the present specification, the organic material layer may include a light emitting layer, the anthracene derivative as a host of the light emitting layer, and a compound represented by the following Chemical Formula 1-D as a dopant in the light emitting layer.

[Formula 1-D]

In Chemical Formula 1-D,

x is an integer of 1 or more, and when x is 2 or more, structures in parentheses are the same or different from each other,

Ar11 is a substituted or unsubstituted monovalent or higher benzofluorene group; A substituted or unsubstituted monovalent or higher fluoranthene group; A substituted or unsubstituted monovalent or higher pyrene group; Or a substituted or unsubstituted monovalent or higher chrysene group,

L11 is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

R21 and R22 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted arylalkyl group; Or it may be a substituted or unsubstituted heteroaryl group, or combine with each other to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, L11 is a direct bond.

According to an exemplary embodiment of the present specification, x is 2.

According to the exemplary embodiment of the present specification, Ar11 is a divalent pyrene group unsubstituted or substituted with deuterium, a methyl group, an ethyl group, an iso-propyl group, or a tert-butyl group; Or a divalent chrysene group substituted or unsubstituted with deuterium, methyl group, ethyl group, iso-propyl group or tert-butyl group.

According to an exemplary embodiment of the present specification, Ar11 is a divalent pyrene group unsubstituted or substituted with deuterium, methyl group, ethyl group, iso-propyl group, or tert-butyl group.

According to an exemplary embodiment of the present specification, R21 and R22 are the same as or different from each other, and each independently substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

According to one embodiment of the present specification, R21 and R22 are the same as or different from each other, and each independently deuterium, an alkyl group, a nitrile group, an aryl group, an alkylsilyl group, or an alkyl germanium group substituted or unsubstituted carbon number 6 to 60 Aryl group; Or a heteroaryl group having 2 to 60 carbon atoms unsubstituted or substituted with deuterium, an alkyl group, a nitrile group, an aryl group, an alkylsilyl group, or an alkyl germanium group.

According to one embodiment of the present specification, R21 and R22 are the same as or different from each other, and each independently deuterium, methyl group, ethyl group, iso-propyl group, tert-butyl group, nitrile group, phenyl group, trimethylsilyl group, or trimethyl germanium An aryl group having 6 to 60 carbon atoms unsubstituted or substituted with a group; Or a heteroaryl group having 2 to 60 carbon atoms unsubstituted or substituted with deuterium, methyl, ethyl, iso-propyl, tert-butyl, nitrile, phenyl, trimethylsilyl or trimethylgermanium.

According to one embodiment of the present specification, R21 and R22 are the same as or different from each other, and each independently deuterium, methyl group, ethyl group, iso-propyl group, tert-butyl group, nitrile group, phenyl group, trimethylsilyl group, or trimethyl germanium A phenyl group unsubstituted or substituted with a group; A biphenyl group unsubstituted or substituted with deuterium, methyl group, ethyl group, iso-propyl group, tert-butyl group, nitrile group, phenyl group, trimethylsilyl group or trimethyl germanium group; A dephenyl group unsubstituted or substituted with deuterium, methyl, ethyl, iso-propyl, tert-butyl, nitrile, phenyl, trimethylsilyl or trimethylgermanium; Or a dibenzofuran group unsubstituted or substituted with deuterium, methyl, ethyl, iso-propyl, tert-butyl, nitrile, phenyl, trimethylsilyl or trimethylgermanium groups.

According to an exemplary embodiment of the present specification, the formula 1-D may be selected from the following compounds.

According to an exemplary embodiment of the present specification, R21 and R22 are the same as or different from each other, and each independently a methyl group or a phenyl group unsubstituted or substituted with an ethyl group; Or dibenzofuran group.

According to an exemplary embodiment of the present specification, R21 is a phenyl group substituted with a methyl group.

According to an exemplary embodiment of the present specification, R22 is a dibenzofuran group.

An organic light emitting device according to an exemplary embodiment of the present specification, the first electrode; A second electrode; And an emission layer provided between the first electrode and the second electrode, and the emission layer includes an anthracene derivative represented by Chemical Formula 1. However, the structure of the organic light emitting device is not limited to this, and may include fewer or more organic material layers.

An organic light emitting device according to an exemplary embodiment of the present specification, the first electrode; A second electrode; And a light emitting layer provided between the first electrode and the second electrode, the light emitting layer including an anthracene derivative represented by Formula 1 as a host, and a compound represented by Formula 1-D as a dopant. In addition, one or more organic material layers selected from the hole transport layer, the hole injection layer, the electron transport layer and the electron injection layer may be further included. However, the structure of the organic light emitting device is not limited to this, and may include fewer or more organic material layers.

An organic light emitting device according to an exemplary embodiment of the present specification, the first electrode; A second electrode; And a light emitting layer provided between the first electrode and the second electrode, and may include a hole injection layer or a hole transport layer between the first electrode and the light emitting layer, and between the second electrode and the light emitting layer. It may include a layer for electron transport and electron injection at the same time. However, the structure of the organic light emitting device is not limited to this, and may include fewer or more organic material layers.

An organic light emitting device according to an exemplary embodiment of the present specification, the first electrode; A second electrode; And a light emitting layer provided between the first electrode and the second electrode, the light emitting layer including an anthracene derivative represented by Chemical Formula 1 as a host, and a hole injection layer between the first electrode and the light emitting layer. It may be, and may include a hole transport layer between the light emitting layer and the hole injection layer, it may include a layer that performs electron transport and electron injection between the second electrode and the light emitting layer at the same time. However, the structure of the organic light emitting device is not limited to this, and may include fewer or more organic material layers.

The organic light-emitting device of the present specification may be manufactured by a conventional method and material for manufacturing an organic light-emitting device, except that one or more layers of organic materials are formed using the compounds described above.

The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes anthracene derivatives of the present specification, that is, anthracene derivatives represented by Chemical Formula 1 above. .

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device of the present specification can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition method (PVD: Physical Vapor Deposition) such as sputtering or e-beam evaporation, metal oxide or conductive metal oxide or alloys thereof are deposited on the substrate. 1 electrode is formed, a hole injection layer, a hole transport layer, a light emitting layer and an organic material layer including an electron injection and electron transport layer are formed on the same layer, and then a material that can be used as a second electrode is deposited thereon. Can. In addition to this method, an organic light emitting device may be formed by sequentially depositing a second electrode material, an organic material layer, and a first electrode material on a substrate. In addition, the anthracene derivative represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.

According to an exemplary embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.

According to another exemplary embodiment of the present specification, the first electrode is a cathode, and the second electrode is an anode.

The positive electrode material is usually a material having a large work function to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of metal and oxide such as ZnO:Al or SnO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into an organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; A multilayer structure material such as LiF/Al or LiO ₂ /Al, Mg/Ag, and the like, but are not limited thereto.

The hole injection layer is a layer for injecting holes from an electrode, and has the ability to transport holes as a hole injection material, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is produced in the light emitting layer. A compound that prevents the movement of exciton to the electron injection layer or the electron injection material, and which has excellent thin film formation ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic matter, hexanitrile hexaazatriphenylene-based organic matter, quinacridone-based organic matter, and perylene-based Organic materials, anthraquinones, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes from the hole injection layer to the light emitting layer. As the hole transport material, the hole is transported to the light emitting layer by transporting holes from the anode or the hole injection layer, and the mobility of holes is large. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.

As a light emitting material of the light emitting layer, a material capable of emitting light in the visible light region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzothiazole and benzimidazole compounds; Poly(p-phenylenevinylene) (PPV)-based polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.

The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladders. Type furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periplanene, etc. having an arylamino group, and substituted or unsubstituted as a styrylamine compound. As a compound in which at least one arylvinyl group is substituted in the substituted arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes, platinum complexes, and the like.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer, a material having high mobility for electrons Suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these. The electron transport layer can be used with any desired negative electrode material as used according to the prior art. In particular, examples of suitable negative electrode materials are conventional materials having a low work function followed by an aluminum layer or a silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, followed by an aluminum layer or a silver layer in each case.

The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, and injects excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

The hole blocking layer is a layer that prevents the cathode from reaching the hole, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato) zinc, bis(8-hydroxyquinolinato) copper, bis(8-hydroxyquinolinato) manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato) zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.

The organic light emitting device according to the present specification may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.

According to the exemplary embodiment of the present specification, the anthracene derivative represented by Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below.

<Production Example>

Preparation Example 1 Synthesis of Compound A

1. Synthesis of Compound A-1

2-Dibenzo[b,d]furanol (50 g, 271.7 mmol) was dissolved in AcOH (100 ml), iodine monochloride (48.4 g, 298.9 mmol) was added, and the mixture was stirred at about 100°C for 4 hours. After the reaction was completed, cooled to room temperature, filtered, the organic layer was separated from the filtrate, the organic layer was dried over magnesium sulfate, distilled under reduced pressure, and recrystallized with ethanol to dry the obtained solid, thereby obtaining Compound A-1 (60.6g, 72%). .: MS [M]=309.9

2. Synthesis of Compound A-2

Compound A-1 (20 g, 64.5 mmol), 5-chloro-2-fluorophenylboronic acid (13.4 g, 77.4 mmol), Pd(t-Bu ₃ P) ₂ (0.066 g, 0.129 mmol) in 2M K ₂ CO ₃ aqueous solution (60 mL) and tetrahydrofuran (THF) (200 mL) were added and stirred at reflux for about 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, distilled under reduced pressure, and recrystallized with toluene/ethyl acetate (Tol/EA) to obtain Compound A-2 (14.9 g, 68%). Obtained: MS [M] = 312.0

3. Synthesis of Compound A-3

Compound A-2 (20 g, 64.1 mmol) and K ₂ CO ₃ were dissolved in (17.7 g, 128.2 mmol) in dimethylacetamide (DMAc) (300 ml) and stirred at about 100° C. for 4 hours. After the reaction was completed, after cooling to room temperature, H ₂ O (100 ml) was added, stirred for 1 hour, and then filtered. After dissolving the filtrate in toluene, the layers were separated, the organic layer was dried over magnesium sulfate, distilled under reduced pressure, and recrystallized with ethyl acetate/hexane (EA/Hexane) to obtain compound A-3 (15.9 g, 85%): MS [M ] = 292.0

4. Synthesis of Compound A

Compound A-3 (17.5 g, 59.9 mmol) and bis(pinacolato)diborane (36.6 g, 143.8 mmol), potassium acetic acid (17.6 g, 179.9 mmol), Pd(dba) ₂ (1.0 g, 1.8 mmol), PCy ₃ (1.1 g, 3.6 mmol) was added, 1,4-dioxane (400 ml) was added, and the mixture was stirred at reflux for about 12 hours. After the reaction was completed, it was cooled to room temperature and filtered. The organic layer was separated from the filtrate, and the organic layer was distilled under reduced pressure, and then recrystallized with EA/Hexane to obtain Compound A (25.1 g, 61%).: MS [M] = 384.2

Preparation Example 2: Synthesis of Compound B

1. Synthesis of Compound B-1

1,8-dichloroanthraquinone (50 g, 180 mmol), dissolved in ammonia water (2000 L), zinc dust (Zn dust) (1500 g) was added and stirred under reflux. After the reaction was completed, cooled to room temperature, filtered, the organic layer was separated from the reaction filtrate, the organic layer was dried over magnesium sulfate, distilled under reduced pressure, and recrystallized with hexane to dissolve the obtained solid in isopropyl alcohol, add concentrated hydrochloric acid, and reflux for 5 hours. Order. After the reaction was completed, the mixture was cooled to room temperature, and the resulting solid was filtered, washed with water, and dried to obtain Compound B-1 (27.8 g, 63%).: MS [M] = 246

2. Synthesis of Compound B-2

Compound B-1 (20 g, 81.3 mmol) with phenylboronic acid (23.8 g, 195.12 mmol) and Pd(dba) ₂ (1.40 g, 2.43 mmol), PCy ₃ (1.36 g, 4.86 mmol) with 2M K ₃ PO ₄ (60 mL) and THF (200 mL), and stirred at reflux for about 12 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, and distilled under reduced pressure and recrystallized from Tol/EA to obtain Compound B-2 (19.33 g, 72%).: MS [M ] = 330.14

3. Synthesis of Compound B-3

Compound B-2 (20 g, 60.58 mmol) was dissolved in dimethylformamide (500 mL), NBS (11.4 g, 63.61 mmol) was added, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the solid produced during the reaction was filtered, washed with distilled water and dried to obtain compound B-3 (20.5 g, 83%).: MS [M] = 408.05

4. Synthesis of Compound B

Compound B-3 (10 g, 24.5 mmol) and Compound A (9.88 g, 25.73 mmol) and Pd(t-Bu ₃ P) ₂ (0.063 g, 0.123 mmol) were added with 2M K ₂ CO ₃ aqueous solution (60 mL). It was added into THF (200 mL) and stirred at reflux for about 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, and distilled under reduced pressure, and recrystallized from Tol/EA to obtain Compound B (10.63 g, 74%).: MS [M] = 586.19

Preparation Example 3: Synthesis of Compound C

1. Synthesis of Compound C-1

Compound B-1 (10 g, 40.6 mmol) and dibenzothiophen-1-boronic acid (22.22 g, 97.44 mmol) and Pd(dba) ₂ (0.7 g, 1.22 mmol), PCy ₃ (0.7 g, 2.43 mmol) ) In 2M K ₃ PO ₄ (30 mL) and THF (200 mL), and stirred at reflux for about 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, and distilled under reduced pressure and recrystallized from Tol/EA to obtain compound C-1 (16.5 g, 75%).: MS [M ] = 542.12

2. Synthesis of Compound C-2

Compound C-1 (10 g, 18.45 mmol) was dissolved in dimethylformamide (500 mL), and then NBS (3.45 g, 19.37 mmol) was added and stirred at room temperature for 12 hours. After completion of the reaction, the solid produced during the reaction was filtered, washed with distilled water and dried to obtain compound C-2 (9.95 g, 87%): MS [M] = 620.03

3. Synthesis of Compound C

Compound C-2 (10 g, 16.13 mmol) and Compound A (7.43 g, 19.36 mmol) and Pd(t-Bu ₃ P) ₂ (0.04 g, 0.081 mmol) were mixed with a 2M K ₂ CO ₃ aqueous solution (60 mL). It was added into THF (200 mL) and stirred at reflux for about 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, and distilled under reduced pressure and recrystallized from Tol/EA to obtain Compound C (9.14 g, 71%).: MS [M] = 798.17

Preparation Example 4 Synthesis of Compound D

1. Synthesis of Compound D-1

9,9'-spirobifluoren-3-ol (10 g, 30.1 mmol) was dissolved in AcOH (100 ml), iodine monochloride (5.1 g, 31.6 mmol) was added, and the mixture was stirred at about 100°C for 4 hours. . After the reaction was completed, cooled to room temperature, filtered, the organic layer was separated from the filtrate, the organic layer was dried over magnesium sulfate, distilled under reduced pressure, and recrystallized with ethanol to dry the obtained solid, thereby obtaining Compound D-1 (9.37g, 68%). .: MS [M]=458.02

2. Synthesis of Compound D-2

Compound D-1 (10 g, 64.5 mmol), 5-chloro-2-fluorophenylboronic acid (13.4 g, 77.4 mmol), Pd(t-Bu ₃ P) ₂ (0.165 g, 0.323 mmol) in 2M K ₂ CO ₃ Aqueous solution (60 mL) and THF (200 mL) were added and stirred at reflux for about 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, and distilled under reduced pressure and recrystallized from Tol/EA to obtain compound D-2 (21.7 g, 73%).: MS [M ] = 460.1

3. Synthesis of Compound D-3

Compound D-2 (10 g, 21.7 mmol) and K ₂ CO ₃ were dissolved in (9.0 g, 65.2 mmol) in DMAc (300 ml) and stirred at about 100° C. for 4 hours. After the reaction was completed, after cooling to room temperature, H ₂ O (100 ml) was added, stirred for 1 hour, and then filtered. After dissolving the filtrate in toluene and separating the layers, the organic layer was dried over magnesium sulfate, distilled under reduced pressure, and recrystallized with EA/Hexane to obtain compound D-3 (8.79 g, 92%).: MS [M] = 440.1

4. Synthesis of Compound D

Compound D-3 (10 g, 18.79 mmol) and bis(pinacolato)diborane (7.2 g, 28.19 mmol), potassium acetic acid (5.53 g, 56.37 mmol), Pd(dba) ₂ ( 0.32 g, 1.13 mmol), PCy ₃ (0.32 g, 0.56 mmol) was added, 1,4-dioxane (400 ml) was added, and the mixture was stirred at reflux for about 12 hours. After the reaction was completed, it was cooled to room temperature and filtered. The organic layer was separated from the filtrate, and the organic layer was distilled under reduced pressure, and then recrystallized with EA/Hexane to obtain Compound D (7.5 g, 75%).: MS [M] = 532.2

Preparation Example 5 Synthesis of Compound E

1. Synthesis of Compound E-1

Compound B-1 (10 g, 40.6 mmol) and dibenzothiophene-2-boronic acid (20.66 g, 97.44 mmol) and Pd(dba) ₂ (0.7 g, 1.22 mmol), PCy ₃ (0.7 g, 2.43 mmol) ) In 2M K ₃ PO ₄ (30 mL) and THF (200 mL), and stirred at reflux for about 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, and distilled under reduced pressure and recrystallized from Tol/EA to obtain compound E-1 (17.8 g, 86%).: MS [M ] = 510.16

2. Synthesis of Compound E-2

Compound E-1 (10 g, 19.60 mmol) was dissolved in dimethylformamide (500 mL), NBS (3.84 g, 21.56 mmol) was added, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the solid produced during the reaction was filtered, washed with distilled water and dried to obtain compound E-2 (10 g, 87%).: MS [M] = 588.07

3. Synthesis of Compound E

Compound E-2 (10 g, 17.00 mmol) and Compound D (10.86 g, 20.4 mmol) and Pd(t-Bu ₃ P) ₂ (0.04 g, 0.085 mmol) were added with 2M K ₂ CO ₃ aqueous solution (60 mL). It was added into THF (400 mL) and stirred at reflux for about 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, and distilled under reduced pressure and recrystallized from Tol/EA to obtain Compound E (11.5 g, 74%).: MS [M] = 914.28

Preparation Example 6: Synthesis of Compound F

1. Synthesis of Compound F-1

Dissolve 9,9'-dimethyl-9H-fluoren-3-ol (10 g, 47.60 mmol) in AcOH (100 ml), add iodine monochloride (8.09 g, 49.98 mmol) and 4 hours at about 100 ℃ It was stirred. After the reaction was completed, cooled to room temperature, filtered, and the organic layer was separated from the filtrate, the organic layer was dried over magnesium sulfate, distilled under reduced pressure, and recrystallized with ethanol to dry the obtained solid, thereby obtaining Compound F-1 (12.60g, 75%). .: MS [M]=336.0

2. Synthesis of Compound F-2

Compound F-1 (10 g, 29.76 mmol), 5-chloro-2-floorophenylboronic acid (6.21 g, 35.71 mmol), Pd(t-Bu ₃ P) ₂ (0.076 g, 0.149 mmol) in 2M K ₂ CO ₃ Aqueous solution (60 mL) and THF (200 mL) were added and stirred at reflux for about 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, and distilled under reduced pressure and recrystallized from Tol/EA to obtain compound F-2 (8.25 g, 82%).: MS [M ] = 338.09

3. Synthesis of Compound F-3

Compound F-2 (10 g, 29.58 mmol) and K ₂ CO ₃ were dissolved in (12.25 g, 88.73 mmol) in DMAc (300 ml) and stirred at about 100° C. for 4 hours. After the reaction was completed, after cooling to room temperature, H ₂ O (100 ml) was added, stirred for 1 hour, and then filtered. After dissolving the filtrate in toluene and separating the layers, the organic layer was dried over magnesium sulfate, distilled under reduced pressure, and recrystallized with EA/Hexane to obtain compound F-3 (8.23 g, 88%).: MS [M] = 318.08

4. Synthesis of Compound F

Compound F-3 (10 g, 31.43 mmol) and bis(pinacolato)diborane (11.99 g, 47.16 mmol), potassium acetic acid (9.25 g, 94.29 mmol), Pd(dba) ₂ ( 0.36 g, 0.63 mmol), PCy ₃ (0.35 g, 1.26 mmol) was added, 1,4-dioxane (400 ml) was added, and the mixture was stirred at reflux for about 12 hours. After the reaction was completed, it was cooled to room temperature and filtered. The organic layer was separated from the filtrate, and the organic layer was distilled under reduced pressure and recrystallized with EA/Hexane to obtain compound F (10.4 g, 81%).: MS [M] = 410.2

Preparation Example 7: Synthesis of Compound G

1. Synthesis of Compound G-1

Compound B-1 (10 g, 40.6 mmol) and biphenyl-4-boronic acid (19.3 g, 97.44 mmol) and Pd(dba) ₂ (0.7 g, 1.22 mmol), PCy ₃ (0.7 g, 2.43 mmol) Put in 2M K ₃ PO ₄ (30 mL) and THF (200 mL), and stirred at reflux for about 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, and distilled under reduced pressure and recrystallized from Tol/EA to obtain compound G-1 (16.25 g, 83%).: MS [M ] = 482.20

2. Synthesis of Compound G-2

Compound G-1 (10 g, 20.73 mmol) was dissolved in dimethylformamide (500 mL), and then NBS (3.87 g, 21.78 mmol) was added and stirred at room temperature for 12 hours. After completion of the reaction, the solid produced during the reaction was filtered, washed with distilled water and dried to obtain compound G-2 (8.24g, 71%).: MS [M]= 560.1

3. Synthesis of Compound G

Compound G-2 (10 g, 17.85 mmol) and compound F (8.79 g, 21.4 mmol) and Pd(t-Bu ₃ P) ₂ (0.04 g, 0.089 mmol) were added with 2M K ₂ CO ₃ aqueous solution (60 mL). It was added into THF (400 mL) and stirred at reflux for about 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, and distilled under reduced pressure, and recrystallized from Tol/EA to obtain compound G (10.1 g, 74%).: MS [M] = 764.3

<Experimental Example 1>

A glass substrate coated with a thin film coated with ITO (indium tin oxide) at a thickness of 1,500 에 was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer (Fischer Co.) was used as the detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic washing was repeated for 10 minutes by repeating it twice with distilled water. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying, and then transported to a plasma cleaner. In addition, the substrate was washed for 5 minutes using oxygen plasma, and then transferred to a vacuum evaporator.

On the prepared ITO transparent electrode, hexanitrilehexaazatriphenylene (HAT) of the following chemical formula was thermally vacuum-deposited to a thickness of 500 Pa to form a hole injection layer.

A hole transport layer is vacuum-deposited by depositing 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) (400 Å) of the following formula, which is a material for transporting holes on the hole injection layer. Formed.

Subsequently, the compound B was vacuum-deposited to a thickness of 300 Pa as a light emitting layer host on the hole transport layer to form a light emitting layer.

The following compound N1,N6-bis(dibenzofuran-4-yl)-N1,N6-di-m-tolylpyrene-1,6-diamine (N1,N6-bis( Dibenzo[b,d]furan-4-yl)-N1,N6-di-m-tolylpyrene-1,6-diamine; BD1) was used in 4% by weight.

On the light emitting layer, Alq ₃ (aluminum tris(8-hydroxyquinoline)) of the following chemical formula was vacuum deposited to a thickness of 200 mm 2 to form a layer for simultaneous electron injection and transport.

On the electron injection and transport layer, lithium fluoride (LiF) with a thickness of 12 mm 2 and aluminum with a thickness of 2,000 mm 2 were sequentially deposited to form a negative electrode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å/sec, the lithium fluoride of the negative electrode was maintained at a deposition rate of 0.3 Å/sec, and the aluminum was maintained at a deposition rate of 2 Å/sec. ^-8 to 2 x 10 ^-7 torr was maintained.

<Experimental Example 2>

In Experimental Example 1, an organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that Compound C was used instead of Compound B as the light emitting layer host material.

<Experimental Example 3>

In Experimental Example 1, an organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that Compound E was used instead of Compound B as the light emitting layer host material.

<Experimental Example 4>

In Experimental Example 1, an organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that Compound G was used instead of Compound B as the light emitting layer host material.

<Comparative Examples 1 to 5>

In Experimental Example 1, an organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compounds represented by the following H1 to H5 were used instead of Compound B as the light emitting layer host material.

As a result of applying a forward electric field with the voltages shown in Table 1 below to the organic light-emitting devices prepared in Experimental Examples 1 to 4 and Comparative Examples 1 to 5, Table 1 below based on 1931 CIE color coordinates at a current density of 10 mA/cm 2 Light having x and y values as described in was observed. The device life was measured at a time (T ₉₅ ) of 95% compared to the initial luminance at a current density of 20 mA/cm ² . The results are shown in Table 1 below.

matter Voltage
(V) efficiency
(cd/A) Color coordinate life span
T ₉₅
(%) CIE (x) CIE (y) Experimental Example 1 B 3.80 8.72 0.131 0.122 145 Experimental Example 2 C 3.63 8.13 0.132 0.134 140 Experimental Example 3 E 3.70 9.05 0.131 0.141 100 Experimental Example 4 G 3.61 7.42 0.132 0.137 90 Comparative Example 1 H1 4.08 7.23 0.134 0.112 85 Comparative Example 2 H2 4.26 6.70 0.133 0.108 80 Comparative Example 3 H3 4.25 6.01 0.134 0.122 75 Comparative Example 4 H4 4.26 6.70 0.133 0.108 80 Comparative Example 5 H5 4.25 7.01 0.134 0.122 75

The compound represented by Chemical Formula 1 has three substituents on carbons 1, 8, and 10 of anthracene, but H1 to H5 of Comparative Examples have 2 substituents on carbons 9 and 10 of anthracene, and carbon 10 Has a 5-ring ring substituent. When comparing Experimental Examples 1 to 4 and Comparative Examples 1 to 5 of Table 1, the device including the compound represented by Chemical Formula 1 has characteristics of low voltage, high efficiency, and long life.

In Experimental Examples 1 to 4 including the compound represented by Formula 1, the driving voltage was reduced by up to 15.3%, the efficiency was increased by up to 50.6%, and the life was increased by up to 93.3% compared to the comparative example.

Although the preferred embodiment of the present invention has been described through the above, the present invention is not limited to this, and it is possible to carry out various modifications within the scope of the claims and the detailed description of the invention, and this also belongs to the scope of the invention. .

10, 11: organic light emitting device
20: substrate
30: first electrode
40: light emitting layer
50: second electrode
60: hole injection layer
70: hole transport layer
80: electron transport layer
90: electron injection layer

Claims (13)

Anthracene derivative represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
X1 is O; S; Or CRR',
R, R'and R1 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Nitrile group; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or adjacent substituents combine with each other to form a substituted or unsubstituted ring,
R2 is hydrogen; Or deuterium,
L1 and L2 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
n and m are each an integer of 1 or 2,
When n is an integer of 2, L1 is the same as or different from each other,
When m is an integer of 2, L2 is the same as or different from each other,
Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group; Biphenyl group; Naphthyl group; Fluorenyl group; Dibenzothiophene group; Or a dibenzofuranyl group,
The phenyl group, biphenyl group, naphthyl group, fluorenyl group, dibenzothiophene group, or dibenzofuranyl group has an aryl group having 6 to 13 carbon atoms; Or substituted or unsubstituted with a heteroaryl group having 2 to 13 carbon atoms,
a is an integer from 0 to 9,
b is an integer from 0 to 7,
When a is an integer of 2 or more, R1 is the same as or different from each other,
When b is an integer of 2 or more, R2 is the same as or different from each other. The method according to claim 1,
L1 and L2 are the same as or different from each other, and each independently a direct bond; Or an anthracene derivative which is a phenylene group. delete The method according to claim 1,
X1 is O; Or CRR',
R and R'are the same as or different from each other, and each independently a methyl group; Or it is a phenyl group, or an anthracene derivative in which R and R'are bonded to each other to form a fluorene ring. The method according to claim 1,
n and m are 1 anthracene derivatives. The method according to claim 1,
Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group; Biphenyl group; Dibenzothiophene group; Or an anthracene derivative which is a dibenzofuranyl group. The method according to claim 1,
R1 and R2 are hydrogen anthracene derivatives. The method according to claim 1, wherein Formula 1 is an anthracene derivative represented by one selected from Formulas 1-1 to 1-4:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Chemical Formulas 1-1 to 1-4,
The definitions of X1, R1, R2, L1, L2, Ar1, Ar2, n, m, a and b are as defined in Formula 1. The method according to claim 1, wherein the formula 1 is an anthracene derivative is one selected from the following compounds:

. A first electrode; A second electrode provided opposite to the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the anthracene derivative of claim 1, 2 and 4 to 9. Organic light emitting device. The method according to claim 10, The organic layer comprises a light emitting layer, the light emitting layer is an organic light emitting device comprising the anthracene derivative. The method according to claim 10, The organic layer comprises a hole injection layer, a hole transport layer or an electron blocking layer, and the hole injection layer, the hole transport layer or the electron blocking layer comprises the anthracene derivative. The method according to claim 10, The organic material layer comprises a hole blocking layer, an electron transport layer or an electron injection layer, and the hole blocking layer, the electron transport layer or the electron injection layer comprises the anthracene derivative.

Images