KR102657637B1 - Anthracene compound, coating composition and organic light emitting device comprising same - Google Patents

Abstract

This specification relates to an anthracene-based compound represented by Formula 1, a composition containing the same, and an organic light-emitting device.

Description

Anthracene-based compound, coating composition containing the same, and organic light-emitting device

This specification relates to anthracene-based compounds and organic light-emitting devices containing the same.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices that utilize the organic light-emitting phenomenon usually have a structure including 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 When it falls back to the ground state, it glows.

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

KR 10-1538534 B1

The present specification is intended to provide an anthracene-based compound, a coating composition containing the same, and an organic light-emitting device.

The present specification provides an anthracene-based compound represented by the following formula (1).

[Formula 1]

In Formula 1,

L1 and L2 are the same or different from each other and are each independently directly bonded; Or a substituted or unsubstituted arylene group,

At least one of Ar1 and Ar1' is a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and the remainder is hydrogen; or deuterium,

Ar2 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

At least one of R1 to R3 is the same as or different from each other, and each independently is a halogen group; Cyano group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, the remainders being the same or different from each other, and each independently hydrogen; or deuterium,

D is deuterium,

n1 is an integer from 0 to 6,

r1 is an integer from 0 to 4, r2 is an integer from 0 to 2, r3 is an integer from 0 to 4,

r1 + r2 is an integer from 0 to 5,

r1 + r2 + r3 is 1 or more,

When r1 to r3 are each 2 or more, the substituents in parentheses are the same or different from each other.

Additionally, the present specification provides a coating composition containing an anthracene-based compound represented by Formula 1 above. At this time, the coating composition can be used for solution processing.

Additionally, the present specification includes 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 layers includes the anthracene-based compound described above.

The compound according to an exemplary embodiment of the present specification can be used in an organic light-emitting device to lower the driving voltage of the organic light-emitting device and improve light efficiency. Additionally, the lifespan characteristics of the device can be improved due to the thermal stability of the compound.

The compound or composition according to an exemplary embodiment of the present specification can be subjected to a solution process, and it is possible to increase the area of the device.

1 to 3 show examples of organic light-emitting devices according to an exemplary embodiment of the present specification.

Hereinafter, this specification will be described in more detail.

The anthracene-based compound represented by Formula 1 contains one or more substituents of R1 to R3 in the 5-ring heterocyclic group, and includes a substituent of Ar1 or Ar1' in the anthracene core, and when used as a light-emitting layer host of an organic light-emitting device, This has the effect of low voltage, high efficiency or/and long life of the device.

When Formula 1 contains one or more deuterium, the efficiency and lifespan of the device are improved. When hydrogen is replaced with deuterium, the weight of deuterium, which is an oscillator, increases, resulting in an effect of damping the vibration of the molecule. This leads to a change in vibrational energy that contributes to the energy of the molecule and stabilizes it by lowering the energy of the molecule. The effect of increasing the activation energy required to cleave the bond of a stabilized molecule appears. Accordingly, Chemical Formula 1 can improve the efficiency and lifespan of the device by including deuterium.

The compound of Formula 1 containing deuterium can be prepared by a known deuteration reaction. According to an exemplary embodiment of the present specification, the compound represented by Formula 1 is formed by using a deuterated compound as a precursor, or by introducing deuterium into the compound through a hydrogen-deuterium exchange reaction under an acid catalyst using a deuterated solvent. You may.

In this specification, Alternatively, the dotted line indicates the connected area.

In this specification, Cn means n carbon atoms, and Cn-Cm means n to m carbon atoms.

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

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent. The position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and if two or more substituents are substituted. , two or more substituents may be the same or different from each other.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Nitrile group; Alkyl group; Aryl group; and a heteroaryl group containing at least one heteroatom other than carbon, or is substituted with a substituent where two or more of the above-exemplified substituents are linked, or does not have any substituent. means that

In this specification, linking two or more substituents means that the hydrogen of one substituent is linked to another substituent. For example, an isopropyl group and a phenyl group are connected to or It can be a substituent of .

In the present specification, three substituents are connected not only by (substituent 1) - (substituent 2) - (substituent 3) connected in succession, but also by (substituent 1) with (substituent 2) and (substituent 3) It also includes being connected. For example, two phenyl groups and an isopropyl group are connected or It can be a substituent of . The same applies as above to when 4 or more substituents are connected.

In this specification, N% deuterated means that N% of the hydrogen available in the structure is replaced with deuterium. For example, if 25% of dibenzofuran is replaced with deuterium, it means that 2 out of 8 hydrogens in dibenzofuran are replaced with deuterium.

In this specification, the degree of deuteration can be confirmed by known methods such as nuclear magnetic resonance spectroscopy ( ^1H NMR) or GC/MS.

In this specification, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is 1 to 30; 1 to 20; 1 to 10; Or it is preferably 1 to 5. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, t-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, iso Pentyl, neopentyl, t-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentyl Methyl, cyclohexylmethyl, octyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1 -Dimethylpropyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc., but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 6. Cycloalkyl groups include not only single ring groups but also double ring groups such as bridgeheads, fused rings, and spiro rings. Specifically, it includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and adamantyl group, but is not limited thereto.

In this specification, an aryl group refers to a monovalent group of a monovalent aromatic hydrocarbon or an aromatic hydrocarbon derivative. An aromatic hydrocarbon refers to a compound containing a planar ring in which pi electrons are fully conjugated, and a group derived from an aromatic hydrocarbon refers to a structure in which an aromatic hydrocarbon or a cyclic aliphatic hydrocarbon is condensed with an aromatic hydrocarbon. Additionally, in the present specification, the aryl group is intended to include a monovalent group in which two or more aromatic hydrocarbons or derivatives of aromatic hydrocarbons are linked together. The aryl group is not particularly limited, but has 6 to 50 carbon atoms; 6 to 30; 6 to 25; 6 to 20; 6 to 18; Or preferably 6 to 13, and the aryl group may be monocyclic or polycyclic. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, triphenyl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

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

In this specification, when it is said that a fluorenyl group can be substituted, the substituted fluorenyl group includes all compounds in which the substituents of the 5-membered fluorene ring are spiro bonded to each other to form an aromatic hydrocarbon ring. The substituted fluorenyl group includes 9,9'-spirobifluorene, spiro[cyclopentane-1,9'-fluorene], spiro[benzo[c]fluorene-7,9-fluorene], etc. However, it is not limited to this.

In the present specification, the substituted aryl group may also include a form in which an aliphatic ring is condensed with an aryl group. For example, a tetrahydronaphthalene group having the following structure can be exemplified. In the structure below, one of the carbons of the benzene ring may be connected to another position.

In the present specification, heteroaryl group refers to a monovalent aromatic heterocycle. Here, the aromatic heterocycle refers to a monovalent group of an aromatic ring or a derivative of an aromatic ring, and includes one or more of N, O, and S as heteroatoms in the ring. The derivatives of the aromatic ring include all structures in which an aromatic ring or an aliphatic ring is condensed with an aromatic ring. In addition, in the present specification, the heteroaryl group is intended to include a monovalent group in which aromatic rings containing two or more heteroatoms or derivatives of aromatic rings containing heteroatoms are linked together. 2 to 50 carbon atoms in the heteroaryl group; 2 to 30; 2 to 20; 2 to 18; Or it is preferably 2 to 13. Examples of heteroaryl groups include thiophene group, furanyl group, pyrrole group, imidazole group, thiazole group, oxazole group, pyridine group, pyrimidine group, triazine group, triazole group, acridine group, pyridazine group, pyrazine group, Quinoline group, quinazoline group, quinoxaline group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzo These include, but are not limited to, furan groups, phenanthrolinyl groups, and dibenzofuran groups.

In the present specification, the heteroaryl group may be monocyclic or polycyclic, and may be aromatic, aliphatic, or a condensed ring of aromatic and aliphatic.

In the present specification, an aromatic hydrocarbon ring refers to a hydrocarbon ring in which the pi electron is completely conjugated and is planar, and the description of the aryl group described above can be applied except that it is a divalent group.

In the present specification, an aliphatic hydrocarbon ring refers to all hydrocarbon rings excluding aromatic hydrocarbon rings, and may include a cycloalkyl ring and a cycloalkene ring. The description of the cycloalkyl group described above can be applied except that the cycloalkyl ring is a divalent group, and the description of the cycloalkenyl group described above can be applied to the cycloalkene ring except that it is a divalent group. Additionally, substituted aliphatic hydrocarbon rings also include aliphatic hydrocarbon rings in which an aromatic ring is condensed.

In the present specification, an arylene group refers to an aryl group having two bonding positions, that is, a bivalent group. The description of the aryl group described above can be applied, except that each of these is a divalent group.

In the present specification, a heteroarylene group refers to a heteroaryl group having two bonding positions, that is, a bivalent group. The description of the heteroaryl group described above can be applied, except that each of these is a divalent group.

Hereinafter, the anthracene-based compound represented by the following formula (1) will be described in detail.

[Formula 1]

In an exemplary embodiment of the present specification, L1 and L2 are the same or different from each other and are each independently directly bonded; Or it is a substituted or unsubstituted arylene group.

In an exemplary embodiment of the present specification, L1 and L2 are the same or different from each other and are each independently directly bonded; Or it is a substituted or unsubstituted C6-C30 arylene group.

In an exemplary embodiment of the present specification, L1 and L2 are the same or different from each other and are each independently directly bonded; Or it is a substituted or unsubstituted C6-C20 arylene group.

In an exemplary embodiment of the present specification, L1 and L2 are the same or different from each other and are each independently directly bonded; Substituted or unsubstituted phenylene group; Substituted or unsubstituted biphenylene group; Substituted or unsubstituted naphthylene group; Or it is a substituted or unsubstituted divalent phenanthrenyl group.

In an exemplary embodiment of the present specification, L1 and L2 are the same or different from each other and are each independently directly bonded; Or it is a C6-C30 arylene group substituted or unsubstituted with deuterium.

In an exemplary embodiment of the present specification, L1 and L2 are the same or different from each other and are each independently directly bonded; Or it is a C6-C20 arylene group substituted or unsubstituted with deuterium.

In an exemplary embodiment of the present specification, L1 and L2 are the same or different from each other and are each independently directly bonded; A phenylene group substituted or unsubstituted with deuterium; A biphenylene group substituted or unsubstituted with deuterium; Naphthylene group substituted or unsubstituted with deuterium; Or it is a divalent phenanthrenyl group substituted or unsubstituted with deuterium.

In one embodiment of the present specification, L1 is a direct bond; Or a substituted or unsubstituted phenylene group.

In one embodiment of the present specification, L2 is a direct bond; Substituted or unsubstituted phenylene group; Substituted or unsubstituted naphthylene group; Or it is a substituted or unsubstituted divalent phenanthrenyl group.

In one embodiment of the present specification, L2 is a direct bond; Substituted or unsubstituted phenylene group; Or a substituted or unsubstituted naphthylene group.

In one embodiment of the present specification, one of L1 and L2 is a direct bond.

In one embodiment of the present specification, L1 and L2 may be replaced with deuterium.

In an exemplary embodiment of the present specification, L1 and L2 are the same or different from each other, and are each independently a direct bond or any one selected from the structures below.

In the above structure, D means deuterium, k1 is an integer from 0 to 4, and k2 is an integer from 0 to 6.

In one embodiment of the present specification, k1 is 1 or more. In another embodiment, k1 is 2 or more. In another embodiment, k1 is 3 or more. In another embodiment, k1 is 4.

In one embodiment of the present specification, k2 is 1 or more. In another embodiment, k2 is 2 or more. In another embodiment, k2 is 3 or more. In another embodiment, k2 is 4 or more. In another embodiment, k2 is 5 or more. In another embodiment, k2 is 6.

In an exemplary embodiment of the present specification, at least one of R1 to R3 is a halogen group; Cyano group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In an exemplary embodiment of the present specification, at least one of R1 to R3 is the same as or different from each other, and each independently is a halogen group; Cyano group; Substituted or unsubstituted C1-C20 alkyl group; Substituted or unsubstituted silyl group; A substituted or unsubstituted C3-C60 cycloalkyl group; A substituted or unsubstituted C6-C60 aryl group; Or a substituted or unsubstituted C2-C60 heteroaryl group.

In an exemplary embodiment of the present specification, at least one of R1 to R3 is the same as or different from each other, and each independently is a halogen group; Cyano group; Alkyl group of C1-C10; silyl group; C3-C30 cycloalkyl group; Aryl group at C6-C30; and a C2-C30 heteroaryl group, or a substituent in which two or more groups selected from the group are connected, and the substituent may be substituted with deuterium.

In an exemplary embodiment of the present specification, at least one of R1 to R3 is the same as or different from each other, and each independently is a halogen group; Cyano group; Alkyl group of C1-C6; silyl group; C3-C20 cycloalkyl group; Aryl group at C6-C20; and a C2-C20 heteroaryl group, or a substituent in which two or more groups selected from the group are connected, and the substituent may be substituted with deuterium.

In an exemplary embodiment of the present specification, at least one of R1 to R3 is the same as or different from each other, and each independently is a fluoro group; Cyano group; methyl group; ethyl group; profiler; butyl group; pentyl group; hexyl group; silyl group; Cyclopentyl group; Cyclohexyl group; Adamantyl group; phenyl group; Biphenyl group; Terphenyl group; naphthyl group; phenanthrenyl group; triphenylene group; tetrahydronathalene group; furan group; benzofuran group; Dibenzofuran group; thiophene group; Benzothiophene group; and a substituent selected from the group consisting of a dibenzothiophene group, or a substituent in which two or more groups selected from the group are linked, and the substituent may be substituted with deuterium.

In an exemplary embodiment of the present specification, at least one of R1 to R3 is the same as or different from each other, and each independently is a cyano group; A C1-C10 alkyl group substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium and halogen groups or a substituent linked with two or more groups selected from the group; Silyl group substituted or unsubstituted with a C1-C10 alkyl group; C3-C30 cycloalkyl group substituted or unsubstituted with deuterium; C6- is substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, cyano group, and C1-C10 alkyl group or a substituent linked with two or more groups selected from the group, and the C5-C30 aliphatic hydrocarbon ring is condensed or unfused. Aryl group at C30; Or deuterium. It is a C2-C30 heteroaryl group substituted or unsubstituted with one or more substituents selected from the group consisting of a C1-C10 alkyl group and a C6-C30 aryl group, or a substituent linked to two or more groups selected from the group.

In an exemplary embodiment of the present specification, at least one of R1 to R3 is the same as or different from each other, and each independently is a cyano group; A C1-C6 alkyl group substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium and halogen groups or a substituent linked with two or more groups selected from the group; Silyl group substituted or unsubstituted with a C1-C6 alkyl group; C3-C20 cycloalkyl group substituted or unsubstituted with deuterium; A C6-C20 aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, cyano group, and C1-C6 alkyl group or a substituent linked with two or more groups selected from the group; A C6-C40 polycyclic hydrocarbon ring substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium and C1-C6 alkyl groups or with two or more substituents selected from the group connected, and in which aromatic and aliphatic rings are condensed; Or deuterium. It is a C2-C20 heteroaryl group substituted or unsubstituted with one or more substituents selected from the group consisting of a C1-C6 alkyl group and a C6-C20 aryl group, or a substituent linked to two or more groups selected from the group.

In an exemplary embodiment of the present specification, at least one of R1 to R3 is the same as or different from each other, and each independently is a C1-C6 alkyl group substituted or unsubstituted with deuterium; C3-C20 cycloalkyl group substituted or unsubstituted with deuterium; A C6-C20 aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium and C1-C6 alkyl groups or a substituent linked with two or more groups selected from the group; A C6-C40 polycyclic hydrocarbon ring substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium and C1-C6 alkyl groups or with two or more substituents selected from the group connected, and in which aromatic and aliphatic rings are condensed; or a C2-C20 heteroaryl group substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium and a C1-C6 alkyl group or a substituent linked with two or more groups selected from the group.

In an exemplary embodiment of the present specification, the heteroaryl group of R1 to R3 includes O or S as a heteroelement.

In one embodiment of the present specification, R1 to R3 may be replaced with deuterium.

In an exemplary embodiment of the present specification, at least one of R1 to R3 is the same as or different from each other, and each independently is a cyano group; A methyl group substituted or unsubstituted with a fluoro group; ethyl group; profiler; butyl group; hexyl group; trimethylsilyl group; Cyclopentyl group; Cyclohexyl group; Adamantyl group; Phenyl group substituted or unsubstituted with deuterium, cyano group, methyl group, or butyl group; Biphenyl group substituted or unsubstituted with deuterium; Naphthyl group substituted or unsubstituted with deuterium; phenanthrenyl group; Tetrahydronaphthalene group substituted or unsubstituted with a methyl group; A furan group substituted or unsubstituted by a butyl group or phenyl group; benzofuran group; thiophene group; Or it is a benzothiophene group.

In an exemplary embodiment of the present specification, at least one of R1 to R3 is the same as or different from each other, and each independently is a methyl group; ethyl group; profiler; butyl group; hexyl group; Cyclopentyl group; Cyclohexyl group; Adamantyl group; Phenyl group substituted or unsubstituted with deuterium, methyl group, or butyl group; Biphenyl group substituted or unsubstituted with deuterium; Naphthyl group substituted or unsubstituted with deuterium; phenanthrenyl group; Tetrahydronaphthalene group substituted or unsubstituted with a methyl group; Or it is a furan group substituted or unsubstituted with a butyl group.

In an exemplary embodiment of the present specification, three of R1 to R3 are the above-mentioned substituents and are the same or different from each other. In another embodiment, two of R1 to R3 are the above-mentioned substituents and are the same or different from each other. In another exemplary embodiment, one of R1 to R3 is the above-described substituent.

In an exemplary embodiment of the present specification, the remainder of R1 to R3 other than the above-mentioned substituents is hydrogen; Or it is deuterium.

In one embodiment of the present specification, R2 is hydrogen; heavy hydrogen; Or it is a methyl group substituted or unsubstituted with deuterium.

In one embodiment of the present specification, R2 is hydrogen; Or it is deuterium.

In an exemplary embodiment of the present specification, at least one of Ar1 and Ar1' is a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and the remainder is hydrogen; Or it is deuterium.

In one embodiment of the present specification, at least one of Ar1 and Ar1' is a substituted or unsubstituted C6-C60 aryl group; or a substituted or unsubstituted C2-C60 heteroaryl group, and the remainder is hydrogen; Or it is deuterium.

In an exemplary embodiment of the present specification, at least one of Ar1 and Ar1' is a substituted or unsubstituted C6-C30 aryl group; or a substituted or unsubstituted C2-C30 heteroaryl group, and the remainder is hydrogen; Or it is deuterium.

In an exemplary embodiment of the present specification, at least one of Ar1 and Ar1' is a substituted or unsubstituted C6-C20 aryl group; or a substituted or unsubstituted C2-C20 heteroaryl group, and the remainder is hydrogen; Or it is deuterium.

In an exemplary embodiment of the present specification, any one of Ar1 and Ar1' is substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, a halogen group, and a C1-C10 alkyl group, or a substituent linked to two or more groups selected from the group. is an aryl group from C6-C30, and the remaining one is hydrogen; Or it is deuterium.

In an exemplary embodiment of the present specification, any one of Ar1 and Ar1' is substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, halogen group, and C1-C6 alkyl group, or a substituent linked to two or more groups selected from the group. is an aryl group from C6-C20, and the remaining one is hydrogen; Or it is deuterium.

In one embodiment of the present specification, one of Ar1 and Ar1' is a C6-C20 aryl group substituted or unsubstituted with deuterium, a C1-C6 alkyl group, or a C1-C6 haloalkyl group, and the other is hydrogen; Or it is deuterium.

In an exemplary embodiment of the present specification, at least one of Ar1 and Ar1' is a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted naphthyl group; or a substituted or unsubstituted phenanthrenyl group, and the remainder is hydrogen; Or it is deuterium.

In an exemplary embodiment of the present specification, at least one of Ar1 and Ar1' is a phenyl group substituted or unsubstituted by deuterium, trifluoromethyl group, or butyl group; Biphenyl group substituted or unsubstituted with deuterium; Naphthyl group substituted or unsubstituted with deuterium; or a phenanthrenyl group substituted or unsubstituted with deuterium, and the remainder is hydrogen; Or it is deuterium.

In an exemplary embodiment of the present specification, any one of Ar1 and Ar1' is a phenyl group substituted or unsubstituted by deuterium, trifluoromethyl group, or butyl group; Biphenyl group substituted or unsubstituted with deuterium; Naphthyl group substituted or unsubstituted with deuterium; or a phenanthrenyl group substituted or unsubstituted with deuterium, and the other one is hydrogen; Or it is deuterium.

In one embodiment of the present specification, Ar2 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In one embodiment of the present specification, Ar2 is a substituted or unsubstituted aryl group of C6-C60; Or a substituted or unsubstituted C6-C60 heteroaryl group.

In one embodiment of the present specification, Ar2 is a substituted or unsubstituted aryl group of C6-C30; Or a substituted or unsubstituted C6-C20 heteroaryl group.

In one embodiment of the present specification, Ar2 is one or more substituents selected from the group consisting of deuterium, halogen group, cyano group, C1-C10 alkyl group, silyl group, and C6-C30 aryl group, or two or more groups selected from the group are connected. Aryl group of C6-C30 substituted or unsubstituted with a substituent; or C6-C30 substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, halogen group, cyano group, C1-C10 alkyl group, silyl group, and C6-C30 aryl group, or a substituent linked with two or more groups selected from the above group. It is a heteroaryl group.

In one embodiment of the present specification, Ar2 is one or more substituents selected from the group consisting of deuterium, halogen group, cyano group, C1-C6 alkyl group, silyl group, and C6-C20 aryl group, or two or more groups selected from the group are connected. Aryl group of C6-C20 substituted or unsubstituted with a substituent; or a C6-C30 heteroaryl group substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium and a C6-C20 aryl group or a substituent linked with two or more groups selected from the group.

In one embodiment of the present specification, Ar2 is a substituted or unsubstituted C6-C20 aryl group with deuterium, a halogen group, a cyano group, a C1-C6 alkyl group, a C3-C18 trialkylsilyl group, or a C6-C20 aryl group. energy; Or it is a C6-C30 heteroaryl group substituted or unsubstituted with deuterium or a C6-C20 aryl group.

In one embodiment of the present specification, Ar2 is a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted phenanthrenyl group; Substituted or unsubstituted triphenylene group; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted N-phenylcarbazole group.

In an exemplary embodiment of the present specification, Ar2 is a phenyl group unsubstituted or substituted with deuterium, a fluoro group, a cyano group, a methyl group, a butyl group, a trimethylsilyl group, or a naphthyl group; Biphenyl group substituted or unsubstituted with deuterium, fluoro group, cyano group, methyl group, butyl group, or trimethylsilyl group; Terphenyl group; Naphthyl group substituted or unsubstituted with deuterium or phenyl group; Phenanthrenyl group substituted or unsubstituted with deuterium or phenyl group; triphenylene group; Dibenzofuran group; Dibenzothiophene group; Or it is an N-phenylcarbazole group.

In one embodiment of the present specification, Ar2 may be substituted with deuterium.

In one embodiment of the present specification, n1 is an integer from 0 to 6.

In one embodiment of the present specification, n1 is 1 or more. In another embodiment, n1 is 2 or more. In another exemplary embodiment, n1 is 3 or more. In another exemplary embodiment, n1 is 4 or more. In another embodiment, n1 is 5 or more. In another embodiment, n1 is 6.

In one embodiment of the present specification, r1 is an integer from 0 to 4.

In one embodiment of the present specification, r2 is an integer from 0 to 2.

In one embodiment of the present specification, r3 is an integer from 0 to 3.

When r1 is 2 or more, the plurality of R1 are the same or different from each other.

When r2 is 2, the two R2's are the same or different from each other.

When r3 is 2 or more, a plurality of R3's are the same or different from each other.

In one embodiment of the present specification, r1 + r2 + r3 is an integer from 1 to 4.

In one embodiment of the present specification, Formula 1 is deuterated by 20% or more. In another embodiment, Formula 1 is deuterated by more than 30%. In another embodiment, Formula 1 is deuterated by more than 40%. In another exemplary embodiment, Formula 1 is deuterated by more than 50%. In another exemplary embodiment, Formula 1 is deuterated by more than 60%. In another exemplary embodiment, Formula 1 is deuterated by more than 70%. In another exemplary embodiment, Chemical Formula 1 is deuterated by more than 80%. In another exemplary embodiment, Formula 1 is deuterated by more than 90%. In another embodiment, Formula 1 is 100% deuterated.

In one embodiment of the present specification, Formula 1 includes at least one hydrogen.

In an exemplary embodiment of the present specification, L1 and L2 are the same or different from each other and are each independently directly bonded; or an arylene group of C6-C30 substituted or unsubstituted with deuterium,

At least one of R1 to R3 is the same as or different from each other, and each independently is a halogen group; Cyano group; Alkyl group of C1-C10; silyl group; C3-C30 cycloalkyl group; Aryl group at C6-C30; and a substituent selected from the group consisting of a C2-C30 heteroaryl group, or a substituent in which two or more groups selected from the group are linked, and the substituent may be substituted with deuterium,

Ar2 is C6- substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, halogen group, cyano group, C1-C10 alkyl group, silyl group, and C6-C30 aryl group, or a substituent linked to two or more groups selected from the above group. Aryl group at C30; or C6-C30 substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, halogen group, cyano group, C1-C10 alkyl group, silyl group, and C6-C30 aryl group, or a substituent linked with two or more groups selected from the above group. It is a heteroaryl group.

In an exemplary embodiment of the present specification, Formula 1 is represented by the following Formula 101 or 102.

[Formula 101]

[Formula 102]

In the above formulas 101 and 102,

The definitions of L1, L2, Ar1, Ar1', Ar2, R1 to R3, D, n1 and r1 to r3 are as defined in Formula 1,

r1' is an integer from 0 to 3, and r2' is 0 or 1.

In one embodiment of the present specification, is any one selected from the structures below.

In one embodiment of the present specification, Formula 1 is represented by any one of the following Formulas 201 to 206.

In one embodiment of the present specification, Formula 1 is represented by any one of the following Formulas 201 to 206.

[Formula 201]

[Formula 202]

[Formula 203]

[Formula 204]

[Formula 205]

[Formula 206]

In the above formulas 201 to 206,

The definitions of L1, L2, Ar1, Ar1', Ar2, R1 to R3, D, n1 and r1 to r3 are as defined in Formula 1.

In one embodiment of the present specification, Formula 101 is one selected from Formulas 301 to 304 below.

[Formula 301] [Formula 302]

[Formula 303] [Formula 304]

In the above formulas 301 to 304,

The definitions of L1, L2, Ar1, Ar1', Ar2, R1 to R3, D, n1, r1', r2 and r3 are as defined in Formula 101.

In an exemplary embodiment of the present specification, Formula 102 is represented by any one of the following Formulas 305 to 308.

[Formula 305] [Formula 306]

[Formula 307] [Formula 308]

In Formulas 305 to 308,

The definitions of L1, L2, Ar1, Ar1', Ar2, R1 to R3, D, n1, r1, r2' and r3 are as defined in Formula 102.

In one embodiment of the present specification, is any one selected from the structures below.

In the above structure,

Any one of a* to f* is a position connected to L1,

At least one of R11 is a cyano group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and the remainders are the same or different from each other,

r11 is an integer from 1 to 9, and when r11 is 2 or more, a plurality of R11 are the same or different from each other.

In an exemplary embodiment of the present specification, R11 is the same as the definitions of R1 to R3 described above.

In one embodiment of the present specification, a* is a position connected to L1. In another embodiment, b* is a position connected to L1. In another embodiment, c* is a position connected to L1. In another embodiment, d* is a position connected to L1. In another embodiment, e* is a position connected to L1. In another embodiment, f* is a position connected to L1.

In an exemplary embodiment of the present specification, the anthracene-based compound represented by Formula 1 is any one selected from the following compounds.

A compound according to an exemplary embodiment of the present specification may be produced by the production method described later. As needed, substituents can be added or excluded, and the positions of the substituents can be changed. Additionally, starting materials, reactants, reaction conditions, etc. can be changed based on techniques known in the art.

For example, the compound represented by Formula 1 may be more specific in the production examples described later, the reaction order may change depending on the compound, and the method for synthesizing the anthracene-based compound of Formula 1 is not limited to the above method.

The present specification provides a coating composition containing an anthracene-based compound represented by Formula 1 above. At this time, the coating composition is used in a solution process in the production of organic light-emitting devices.

In one embodiment of the present specification, the coating composition further includes a dopant material. As the dopant material, a dopant material described later may be used.

The present specification provides a composition containing an anthracene-based compound represented by Formula 1 above. The composition may further include additional anthracene-based compounds. The anthracene-based compound additionally included is not limited to the compound represented by Formula 1, and may be a known anthracene-based host material.

The present specification provides an organic light-emitting device containing the above-mentioned compound.

This specification includes: a first electrode; a second electrode provided opposite to the first electrode; and an organic light-emitting device comprising 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 an anthracene-based compound represented by Formula 1. provides.

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

In this specification, when a part “includes” a certain element, this means that it may further include other elements rather than excluding other elements, unless specifically stated to the contrary.

In this specification, the “layer” is interchangeable with the “film” mainly used in the present technical field, and refers to a coating that covers the target area. The size of the “layer” is not limited, and each “layer” may have the same or different size. In one embodiment, the size of a “layer” may be equal to the entire device, may correspond to the size of a specific functional area, or may be as small as a single sub-pixel.

In this specification, the inclusion of a specific material A in the layer B means i) one or more types of material A are included in one layer B, and ii) the layer B is composed of one or more layers, and the material A is comprised of multiple layers of B. Includes everything on the first or higher floors.

In this specification, the meaning that a specific material A is included in the C layer or D layer means that it is i) included in one or more layers of one or more layers of C, ii) included in one or more layers of one or more layers of D, or iii ) This means that it is included in each of the C floors above the first floor and the D floors above the first floor.

The organic light emitting device according to the present specification may include an additional organic material layer in addition to the light emitting layer.

The organic material layer of the organic light emitting device of the present specification may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, a hole blocking layer, etc. However, the structure of the organic light emitting device is not limited to this.

In one embodiment of the present specification, the organic material layer includes a light-emitting layer, and the light-emitting layer includes an anthracene-based compound represented by Formula 1 above.

In one embodiment of the present specification, the organic layer includes a light-emitting layer, and the light-emitting layer includes the anthracene-based compound represented by Formula 1 as a host.

In one embodiment of the present specification, the light emitting layer includes a host and a dopant. In one embodiment, the host includes an anthracene-based compound represented by Formula 1 above.

In one embodiment of the present specification, the dopant is a phosphorescent dopant or a fluorescent dopant.

In one embodiment of the present specification, the light-emitting layer includes an arylamine-based compound as a dopant.

In one embodiment of the present specification, the arylamine-based compound includes deuterium.

In another exemplary embodiment, the light emitting layer includes a boron compound as a dopant.

In one embodiment of the present specification, the dopant in the light-emitting layer may be included in an amount of 0.1 parts by weight to 50 parts by weight, preferably 1 part by weight to 30 parts by weight, based on 100 parts by weight of the host. When within the above range, energy transfer from host to dopant occurs efficiently.

In one embodiment of the present specification, the organic light emitting device further includes one or more light emitting layers. Each of the one or more light emitting layers may include the above-described dopant.

According to an exemplary embodiment of the present specification, the organic light-emitting device includes two or more light-emitting layers, one layer of the two or more light-emitting layers includes a fluorescent dopant, and the other layer includes a phosphorescent dopant.

According to an exemplary embodiment of the present invention, the maximum emission peak of the light-emitting layer containing the compound represented by Formula 1 is 400 nm to 500 nm.

In one embodiment of the present specification, the anthracene-based compound represented by Formula 1 is included in an amount of 50 parts by weight or more and less than 100 parts by weight, more preferably 70 parts by weight or more and 99 parts by weight or less, based on 100 parts by weight of the total weight of the light emitting layer. .

An organic light-emitting device according to an exemplary embodiment of the present specification includes two or more light-emitting layers, and at least one of the two or more light-emitting layers includes an anthracene-based compound represented by Formula 1 above. The light-emitting layer containing the anthracene-based compound represented by Formula 1 has a blue color, and the light-emitting layer that does not contain the anthracene-based compound represented by Formula 1 may include blue, red, or green light-emitting compounds known in the art.

In one embodiment of the present specification, the organic material layer includes a hole injection layer, a hole transport layer, an electron blocking layer, an electron injection layer, an electron transport layer, or a hole blocking layer, and the hole injection layer, the hole transport layer, the electron blocking layer, and the electron blocking layer The injection layer, electron transport layer, or hole blocking layer includes an anthracene-based compound represented by Formula 1 above.

In one embodiment of the present specification, the organic material layer is a hole injection layer or a hole transport layer. It further includes one or two layers selected from the group consisting of a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron blocking layer.

In one embodiment of the present specification, the first electrode is an anode and the second electrode is a cathode.

In one embodiment of the present specification, the second electrode is a cathode and the first electrode is an anode.

In one embodiment of the present specification, the organic light emitting device may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

In one embodiment of the present specification, the organic light emitting device may be an inverted type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

For example, the structure of an organic light-emitting device according to an exemplary embodiment of the present specification is illustrated in FIGS. 1 to 3, but is not limited thereto.

Figure 1 illustrates the structure of an organic light emitting device in which an anode 102, a light emitting layer 106, and a cathode 110 are sequentially stacked on a substrate 101. The compound represented by Formula 1 is included in the light-emitting layer.

2 shows an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light emitting layer 106, a hole blocking layer 107, and an electron transport layer 108 on the substrate 101. , electron injection layer (109). The structure of an organic light emitting device in which the cathode 110 and the capping layer 111 are sequentially stacked is illustrated. The compound represented by Formula 1 is included in the light-emitting layer.

3 shows an anode 102, a first hole transport layer 104a, a second hole transport layer 104b, a light emitting layer 106, an electron transport layer 108, a cathode 110, and a capping layer 111 on the substrate 101. The structure of this sequentially stacked organic light emitting device is illustrated. The compound represented by Formula 1 is included in the light-emitting layer.

The organic light emitting device of the present specification can be manufactured using materials and methods known in the art, except that the organic material layer includes the above compound.

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 stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a metal or conductive metal oxide or alloy thereof is deposited on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form an anode. It can be manufactured by forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device can be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate.

In addition, the anthracene-based compound represented by 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 refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited thereto.

In addition to this method, an organic light-emitting device can also be made by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate. However, the manufacturing method is not limited to this.

The anode material is generally preferably a material with a large work function to facilitate hole injection into the organic layer. For example, 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); ZnO:Al or SnO ₂ : A combination of a metal such as Sb and an oxide; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline are included, but are not limited thereto.

The cathode material is generally preferably a material with a small work function to facilitate electron injection into the organic layer. metals or alloys thereof, for example magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead; Examples include, but are not limited to, multi-layered materials such as LiF/Al or LiO ₂ /Al.

The light emitting layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic ring-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include dibenzofuran derivatives, ladder-type furan compounds, These include, but are not limited to, pyrimidine derivatives.

The dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamine group, and include pyrene, anthracene, chrysene, periplanthene, etc. having an arylamine group. In addition, a styrylamine compound is a compound in which at least one arylvinyl group is substituted on a substituted or unsubstituted arylamine, and is one or two or more selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamine group. The substituent is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc. are included, but are not limited thereto. Additionally, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

The hole injection layer is a layer that receives holes from the electrode. The hole injection material preferably has the ability to transport holes and has an excellent hole receiving effect from the anode and an excellent hole injection effect with respect to the light emitting layer or light emitting material. Additionally, a material that has an excellent ability to prevent the movement of excitons generated in the light-emitting layer to the electron injection layer or electron injection material is desirable. Additionally, materials with excellent thin film forming ability are desirable. Additionally, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, and arylamine-based organic materials; Hexanitrilehexaazatriphenylene series organic substances; Organic substances of the quinacridone series; Perylene-based organic substances; These include, but are not limited to, polythiophene-based conductive polymers such as anthraquinone and polyaniline.

The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer, and may have a single-layer structure or a multi-layer structure of two or more layers. The hole transport material is preferably a material that can receive holes from the anode or hole injection layer and transfer them to the light emitting layer, and has high mobility for holes. Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions.

In one embodiment of the present specification, the hole transport layer has a multi-layer structure of two or more layers. Specifically, it has a two-layer structure, and each layer contains different materials.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer. The electron transport material is a material that can easily receive electrons from the cathode and transfer them to the light-emitting layer, and a material with high electron mobility is preferred. Specific examples include Al complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; organic radical compounds; These include, but are not limited to, hydroxyflavone-metal complexes. The electron transport layer can be used with any desired cathode material, as used according to the prior art. In particular, suitable cathode materials are conventional materials with a low work function followed by an aluminum or silver layer. Specifically, there are cesium, barium, calcium, ytterbium, and samarium, and in each case, an aluminum layer or a silver layer follows.

The electron injection layer is a layer that receives electrons from the electrode. It is preferable that the electron injection material has excellent electron transport ability, has an electron receiving effect from the second electrode, and has an excellent electron injection effect with respect to the light emitting layer or light emitting material. In addition, a material that prevents excitons generated in the light-emitting layer from moving to the hole injection layer and has excellent thin film forming ability is desirable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. and their derivatives, These include, but are not limited to, metal complex compounds and nitrogen-containing five-membered ring derivatives.

The metal complex compounds include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, and 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-naphtolato) aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato) gallium. , but is not limited to this.

The electron blocking layer is a layer that can improve the lifespan and efficiency of the device by preventing electrons injected from the electron injection layer from passing through the light emitting layer and entering the hole injection layer. Known materials can be used without limitation, and can be formed between a light-emitting layer and a hole injection layer, or between a light-emitting layer and a layer that simultaneously performs hole injection and hole transport.

The hole blocking layer is a layer that prevents holes from reaching the cathode, and can generally be formed under the same conditions as the electron injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, aluminum complexes, etc., but it is not limited thereto.

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

Hereinafter, in order to explain the present specification in detail, examples and comparative examples will be described in detail. However, the Examples and Comparative Examples according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the Examples and Comparative Examples detailed below. The examples and comparative examples of this specification are provided to more completely explain the present specification to those with average knowledge in the art.

Preparation Example 1 (Synthesis of A1 to A18)

As shown in Table 1 below, SM1 (1eq) and SM2 (1.05eq) were added to tetrahydrofuran (excess), then 2M potassium carbonate aqueous solution (30 volume ratio compared to THF) was added, and tetrakistriphenyl-phosphinopalladium (2 mol) was added. %) was added, and then heated and stirred for 10 hours. After lowering the temperature to room temperature and completing the reaction, the potassium carbonate aqueous solution was removed and the layers were separated. After removing the solvent, dimethylacetamide (DMAc, excess) and potassium carbonate (3eq) were added and stirred and heated to reflux for 5 hours. After confirming the completion of the reaction, the temperature was lowered to room temperature, water (1.5 times the volume ratio compared to DMAc) was added, and the obtained solid was filtered and purified by column chromatography using methylene chloride and hexane to obtain A1 (yield: 58%).

In the synthesis of A1, A1 to A18 were synthesized in the same manner, except that SM1 and SM2 were changed as shown in Table 1 below.

Preparation Example 2 (Synthesis of B1 to B8)

As shown in Table 2 below, SM1 (1eq) and (2-hydroxyphenyl)boronic acid (1.05eq) were added to tetrahydrofuran (excess), then 2M potassium carbonate aqueous solution (30 volume ratio compared to THF) was added, and tetrakistriphenyl -Phosphinopalladium (2 mol%) was added, followed by heating and stirring for 10 hours. After lowering the temperature to room temperature and completing the reaction, the potassium carbonate aqueous solution was removed, washed twice with water, and the layers were separated. After removing the solvent, it was dissolved in chloroform (excess) and the temperature was stabilized at 0°C. Then, N-bromosuccinimide (NBS, 1eq) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 3 hours. Afterwards, a saturated aqueous solution of sodium sulfate (1.5 times the volume ratio compared to chloroform) was added dropwise for extraction, and after removing the solvent, dimethylacetamide (DMAc, excess) and potassium carbonate (3eq) were added, followed by stirring and heating to reflux for 5 hours. After confirming the completion of the reaction, the temperature was lowered to room temperature, water (1.5 times the volume ratio compared to DMAc) was added, and the obtained solid was filtered and purified by column chromatography using methylene chloride and hexane to obtain B1 (yield: 59%).

In the synthesis of B1, B1 to B8 were synthesized in the same manner, except that SM1 was changed as shown in Table 2 below.

Preparation Example 3 (Synthesis of C1 to C11)

In the synthesis of A1, C1 to C11 were synthesized in the same manner, except that SM1 and SM2 were changed as shown in Table 3 below.

Preparation Example 4 (Synthesis of D1 to D5)

SM1 (1eq) and SM2 (1.05eq) of Table 4 below were added to tetrahydrofuran (excess), then 2M potassium carbonate aqueous solution (30 volume ratio compared to THF) was added, and tetrakistriphenyl-phosphinopalladium (2 mol%) was added. ) was added, and then heated and stirred for 10 hours. After lowering the temperature to room temperature and completing the reaction, the potassium carbonate aqueous solution was removed and the layers were separated. After confirming the completion of the reaction, the temperature was brought to room temperature, the solvent was removed, and purified by recrystallization using ethyl acetate and hexane to obtain D1 (yield: 70%).

In the synthesis of D1, D1 to D5 were synthesized in the same manner, except that SM1 and SM2 were changed as shown in Table 4 below.

Preparation Example 5 (Synthesis of E1)

SM1 (1eq) of Table 5 below was dissolved in chloroform (excess) and the temperature was stabilized at 0°C. Then, N-bromosuccinimide (NBS, 1eq) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 3 hours. Afterwards, saturated sodium sulfate aqueous solution (1.5 times the volume ratio compared to chloroform) was added dropwise for extraction, and after removal of the solvent, the extract was purified by column chromatography using methylene chloride and hexane to obtain E1 (yield: 65%).

Preparation Example 6 (Synthesis of F1)

로 냉각하고, I₂ (1eq)를 가하고 1시간 동안 교반하고 상온으로 온도를 올린 후 물(excess)을 투입하고 추출하였다 용매 제거 후 메틸렌클로라이드와 헥산을 사용하여 컬럼크로마토그래피로 정제하여 하기 표 6과 같이 F1 (수득량 : 48%)를 얻었다.SM1 (1eq) of Table 6 below was dissolved in THF (excess), the temperature was lowered to -78°C, 2.5M n-BuLi (1.5eq) was added dropwise, the temperature was stabilized at room temperature, and the mixture was stirred for 30 minutes. Again -78

After cooling, I ₂ (1eq) was added and stirred for 1 hour, the temperature was raised to room temperature, water (excess) was added and extracted. After removal of the solvent, purification was performed by column chromatography using methylene chloride and hexane, and the results are shown in Table 6 below. F1 (yield: 48%) was obtained as follows.

Preparation Example 7 (Synthesis of G1 to G19)

SM1 (1eq) and 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (1.3eq) in Table 7 below. Add to 1,4-dioxane (12 times <mass ratio> compared to SM1), add potassium acetate (3eq), stir and reflux. Palladium acetate (0.02eq) and tricyclohexylphosphine (0.04eq) were added after stirring in 1,4-dioxane for 5 minutes, and after 2 hours, the reaction was confirmed to be complete and cooled to room temperature. Ethanol and water were added, filtered, and recrystallized with ethyl acetate and hexane to obtain G1 (yield: 82%).

In the synthesis of G1, G1 to G19 were synthesized in the same manner, except that SM1 was changed as shown in Table 7 below.

Preparation Example 8 (Synthesis of H1 to H3)

In the synthesis of D1, H1 to H3 were synthesized in the same manner, except that SM1 and SM2 were changed as shown in Table 8 below.

Preparation Example 9 (Synthesis of I1 to I3)

In the synthesis of G1, I1 to I3 were synthesized in the same manner, except that SM1 was changed as shown in Table 9 below.

Preparation Example 10 (Synthesis of W1 to W8)

As shown in Table 10 below, SM1 (1eq) and SM2 (1.05eq) were added to tetrahydrofuran (excess), then 2M potassium carbonate aqueous solution (30 volume ratio compared to THF) was added, and tetrakistriphenyl-phosphinopalladium (2 mol) was added. %) was added, and then heated and stirred for 10 hours. After lowering the temperature to room temperature and completing the reaction, the potassium carbonate aqueous solution was removed and the layers were separated. After removing the solvent, the solid was purified by column chromatography using methylene chloride and hexane to obtain W1 to W8.

Preparation Example 11 (Synthesis of X1 to X8)

As shown in Table 11 below, SM1 (1eq) was dissolved in chloroform (excess) to stabilize the temperature at 0°C, and then N-bromosuccinimide (NBS, 1eq) was dissolved in DMF and added dropwise, raised to room temperature, and stirred for 3 hours. did. Afterwards, a saturated aqueous solution of sodium sulfate (1.5 times the volume ratio compared to chloroform) was added dropwise for extraction, and the solid obtained after removal of the solvent was purified by column chromatography using methylene chloride and hexane to obtain X1 to X8.

Preparation Example 12 (Synthesis of Y1 to Y18)

Scheme12-1

Scheme12-2

By the method of scheme12-1 or scheme12-2, SM1 (1eq) and SM2 (1.05eq) were added to tetrahydrofuran (excess) as shown in Table 12 below, and then 2M potassium carbonate aqueous solution (30 volume ratio compared to THF) was added. , tetrakistriphenyl-phosphinopalladium (2 mol%) was added, and then heated and stirred for 10 hours. After lowering the temperature to room temperature and completing the reaction, the potassium carbonate aqueous solution was removed and the layers were separated. The solid obtained after removal of the solvent was purified by column chromatography using methylene chloride and hexane to obtain Y1 to Y18.

Preparation Example 13 (Synthesis of Z1 to Z18)

scheme13-1

. scheme13-2

By the method of scheme13-1 or scheme13-2, SM1 (1eq) was dissolved in chloroform (excess) as shown in Table 13 below, the temperature was stabilized at 0°C, and N-bromosuccinimide (NBS, 1eq) was dissolved in DMF. It was added dropwise, raised to room temperature, and stirred for 3 hours. Afterwards, a saturated aqueous solution of sodium sulfate (1.5 times the volume ratio compared to chloroform) was added dropwise for extraction, and the solid obtained after removal of the solvent was purified by column chromatography using methylene chloride and hexane to obtain Z1 to Z18.

Preparation Example 14 (Synthesis of U1)

As shown in Table 14 below, SM1 (1eq) and SM2 (1.05eq) were added to tetrahydrofuran (excess), then 2M potassium carbonate aqueous solution (30 volume ratio compared to THF) was added, and tetrakistriphenyl-phosphinopalladium (2 mol) was added. %) was added, and then heated and stirred for 10 hours. After lowering the temperature to room temperature and completing the reaction, the potassium carbonate aqueous solution was removed and the layers were separated. After removing the solvent, the obtained solid was purified by column chromatography using methylene chloride and hexane to obtain U1.

Preparation Example 15 (Synthesis of Compounds 1 to 19)

scheme15-1

scheme15-2

scheme15-3

By the method of scheme15-1 to scheme15-3, SM1 (1eq) and SM2 (1.05eq) were added to tetrahydrofuran (excess) as shown in Table 15 below, and then 2M potassium carbonate aqueous solution (30 volume ratio compared to THF) was added. , tetrakistriphenyl-phosphinopalladium (2 mol%) was added, and then heated and stirred for 10 hours. After lowering the temperature to room temperature and completing the reaction, the potassium carbonate aqueous solution was removed and the layers were separated. After removing the solvent, the obtained solid was purified by recrystallization using chloroform and toluene to obtain compounds 1 to 19.

Preparation Example 16 (Synthesis of Compounds 20 to 22)

scheme16-1

scheme16-2

By the method of scheme16-1 or scheme16-2, add the reactant (1eq) and Trifluoromethanesulfonic acid (cat.) in Table 16 to C ₆ D ₆ (10 to 100 times the mass ratio compared to the reactant) and incubate at 70°C for 10 to 100 minutes. It was stirred between them. After completion of the reaction, D ₂ O (excess) was added and stirred for 30 minutes, and then trimethylamine (excess) was added dropwise. The reaction solution was transferred to a separatory funnel and extracted with water and chloroform. The extract was dried with MgSO ₄ and recrystallized by heating with toluene to obtain compounds 20 to 22 (deuterium-substituted compounds of compounds 4, 12, and 19) in Table 15 below.

[Each product has different degrees of deuterium substitution depending on the reaction time, and the substitution rate is determined based on the maximum m/z (M+) value]

For deuterium substitution of the above product, reference was made to the prior literature of KR 10-1538534 B1.

<Example 1> Manufacturing of OLED

A substrate on which 70/1000/70Å ITO/Ag/ITO was deposited as an anode was placed in distilled water with a dispersant dissolved in it and washed with ultrasonic waves. Detergent was used from Fischer Co., and distilled water was from Millipore Co. Distilled water that was filtered secondarily was used as a filter for the product. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed in the order of isopropyl alcohol, acetone, and methanol and dried.

On the anode prepared in this way, HI-1 was thermally vacuum deposited to a thickness of 50 Å to form a hole injection layer, and HT1, a hole transport material, was vacuum deposited to a thickness of 1150 Å on top of it to form a hole transport layer. Next, an electron blocking layer (150 Å) was formed using EB1, and then a light emitting layer (360 Å, vacuum deposition) was formed using Compound 1 as a host and BD1 as a dopant (2% by weight). Afterwards, 50Å of ET1 was deposited to form a hole blocking layer, and compounds ET2 and Liq were mixed in a ratio of 7:3 to form an electron transport layer with a thickness of 250Å. Magnesium and lithium fluoride (LiF) with a thickness of 50 Å were sequentially formed as an electron injection layer, and then 200 Å of magnesium and silver (1:4) were formed as a cathode, and then 600 Å of CP1 was deposited to complete the device. In the above process, the deposition rate of organic matter was maintained at 1 Å/sec.

<Examples 2 to 24>

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the host and dopant of the light-emitting layer were as shown in Table 17 below.

<Comparative Examples 1 to 9>

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the host and dopant of the light-emitting layer were as shown in Table 17 below.

A current of 20 mA/cm ² was applied to the organic light emitting device manufactured in Examples and Comparative Examples to measure voltage, efficiency, and lifespan (T95), and the results are shown in Table 17 below. At this time, T95 means the time until the initial luminance decreases to 95% at a current density of 20 mA/cm ² .

Experiment example
20 mA/㎠ host dopant Voltage (V)
(@20mA/cm ² ) Cd/A
(@20mA/cm ² ) Color coordinates
(x,y) life span
(T95,h)
(@20mA/cm ² ) Example 1 Compound 1 BD1 3.48 6.90 (0.135, 0.143) 50.1 Example 2 compound 2 BD1 3.44 6.88 (0.134, 0.142) 51.3 Example 3 Compound 4 BD1 3.50 6.64 (0.135, 0.145) 54.8 Example 4 Compound 6 BD1 3.38 6.67 (0.134, 0.143) 53.4 Example 5 Compound 7 BD1 3.41 6.70 (0.136, 0.140) 55.1 Example 6 Compound 9 BD1 3.35 6.80 (0.135, 0.147) 53.5 Example 7 Compound 11 BD1 3.48 6.81 (0.133, 0.145) 52.8 Example 8 Compound 12 BD1 3.45 6.85 (0.135, 0.142) 51.3 Example 9 Compound 13 BD1 3.39 6.70 (0.134, 0.148) 50.9 Example 10 Compound 14 BD1 3.42 6.74 (0.136, 0.144) 53.4 Example 11 Compound 15 BD1 3.44 6.89 (0.136, 0.139) 54.8 Example 12 Compound 17 BD1 3.35 6.88 (0.135, 0.145) 55.9 Example 13 Compound 18 BD1 3.30 6.67 (0.134, 0.143) 50.2 Example 14 Compound 19 BD1 3.48 6.89 (0.136, 0.140) 49.8 Example 15 Compound 20 BD1 3.44 6.92 (0.135, 0.147) 70.5 Example 16 Compound 21 BD1 3.40 6.69 (0.134, 0.148) 78.1 Example 17 Compound 22 BD1 3.51 6.94 (0.136, 0.144) 75.1 Example 18 Compound 20 BD2 3.48 7.88 (0.136, 0.131) 69.7 Example 19 Compound 1 BD2 3.49 7.23 (0.136, 0.131) 44.2 Example 20 Compound 7 BD2 3.49 7.28 (0.134, 0.133) 48.5 Example 21 Compound 9 BD2 3.44 7.30 (0.136, 0.131) 47.9 Example 22 Compound 12 BD2 3.48 7.29 (0.136, 0.132) 48.1 Example 23 Compound 15 BD2 3.47 7.30 (0.136, 0.131) 45.6 Example 24 Compound 17 BD2 3.45 7.33 (0.136, 0.132) 46.1 Comparative Example 1 BH1 BD1 3.59 5.68 (0.136, 0.139) 30.1 Comparative Example 2 BH2 BD1 3.58 5.23 (0.136, 0.139) 38.1 Comparative Example 3 BH3 BD1 3.70 5.27 (0.136, 0.139) 34.5 Comparative Example 4 BH4 BD1 3.59 5.30 (0.135, 0.138) 32.6 Comparative Example 5 BH5 BD1 3.62 5.78 (0.136, 0.139) 38.4 Comparative Example 6 BH6 BD1 3.68 4.89 (0.136, 0.139) 30.5 Comparative Example 7 BH7 BD1 3.71 5.37 (0.135, 0.138) 39.1 Comparative Example 8 BH8 BD1 3.72 5.44 (0.135, 0.138) 20.5 Comparative Example 9 BH9 BD1 3.83 5.68 (0.139, 0.158) 39.0

By using the compound of Formula 1 according to the present invention as a host of a blue organic electroluminescent device, the role of smooth hole injection into the light emitting layer can be controlled, and the present invention can be achieved through the balance of holes and electrons in the organic light emitting device according to the chemical structure. The following devices exhibit excellent characteristics in terms of efficiency, driving voltage, and stability.

<Example 25> Manufacturing of solution-type OLED

A glass substrate coated with a thin film of indium tin oxide (ITO) to a thickness of 1,300 Å was placed in distilled water with a detergent dissolved in it and washed ultrasonically. At this time, a detergent from Fischer Co. was used, and distilled water filtered secondarily using a filter from Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed with solvents of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Additionally, the substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum evaporator.

A solution of poly(3,4-ethylene dioxythiophene)-polystyrene sulfonate (PEDOT/PSS, Bayer, Baytron P Al 4083) diluted to 70% with pure water was prepared by spin coating on the ITO transparent electrode prepared as above. After forming the film by spin coating at 3000 rpm for 30 seconds, it was dried at 200°C for 1 hour to prepare a first hole transport layer with a film thickness of 30 nm. Subsequently, the HT1 solution (xylene solution, 1 wt%) was spin-coated and dried at 210°C for 30 minutes in a nitrogen atmosphere to form a second hole transport layer with a thickness of 20 nm.

After cooling, the substrate was spin-coated with the emissive layer solution and heated to remove the solvent to form the emissive layer. At this time, the emitting layer solution was prepared as a host (compound 3) : dopant (BD11) = 10 : 1, 1 wt% methylbenzoate solution.

After masking the substrate and placing it in a vacuum chamber, ET11 (300Å) was deposited with LiQ at a 2:1 ratio and thermally vacuum deposited as an electron transport layer. Lithium fluoride (LiF) with a thickness of 12 Å and aluminum with a thickness of 2,000 Å were sequentially deposited on the electron transport layer to form a cathode, thereby manufacturing an organic light-emitting device. The vacuum chamber was evacuated and the device was encapsulated using a glass cover, desiccant, and UV curable epoxy.

In the above process, the deposition rate of organic matter was maintained at 0.4 ~ 0.7 Å/sec, the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was maintained at 1 × 10 ^-7 ~ 5 × 10 ^-8 torr. did.

<Examples 26 to 29>

An organic light-emitting device was manufactured in the same manner as Example 25, except that the host and dopant of the light-emitting layer in Example 25 were as shown in Table 18 below.

<Comparative Example 10>

An organic light-emitting device was manufactured in the same manner as Example 25, except that the host and dopant of the light-emitting layer in Example 25 were as shown in Table 18 below.

Experiment example
20 mA/㎠ host dopant Voltage (V)
(@20mA/cm ² ) Cd/A
(@20mA/cm ² ) Color coordinates
(x,y) life span
(T95,h)
(@20mA/cm ² ) Example 25 Compound 3 BD11 4.55 6.70 (0.134, 0.142) 12584 Example 26 Compound 5 BD11 4.60 6.77 (0.135, 0.145) 11023 Example 27 compound 8 BD11 4.59 6.68 (0.134, 0.143) 12680 Example 28 Compound 10 BD11 4.62 6.60 (0.136, 0.140) 12048 Example 29 Compound 16 BD11 4.60 6.72 (0.135, 0.147) 12567 Comparative Example 10 BH11 BD11 5.67 5.12 (0.136, 0.139) 7200

Looking at Table 18, it can be seen that the compound of Formula 1 according to the present invention can be used in a solution process, and when used as a host for a blue organic electroluminescent device, the device has excellent low voltage, high efficiency, and long life characteristics. You can.

101: substrate
102: anode
103: Hole injection layer
104: Hole transport layer
104a: first hole transport layer
104b: second hole transport layer
105: Electronic blocking layer
106: light emitting layer
107: Hole blocking layer
108: Electron transport layer
109: Electron injection layer
110: cathode
111: capping layer

Claims (14)

Anthracene-based compound represented by the following formula (1):
[Formula 1]

In Formula 1,
L1 and L2 are the same or different from each other and are each independently directly bonded; or an arylene group of C6-C30 substituted or unsubstituted with deuterium,
At least one of Ar1 and Ar1' is a C6-C20 aryl substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, a C1-C6 alkyl group, and a C6-C20 aryl group, or a substituent linked to two or more groups selected from the group. group, and the remainder is hydrogen; or deuterium,
Ar2 is a C6-C30 aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, C1-C10 alkyl group, silyl group, and C6-C30 aryl group, or a substituent linked to two or more groups selected from the group,
At least one of R1 to R3 is the same or different from each other, and each independently selected from the group consisting of a C1-C10 alkyl group, a silyl group, a C3-30 cycloalkyl group, a C6-C30 aryl group, and a C2-C30 heteroaryl group. It is a substituent, or a substituent in which two or more groups selected from the above group are connected, the substituent may be substituted with deuterium, the remainders are the same or different from each other, and each independently hydrogen; or deuterium,
D is deuterium,
n1 is an integer from 0 to 6,
r1 is an integer from 0 to 4, r2 is an integer from 0 to 2, r3 is an integer from 0 to 4,
r1 + r2 is an integer from 0 to 5,
r1 + r2 + r3 is 1 or more,
When r1 to r3 are each 2 or more, the substituents in parentheses are the same or different from each other. The anthracene-based compound according to claim 1, wherein Formula 1 is represented by the following Formula 101 or 102:
[Formula 101]

[Formula 102]

In the above formulas 101 and 102,
The definitions of L1, L2, Ar1, Ar1', Ar2, R1 to R3, D, n1 and r1 to r3 are as defined in Formula 1,
r1' is an integer from 0 to 3, and r2' is 0 or 1. The anthracene-based compound according to claim 1, wherein Formula 1 is represented by any one of the following Formulas 201 to 206:
[Formula 201]

[Formula 202]

[Formula 203]

[Formula 204]

[Formula 205]

[Formula 206]

In the above formulas 201 to 206,
The definitions of L1, L2, Ar1, Ar1', Ar2, R1 to R3, D, n1 and r1 to r3 are as defined in Formula 1. delete In claim 1,
One of Ar1 and Ar1' is a C6-C20 aryl group substituted or unsubstituted by one or more substituents selected from the group consisting of deuterium and a C1-C6 alkyl group or a substituent linked by two or more groups selected from the group, and the other is a C6-C20 aryl group. hydrogen; Or an anthracene-based compound that is deuterium. The method according to claim 1, wherein Formula 1 is an anthracene-based compound deuterated by 20% or more, The method according to claim 1, wherein Formula 1 is an anthracene-based compound containing at least one hydrogen, The anthracene-based compound according to claim 1, wherein the anthracene-based compound represented by Formula 1 is any one selected from the following compounds:

. A coating composition comprising the anthracene-based compound of any one of claims 1 to 3 and 5 to 8. first electrode; a second electrode provided opposite to the first electrode; And an organic light emitting device comprising one or more organic material layers provided between the first electrode and the second electrode,
An organic light-emitting device wherein at least one layer of the organic material layer includes an anthracene-based compound according to any one of claims 1 to 3 and 5 to 8. The organic light-emitting device of claim 10, wherein the organic material layer includes a light-emitting layer, and the light-emitting layer includes the anthracene-based compound as a host. The organic light-emitting device of claim 11, wherein the light-emitting layer includes an arylamine-based compound as a dopant. The organic light emitting device of claim 11, wherein the light emitting layer includes a boron compound as a dopant. The method according to claim 10, wherein the organic material layer is a hole injection layer or a hole transport layer. An organic light-emitting device further comprising one or two layers selected from the group consisting of a light-emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron blocking layer.