Composition for organic electroluminescent elements and organic electroluminescent elements containing the same

Abstract

The present invention relates to a composition for an organic EL element and an organic EL element containing the same. The composition for an organic EL element contains a first host represented by [Chemical Formula 1] and a second host represented by [Chemical Formula 2], and the above [Chemical Formula 1] and [Chemical Formula 2] are as defined in this specification.

Description

[Technical Field]

[0001] The present invention relates to a composition for an organic electroluminescent element and an organic electroluminescent element containing the same. [Background technology]

[0002] In organic electroluminescent devices (hereinafter abbreviated as "organic EL devices"), when a voltage is applied between the two electrodes, holes are injected from the positive electrode and electrons are injected from the negative electrode into the organic layer. When the injected holes and electrons meet, excitons are formed, and light is emitted when these excitons return to the ground state. At this time, the materials used as the organic layer are classified according to their function into light-emitting materials, hole-injecting materials, hole-transporting materials, electron-transporting materials, electron-injecting materials, etc.

[0003] The light-emitting layer forming materials for organic EL devices can be classified into blue, green, and red light-emitting materials according to the emitted color. Furthermore, yellow and orange light-emitting materials are sometimes used to achieve better natural colors. In addition, host / dopant systems are used as light-emitting materials to improve color purity and increase luminescence efficiency through energy transfer. Dopant materials are broadly classified into fluorescent dopants, which use organic substances, and phosphorescent dopants, which use metal complex compounds containing heavy atoms such as Ir and Pt. Because such phosphorescent materials can theoretically improve luminescence efficiency by up to four times compared to fluorescent materials, there is growing interest not only in phosphorescent dopants but also in phosphorescent host materials.

[0004] Currently, NPB, BCP, and Alq3 are widely known materials used in hole injection layers, hole transport layers, hole blocking layers, and electron transport layers, while anthracene derivatives have been reported as fluorescent dopant / host materials. In particular, among the luminescent materials, metal complex compounds containing Ir, such as Firpic, Ir(ppy)3, and (acac)Ir(btp)2, are used as blue, green, and red dopant materials, offering significant advantages in terms of efficiency improvement. Currently, CBP is showing excellent properties as a phosphorescent host material.

[0005] However, while conventional organic layer materials have advantages in terms of luminescence properties, their low glass transition temperature and poor thermal stability have resulted in unsatisfactory lifespans for organic EL devices. Therefore, there is a need to develop organic layer materials with superior performance. [Overview of the project] [Problems that the invention aims to solve]

[0006] The object of the present invention is to provide a composition that can realize an organic EL element having high efficiency and long lifespan.

[0007] Another object of the present invention is to provide an organic EL element with improved low driving voltage, high luminous efficiency, and long lifespan characteristics by including the above composition as an organic layer material (e.g., a light-emitting layer material). [Means for solving the problem]

[0008] To achieve the above objectives, the present invention provides an organic EL element composition comprising a first host represented by the following [Chemical Formula 1] and a second host represented by the following [Chemical Formula 2]. [ka] [ka] (In the above formula, D is deuterium, a, d, f, and h are integers from 0 to 3, b, c, e, g, and i are integers from 0 to 4 respectively, j and k are integers from 0 to 5 respectively, n1 is an integer from 1 to 5, n2 is an integer of 0 or 1, X1 is selected from the group consisting of O, S, Se, N(Ar3), C(Ar4)(Ar5), and Si(Ar6)(Ar7), Y1 and Y2 are the same as or different from each other, and each independently is N or C(Ar8), and at this time, at least one of Y1 and Y2 is N, Ar1 to Ar8 and R1 to R5 are the same as or different from each other, and each independently is hydrogen, deuterium (D), a halogen group, a cyano group, a nitro group, an amino group, a C1 - C 60 , 40 , , 40 , 60 , 60 , 60 , 60 alkyl group, a C2 - C 40 alkenyl group, a C2 - C 40 alkynyl group, a C3 - C 40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6 - C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1 - C 40 alkyloxy group, a C6 - C 60 aryloxy group, a C1 - C 40 alkylsilyl group, a C6 - C 60 arylsilyl group, a C1 - C<000​​​​​​​​​​​​The alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups, heteroaryl groups, alkyloxy groups, aryloxy groups, alkylsilyl groups, arylsilyl groups, alkylboron groups, arylboron groups, alkylphosphine oxide groups, arylphosphine groups, arylphosphine oxide groups, arylamine groups, and condensed rings of the above Ar1-Ar8 and R1-R5 are each independently deuterium, halogen, cyano group, nitro group, C2-C 40 alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl groups, heterocycloalkyl groups with 3-40 nuclear atoms, C1-C 40 alkyl groups, C6~C 60 aryl groups, heteroaryl groups with 5-60 nuclear atoms, C1-C 40 alkyloxy group, C6~C 60 The aryloxy group, C1~C 40 alkylsilyl group, C6~C 60 The arylsilyl group, C1~C 40 alkylboron group, C6~C 60 The arylboron group, C6~C 60 The arylphosphine group, C6~C 60 The arylphosphine oxide group, and C6~C 60 The molecule is substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, and if there are multiple substituents, they may be identical or different from one another.

[0009] Furthermore, the present invention provides an organic EL element comprising an anode; a cathode; and one or more organic layers interposed between the anode and the cathode, wherein the one or more organic layers contain the composition described above. [Effects of the Invention]

[0010] According to one embodiment of the present invention, by using a compound having high hole characteristics and a compound having high electronic characteristics as a host in combination, it is possible to realize an organic EL element that has low driving voltage, high efficiency, and long life characteristics, as well as excellent phosphorescence generation characteristics.

[0011] The effects of the present invention are not limited to those described above, and a wider variety of effects are included herein. [Brief explanation of the drawing]

[0012] [Figure 1] This is a cross-sectional view showing the structure of an organic EL element according to one embodiment of the present invention. [Explanation of Symbols]

[0013] 100: Positive electrode 200: Negative electrode 300:Organic layer 310: Hole transport region 311: Hole injection layer 312: Hole transport layer 320: Emitting layer 330: Electron transport area 331:Electron transport layer 332: Electron injection layer [Modes for carrying out the invention]

[0014] The advantages and features of the present invention, as well as methods for achieving them, will become apparent from the embodiments detailed with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below and can be implemented in various different forms, provided that the embodiments described below are for the complete disclosure of the present invention and so that a person ordinary skill in the art to which the present invention belongs can fully understand the scope of the invention, and the present invention should be defined by the scope of the claims. Accordingly, in some embodiments, known processes and steps, known element structures, and known techniques are omitted in detail to avoid ambiguity of the present invention. Throughout this specification, the same reference numerals refer to the same components.

[0015] Unless otherwise specified, all terms used herein (including technical and scientific terms) are to be understood in common by those skilled in the art to which this invention pertains. Furthermore, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively unless otherwise noted.

[0016] Furthermore, throughout this specification, when a part "includes" a certain component, unless otherwise specified, it means that it may include other components rather than excluding them. Also, throughout this specification, "above" or "on top of" includes not only cases where the part in question is located above or below it, but also cases where other parts are located in between, and does not necessarily mean that the part is located above the direction of gravity.

[0017] Furthermore, in this specification, terms such as "first," "second," etc., do not indicate any arbitrary order or importance, but are used to distinguish between components.

[0018] <Composition for Organic EL Devices> The composition for organic EL elements according to the present invention is a composition for forming the organic layer (e.g., light-emitting layer) of an organic EL element, and comprises a first host represented by [Chemical Formula 1] and a second host represented by [Chemical Formula 2]. In this case, the first host is a compound having a structure in which three carbazoles are directly bonded without a linker, and is a P-type host with relatively high hole properties. The second host is a compound having a structure in which a dibenzo-type moisture is bonded via a linker to one phenyl portion of a 2,4,6-triphenyl-N-containing heterocyclic moisture, and is an N-type host with relatively high electronic properties. By using such a first host and a second host in combination, the composition according to the present invention can realize an organic EL element with high efficiency and long lifespan.

[0019] In the first host represented by [Chemical Formula 1] above, a, d, and f are integers from 0 to 3, and b, c, and e are integers from 0 to 4. Here, if a, b, c, d, e, and f are all 0, it means that hydrogen is not substituted with deuterium (D). If a, d, and f are integers from 1 to 3, and if b, c, and e are integers from 1 to 4, it means that one or more hydrogen atoms are substituted with deuterium (D). In this case, 13 ≤ a + b + c + d + e + f ≤ 21. As an example, the number of deuterium (D) atoms in the first host may be at least 13, specifically at least 21. By substituting deuterium (D) into such a first host, the stability of the chemical structure can be enhanced, and the characteristics of the organic EL element, such as low voltage, high efficiency, and long lifespan, can be simultaneously realized.

[0020] Such deuterium may be substituted with other substituents (R). In this case, if there are multiple other substituents (R), they may be the same or different from one another. The other substituents (R) may be halogen groups, cyano groups, nitro groups, amino groups, C1-C13 40 alkyl groups, C2~C 40 alkenyl group, C2~C 40Alkynyl group, C3~C 40 Cycloalkyl groups, heterocycloalkyl groups with 3-40 nuclear atoms, C6-C 60 aryl groups, heteroaryl groups with 5-60 nuclear atoms, C1-C 40 Alkyloxy, C6~C 60 The aryloxy group, C1~C 40 alkylsilyl group, C6~C 60 The arylsilyl group, C1~C 40 alkylboron group, C6~C 60 The arylboron group, phosphine oxide group, C1~C 40 alkylphosphine oxide group, C6~C 60 The arylphosphine group, C6~C 60 The arylphosphine oxide group, and C6~C 60 The group consisting of arylamine groups may be selected.

[0021] In the first host represented by the above [Chemical Formula 1], Ar1 and Ar2 are either identical or different from each other, and independently consist of hydrogen, deuterium (D), a halogen group, a cyano group, a nitro group, an amino group, and C1-C1. 40 alkyl groups, C2~C 40 alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl groups, heterocycloalkyl groups with 3-40 nuclear atoms, C6-C 60 aryl groups, heteroaryl groups with 5-60 nuclear atoms, C1-C 40 alkyloxy group, C6~C 60 The aryloxy group, C1~C 40 alkylsilyl group, C6~C 60 The arylsilyl group, C1~C 40 alkylboron group, C6~C 60 The arylboron group, phosphine oxide group, C1~C 40 alkylphosphine oxide group, C6~C 60 The arylphosphine group, C6~C 60 The arylphosphine oxide group, and C6~C 60They are selected from the group consisting of arylamine groups, or they may form fused rings with adjacent groups. Specifically, Ar1 and Ar2 are identical or different from each other, and each independently forms a C6-C 60 The group may be selected from the group consisting of aryl groups and heteroaryl groups with 5 to 60 nuclear atoms.

[0022] For example, Ar1 and Ar2 may be the same or different from each other, and each may be an independent substituent selected from the group consisting of the substituents S1 to S4 below. [ka] In the above formula, * represents the bonding site with [Chemical Formula 1] above.

[0023] With such Ar1 and Ar2, the first host represented by [Chemical Formula 1] above may be, but is not limited to, the compound represented by [Chemical Formula 3] below. [ka] In the above formula, a, b, c, d, e, and f are defined as shown in [Chemical Formula 1] above, m1 and m2 are either 0 or 1, respectively.

[0024] Furthermore, the first host represented by [Chemical Formula 1] above can have various structures depending on the bonding positions of each carbazole-based moiety. For example, the first host represented by [Chemical Formula 1] above may be the compound represented by [Chemical Formula 4] below. [ka] In the above formula, a, b, c, d, e, and f are defined as shown in [Chemical Formula 1] above, m1 and m2 are either 0 or 1, respectively.

[0025] Specifically, the first host represented by [Chemical Formula 1] above may be the compound represented by [Chemical Formula 5] below. [ka] In the above formula, a, b, c, d, e, and f are defined as shown in [Chemical Formula 1] above, m1 and m2 are either 0 or 1, respectively.

[0026] The first host represented by [Chemical Formula 1] according to the present invention, as described above, can be embodied in the following compounds, for example, compounds A-1 to D-4, but is not limited to these examples. [ka] [ka]

[0027] In the second host represented by the above [Chemical Formula 2], Y1 and Y2 are either the same or different from each other, and are independently N or C(Ar8), provided that at least one of Y1 and Y2 is N.

[0028] In the second host represented by [Chemical Formula 2] above, Y1 and Y2 are used in this manner. [ka] The moiety may be selected from the group consisting of the following moieties Mo-1 to Mo-3. [ka] In the above formula, * represents the bonding site with [Chemical Formula 2] above. Y1 and Y2 are each independently C(Ar8), Ar8 is defined as shown in [Chemical Formula 2] above.

[0029] In the second host represented by [Chemical Formula 2] above, n1 is an integer between 1 and 5, and n2 is 0 or 1. For example, n1 may be 1 or 2, and n2 may be 0 or 1. However, in [Chemical Formula 2] above, if n2 is 0, then j is 1.

[0030] In the second host represented by [Chemical Formula 2] above, X1 is selected from the group consisting of O, S, Se, N(Ar3), C(Ar4)(Ar5), and Si(Ar6)(Ar7). Depending on such X1, the dibenzo-based moiety may be a monovalent dibenzofuran group, a monovalent dibenzothiophene group, a monovalent fluorene group, etc.

[0031] Ar3 to Ar8 are either identical or different from each other, and each independently comprises hydrogen, deuterium (D), halogen group, cyano group, nitro group, amino group, and C1 to C. 40 alkyl groups, C2~C 40 alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl groups, heterocycloalkyl groups with 3-40 nuclear atoms, C6-C 60 aryl groups, heteroaryl groups with 5-60 nuclear atoms, C1-C 40 alkyloxy group, C6~C 60 The aryloxy group, C1~C 40 alkylsilyl group, C6~C 60 The arylsilyl group, C1~C 40 alkylboron group, C6~C 60 The arylboron group, phosphine oxide group, C1~C 40 alkylphosphine oxide group, C6~C 60 The arylphosphine group, C6~C 60 The arylphosphine oxide group, and C6~C 60They are selected from the group consisting of arylamine groups, or they may form fused rings with adjacent groups (e.g., Ar3-R1, Ar3-R2, Ar4-Ar5, Ar6-Ar7, Ar4-R1, Ar4-R2, Ar6-R1, Ar6-R2, etc.). Specifically, Ar3-Ar8 are identical or different from each other, and each independently forms a C1-C 40 alkyl groups, C6~C 60 The group is selected from the group consisting of aryl groups and heteroaryl groups with 5 to 60 nuclear atoms, or these may form a fused ring with adjacent groups (e.g., Ar3-R1, Ar3-R2, Ar4-Ar5, Ar6-Ar7, Ar4-R1, Ar4-R2, Ar6-R1, Ar6-R2, etc.). Here, the fused ring is C3-C 60 The condensed aliphatic ring (specifically, C3~C 30 (A condensed aliphatic ring), C6~C 60 The condensed aromatic ring (specifically, C6~C 30 (a condensed aromatic ring of 5-60 members), a condensed heteroaromatic ring of 5-30 members, C3-C 60 It may be one or more selected from the group consisting of spiro rings and combinations thereof.

[0032] As an example, in the above [Chemical Formula 2], [ka] The moiety may be selected from the group consisting of moieties Dz-1 to Dz-32 listed below, but is not limited to these. [ka] [ka] In the above formula, * represents the bonding site with [Chemical Formula 2] above. R1 is C6~C 60 It is an aryl group, specifically a phenyl group.

[0033] In the second host represented by the above [Chemical Formula 2], h is an integer from 0 to 3, g and i are each an integer from 0 to 4, and j and k are each an integer from 0 to 5. Here, when g, h, i, j, and k are each 0, it means that hydrogen is not substituted for R1 to R5 which are substituents. When h is an integer from 1 to 3, when g and i are each an integer from 1 to 4, and when j and k are each an integer from 1 to 5, one or more of R1 to R5 are the same as or different from each other, and each independently is deuterium (D), a halogen group, a cyano group, a nitro group, an amino group, a C1-C 40 alkyl group, a C2-C 40 alkenyl group, a C2-C 40 alkynyl group, a C3-C 40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6-C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1-C 40 alkyloxy group, a C6-C 60 aryloxy group, a C1-C 40 alkylsilyl group, a C6-C 60 arylsilyl group, a C1-C 40 alkylboron group, a C6-C 60 arylboron group, a phosphine oxide group, a C1-C 40 alkylphosphine oxide group, a C6-C 60 arylphosphine group, a C6-C 60 arylphosphine oxide group, and a C6-C 60 arylamine group, or they may form a condensed ring with adjacent groups. Specifically, one or more of R1 to R5 are the same as or different from each other, and each independently is hydrogen, a halogen group, a cyano group, a nitro group, an amino group, a C1-C 40 alkyl group, a C6-C 60 aryl group, and a heteroaryl group having 5 to 60 nuclear atoms, and may be selected from the group consisting of.

[0034] The alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups, heteroaryl groups, alkyloxy groups, aryloxy groups, alkylsilyl groups, arylsilyl groups, alkylboron groups, arylboron groups, alkylphosphine oxide groups, arylphosphine groups, arylphosphine oxide groups, arylamine groups, and condensed rings are each independently deuterium, halogen, cyano group, nitro group, C2-C 40 alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl groups, heterocycloalkyl groups with 3-40 nuclear atoms, C1-C 40 alkyl groups, C6~C 60 aryl groups, heteroaryl groups with 5-60 nuclear atoms, C1-C 40 alkyloxy group, C6~C 60 The aryloxy group, C1~C 40 alkylsilyl group, C6~C 60 The arylsilyl group, C1~C 40 alkylboron group, C6~C 60 The arylboron group, C6~C 60 The arylphosphine group, C6~C 60 The arylphosphine oxide group, and C6~C 60 The molecule is substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups. In this case, if there are multiple substituents, they may be the same or different from one another.

[0035] The second host represented by [Chemical Formula 2] above may be, but is not limited to, the compound represented by [Chemical Formula 6] below. [ka] In the above formula, i, j, k, R1, R3-R5, n1, n2, X1, Y1, and Y2 are defined as shown in [Chemical Formula 2] above.

[0036] Specifically, the second host represented by [Chemical Formula 2] above may be, but is not limited to, the compound represented by [Chemical Formula 7] or [Chemical Formula 8] below. [ka] [ka] In the above formula, i, k, R1, R3, R5, n1, n2, Y1, and Y2 are as defined in [Chemical Formula 2] above, X1 and X2 are either O or S, and specifically, they are O.

[0037] More specifically, the second host represented by [Chemical Formula 2] above may be, but is not limited to, the compound represented by [Chemical Formula 9] or [Chemical Formula 10] below. [ka] [ka] In the above formula, n1, n2, Y1, and Y2 are defined as shown in [Chemical Formula 2] above, specifically, n1 is 1 or 2, n2 is 0 or 1, and Y1 and Y2 are both N. x and y are either 0 or 1, X1 and X2 are either O or S, and specifically, they are O. D is deuterium, o1 is an integer between 0 and 5. o2 is an integer between 0 and 6. o3 is an integer between 0 and 4. o4 is an integer between 0 and 3. o5 is an integer between 0 and 7.

[0038] The second host represented by [Chemical Formula 2] according to the present invention, as described above, can be embodied in the following compounds, for example, compounds E-1 to E-13, but is not limited to these examples. [ka]

[0039] In the present invention, "alkyl" means a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, and hexyl.

[0040] In the present invention, "alkenyl" means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

[0041] In the present invention, "alkynyl" means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon triple bonds. Examples include, but are not limited to, ethynyl and 2-propynyl.

[0042] In the present invention, "cycloalkyl" means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

[0043] In the present invention, "heterocycloalkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon with 3 to 40 nuclear atoms, wherein one or more carbon atoms in the ring, preferably 1 to 3 carbon atoms, are substituted with heteroatoms such as N, O, S, or Se. Examples include, but are not limited to, morpholine and piperazine.

[0044] In the present invention, "aryl" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms, either as a single ring or a combination of two or more rings. The two or more rings may be in the form of a pendant or condensation. Examples include, but are not limited to, phenyl, naphthyl, phenanthryl, and anthryl.

[0045] In the present invention, "heteroaryl" means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. In this case, one or more carbon atoms in the ring, preferably 1 to 3 carbon atoms, are substituted with heteroatoms such as N, O, S, or Se. Two or more rings may be in the form of a pendant or condensation, and furthermore, a condensation with an aryl group. Examples include, but are not limited to, six-membered monocyclic rings such as pyridinyl, pyrazinyl, pyrimidinyl, pyridadinyl, and triazinyl; polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl; and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, and 2-pyrimidinyl.

[0046] In the present invention, "alkyloxy" refers to a monovalent substituent represented by R'O-, where R' means an alkyl group having 1 to 40 carbon atoms. Such alkyloxys may have a linear, branched, or cyclic structure. Examples include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, and pentoxy.

[0047] In the present invention, "aryloxy" refers to a monovalent substituent represented by RO-, where R means an aryl molecule having 5 to 40 carbon atoms. Examples include, but are not limited to, phenyloxy, naphthyloxy, and diphenyloxy.

[0048] In this invention, "alkylsilyl" means a silyl substituted with an alkyl group having 1 to 40 carbon atoms, and includes not only mono-silyls but also di- and tri-alkylsilyls. Furthermore, "arylsilyl" means a silyl substituted with an aryl group having 5 to 60 carbon atoms, and includes not only mono-silyls but also polyarylsilyls such as di- and tri-arylsilyls.

[0049] In the present invention, "alkylboron" means boron substituted with alkyl groups having 1 to 40 carbon atoms, and "arylboron" means boron substituted with aryl groups having 6 to 60 carbon atoms.

[0050] In the present invention, "alkylphosphinyl group" means a phosphine group substituted with an alkyl group having 1 to 40 carbon atoms, and includes not only mono-alkylphosphinyl groups but also di-alkylphosphinyl groups. Furthermore, in the present invention, "arylphosphinyl group" means a phosphine group substituted with a monoaryl or diaryl group having 6 to 60 carbon atoms, and includes not only mono-alkylphosphinyl groups but also di-arylphosphinyl groups.

[0051] In this invention, "arylamine" means an amine substituted with an aryl group having 6 to 60 carbon atoms, and includes not only mono-arylamines but also di-arylamines.

[0052] In the present invention, "heteroarylamine" means an amine substituted with a heteroaryl group having 5 to 60 nuclear atoms, and includes not only mono-heteroarylamines but also di-heteroarylamines.

[0053] In the present invention, (aryl)(heteroaryl)amine means an amine substituted with an aryl atom having 6 to 60 carbon atoms and a heteroaryl atom having 5 to 60 nuclear atoms.

[0054] In the present invention, "condensed ring" means a condensed aliphatic ring having 3 to 40 carbon atoms, a condensed aromatic ring having 6 to 60 carbon atoms, a condensed heteroaliphatic ring having 3 to 60 nuclear atoms, a condensed heteroaromatic ring having 5 to 60 nuclear atoms, a spiro ring having 3 to 60 carbon atoms, or a combination thereof.

[0055] The weight ratio of the first and second hosts described above may be between 99:1 and 1:99. Within this range, bipolar characteristics can be more effectively realized, and efficiency and lifespan can be improved simultaneously.

[0056] The composition according to the present invention may further contain a phosphorescent dopant. The phosphorescent dopant is a substance that, when mixed in trace amounts with the first and second hosts, causes luminescence, and is not particularly limited as long as it is known in the art. Examples include, but are not limited to, metal complex compounds containing iridium (Ir) or platinum (Pt). Such dopants can cause luminescence by multiple excitation, which excites them to a triplet or higher state.

[0057] The above-mentioned dopants are classified into red dopants, green dopants, and blue dopants, but any ordinary red dopants, green dopants, and blue dopants known in the field may be used without particular restriction.

[0058] Specifically, examples of red dopants include, but are not limited to, PtOEP (Pt(II) octaethylporfin), Ir(piq)3 (tris(2-phenylisoquinoline)iridium), Btp2Ir(acac) (bis(2-(2'-benzothienyl)-pyridinate-N,C3')iridium (acetylacetonate), or mixtures of two or more of these.

[0059] Examples of green dopants include, but are not limited to, Ir(ppy)3 (tris-(2-phenylpyridine)iridium), Ir(ppy)2(acac) (bis(2-phenylpyridine)(acetylacetonate)iridium(III)), Ir(mppy)3 (tris(2-4-tolyl)phenylpyridine)iridium), or mixtures of two or more of these.

[0060] Furthermore, examples of blue dopants include, but are not limited to, F2Irpic (bis[3,5-difluoro-2-(2-pyridyl)phenyl](picolinato)iridium(III)), (F2ppy)2Ir(tmd), Ir(dfppz)3, or mixtures of two or more of these.

[0061] The dopant content described above is not particularly limited, and for example, it is about 0 to 10% by weight, more specifically about 0.1 to 10% by weight, and more specifically about 1 to 30% by weight, relative to the total weight of the composition.

[0062] <Organic EL element> An organic EL element according to one embodiment of the present invention comprises an anode; a cathode; and one or more organic layers interposed between the anode and the cathode, wherein the one or more organic layers comprise the composition described above. For example, the one or more organic layers comprise a light-emitting layer, and the composition is included as a host material for the light-emitting layer. As a result, the organic EL element of the present invention has low driving voltage, high efficiency, and long life characteristics, as well as excellent phosphorescence characteristics.

[0063] Hereinafter, preferred embodiments of the organic EL element according to the present invention will be described based on the attached drawings. However, the embodiments of the present invention can be implemented with various modifications, and the scope of the present invention is not limited to the embodiments described later. To avoid redundant explanation, the components of the organic EL element composition described above will not be described.

[0064] Figure 1 is a schematic cross-sectional view showing the structure of an organic EL element according to one embodiment of the present invention.

[0065] As shown in Figure 1, an organic EL element according to one embodiment of the present invention includes an anode 100 disposed on a substrate (not shown); a cathode 200 disposed opposite the anode; and one or more organic layers 300 between the anode 100 and the cathode 200, wherein the one or more organic layers 300 include a hole transport region 310, an emissive layer 320, and an electron transport region. In this case, the emissive layer 320 contains the above-described composition as a host. Selectively, the organic EL element according to the present invention may further include a capping layer (not shown) disposed on the cathode 200.

[0066] The following describes in detail each component of the organic EL element according to the present invention.

[0067] (1) Anode In the organic EL element of the present invention, the anode 100 is mainly placed on a substrate and is electrically connected to a driving thin-film transistor, from which a driving current is supplied. Since such an anode 100 is formed of a material with a relatively high work function, it plays the role of injecting holes into the organic material layer 300, i.e., the hole transport region 310 (for example, the hole injection layer 311).

[0068] The material used to form such an anode is not particularly limited, and any commonly known material in the field can be used. Examples include, but are not limited to, metals such as vanadium, chromium, copper, zinc, and gold, and their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al and SnO2:Sb; conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline; and carbon black.

[0069] The method for manufacturing the above-mentioned anode is not particularly limited and can be manufactured by conventional methods in the field. For example, the anode material can be formed by coating it onto a substrate using well-known thin-film formation methods such as sputtering, ion plating, vacuum deposition, or spin coating.

[0070] The above-mentioned substrate is a plate-shaped member that supports an organic EL element, and examples include, but are not limited to, silicon wafers, quartz, glass plates, metal plates, plastic films, and sheets.

[0071] (2) Cathode In the organic EL element of the present invention, the cathode 200 is an electrode positioned opposite the anode, and specifically, it is positioned on the electron transport region 330. Since such a cathode 200 is formed of a material with a relatively low work function, it plays the role of injecting electrons into the adjacent organic layer, i.e., the electron transport region 330 (for example, the electron injection layer 332).

[0072] The material used to form such a cathode is not particularly limited, and any common material known in the art can be used. Examples include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver (Ag), tin, and lead, and their alloys; as well as multilayer materials such as LiF / Al and LiO2 / Al.

[0073] The method for manufacturing the cathode described above is not particularly limited and, like the anode, can be manufactured by conventional methods in the field. For example, the cathode material can be formed by coating one or more organic layers 300, specifically an electron transport region, for example, an electron injection layer 332, with the thin film formation method described above.

[0074] (3)Organic layer In the organic EL element of the present invention, one or more organic layers 300 are arranged between the anode 100 and the cathode 200 and include a hole transport region 310, an emissive layer 320, and an electron transport region 330.

[0075] In one example, as shown in Figure 1, one or more organic layers 300 include a hole injection layer 311, a hole transport layer 312, a light-emitting layer 320, an electron transport layer 331, and an electron injection layer 332, which are sequentially arranged on the anode 100.

[0076] The following describes each organic layer.

[0077] 1) Hole transport region In the organic EL element 100 of the present invention, the hole transport region 310 is a part of the organic material layer 300 arranged on the anode 100, and plays the role of moving holes injected from the anode 100 to the adjacent light-emitting layer 320.

[0078] Such a hole transport region 310 includes one or more selected from the group consisting of a hole injection layer 311 and a hole transport layer 312. In this case, considering the characteristics of the organic EL element, it is preferable to include both the hole injection layer 31 and the hole transport layer 312. As an example, the hole transport region 310 includes a hole injection layer 311 and a hole transport layer 312 sequentially stacked on the anode 100, as shown in Figure 1.

[0079] The materials used to form the hole injection layer 311 and the hole transport layer 312 are not particularly limited, as long as they have a low hole injection barrier and high hole mobility. Any hole injection layer / transport layer material used in the field can be used without restriction. The materials used to form the hole injection layer 311 and the hole transport layer 312 may be the same or different.

[0080] Specifically, the hole injection layer 311 comprises a hole injection material known in the art. Examples of the hole injection material include phthalocyanine compounds such as copper phthalocyanine; DNTPD (N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine), m-MTDATA (4,4',4”-tris(3-methylphenylphenylamino)triphenylamine), TDATA (4,4',4”-tris(N,N-diphenylamino)triphenylamine), 2TNATA (4,4',4”-tris{N,-(2- Examples include, but are not limited to, naphthyl)-N-phenylamino}-triphenylamine), PEDOT / PSS (poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate)), PANI / DBSA (polyaniline / dodecylbenzenesulfonic acid), PANI / CSA (polyaniline / camphorsulfonic acid), PANI / PSS (polyaniline) / poly(4-styrenesulfonate), etc. These may be used individually or in combination of two or more.

[0081] The hole transport 312 described above comprises hole transport materials known in the art. Examples of the hole transport materials include, but are not limited to, carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole; fluorene derivatives; amine derivatives; triphenylamine derivatives such as TPD (N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine) and TCTA (4,4'-4"-tris(N-carbazolyl)triphenylamine); and NPB (N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine) and TAPC (4,4'-cyclohexylidenebis[N,N-bis(4-methylphenyl)benzeneamine]). These may be used individually or in combination of two or more.

[0082] The hole transport region 310 described above can be manufactured by conventional methods in the field. Examples include, but are not limited to, vacuum deposition, spin coating, casting, LB (Langmuir-Blodgett) method, inkjet printing, laser printing, and laser-induced thermal imaging (LITI).

[0083] 2) Light-emitting layer In the organic EL element of the present invention, the light-emitting layer 320 is a part of the organic material layer 300 interposed between the anode 100 and the cathode 200, and specifically, is disposed on the hole transport region 320. As shown in Figure 1, the light-emitting layer 320 may also be disposed on the hole transport layer 312.

[0084] Such a light-emitting layer 320 is a layer in which holes and electrons injected from the anode and cathode, respectively, combine to form excitons, and the color of the light emitted by the organic EL element changes depending on the material used to form the light-emitting layer 320.

[0085] The light-emitting layer 320 according to the present invention comprises a composition containing a first host represented by [Chemical Formula 1] and a second host represented by [Chemical Formula 2]. The composition may further optionally contain a phosphorescent dopant. By including such a composition as the light-emitting layer 320 material, the organic EL element of the present invention can have low driving voltage, high efficiency, and long life characteristics, as well as exhibit excellent phosphorescent characteristics.

[0086] The light-emitting layer 320 according to the present invention may be a red light-emitting layer containing a red phosphorescent material, a green light-emitting layer containing a green phosphorescent material, or a blue light-emitting layer containing a blue phosphorescent material. In one example, it may be a light-emitting layer containing a green phosphorescent material.

[0087] The light-emitting layer 320 may consist of a single layer made of one type of material, a single layer made of multiple different materials, or two or more layers made of different materials. When the light-emitting layer 320 consists of multiple layers, the organic EL element can emit light of various colors. Specifically, the present invention can provide an organic EL element that exhibits mixed colors by having multiple light-emitting layers made of different materials arranged in series. Furthermore, when there are multiple light-emitting layers, the driving voltage of the element increases, but the current value within the organic EL element remains constant, and an organic EL element can be provided in which the luminous efficiency is improved by the number of light-emitting layers.

[0088] Although not shown in the figures, the organic EL element of the present invention may comprise a plurality of light-emitting stacks (not shown) each containing at least one light-emitting layer.

[0089] The multiple light-emitting layers contained in such a light-emitting stack may each emit light of a different color, or they may each emit light of the same color. In other words, the color of emission will change depending on the material that makes up the light-emitting layers. As an example, multiple light-emitting stacks may contain substances that emit blue, green, red, yellow, white, etc., and be formed using phosphorescent or fluorescent materials. In this case, the colors shown by each light-emitting layer may be complementary colors to each other. Alternatively, a combination of colors that emit white may be selected. Each of these light-emitting layers may contain a phosphorescent dopant or a fluorescent dopant corresponding to the selected color.

[0090] Although not shown in the figures, the organic EL element of the present invention may further include a charge generation layer (CGL) (not shown) which is placed between adjacent stacks among a plurality of light-emitting stacks and connects them.

[0091] A charge generation layer (CGL) in an organic light-emitting diode (EL) device comprising multiple light-emitting stacks refers to a layer that separates adjacent light-emitting stacks without directly contacting the two electrodes (e.g., anode and cathode). Such a charge generation layer is positioned between two adjacent light-emitting stacks and acts as a cathode, generating and supplying electrons to one light-emitting stack, while acting as an anode, generating and supplying holes to the other light-emitting stack. Any charge generation layer material known in the art can be used without limitation as such a charge generation layer. Furthermore, the material for the charge generation layer may be doped with a conventional n-type and / or p-type material known in the art.

[0092] The above-mentioned light-emitting layer 320 can be manufactured by conventional methods in the field. Examples include, but are not limited to, vacuum deposition, spin coating, casting, LB method, inkjet printing, laser printing, and laser thermal transfer (LITI). As an example, the light-emitting layer can be formed by co-deposition of a first host represented by [Chemical Formula 1] and a second host represented by [Chemical Formula 2]. In this case, a dopant may also be deposited together.

[0093] 3) Electron transport area In the organic EL element according to the present invention, the electron transport region 330 is an organic layer disposed on the light-emitting layer 320, which moves electrons injected from the cathode 200 to the light-emitting layer 320.

[0094] Such an electron transport region 330 includes one or more selected from the group consisting of an electron transport layer 331 and an electron injection layer 332.

[0095] As an example, the electron transport region 330 includes an electron transport layer 331 and an electron injection layer 332 sequentially stacked on the light-emitting layer 320, as shown in Figure 1.

[0096] In the electron transport region 330 according to the present invention, the electron transport layer 331 can be used without particular limitation as long as it is an electron transport material that is easily injected with electrons and has high electron mobility. Examples of such electron transport materials include, but are not limited to, oxazole compounds, isoxazole compounds, triazole compounds, isothiazole compounds, oxadiazole compounds, thiadiazole compounds, perylene compounds, aluminum complexes (e.g., Alq3 (tris(8-quinolinolato)-aluminum), BAlq, SAlq, Alph3, Almq3), and gallium complexes (e.g., Gaq'2OPiv, Gaq'2OAc, 2(Gaq'2)). These may be used individually or in combination of two or more.

[0097] Furthermore, the electron injection layer 332 can be used without particular limitations as long as it is an electron injection material that is easy to inject electrons into and has high electron mobility. Examples of the electron injection materials include, but are not limited to, lanthanum group metals such as LiF, Li2O, BaO, NaCl, CsF;Yb, etc., or metal halides such as RbCl, RbI, etc. These may be used individually or in mixtures of two or more.

[0098] In the present invention, the electron transport region 330, specifically the electron transport layer 331 and / or electron injection layer 332, may be co-deposited with an n-type dopant so that electrons can be easily injected from the cathode 200. In this case, any alkali metal complex compound known in the art can be used as the n-type dopant without limitation, and examples include alkali metals, alkaline earth metals, or rare earth metals.

[0099] The electron transport region 330 described above can be manufactured by conventional methods in that field. Examples include, but are not limited to, vacuum deposition, spin coating, casting, LB method, inkjet printing, laser printing, and laser thermal transfer (LITI).

[0100] 4) Luminescent auxiliary layer Although not shown in the figures, the organic EL element of the present invention may further include a light-emitting auxiliary layer disposed between the hole transport region 310 and the light-emitting layer 320.

[0101] The luminescence auxiliary layer plays a role in adjusting the thickness of the organic layer 300 by transporting holes from the hole transport region 310 to the luminescence layer 320, or by blocking the movement of electrons and / or excitons. In particular, because the luminescence auxiliary layer has a high LUMO value, it blocks the movement of electrons to the hole transport layer 32, and because it has a high triplet energy, it blocks the diffusion of excitons from the luminescence layer 320 to the hole transport layer 32.

[0102] Such light-emitting auxiliary layers may contain hole transport material and may be manufactured from the same material as the hole transport region. Furthermore, the light-emitting auxiliary layers of red, green, and blue organic light-emitting devices may be manufactured from the same material as each other.

[0103] The luminescence auxiliary layer material is not particularly limited, and examples include carbazole derivatives and arylamine derivatives. Specifically, examples include, but are not limited to, NPD (N,N-dinaphthyl-N,N'-diphenylbenzidine), TPD (N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-benzidine), s-TAD, and MTDATA (4,4',4”-tris(N-3-methylphenyl-Nphenyl-amino)-triphenylamine). These may be used individually or in combination of two or more.

[0104] Furthermore, the light-emitting auxiliary layer may further contain a p-type dopant in addition to the materials described above. In the present invention, any p-type dopant known in the art can be used without particular limitation. In this case, the content of the p-type dopant can be appropriately adjusted within the range known in the art, and may be, for example, about 0.5 to 50 parts by weight per 100 parts by weight of hole transport material.

[0105] The above-mentioned light-emitting auxiliary layer can be formed by methods such as vacuum deposition, spin coating, casting, LB method, inkjet printing, laser printing, and laser thermal transfer (LITI), as is well known in the field, but is not limited to these methods.

[0106] 5) Hole blocking layer Although not shown in the figures, the organic EL element 100 of the present invention may further include a hole blocking layer disposed between the light-emitting layer 320 and the electron transport region 330.

[0107] The hole blocking layer 333 prevents excitons or holes generated in the light-emitting layer 320 from diffusing (moving) to the electron transport layer 331, thereby improving the lifespan of the organic EL element.

[0108] Such hole-blocking layer materials can be used without particular limitations as long as they are substances with ordinary electron transport properties known in the field, for example, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) and BAlq (bis(2-methyl-8-quinolinolate)(4-phenylphenolate)aluminum(III)).

[0109] The hole blocking layer described above can be formed by methods such as vacuum deposition, spin coating, casting, LB, inkjet printing, laser printing, and laser thermal transfer (LITI), as is well known in the field, but is not limited to these methods.

[0110] (4) Capping layer Selectively, the organic EL element 100 of the present invention may further include a capping layer (not shown) disposed on the cathode 200.

[0111] The capping layer described above protects the organic EL element and also helps to efficiently release light emitted from the organic layer to the outside.

[0112] As the capping layer, at least one selected from the group consisting of tris-8-hydroxyquinoline aluminum (Alq3), ZnSe, 2,5-bis(6'-(2',2”-bipyridyl))-1,1-dimethyl-3,4-diphenylsilole, 4'-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl (α-NPD), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), and 1,1'-bis(di-4-tolylaminophenyl)cyclohexane (TAPC) can be used. The material used to form such a capping layer is less expensive than the material used to form other layers of the organic light-emitting element.

[0113] Such a capping layer may be a single layer, but it can also include two or more layers having different refractive indices, so that the refractive index gradually changes as the user passes through the two or more layers.

[0114] The above-mentioned capping layer can be manufactured by various methods, such as vacuum deposition, spin coating, casting, or LB method, according to common practices in the field.

[0115] The organic EL element according to the present invention, as described above, has a structure in which an anode 100, an organic material layer 300, and a cathode 200 are sequentially stacked. If necessary, it may further include an insulating layer (not shown) or an adhesive layer (not shown) disposed between the anode 100 and the organic material layer 300, or between the cathode 200 and the organic material layer 300. Such an organic EL element of the present invention maintains maximum luminous efficiency when voltage and current are applied, while increasing the half-time of the initial brightness (lifetime), thus providing excellent lifetime characteristics.

[0116] The organic EL element of the present invention described above can be manufactured by conventional methods in the field. For example, an organic EL element can be manufactured by vacuum depositing an anode material onto a substrate, and then sequentially vacuum depositing a hole transport region material, an emissive layer material, an electron transport region material, and a cathode material onto the anode. [Examples]

[0117] The present invention will be described in detail below with reference to examples. However, the examples described below are merely illustrative of the present invention, and the present invention is not limited to these examples.

[0118] <Preparation Example 1-1> Synthesis of Cz-D1 [ka] Under a nitrogen atmosphere, 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7 (134.3g, 530.6 mmol), iodobenzene (130.0g, 636.7 mmol), Cu (16.8g, 265.3 mmol), K2CO3 (146.7g, 1,061.3 mmol), and toluene (1000 ml) were mixed and stirred at 110°C for 12 hours.

[0119] After the reaction was complete, the solution was extracted with ethyl acetate, followed by water removal with MgSO4. The solution was then purified by column chromatography (hexane:EA = 5:1 (v / v)) to obtain Cz-D1 (125.7 g, yield 72%). Mass (Theoretical value: 329.25, Measured value: 329 g / mol)

[0120] <Preparation Example 1-2> Synthesis of Cz-D2 [ka] The target compound Cz-D2 (135.5 g, 63% yield) was obtained in the same manner as in Preparation Example 1-1, except that 4-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of the iodobenzene used in Preparation Example 1-1. Mass (Theoretical value: 405.35, Measured value: 405 g / mol)

[0121] <Preparation Example 1-3> Synthesis of Cz-D3 [ka] The target compound Cz-D3 (148.4 g, 69% yield) was obtained in the same manner as in Preparation Example 1-1, except that 3-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of the iodobenzene used in Preparation Example 1-1. Mass (Theoretical value: 405.35, Measured value: 405 g / mol)

[0122] <Preparation Example 1-4> Synthesis of Cz-D4 [ka] The target compound Cz-D4 (96.8 g, 45% yield) was obtained in the same manner as in Preparation Example 1-1, except that 2-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of the iodobenzene used in Preparation Example 1-1. Mass (Theoretical value: 405.35, Measured value: 405 g / mol)

[0123] <Preparation Example 2-1> Synthesis of Cz-D5 [ka] The target compound Cz-D5 (117.1 g, 67% yield) was obtained in the same manner as in Preparation Example 1-1, except that 4-bromo-9H-carbazole-1,2,3,5,6,7,8-d7 (134.3 g, 530.6 mmol) was used instead of 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7 used in Preparation Example 1-1. Mass (Theoretical value: 329.25, Measured value: 329 g / mol)

[0124] <Preparation Example 2-2> Synthesis of Cz-D6 [ka] The target compound, Cz-D6 (139.8 g, 65% yield), was obtained in the same manner as in Preparation Example 2-1, except that 4-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of the iodobenzene used in Preparation Example 2-1. Mass (Theoretical value: 405.35, Measured value: 405 g / mol)

[0125] <Preparation Example 2-3> Synthesis of Cz-D7 [ka] The target compound Cz-D7 (152.7 g, 71% yield) was obtained in the same manner as in Preparation Example 2-1, except that 3-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of the iodobenzene used in Preparation Example 2-1. Mass (Theoretical value: 405.35, Measured value: 405 g / mol)

[0126] <Preparation Example 2-4> Synthesis of Cz-D8 [ka] The target compound Cz-D8 (75.2 g, 35% yield) was obtained in the same manner as in Preparation Example 2-1, except that 2-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of the iodobenzene used in Preparation Example 2-1. Mass (Theoretical value: 405.35, Measured value: 405 g / mol)

[0127] <Preparation Example 3-1> Synthesis of Cz-D9 [ka] The target compound Cz-D9 (134.5 g, 77% yield) was obtained in the same manner as in Preparation Example 1-1, except that 2-bromo-9H-carbazole-1,3,4,5,6,7,8-d7 (134.3 g, 530.6 mmol) was used instead of 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7 used in Preparation Example 1-1. Mass (Theoretical value: 329.25, Measured value: 329 g / mol)

[0128] <Preparation Example 3-2> Synthesis of Cz-D10 [ka] The target compound Cz-D10 (159.1 g, 74% yield) was obtained in the same manner as in Preparation Example 3-1, except that 4-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of the iodobenzene used in Preparation Example 3-1. Mass (Theoretical value: 405.35, Measured value: 405 g / mol)

[0129] <Preparation Example 3-3> Synthesis of Cz-D11 [ka] The target compound Cz-D11 (163.4 g, 76% yield) was obtained in the same manner as in Preparation Example 3-1, except that 3-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of the iodobenzene used in Preparation Example 3-1. Mass (Theoretical value: 405.35, Measured value: 405 g / mol)

[0130] <Preparation Example 3-4> Synthesis of Cz-D12 [ka] The target compound Cz-D12 (92.4 g, 43% yield) was obtained in the same manner as in Preparation Example 3-1, except that 2-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of the iodobenzene used in Preparation Example 3-1. Mass (Theoretical value: 405.35, Measured value: 405 g / mol)

[0131] <Preparation Example 4-1> Synthesis of Cz-D13 [ka] The target compound Cz-D13 (94.3g, yield 54%) was obtained in the same manner as in Preparation Example 1-1, except that 1-bromo-9H-carbazole-2,3,4,5,6,7,8-d7 (134.3g, 530.6 mmol) was used instead of 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7 used in Preparation Example 1-1. Mass (Theoretical value: 329.25, Measured value: 329 g / mol)

[0132] <Preparation Example 4-2> Synthesis of Cz-D14 [ka] The target compound Cz-D14 (122.6 g, 57% yield) was obtained in the same manner as in Preparation Example 4-1, except that 4-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of the iodobenzene used in Preparation Example 4-1. Mass (Theoretical value: 405.35, Measured value: 405 g / mol)

[0133] <Preparation Example 4-3> Synthesis of Cz-D15 [ka] The target compound Cz-D15 (111.8 g, 52% yield) was obtained in the same manner as in Preparation Example 4-1, except that 3-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of the iodobenzene used in Preparation Example 4-1. Mass (Theoretical value: 405.35, Measured value: 405 g / mol)

[0134] <Preparation Example 4-4> Synthesis of Cz-D16 [ka] The target compound, Cz-D16 (68.8 g, 32% yield), was obtained in the same manner as in Preparation Example 4-1, except that 2-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of the iodobenzene used in Preparation Example 4-1. Mass (Theoretical value: 405.35, Measured value: 405 g / mol)

[0135] <Preparation Example 5-1> Synthesis of BCz-D1 <Step 1> Synthesis of 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,2,4,5,6,7,8-d7 [ka] Under a nitrogen atmosphere, Cz-D1 (100.0 g, 303.7 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (84.8 g, 334.1 mmol), Pd(dppf)Cl2 (26.6 g, 30.3 mmol), KOAc (85.8 g, 911.1 mmol), and 1,4-dioxane (1000 ml) were mixed and stirred at 130°C for 12 hours.

[0136] After the reaction was complete, the solution was extracted with ethyl acetate, followed by removal of water with MgSO4. The solution was then purified by column chromatography (hexane:EA=8:1(v / v)) to obtain 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,2,4,5,6,7,8-d7 (96.0g, yield 84%). Mass (Theoretical value: 376.3, Measured value: 376 g / mol)

[0137] <Step 2> Synthesis of BCz-D1 [ka] Under a nitrogen atmosphere, 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,2,4,5,6,7,8-d7 (96.0 g, 255.1 mmol), 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7 (77.5 g, 306.1 mmol), Pd(PPh3)4 (14.7 g, 12.7 mmol), K2CO3 (88.1 g, 637.8 mmol), and 1,4-dioxane / H2O (1000 ml / 250 ml) were mixed and stirred at 120°C for 4 hours.

[0138] After the reaction was complete, the mixture was extracted with methylene chloride, and then filtered with MgSO4. Next, the solvent was removed from the resulting organic layer, and the mixture was purified by column chromatography (hexane:EA=7:1 (v / v)) to obtain BCz-D1 (71.1 g, yield 66%). Mass (Theoretical value: 422.59, Measured value: 422 g / mol)

[0139] <Preparation Example 5-2> Synthesis of BCz-D2 [ka] Except for using Cz-D2 (100g, 246.7 mmol) obtained in Preparation Example 1-2 instead of Cz-D1 used in Preparation Example 5-1, the target compound BCz-D2 (66.4g, final yield 54.0%) was obtained in the same manner as in Preparation Example 5-1. Mass (Theoretical value: 498.69, Measured value: 498 g / mol)

[0140] <Preparation Example 5-3> Synthesis of BCz-D3 [ka] Except for using Cz-D3 (100g, 246.7 mmol) obtained in Preparation Example 1-3 instead of Cz-D1 used in Preparation Example 5-1, the target compound BCz-D3 (59.7g, final yield 48.5%) was obtained in the same manner as in Preparation Example 5-1. Mass (Theoretical value: 498.69, Measured value: 498 g / mol)

[0141] <Preparation Example 5-4> Synthesis of BCz-D4 [ka] Except for using Cz-D4 (100g, 246.7 mmol) obtained in Preparation Example 1-4 instead of Cz-D1 used in Preparation Example 5-1, the target compound BCz-D4 (59.4g, final yield 48.3%) was obtained in the same manner as in Preparation Example 5-1. Mass (Theoretical value: 498.69, Measured value: 498 g / mol)

[0142] [Synthesis Example 1] Synthesis of A-1 [ka] Under a nitrogen atmosphere, BCz-D1 (10.0 g, 23.6 mmol) obtained in Preparation Example 5-1, Cz-D1 (9.3 g, 28.3 mmol) obtained in Preparation Example 1-1, Pd(OAc)2 (1.36 g, 1.18 mmol), P(t-Bu)3 (0.57 ml, 2.36 mmol), NaO(t-Bu) (4.55 g, 47.3 mmol), and toluene (100 ml) were mixed and stirred at 110°C for 5 hours. After the reaction was complete, the toluene was concentrated, the solid salt was filtered, and then purified by recrystallization to obtain the target compound A-1 (13.0 g, yield 82%). Mass (Theoretical value: 670.93, Measured value: 670 g / mol)

[0143] [Synthesis Example 2] Synthesis of A-2 [ka] The target compound A-2 (13.8 g, 78% yield) was obtained in the same manner as in Synthesis Example 1, except that Cz-D2 (10.0 g, 23.6 mmol) obtained in Preparation Example 1-2 was used instead of Cz-D1 used in Synthesis Example 1. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0144] [Synthesis Example 3] Synthesis of A-3 [ka] The target compound A-3 (13.8 g, 75% yield) was obtained in the same manner as in Synthesis Example 1, except that Cz-D3 (10.0 g, 23.6 mmol) obtained in Preparation Example 1-3 was used instead of Cz-D1 used in Synthesis Example 1. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0145] [Synthesis Example 4] Synthesis of A-4 [ka] The target compound A-4 (12.2 g, 69% yield) was obtained in the same manner as in Synthesis Example 1, except that Cz-D4 (10.0 g, 23.6 mmol) obtained in Preparation Example 1-4 was used instead of Cz-D1 used in Synthesis Example 1. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0146] [Synthesis Example 5] Synthesis of A-5 [ka] The target compound A-5 (8.73 g, 55% yield) was obtained in the same manner as in Synthesis Example 1, except that Cz-D5 (9.3 g, 23.6 mmol) obtained in Preparation Example 2-1 was used instead of Cz-D1 used in Synthesis Example 1. Mass (Theoretical value: 670.93, Measured value: 670 g / mol)

[0147] [Synthesis Example 6] Synthesis of A-6 [ka] The target compound A-6 (7.42 g, 42% yield) was obtained in the same manner as in Synthesis Example 1, except that Cz-D6 (10.0 g, 23.6 mmol) obtained in Preparation Example 2-2 was used instead of Cz-D1 used in Synthesis Example 1. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0148] [Synthesis Example 7] Synthesis of A-7

Chem.

[0149] [Synthesis Example 8] Synthesis of A-8

Chem.

[0150] [Synthesis Example 9] Synthesis of A-9

Chem.

[0151] [Synthesis Example 10] Synthesis of A-10 [[ID='44']]

Chem.

[0152] [Synthesis Example 11] Synthesis of A-11 [ka] The target compound A-11 (9.01 g, 51% yield) was obtained in the same manner as in Synthesis Example 1, except that Cz-D11 (10.0 g, 23.6 mmol) obtained in Preparation Example 3-3 was used instead of Cz-D1 used in Synthesis Example 1. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0153] [Synthesis Example 12] Synthesis of A-12 [ka] The target compound A-12 (9.19 g, 52% yield) was obtained in the same manner as in Synthesis Example 1, except that Cz-D12 (10.0 g, 23.6 mmol) obtained in Preparation Example 3-4 was used instead of Cz-D1 used in Synthesis Example 1. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0154] [Synthesis Example 13] Synthesis of A-13 [ka] The target compound A-13 (9.52 g, 60% yield) was obtained in the same manner as in Synthesis Example 1, except that Cz-D13 (9.3 g, 23.6 mmol) obtained in Preparation Example 4-1 was used instead of Cz-D1 used in Synthesis Example 1. Mass (Theoretical value: 670.93, Measured value: 670 g / mol)

[0155] [Synthesis Example 14] Synthesis of A-14 [ka] Compound A-14 (10.78 g, yield 61%) was obtained in the same manner as in Synthesis Example 1, except that Cz-D14 (10.0 g, 23.6 mmol) obtained in Preparation Example 4-2 was used instead of Cz-D1 used in Synthesis Example 1. Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0156] [Synthesis Example 15] Synthesis of A-15

Chemical Structure

[0157] [Synthesis Example 16] Synthesis of A-16

Chemical Structure

[0158] [Synthesis Example 17] Synthesis of B-1

Chemical Structure

[0159] [Synthesis Example 18] Synthesis of B-2 [ka] The target compound B-2 (8.5 g, 48% yield) was obtained in the same manner as in Synthesis Example 17, except that Cz-D5 (7.9 g, 24.1 mmol) obtained in Preparation Example 2-1 was used instead of Cz-D1 used in Synthesis Example 17. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0160] [Synthesis Example 19] Synthesis of B-3 [ka] The target compound B-3 (11.1 g, 63% yield) was obtained in the same manner as in Synthesis Example 17, except that Cz-D9 (7.9 g, 24.1 mmol) obtained in Preparation Example 3-1 was used instead of Cz-D1 used in Synthesis Example 17. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0161] [Synthesis Example 20] Synthesis of B-4 [ka] The target compound B-4 (7.42 g, 42% yield) was obtained in the same manner as in Synthesis Example 17, except that Cz-D13 (7.9 g, 24.1 mmol) obtained in Preparation Example 4-1 was used instead of Cz-D1 used in Synthesis Example 17. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0162] [Synthesis Example 21] Synthesis of C-1 [ka] Under a nitrogen atmosphere, BCz-D3 (10.0 g, 20.1 mmol) obtained in Preparation Example 5-3, Cz-D1 (7.9 g, 24.1 mmol) obtained in Preparation Example 1-1, Pd(OAc)2 (1.15 g, 1.0 mmol), P(t-Bu)3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol), and toluene (100 ml) were mixed and stirred at 110°C for 5 hours. After the reaction was complete, the toluene was concentrated, the solid salt was filtered, and then purified by recrystallization to obtain the target compound C-1 (9.4 g, yield 63%). Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0163] [Synthesis Example 22] Synthesis of C-2 [ka] The target compound C-2 (7.78 g, 44% yield) was obtained in the same manner as in Synthesis Example 21, except that Cz-D5 (7.9 g, 24.1 mmol) obtained in Preparation Example 2-1 was used instead of Cz-D1 used in Synthesis Example 21. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0164] [Synthesis Example 23] Synthesis of C-3 [ka] The target compound C-3 (11.67 g, 66% yield) was obtained in the same manner as in Synthesis Example 21, except that Cz-D9 (7.9 g, 24.1 mmol) obtained in Preparation Example 3-1 was used instead of Cz-D1 used in Synthesis Example 21. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0165] [Synthesis Example 24] Synthesis of C-4 [ka] The target compound C-4 (6.89 g, 39% yield) was obtained in the same manner as in Synthesis Example 21, except that Cz-D13 (7.9 g, 24.1 mmol) obtained in Preparation Example 4-1 was used instead of Cz-D1 used in Synthesis Example 21. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0166] [Synthesis Example 25] Synthesis of D-1 [ka] Under a nitrogen atmosphere, BCz-D4 (10.0 g, 20.1 mmol) obtained in Preparation Example 5-4, Cz-D1 (7.9 g, 24.1 mmol) obtained in Preparation Example 1-1, Pd(OAc)2 (1.15 g, 1.0 mmol), P(t-Bu)3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol), and toluene (100 ml) were mixed and stirred at 110°C for 5 hours. After the reaction was complete, the toluene was concentrated, the solid salt was filtered, and then purified by recrystallization to obtain the target compound D-1 (8.1 g, yield 54%). Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0167] [Synthesis Example 26] Synthesis of D-2 [ka] The target compound D-2 (7.24 g, 41% yield) was obtained in the same manner as in Synthesis Example 25, except that Cz-D5 (7.9 g, 24.1 mmol) obtained in Preparation Example 2-1 was used instead of Cz-D1 used in Synthesis Example 25. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0168] [Synthesis Example 27] Synthesis of D-3 [ka] The target compound D-3 (8.41 g, 51% yield) was obtained in the same manner as in Synthesis Example 25, except that Cz-D9 (7.9 g, 24.1 mmol) obtained in Preparation Example 3-1 was used instead of Cz-D1 used in Synthesis Example 25. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0169] [Synthesis Example 28] Synthesis of D-4 [ka] The target compound D-4 (5.47 g, 31% yield) was obtained in the same manner as in Synthesis Example 25, except that Cz-D13 (7.9 g, 24.1 mmol) obtained in Preparation Example 4-1 was used instead of Cz-D1 used in Synthesis Example 25. Mass (Theoretical value: 747.02, Measured value: 747 g / mol)

[0170] [Preparation Example 6] Synthesis of DBF-1 <Step 1> Synthesis of 4-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan [ka] Under a nitrogen atmosphere, 4,4,5,5-tetramethyl-2-(6-phenyldibenzo[b,d]furan-4-yl)-1,3,2-dioxaborolane (100.0 g, 270.0 mmol), 1-bromo-3-chlorobenzene (62.0 g, 324.1 mmol), Pd(PPh3)4 (15.6 g, 13.5 mmol), K2CO3 (93.3 g, 675.2 mmol), and 1,4-dioxane / H2O (1000 ml / 250 ml) were mixed and stirred at 120°C for 4 hours.

[0171] After the reaction was complete, the mixture was extracted with methylene chloride and filtered with MgSO4. Next, the solvent was removed from the resulting organic layer, and the mixture was purified by column chromatography (hexane:DCM = 9:1 (v / v)) to obtain 4-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan (48.9g, yield 51%). Mass (Theoretical value: 354.83, Measured value: 354 g / mol)

[0172] <Step 2> Synthesis of DBF-1 [ka] Under a nitrogen atmosphere, the 4-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan obtained in Step 1 above (48.9 g, 137.7 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (38.5 g, 151.5 mmol), Pd(dppf)Cl2 (12.1 g, 13.8 mmol), KOAc (38.9 g, 413.2 mmol), and 1,4-dioxane (1000 ml) were mixed and stirred at 130°C for 12 hours.

[0173] After the reaction was complete, the solution was extracted with ethyl acetate, followed by removal of water with MgSO4. The solution was then purified by column chromatography (hexane:DCM = 4:1 (v / v)) to obtain DBF-1 (26.4 g, yield 43%). Mass (Theoretical value: 446.35, Measured value: 446 g / mol)

[0174] [Preparation Example 7] Synthesis of DBF-2 <Step 1> Synthesis of 4-(4-chlorophenyl)-6-phenyldibenzo[b,d]furan [ka] Under a nitrogen atmosphere, 4,4,5,5-tetramethyl-2-(6-phenyldibenzo[b,d]furan-4-yl)-1,3,2-dioxaborolane (100.0 g, 270.0 mmol), 1-bromo-4-chlorobenzene (62.0 g, 324.1 mmol), Pd(PPh3)4 (15.6 g, 13.5 mmol), K2CO3 (93.3 g, 675.2 mmol), and 1,4-dioxane / H2O (1000 ml / 250 ml) were mixed and stirred at 120°C for 4 hours.

[0175] After the reaction was complete, the mixture was extracted with methylene chloride and filtered with MgSO4. Next, the solvent was removed from the resulting organic layer, and the mixture was purified by column chromatography (hexane:DCM = 9:1 (v / v)) to obtain 4-(4-chlorophenyl)-6-phenyldibenzo[b,d]furan (60.4 g, yield 63%). Mass (Theoretical value: 354.83, Measured value: 354 g / mol)

[0176] <Step 2> Synthesis of DBF-2 [ka] Under a nitrogen atmosphere, the 4-(4-chlorophenyl)-6-phenyldibenzo[b,d]furan (60.4g, 170.2 mmol) obtained in Step 1 above, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (47.5g, 187.2 mmol), Pd(dppf)Cl2 (14.9g, 17.0 mmol), KOAc (48.1g, 510.4 mmol), and 1,4-dioxane (1000 ml) were mixed and stirred at 130°C for 12 hours.

[0177] After the reaction was complete, the solution was extracted with ethyl acetate, followed by removal of water with MgSO4. The solution was then purified by column chromatography (hexane:DCM = 4:1 (v / v)) to obtain DBF-2 (36.5 g, yield 48%). Mass (Theoretical value: 446.35, Measured value: 446 g / mol)

[0178] [Preparation Example 8] Synthesis of DBF-3 <Step 1> Synthesis of 3-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan [ka] Under a nitrogen atmosphere, 4,4,5,5-tetramethyl-2-(6-phenyldibenzo[b,d]furan-3-yl)-1,3,2-dioxaborolane (100.0 g, 270.0 mmol), 1-bromo-3-chlorobenzene (62.0 g, 324.1 mmol), Pd(PPh3)4 (15.6 g, 13.5 mmol), K2CO3 (93.3 g, 675.2 mmol), and 1,4-dioxane / H2O (1000 ml / 250 ml) were mixed and stirred at 120°C for 4 hours.

[0179] After the reaction was complete, the mixture was extracted with methylene chloride and filtered with MgSO4. Next, the solvent was removed from the resulting organic layer, and the mixture was purified by column chromatography (hexane:DCM = 9:1 (v / v)) to obtain 3-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan (68.0 g, yield 71%). Mass (Theoretical value: 354.83, Measured value: 354 g / mol)

[0180] <Step 2> Synthesis of DBF-3 [ka] Under a nitrogen atmosphere, the 3-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan (68.0 g, 191.8 mmol) obtained in Step 1 above, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (53.6 g, 210.9 mmol), Pd(dppf)Cl2 (16.8 g, 19.2 mmol), KOAc (54.2 g, 575.3 mmol), and 1,4-dioxane (1000 ml) were mixed and stirred at 130°C for 12 hours.

[0181] After the reaction was complete, the solution was extracted with ethyl acetate, followed by water removal with MgSO4. The solution was then purified by column chromatography (hexane:DCM = 4:1 (v / v)) to obtain DBF-3 (54.8 g, yield 64%). Mass (Theoretical value: 446.35, Measured value: 446 g / mol)

[0182] [Preparation Example 9] Synthesis of DBF-4 <Step 1> Synthesis of 1-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan [ka] Under a nitrogen atmosphere, 4,4,5,5-tetramethyl-2-(6-phenyldibenzo[b,d]furan-1-yl)-1,3,2-dioxaborolane (100.0 g, 270.0 mmol), 1-bromo-3-chlorobenzene (62.0 g, 324.1 mmol), Pd(PPh3)4 (15.6 g, 13.5 mmol), K2CO3 (93.3 g, 675.2 mmol), and 1,4-dioxane / H2O (1000 ml / 250 ml) were mixed and stirred at 120°C for 4 hours.

[0183] After the reaction was complete, the mixture was extracted with methylene chloride and filtered with MgSO4. Next, the solvent was removed from the resulting organic layer, and the mixture was purified by column chromatography (hexane:DCM = 9:1 (v / v)) to obtain 1-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan (62.3g, yield 65%). Mass (Theoretical value: 354.83, Measured value: 354 g / mol)

[0184] <Step 2> Synthesis of DBF-4 [ka] Under a nitrogen atmosphere, the 1-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan (62.3g, 175.6 mmol) obtained in Step 1 above, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (49.0g, 193.1 mmol), Pd(dppf)Cl2 (15.4g, 17.6 mmol), KOAc (49.6g, 526.7 mmol), and 1,4-dioxane (1000 ml) were mixed and stirred at 130°C for 12 hours.

[0185] After the reaction was complete, the solution was extracted with ethyl acetate, followed by water removal with MgSO4. The solution was then purified by column chromatography (hexane:DCM = 4:1 (v / v)) to obtain DBF-4 (45.4 g, yield 58%). Mass (Theoretical value: 446.35, Measured value: 446 g / mol)

[0186] [Preparation Example 10] Synthesis of DBF-5 <Step 1> Synthesis of 1-(3-chlorophenyl)-9-phenyldibenzo[b,d]furan [ka] Under a nitrogen atmosphere, 4,4,5,5-tetramethyl-2-(9-phenyldibenzo[b,d]furan-1-yl)-1,3,2-dioxaborolane (100.0 g, 270.0 mmol), 1-bromo-3-chlorobenzene (62.0 g, 324.1 mmol), Pd(PPh3)4 (15.6 g, 13.5 mmol), K2CO3 (93.3 g, 675.2 mmol), and 1,4-dioxane / H2O (1000 ml / 250 ml) were mixed and stirred at 120°C for 4 hours.

[0187] After the reaction was complete, the mixture was extracted with methylene chloride and filtered with MgSO4. Next, the solvent was removed from the resulting organic layer, and the mixture was purified by column chromatography (hexane:DCM = 9:1 (v / v)) to obtain 1-(3-chlorophenyl)-9-phenyldibenzo[b,d]furan (68.0 g, yield 71%). Mass (Theoretical value: 354.83, Measured value: 354 g / mol)

[0188] <Step 2> Synthesis of DBF-5 [ka] Under a nitrogen atmosphere, the 1-(3-chlorophenyl)-9-phenyldibenzo[b,d]furan (68.0 g, 191.8 mmol) obtained in Step 1 above, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (53.6 g, 210.9 mmol), Pd(dppf)Cl2 (16.8 g, 19.2 mmol), KOAc (54.2 g, 575.3 mmol), and 1,4-dioxane (1000 ml) were mixed and stirred at 130°C for 12 hours.

[0189] After the reaction was complete, the solution was extracted with ethyl acetate, followed by water removal with MgSO4. The solution was then purified by column chromatography (hexane:DCM = 4:1 (v / v)) to obtain DBF-5 (41.9 g, yield 49%). Mass (Theoretical value: 446.35, Measured value: 446 g / mol)

[0190] [Synthesis Example 29] Synthesis of E-1 [ka] Under a nitrogen atmosphere, DBF-1 (10.0 g, 22.4 mmol) obtained in Preparation Example 6, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (9.6 g, 26.9 mmol), Pd(PPh3)4 (1.3 g, 1.1 mmol), K2CO3 (7.7 g, 56.0 mmol), and 1,4-dioxane / H2O (1000 ml / 250 ml) were mixed and stirred at 120°C for 4 hours.

[0191] After the reaction was complete, the mixture was extracted with methylene chloride and filtered with MgSO4. Next, the solvent was removed from the resulting organic layer, and the mixture was purified by column chromatography (hexane:EA=4:1 (v / v)) to obtain the target compound E-1 (11.8 g, yield 82%). Mass (Theoretical value: 641.73, Measured value: 641 g / mol)

[0192] [Synthesis Example 30] Synthesis of E-2 [ka] The target compound E-2 (11.9 g, 74% yield) was obtained in the same manner as in Synthesis Example 29, except that 2-(3-bromophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (12.9 g, 26.9 mmol) was used instead of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine used in Synthesis Example 29. Mass (Theoretical value: 717.83, Measured value: 717 g / mol)

[0193] [Synthesis Example 31] Synthesis of E-3 [ka] The target compound E-3 (11.4 g, yield 71%) was obtained in the same manner as in Synthesis Example 29, except that 2-(3-bromophenyl)-4-(dibenzo[b,d]furan-4-yl)-6-phenyl-1,3,5-triazine (12.9 g, 26.9 mmol) was used instead of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine used in Synthesis Example 29. Mass (Theoretical value: 717.83, Measured value: 717 g / mol)

[0194] [Synthesis Example 32] Synthesis of E-4 [ka] The target compound E-4 (12.7 g, 79% yield) was obtained in the same manner as in Synthesis Example 29, except that 2-(4-bromophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (12.9 g, 26.9 mmol) was used instead of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine used in Synthesis Example 29. Mass (Theoretical value: 717.83, Measured value: 717 g / mol)

[0195] [Synthesis Example 33] Synthesis of E-5 [ka] The target compound E-5 (9.8 g, 61% yield) was obtained in the same manner as in Synthesis Example 29, except that DBF-4 (10.0 g, 22.4 mmol) obtained in Preparation Example 9 was used instead of DBF-1 (10.0 g, 22.4 mmol) used in Synthesis Example 29, and 2-(3-bromophenyl)-4(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (12.9 g, 26.9 mmol) was used instead of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine. Mass (Theoretical value: 717.83, Measured value: 717 g / mol)

[0196] [Synthesis Example 34] Synthesis of E-6 [ka] The target compound E-6 (9.6 g, 54% yield) was obtained in the same manner as in Synthesis Example 29, except that 2-([1,1':3',1”-terphenyl]-5'-yl)-4-chloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine (13.7 g, 26.9 mmol) was used instead of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine used in Synthesis Example 29. Mass (Theoretical value: 793.93, Measured value: 793 g / mol)

[0197] [Synthesis Example 35] Synthesis of E-7 [ka] The target compound E-7 (9.8 g, 62% yield) was obtained in the same manner as in Synthesis Example 29, except that DBF-4 (10.0 g, 22.4 mmol) obtained in Preparation Example 9 was used instead of DBF-1 (10.0 g, 22.4 mmol) used in Synthesis Example 29, and 2-([1,1'-biphenyl]-4-yl)-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine (12.5 g, 26.9 mmol) was used instead of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine. Mass (Theoretical value: 703.85, Measured value: 703 g / mol)

[0198] [Synthesis Example 36] Synthesis of E-8 [ka] The target compound E-8 (10.8 g, 67% yield) was obtained in the same manner as in Synthesis Example 29, except that DBF-3 (10.0 g, 22.4 mmol) obtained in Preparation Example 8 was used instead of DBF-1 (10.0 g, 22.4 mmol) used in Synthesis Example 29, and 2-(3-bromophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (12.9 g, 26.9 mmol) was used instead of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine. Mass (Theoretical value: 717.83, Measured value: 717 g / mol)

[0199] [Synthesis Example 37] Synthesis of E-9 [ka] The target compound E-9 (11.4 g, 72% yield) was obtained in the same manner as in Synthesis Example 29, except that DBF-3 (10.0 g, 22.4 mmol) obtained in Preparation Example 8 was used instead of DBF-1 (10.0 g, 22.4 mmol) used in Synthesis Example 29, and 2-([1,1'-biphenyl]-4-yl)-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine (12.5 g, 26.9 mmol) was used instead of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine. Mass (Theoretical value: 703.85, Measured value: 703 g / mol)

[0200] [Synthesis Example 38] Synthesis of E-10 [ka] Except for using DBF-5 (10.0 g, 22.4 mmol) obtained in Preparation Example 10 instead of DBF-1 (10.0 g, 22.4 mmol) used in Synthesis Example 29, and using 2-([1,1'-biphenyl]-3-yl)-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine (12.5 g, 26.9 mmol) instead of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine, the target compound E-10 (10.4 g, yield 66%) was obtained in the same manner as in Synthesis Example 29. Mass (Theoretical value: 703.85, Measured value: 703 g / mol)

[0201] [Preparation Example 11] Synthesis of DBF-6 <Step 1> Synthesis of 4-(3'-chloro-[1,1'-biphenyl]-3-yl-2,2',4,4',5,5',6,6'-d8)-6-(phenyl-d5)dibenzo[b,d]furan-1,2,3,7,8,9-d6 [ka] Under a nitrogen atmosphere, 4,4,5,5-tetramethyl-2-(6-(phenyl-d5)dibenzo[b,d]furan-4-yl-1,2,3,7,8,9-d6)-1,3,2-dioxaborolane (100.0 g, 262.2 mmol), 3-bromo-3'-chloro-1,1'-biphenyl-2,2',4,4',5,5',6,6'-d8 (86.7 g, 314.7 mmol), Pd(PPh3)4 (15.2 g, 13.1 mmol), K2CO3 (90.6 g, 655.6 mmol), and 1,4-dioxane / H2O (1000 ml / 250 ml) were mixed and stirred at 120°C for 4 hours.

[0202] After the reaction was complete, the mixture was extracted with methylene chloride and filtered with MgSO4. Next, the solvent was removed from the resulting organic layer, and the mixture was purified by column chromatography (hexane:DCM = 9:1 (v / v)) to obtain 4-(3'-chloro-[1,1'-biphenyl]-3-yl-2,2',4,4',5,5',6,6'-d8)-6-(phenyl-d5)dibenzo[b,d]furan-1,2,3,7,8,9-d6 (83.8g, yield 71%). Mass (Theoretical value: 450.05, Measured value: 450 g / mol)

[0203] <Step 2> Synthesis of DBF-6 [ka] Under a nitrogen atmosphere, 4-(3'-chloro-[1,1'-biphenyl]-3-yl-2,2',4,4',5,5',6,6'-d8)-6-(phenyl-d5)dibenzo[b,d]furan-1,2,3,7,8,9-d6 (83.8g, 186.2mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-(1,3,2-dioxaborolane) (52.0g, 204.8mmol), Pd(dppf)Cl2 (16.3g, 18.6mmol), KOAc (52.6g, 558.6mmol), and 1,4-dioxane (1000ml) were mixed and stirred at 130°C for 12 hours.

[0204] After the reaction was complete, the product was extracted with ethyl acetate, then water was removed with MgSO4, and the product was purified by column chromatography (hexane:DCM = 4:1 (v / v)) to obtain DBF-6 (64.5 g, yield 64%). Mass (Theoretical value: 541.57, Measured value: 541 g / mol)

[0205] [Synthesis Example 39] Synthesis of E-11 [ka] Under a nitrogen atmosphere, DBF-6 (10.0 g, 18.5 mmol) obtained in Preparation Example 11, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (7.9 g, 22.2 mmol), Pd(PPh3)4 (1.1 g, 0.9 mmol), K2CO3 (6.4 g, 46.2 mmol), and 1,4-dioxane / H2O (1000 ml / 250 ml) were mixed and stirred at 120°C for 4 hours.

[0206] After the reaction was complete, the mixture was extracted with methylene chloride and filtered with MgSO4. Next, the solvent was removed from the resulting organic layer, and the mixture was purified by column chromatography (hexane:EA=4:1(v / v)) to obtain the target compound, E-11 (9.9g, yield 73%). Mass (Theoretical value: 736.94, Measured value: 736 g / mol)

[0207] [Synthesis Example 40] Synthesis of E-12 [ka] The target compound E-12 (10.0 g, 75% yield) was obtained in the same manner as in Synthesis Example 39, except that 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (7.6 g, 22.2 mmol) was used instead of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine. Mass (Theoretical value: 722.96, Measured value: 722 g / mol)

[0208] [Synthesis Example 41] Synthesis of E-13 [ka] The target compound E-13 (9.3 g, 77% yield) was obtained in the same manner as in Synthesis Example 39, except that 2-chloro-4,6-bis(phenyl-d5)-1,3,5-triazine (6.2 g, 22.2 mmol) was used instead of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine. Mass (Theoretical value: 656.92, Measured value: 656 g / mol)

[0209] [Example 1] Fabrication of a green organic EL element Compound A-1 synthesized in Synthesis Example 1 and compound E-1 synthesized in Synthesis Example 29 were purified to high purity by conventional sublimation methods, and then green organic EL elements were fabricated according to the following procedure.

[0210] First, a glass substrate coated with a thin film of ITO (Indium Tin Oxide) to a thickness of 1500 Å was cleaned using distilled water ultrasonic cleaning. After cleaning with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, and after drying, the substrate was transferred to a UV ozone cleaner (Power sonic 405, manufactured by Fascintec). The substrate was then cleaned using UV light for 5 minutes, and finally transferred to a vacuum deposition machine.

[0211] An organic EL element was fabricated by stacking the following layers on the prepared ITO transparent electrode: 98 wt% HT + 2 wt% PA (100 Å) / HT (1200 Å) / HA (300 Å) / 60 wt% compound A-1 + 30 wt% compound E-1 + 10 wt% Ir(ppy)3 (400 Å) / EA (50 Å) / ET + LiQ (300 Å, 1:1 molar ratio) / LiF (10 Å) / Al (1000 Å).

[0212] The structures of HT, PA, HA, EA, ET, and Ir(ppy)3 used at this time are as follows. [ka]

[0213] [Examples 2-292] Fabrication of Green Organic EL Devices A green organic EL element was fabricated in the same manner as in Example 1, except that, when forming the light-emitting layer in Example 1, compounds A-1 to D-4 listed in Table 1 were used instead of compound A-1 used as host 1 among the light-emitting host materials, and compounds E-2 to E-13 listed in Table 1 were used instead of compound E-1 used as host 2.

[0214] [Comparative Examples 1-12] Fabrication of Green Organic EL Devices A green organic EL element was fabricated in the same manner as in Example 1, except that, when forming the light-emitting layer in the Example, compounds HT-1 to HT-4 were used instead of compound A-1 used as host 1 among the light-emitting host materials, and compounds ET-1 to ET-7 were used instead of compound E-1 used as host 2.

[0215] The structures of compounds HT-1 to HT-4 and ET-1 to ET-7 used at this time are as follows. [ka]

[0216] [Evaluation Example 1] For the green organic EL elements fabricated in Examples 1-292 and Comparative Examples 1-12, the current density was 10 mA / cm². 2 The drive voltage, current efficiency, luminescence peak, and lifetime were measured, and the results are shown in Table 1 below.

[0217] [Table 1] JPEG0007897340000097.jpg240170JPEG0007897340000098.jpg243170JPEG0007897340000099.jpg241170 JPEG0007897340000100.jpg241170JPEG0007897340000101.jpg241170JPEG0007897340000102.jpg229170

[0218] As shown in Table 1 above, the green organic EL elements obtained in Examples 1 to 292, which include the first host (P-type host) compound represented by [Chemical Formula 1] (A-1 to D-4) and the second host (N-type host) compound represented by [Chemical Formula 2] (E-1 to E-13) as the host material for the light-emitting layer, were found to have improved current efficiency, driving voltage, and lifetime characteristics compared to the green organic EL elements obtained in Comparative Examples 1 to 12, which used both the conventional host materials HT-1 to HT-4 and ET-1 to ET-7.

[0219] Furthermore, it was found that the green organic EL devices obtained in Examples 281 to 292, which included compounds (E-11 to E-13) in which deuterium was substituted as the second host (N-type host), exhibited superior current efficiency, drive voltage, and lifetime characteristics compared to the organic EL devices obtained in Examples 1 to 280, which included compounds (E-1 to E-10) in which deuterium was not substituted as the second host (N-type host). This was confirmed to be because the substitution of deuterium in the N-type host, which is the electronically property material within the device, applies CD bonds, which have a higher bond dissociation energy than CH bonds, thereby increasing the stability of the single molecule itself. In other words, under the same structure, compounds with deuterium substitution (e.g., E-11 to E-13) were able to generate relatively more excitons than compounds without deuterium substitution (e.g., E-1 to E-10), and thermal denaturation due to exciton generation was reduced.

Claims

1. A composition for an organic EL element, comprising a first host represented by the following [Chemical Formula 1] and a second host represented by the following [Chemical Formula 2], wherein the number of deuterium (D) atoms contained in the first host is at least 13. 【Chemistry 1】 【Chemistry 2】 (In the formula, D is deuterium, a, d, f, and h are integers between 0 and 3. b, c, e, g, and i are integers from 0 to 4, j and k are integers from 0 to 5, n1 is an integer between 1 and 5. n2 is an integer of 0 or 1. X １ is O, S, Se, N(Ar ３ ), C (Ar ４ ) (Ar ５ ), and Si(Ar ６ ) (Ar ７ Selected from the group consisting of, Y １ and Y ２ are the same as or different from each other and are each independently N or C(Ar ８ ), and at this time, Y １ and Y ２ at least one of which is N, Ar １ ~Ar ８ and R １ ~R ５ These are either identical or different from each other, and each independently comprises hydrogen, deuterium (D), halogen group, cyano group, nitro group, amino group, and C. １ ~C ４０ alkyl group, C ２ ~C ４０ The alkenyl group, C ２ ~C ４０ The alkynyl group, C ３ ~C ４０ Cycloalkyl groups, heterocycloalkyl groups with 3 to 40 nuclear atoms, C ６ ~C ６０ aryl group, heteroaryl group with 5 to 60 nuclear atoms, C １ ~C ４０ The alkyloxy group, C ６ ~C ６０ The aryloxy group, C １ ~C ４０ alkylsilyl group, C ６ ~C ６０ The arylsilyl group, C １ ~C ４０ alkylboron group, C ６ ~C ６０ The arylboron group, phosphine oxide group, C １ ~C ４０ The alkylphosphine oxide group, C ６ ~C ６０ The arylphosphine group, C ６ ~C ６０ The arylphosphine oxide group and C ６ ~C ６０ Selected from the group consisting of arylamine groups, or these may form fused rings with adjacent groups. The above Ar １ ~Ar ８ and R １ ~R ５ The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkylboron group, arylboron group, alkylphosphine oxide group, arylphosphine group, arylphosphine oxide group, arylamine group, and condensed ring are each independently deuterium, halogen, cyano group, nitro group, C ２ ~C ４０ The alkenyl group, C ２ ~C ４０ The alkynyl group, C ３ ~C ４０ Cycloalkyl groups, heterocycloalkyl groups with 3 to 40 nuclear atoms, C １ ~C ４０ alkyl group, C ６ ~C ６０ aryl group, heteroaryl group with 5 to 60 nuclear atoms, C １ ~C ４０ The alkyloxy group, C ６ ~C ６０ The aryloxy group, C １ ~C ４０ alkylsilyl group, C ６ ~C ６０ The arylsilyl group, C １ ~C ４０ alkylboron group, C ６ ~C ６０ The arylboron group, C ６ ~C ６０ The arylphosphine group, C ６ ~C ６０ The arylphosphine oxide group and C ６ ~C ６０ The molecule is substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, and if there are multiple substituents, they may be identical or different from one another.

2. The above Ar １ and Ar ２ The organic EL element composition according to claim 1, wherein the substituents are identical or different from each other and are independently selected from the group consisting of the substituents S1 to S4 described below. 【Transformation 3】

3. The organic EL element composition according to claim 1, wherein the first host represented by the above [Chemical Formula 1] is a compound represented by the following [Chemical Formula 3]. 【Chemistry 4】 (In the formula, a, b, c, d, e, and f are as defined in claim 1, m1 and m2 are either 0 or 1, respectively.

4. The organic EL element composition according to claim 1, wherein the first host represented by the above [Chemical Formula 1] is a compound represented by the following [Chemical Formula 4]. 【Transformation 5】 (In the formula, a, b, c, d, e, and f are as defined in claim 1, m1 and m2 are either 0 or 1, respectively.

5. The organic EL element composition according to claim 1, wherein the first host represented by the above [Chemical Formula 1] is a compound represented by the following [Chemical Formula 5]. 【Transformation 6】 (In the formula, a, b, c, d, e, and f are as defined in claim 1, m1 and m2 are either 0 or 1, respectively.

6. The organic EL element composition according to claim 1, wherein the first host represented by the above [Chemical Formula 1] is a compound selected from the group consisting of the following compounds A-1 to D-4. 【Transformation 7】 【Transformation 8】

7. In the second host represented by the above [Chemical Formula 2], 【Chemistry 9】 The organic EL element composition according to claim 1, wherein the moiety is a moiety selected from the group consisting of the following moieties Mo-1 to Mo-3. 【Chemistry 10】 (In the formula, * indicates the bonding site with [Chemical Formula 2] above. Y １ and Y ２ Each of them independently, C(Ar ８ ) and Ar ８ (This is as defined in claim 1.)

8. In the above [Chemical Formula 2], 【Chemistry 11】 The composition for an organic EL element according to claim 1, wherein the Moiety is selected from the group consisting of the following Moieties Dz-1 to Dz-32. 【Chemistry 12】 【Chemistry 13】 (In the formula, R １ C ６ ~C ６０ (It is an aryl group.)

9. The organic EL element composition according to claim 1, wherein the second host represented by the above [Chemical Formula 2] is a compound represented by the following [Chemical Formula 6]. 【Chemistry 14】 (In the formula, i, j, k, R １ , R ３ ~R ５ , n1, n2, X １ , Y １ , and Y ２ are as defined in claim 1, respectively.)

10. The organic EL element composition according to claim 1, wherein the second host represented by the above [Chemical Formula 2] is a compound represented by the following [Chemical Formula 7] or [Chemical Formula 8]. 【Chemistry 15】 【Chemistry 16】 (In the formula, i, k, R １ , R ３ , R ５ , n1, n2, Y １ , and Y ２ are as defined in claim 1, respectively, X １ and X ２ (Each is either O or S.)

11. The organic EL element composition according to claim 1, wherein the second host represented by the above [Chemical Formula 2] is a compound represented by the following [Chemical Formula 9] or [Chemical Formula 10]. 【Chemistry 17】 [Chemistry 18] (In the formula, n1, n2, Y １ , and Y ２ These are as defined in claim 1, x and y are either 0 or 1, X １ and X ２ These are either O or S, D is deuterium, o1 is an integer between 0 and 5. o2 is an integer between 0 and 6. o3 is an integer between 0 and 4. o4 is an integer between 0 and 3. o5 is an integer between 0 and 7.

12. The organic EL element composition according to claim 1, wherein the second host represented by the above [Chemical Formula 2] is selected from the group consisting of the following compounds E-1 to E-13. 【Chemistry 19】

13. The organic EL element composition according to claim 1, wherein the weight ratio of the first host to the second host is 99:1 to 1:

99.

14. The composition for an organic EL element according to claim 1, further comprising a phosphorescent dopant.

15. The organic EL element composition according to claim 14, wherein the phosphorescent dopant contains iridium (Ir) or platinum (Pt).

16. It includes an anode; a cathode; and one or more layers of organic material interposed between the anode and the cathode; The above-mentioned one or more organic layers include the composition described in any one of claims 1 to 15, making it an organic EL element.

17. The above one or more organic layers include a light-emitting layer. The organic EL element according to claim 16, wherein the above composition is included in the above-mentioned light-emitting layer.

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