Granules for organic electroluminescent element and organic electroluminescent element using same

Abstract

The present invention relates to a pellet for an organic electroluminescent element and an organic electroluminescent element using the same, the pellet for an organic electroluminescent element being obtained by crimping two or more kinds of organic compound powder containing a first organic compound powder and a second organic compound powder, and has the same maximum emission wavelength as the maximum emission wavelength of an organic compound having a longer emission wavelength among the first organic compound and the second organic compound.

Description

Technical Field

[0001] The present invention relates to a pellet for an organic electroluminescent element and an organic electroluminescent element using the pellet. Background Art

[0002] When a voltage is applied between two electrodes of an organic electroluminescent element (hereinafter referred to as an "organic EL element"), holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. When the injected holes and electrons meet, excitons are formed, and when the excitons transition to the ground state, light is emitted. At this time, the organic substances used for the organic layer can be divided into luminescent substances, hole injection substances, hole transport substances, electron transport substances, electron injection substances, etc. according to their functions.

[0003] In order to improve the performance of such organic electroluminescent elements, especially the lifespan, efficiency and driving voltage, an organic layer is formed from a plurality of organic compounds, such as one or more main materials dispersed with dopants. The organic layer is formed by evaporating the plurality of organic compounds separately. In this case, it is difficult to accurately control each organic compound according to the desired evaporation speed, and it is relatively wasteful from the perspective of material utilization. In addition, the organic compound is in powder form and may carry static electricity, so it is not easy to handle it during evaporation. Summary of the invention

[0004] Technical issues

[0005] An object of the present invention is to provide a pellet for an organic electroluminescent element which has excellent thermal stability and chemical stability, low surface resistance, small specific surface area, high efficiency and long life.

[0006] Solution to the problem

[0007] In order to achieve the above-mentioned purpose, the present invention provides a pellet for an organic electroluminescent element, which is formed by pressing two or more organic compound powders including a first organic compound powder and a second organic compound powder, and has a maximum emission wavelength that is the same as the maximum emission wavelength of the organic compound with a longer emission wavelength among the above-mentioned first organic compound and the second organic compound.

[0008] The pellets of the present invention may have the same maximum light emission wavelength as that of the mixture powder of the first organic compound powder and the second organic compound powder.

[0009] The pellet of the present invention may include a first region portion formed by pressing the first organic compound powder and a second region portion formed by pressing the second organic compound powder and being integrally arranged with the first region portion.

[0010] In the pellet of the present invention, the first region portions and the second region portions may be alternately arranged from the center toward the outside.

[0011] In the pellet of the present invention, the first region and the second region may be arranged along the length direction. In this case, the first region and the second region may be arranged alternately.

[0012] In the pellet of the present invention, the first region and the second region may be alternately arranged in the circumferential direction. In this case, the first region and the second region may be alternately arranged vertically.

[0013] The pellets of the present invention may have a shape selected from the group consisting of a polyhedron, a cylinder, and a sphere.

[0014] The pellets of the present invention may contain the first organic compound powder and the second organic compound powder in a weight ratio of 1:99 to 99:1.

[0015] In the pellets of the present invention, both the first organic compound powder and the second organic compound powder may be sublimable powders.

[0016] In the pellet of the present invention, the first organic compound powder and the second organic compound powder are mixed at 10 -6 The vapor deposition temperature difference may be 0 to 30° C. under a pressure of torr.

[0017] In the pellets of the present invention, the first organic compound may be a hole transporting organic compound, and the second organic compound may be an electron transporting organic compound. In this case, the hole transporting organic compound may be a hole transporting host, and the hole transporting host may be a carbazole compound. The electron transporting organic compound may be an electron transporting host, and the electron transporting host may be an azine compound.

[0018] The pellet of the present invention can be prepared by applying 20,000 to 40,000 kgf / cm 2 A molded body formed by injection molding under pressure without heat treatment.

[0019] The BET specific surface area of ​​the pellets of the present invention may be smaller than the BET specific surface area of ​​a simple mixture of the first organic compound powder and the second organic compound powder.

[0020] The surface resistance of the pellets of the present invention can be lower than the surface resistance of a simple mixture of the first organic compound powder and the second organic compound powder.

[0021] The present invention provides an organic electroluminescent element, which comprises an anode, a cathode, and one or more organic layers between the anode and the cathode, wherein at least one of the one or more organic layers is a homogeneous thin film containing the first organic compound and the second organic compound using the granules.

[0022] Effects of the Invention

[0023] The pellets of the present invention can realize an organic electroluminescent element which has excellent thermal stability and chemical stability, low surface resistance, small specific surface area, excellent film reproducibility and uniformity, high efficiency and long life. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a perspective view schematically showing the shape of the pellets of the present invention.

[0025] Figure 2 This is a cross-sectional view schematically showing the organic electroluminescent element according to the first embodiment of the present invention.

[0026] Figure 3 This is a cross-sectional view schematically showing an organic electroluminescent element according to a second embodiment of the present invention.

[0027] Figure 4 This is a cross-sectional view schematically showing an organic electroluminescent element according to a third embodiment of the present invention.

[0028] <Description of symbols>

[0029] 10: granular material, 11: first zone,

[0030] 12: Second area, 13: Third area,

[0031] 100: anode, 200: cathode,

[0032] 300: organic layer, 310: hole injection layer,

[0033] 320: hole transport layer, 330: light emitting layer,

[0034] 340: electron transport layer, 350: electron injection layer,

[0035] 360: Electron transport auxiliary layer. DETAILED DESCRIPTION

[0036] Hereinafter, the present invention will be described in detail.

[0037] Unless otherwise defined, all terms (including technical and scientific terms) used in this specification may be used with the meanings that are generally understood by those skilled in the art to which the invention belongs. In addition, unless explicitly specifically defined, terms defined in generally used dictionaries should not be ideally or excessively interpreted.

[0038] Throughout the specification, when it is stated that a part “comprises” a certain constituent element, unless there is a specific description to the contrary, it should be understood as an open-ended term that implies that other constituent elements may be further included, rather than excluding other constituent elements.

[0039] In addition, throughout the specification, "above" or "upper" includes not only the case where it is located directly above or below the object part, but also the case where there are other parts in between, and does not mean that it must be located on the upper side based on the direction of gravity.

[0040] In addition, in this specification, the terms such as “first” and “second” are used to distinguish components from each other, and do not indicate any order or importance.

[0041] <Organic electroluminescent element pellets>

[0042] The present invention provides pellets for forming an organic layer (eg, a light-emitting layer) of an organic electroluminescent device.

[0043] The pellets of the present invention are formed by pressing two or more organic compound powders including a first organic compound powder and a second organic compound powder. The maximum emission wavelength of the pellets is the same as the organic compound with a longer emission wavelength among the first organic compound and the second organic compound.

[0044] Specifically, the pellets of the present invention are formed by simply mixing the first organic compound powder and the second organic compound powder and pressing them without heat treatment, so that the first organic compound powder and the second organic compound powder are densified without chemical changes. Therefore, the pellets of the present invention are manufactured without chemical changes in the first organic compound powder and the second organic compound powder. Therefore, the maximum emission wavelength of the pellets of the present invention is the same as the maximum emission wavelength of the organic compound having a longer emission wavelength among the first organic compound and the second organic compound, and is the same as the maximum emission wavelength of the simple mixture powder of the first organic compound powder and the second organic compound powder. In addition, the BET specific surface area of ​​the pellets of the present invention is smaller than the BET specific surface area of ​​the simple mixture of the first organic compound powder and the second organic compound powder. Therefore, the pellets of the present invention have excellent chemical resistance and reagent resistance due to the small area exposed to the air, and also excellent thermal stability. In addition, the surface resistance of the pellets of the present invention is smaller than the surface resistance of the simple mixture of the first organic compound powder and the second organic compound powder, so less static electricity is generated and it is easy to handle, thereby improving the vapor deposition processability (processability) when manufacturing components. In addition, the pellets of the present invention are excellent in storage and ease of handling, and can be designed into various desired shapes. In addition, the pellets of the present invention can be used as a single evaporation source to easily control the evaporation speed, thereby simplifying the evaporation process and reducing manufacturing costs. Furthermore, when the pellets of the present invention are used to form an organic layer of an organic electroluminescent element, compared with the case where the first organic compound powder and the second organic compound powder are used separately or in a state where they are simply mixed, a film in which the first organic compound and the second organic compound are uniformly mixed can be formed, thereby achieving an organic electroluminescent element with high efficiency and long life. In addition, the pellets of the present invention have excellent reproducibility of the film when the film is evaporated by a continuous process, so that the organic electroluminescent element can be continuously manufactured by a continuous process such as roll-to-roll.

[0045] In the pellets of the present invention, the first organic compound powder and the second organic compound powder are both solid at room temperature and are sublimable powders. Therefore, the pellets of the present invention can be easily formed into a uniform thin film by a dry film forming method such as vacuum evaporation.

[0046] As an example, the first organic compound powder and the second organic compound powder are -6 The sublimation temperature difference of the first organic compound powder and the second organic compound powder can be about 0 to 30° C. under a pressure of 10 torr. -6 The vapor deposition temperature difference may be about 0 to 30° C. under the torr pressure. In this case, the pellets of the present invention can be vapor deposited while maintaining the set mixing ratio.

[0047] The first organic compound that can be used in the present invention is not particularly limited as long as it is a compound having a stronger hole transport property than the second organic compound, that is, a hole transporting organic compound.

[0048] The hole transporting organic compound may be a hole transporting host. As an example, the hole transporting host may be a carbazole compound.

[0049] Specifically, examples of the hole transporting organic compound include a compound represented by the following Chemical Formula 1, but the present invention is not limited thereto.

[0050] [Chemical formula 1]

[0051]

[0052] In the above chemical formula 1,

[0053] D is deuterium,

[0054] a, d and f are integers from 0 to 3,

[0055] b, c and e are each an integer from 0 to 4,

[0056] Ar1 and Ar2 are the same or different from each other and can be independently selected from hydrogen, deuterium (D), halogen, cyano, nitro, amino, C1-C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 atomic nuclei, C6~C 60 aryl, heteroaryl with 5 to 60 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkyl silyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, phosphine oxide, C1~C 40 Alkylphosphine oxide group, C6~C 60 Arylphosphine, C6~C 60 The aryl phosphine oxide group and C6~C 60 or they form a condensed ring with adjacent groups,

[0057] The alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, alkylboryl, arylboryl, alkylphosphine oxide, arylphosphine oxide, arylamine and condensed ring of Ar1 and Ar2 are each independently selected from deuterium, halogen, cyano, nitro, C2 to C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 atomic nuclei, C1~C 40 Alkyl, C6~C 60 aryl, heteroaryl with 5 to 60 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkyl silyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 The aryl phosphine oxide group and C6~C 60 The group consisting of the arylamine groups may be substituted or unsubstituted with one or more substituents. When there are multiple substituents, they may be the same as or different from each other.

[0058] In the compound represented by the above chemical formula 1, a, d and f are each an integer from 0 to 3, and b, c and e are each an integer from 0 to 4. Wherein, when a, b, c, d, e and f are each 0, it means that hydrogen is not replaced by deuterium, i.e., D. On the other hand, when a, d and f are each an integer from 1 to 3 and when b, c and e are each 1 to 4, it means that one or more hydrogens are replaced by deuterium (D). At this time, it can be 13≤a+b+c+d+e+f≤21. According to one example, the number of deuterium (D) contained in the compound of the above chemical formula 1 can be at least 13, specifically at least 21. Such a compound of the chemical formula 1 can improve the stability of the chemical structure by substitution with deuterium (D), thereby simultaneously realizing the characteristics of the organic electroluminescent element, such as the low voltage, high efficiency and long life characteristics of the element.

[0059] Such deuterium may also be substituted by other substituents (R). In this case, when there are multiple other substituents (R), they may be the same or different from each other. The above other substituents (R) may be selected from halogen, cyano, nitro, amino, C1-C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40Cycloalkyl, heterocycloalkyl with 3 to 40 atomic nuclei, C6~C 60 aryl, heteroaryl with 5 to 60 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkyl silyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, phosphine oxide, C1~C 40 Alkylphosphine oxide group, C6~C 60 Arylphosphine, C6~C 60 The aryl phosphine oxide group and C6~C 60 A group composed of arylamine groups.

[0060] In the compound represented by the above chemical formula 1, Ar1 and Ar2 are the same or different from each other, and each independently can be selected from hydrogen, deuterium (D), halogen, cyano, nitro, amino, C1-C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 atomic nuclei, C6~C 60 aryl, heteroaryl with 5 to 60 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkyl silyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, phosphine oxide, C1~C 40 Alkylphosphine oxide group, C6~C 60 Arylphosphine, C6~C 60 The aryl phosphine oxide group and C6~C 60 Specifically, Ar1 and Ar2 are the same or different from each other and can be independently selected from C6 to C 60 The group consisting of an aryl group and a heteroaryl group having 5 to 60 atomic nuclei.

[0061] According to one example, Ar1 and Ar2 are the same as or different from each other, and each independently may be a substituent selected from the group consisting of the following substituents S1 to S4.

[0062]

[0063] In the above substituents S1 to S4, * is a site connecting to the above chemical formula 1.

[0064] According to such Ar1 and Ar2, the compound represented by the above Chemical Formula 1 may be a compound represented by the following Chemical Formula 2, but is not limited thereto.

[0065] [Chemical formula 2]

[0066]

[0067] In the above chemical formula 2,

[0068] a, b, c, d, e and f are each the same as defined in the above Chemical Formula 1,

[0069] m1 and m2 are 0 or 1, respectively.

[0070] In addition, the compound represented by the above chemical formula 1 may have various structures depending on the connection positions between the carbazole moieties. According to one example, the compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 3.

[0071] [Chemical formula 3]

[0072]

[0073] In the above chemical formula 3,

[0074] a, b, c, d, e and f are each the same as defined in the above Chemical Formula 1,

[0075] m1 and m2 are 0 or 1, respectively.

[0076] The compound represented by the chemical formula 1 of the present invention described above can be further embodied as the following exemplary compounds, such as compounds A-1 to D-4, but is not limited thereto.

[0077]

[0078]

[0079] The second organic compound that can be used in the present invention is not particularly limited as long as it is a compound having stronger electron transport properties than the first organic compound, that is, an electron transporting organic compound.

[0080] The electron-transporting organic compound may be an electron-transporting host. As an example, the electron-transporting host may be an azine compound containing a triazine group, a pyridyl group, a pyrimidyl group, or the like.

[0081] Specifically, the electron transporting organic compound includes a compound represented by the following Chemical Formula 4, but is not limited thereto.

[0082] [Chemical formula 4]

[0083]

[0084] In the above chemical formula 4,

[0085] h is an integer from 0 to 3,

[0086] g and i are each an integer from 0 to 4,

[0087] j and k are each an integer from 0 to 5,

[0088] n1 is an integer from 1 to 5,

[0089] n2 is an integer of 0 or 1,

[0090] X1 is selected from the group consisting of O, S, Se, N(Ar3), C(Ar4)(Ar5) and Si(Ar6)(Ar7),

[0091] Y1 and Y2 are the same as or different from each other and are independently N or C(Ar8). In this case, at least one of Y1 and Y2 is N.

[0092] Ar3 to Ar8 and R1 to R5 are the same as or different from each other, and each independently can be selected from hydrogen, deuterium (D), halogen, cyano, nitro, amino, C1-C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 atomic nuclei, C6~C 60 aryl, heteroaryl with 5 to 60 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkyl silyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, phosphine oxide, C1~C 40 Alkylphosphine oxide group, C6~C 60 Arylphosphine, C6~C 60 The aryl phosphine oxide group and C6~C 60 or they form a condensed ring with adjacent groups,

[0093] The alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, alkylboryl, arylboryl, alkylphosphine oxide, arylphosphine oxide, arylamine and condensed ring of Ar3 to Ar8 and R1 to R5 are each independently selected from deuterium, halogen, cyano, nitro, C2 to C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 atomic nuclei, C1~C 40 Alkyl, C6~C 60 aryl, heteroaryl with 5 to 60 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkyl silyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 The aryl phosphine oxide group and C6~C 60 The group consisting of the arylamine groups may be substituted or unsubstituted with one or more substituents. When there are multiple substituents, they may be the same as or different from each other.

[0094] In the compound represented by the above Chemical Formula 4, Y1 and Y2 are the same as or different from each other and are independently N or C(Ar8), wherein at least one of Y1 and Y2 is N.

[0095] According to such Y1 and Y2, in the compound represented by the above chemical formula 4,

[0096] The moiety may be a moiety selected from the group consisting of the following moieties Mo-1 to Mo-3.

[0097]

[0098] In the above parts Mo-1 to Mo-3,

[0099] * is the site connected to the above chemical formula 4,

[0100] Y1 and Y2 are each independently C(Ar8),

[0101] Ar8 has the same meaning as in the above Chemical Formula 4.

[0102] In the compound represented by the above chemical formula 4, n1 is an integer from 1 to 5, and n2 is 0 or 1. According to one example, n1 can be 1 or 2, and n2 can be 0 or 1. In the above chemical formula 4, when n2 is 0, j is 1.

[0103] In the compound represented by the above chemical formula 4, X1 is selected from the group consisting of O, S, Se, N(Ar3), C(Ar4)(Ar5) and Si(Ar6)(Ar7). According to such X1, the dibenzo part can be a monovalent dibenzofuranyl group, a monovalent dibenzothiophene group, a monovalent fluorenyl group, etc.

[0104] Ar3 to Ar8 are the same or different from each other and are independently selected from hydrogen, deuterium (D), halogen, cyano, nitro, amino, C1-C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 atomic nuclei, C6~C 60 aryl, heteroaryl with 5 to 60 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkyl silyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, phosphine oxide, C1~C 40 Alkylphosphine oxide group, C6~C 60 Arylphosphine, C6~C 60 The aryl phosphine oxide group and C6~C 60 or they form a condensed ring with adjacent groups (e.g., Ar3-R1, Ar3-R2, Ar4-Ar5, Ar6-Ar7, Ar4-R1, Ar4-R2, Ar6-R1, Ar6-R2, etc.). Specifically, Ar3 to Ar8 are the same or different from each other and can be independently selected from C1 to C 40 Alkyl, C6~C 60 and a heteroaryl group with 5 to 60 atomic nuclei, or they form a condensed ring with adjacent groups (for example: Ar3-R1, Ar3-R2, Ar4-Ar5, Ar6-Ar7, Ar4-R1, Ar4-R2, Ar6-R1, Ar6-R2, etc.). The condensed ring can be selected from C3 to C 60 Condensed aliphatic ring (specifically C3~C 30 Condensed aliphatic ring), C6~C 60Condensed aromatic ring (specifically C6~C 30 condensed aromatic ring), 5-membered to 60-membered condensed heteroaromatic ring (specifically 5-membered to 30-membered condensed heteroaromatic ring), C3-C 60 One or more of the group consisting of a spiro ring and combinations thereof.

[0105] According to one example, in the above chemical formula 4,

[0106] The moiety may be a moiety selected from the group consisting of the following moieties Dz-1 to Dz-32, but is not limited thereto.

[0107]

[0108]

[0109] In the above parts Dz-1 and Dz-32,

[0110] * is the site connected to the above chemical formula 4,

[0111] R1 can be C6~C 60 The aryl group may specifically be a phenyl group.

[0112] In the compound represented by the above chemical formula 4, 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. When g, h, i, j and k are each 0, it means that hydrogen is not replaced by substituents R1 to R5. On the other hand, 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 R1 to R5 are the same or different from each other, and each independently can be selected from deuterium (D), a halogen group, a cyano group, a nitro group, an amino group, a C1~C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 atomic nuclei, C6~C 60 aryl, heteroaryl with 5 to 60 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkyl silyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, phosphine oxide, C1~C 40 Alkylphosphine oxide group, C6~C 60 Arylphosphine, C6~C 60The aryl phosphine oxide group and C6~C 60 Specifically, one or more R1 to R5 are the same or different from each other, and each independently can be selected from hydrogen, halogen, cyano, nitro, amino, C1~C 40 Alkyl, C6~C 60 The group consisting of an aryl group and a heteroaryl group having 5 to 60 atomic nuclei.

[0113] The alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, alkylboryl, arylboryl, alkylphosphine oxide, arylphosphine oxide, arylamine and condensed ring of Ar3 to Ar8 and R1 to R5 can be independently selected from deuterium, halogen, cyano, nitro, C2 to C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 atomic nuclei, C1~C 40 Alkyl, C6~C 60 aryl, heteroaryl with 5 to 60 atomic nuclei, C1~C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkyl silyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 The aryl phosphine oxide group and C6~C 60 The arylamine group may be substituted or unsubstituted with one or more substituents in the group consisting of the arylamine group. At this time, when the substituents are multiple, they may be the same or different from each other.

[0114] The compound represented by the above Chemical Formula 4 may be a compound represented by the following Chemical Formula 5, but is not limited thereto.

[0115] [Chemical formula 5]

[0116]

[0117] In the above chemical formula 5,

[0118] i, j, k, R1, R3 to R5, n1, n2, X1, Y1 and Y2 are each the same as defined in the above Chemical Formula 4.

[0119] Specifically, the compound represented by the above Chemical Formula 4 may be a compound represented by the following Chemical Formula 6 or 7, but is not limited thereto.

[0120] [Chemical formula 6]

[0121]

[0122] [Chemical formula 7]

[0123]

[0124] In the above chemical formulas 6 and 7,

[0125] i, k, R1, R3, R5, n1, n2, Y1 and Y2 are each the same as defined in the above chemical formula 4, and X1 and X2 are each O or S, specifically O.

[0126] More specifically, the compound represented by the above Chemical Formula 4 may be a compound represented by the following Chemical Formula 8 or 9, but is not limited thereto.

[0127] [Chemical formula 8]

[0128]

[0129] [Chemical formula 9]

[0130]

[0131] In the above chemical formulas 8 and 9,

[0132] n1, n2, Y1 and Y2 are each the same as those in the above Chemical Formula 4. Specifically, n1 may be 1 or 2, n2 may be 0 or 1, and Y1 and Y2 may both be N.

[0133] x and y are 0 or 1 respectively,

[0134] X1 and X2 are each O or S, and specifically can be O.

[0135] The compound represented by Chemical Formula 2 of the present invention described above can be further embodied as the following exemplary compounds, such as Compounds E-1 to E-10, but is not limited thereto.

[0136]

[0137] In the present invention, "alkyl" means a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, and hexyl.

[0138] 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 thereof include vinyl, allyl, isopropenyl, 2-butenyl, etc., but are not limited thereto.

[0139] 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 thereof include ethynyl and 2-propynyl, but are not limited thereto.

[0140] 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 of such cycloalkyl include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine, but are not limited thereto.

[0141] In the present invention, "heterocycloalkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon having a nucleus number of 3 to 40, wherein one or more carbon atoms, preferably 1 to 3 carbon atoms, in the ring are substituted with heteroatoms such as N, O, S or Se. Examples of such heterocycloalkyl include morpholinyl and piperazinyl, but are not limited thereto.

[0142] In the present invention, "aryl" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms and composed of a single ring or a combination of two or more rings. In addition, it may also include a form in which two or more rings are simply attached to each other (pendant) or condensed. Examples of such aryl groups include phenyl, naphthyl, phenanthrenyl, anthracenyl, etc., but are not limited thereto.

[0143] In the present invention, "heteroaryl" means a monovalent substituent derived from a monocyclic heterocyclic or polycyclic aromatic hydrocarbon having an atomic nucleus number of 5 to 60. In this case, one or more carbons, preferably 1 to 3 carbons in the ring are substituted by heteroatoms such as N, O, S or Se. In addition, it may also include a form in which two or more rings are simply attached (pendant) or condensed to each other, and further may include a form condensed with an aryl group. Examples of such heteroaryl groups include six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl; and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl, 2-pyrimidinyl, etc., but are not limited thereto.

[0144] In the present invention, "alkoxy" is a monovalent substituent represented by R'O-, wherein R' means an alkyl group having 1 to 40 carbon atoms, and may include a linear, branched or cyclic structure. Examples of such alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, tert-butoxy, n-butoxy, and pentyloxy.

[0145] In the present invention, "aryloxy" is a monovalent substituent represented by RO-, where R means an aryl group having 5 to 40 carbon atoms. Examples of such aryloxy groups include phenoxy, naphthoxy, diphenoxy and the like, but are not limited thereto.

[0146] In the present invention, "alkylsilyl" means a silyl group substituted with an alkyl group having 1 to 40 carbon atoms, including not only a monoalkylsilyl group but also a dialkylsilyl group and a trialkylsilyl group. In addition, "arylsilyl" means a silyl group substituted with an aryl group having 5 to 60 carbon atoms, including not only a monoarylsilyl group but also a diarylsilyl group, a triarylsilyl group and other polyarylsilyl groups.

[0147] In the present invention, the "alkylboryl group" means a boron group substituted by an alkyl group having 1 to 40 carbon atoms, and the "arylboryl group" means a boron group substituted by an aryl group having 6 to 60 carbon atoms.

[0148] In the present invention, "alkylphosphino" means a phosphino group substituted with an alkyl group having 1 to 40 carbon atoms, including not only a monoalkylphosphino group but also a dialkylphosphino group. In addition, in the present invention, "arylphosphino" means a phosphino group substituted with a monoaryl group or a diaryl group having 6 to 60 carbon atoms, including not only a monoarylphosphino group but also a diarylphosphino group.

[0149] In the present invention, the "arylamine group" means an amine group substituted with an aryl group having 6 to 60 carbon atoms, and includes not only a monoarylamine group but also a diarylamine group.

[0150] In the present invention, the "heteroarylamine group" means an amine group substituted with a heteroaryl group having 5 to 60 atomic nuclei, and includes not only a monoheteroarylamine group but also a diheteroarylamine group.

[0151] In the present invention, the (aryl)(heteroaryl)amine group means an amine group substituted with an aryl group having 6 to 60 carbon atoms and a heteroaryl group having 5 to 60 atomic nuclei.

[0152] 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 aliphatic heterocyclic ring having 3 to 60 atomic nuclei, a condensed aromatic heterocyclic ring having 5 to 60 atomic nuclei, a spirocyclic ring having 3 to 60 carbon atoms, or a combination thereof.

[0153] The use ratio (mixing ratio) of the first organic compound powder and the second organic compound powder is not particularly limited, and may be, for example, a weight ratio of 1:99 to 99:1. As an example, the pellet may contain the first organic compound powder and the second organic compound powder in a weight ratio of 20:80 to 80:20. This allows vapor deposition while maintaining a constant mixing ratio, thereby enabling stable and uniform mixing ratio characteristics during vapor deposition.

[0154] The particle size or shape of the first organic compound powder and the second organic compound powder is not particularly limited as long as it is a particle size or shape known in the art, and as an example, they may be white or light yellow powders.

[0155] In the pellets of the present invention, the first organic compound powder and the second organic compound powder can not only be uniformly mixed together and compressed, but the first organic compound powder and the second organic compound powder can also be arranged in a certain area to form a predetermined pattern and compressed. In this way, when the pellets of the present invention are divided into a first area portion containing the first organic compound and a second area portion containing the second organic compound in a certain pattern, compared with the case where the first organic compound and the second organic compound are mixed together, when thin film evaporation is performed through a continuous process (for example: a roll-to-roll process), the mixing ratio of the first organic compound and the second organic compound can be constantly maintained at a set ratio, thereby improving the reproducibility of the thin film. In particular, the pellets of the present invention have a morphology in which either of the first organic compound and the second organic compound with a higher sublimability is surrounded by the other organic compound [refer to Figure 1 (a) Figure 1In the case of (g)], compared with other forms, a thin film can be formed while maintaining a constant mixing ratio during thin film deposition.

[0156] Specifically, Figure 1 As shown, the pellet 10 of the present invention may include a first region 11 formed by pressing the first organic compound powder and a second region 12 formed by pressing the second organic compound powder and integrally arranged with the first region 11. In this case, the first region 11 and the second region 12 may be arranged in various patterns.

[0157] According to one example, Figure 1 As shown in (a) and (g) of the drawings, in the pellet 10 of the present invention, the first region 11 and the second region 11 may be alternately arranged from the center to the outside.

[0158] According to another example, Figure 1 As shown in (c), (d), (h), (i), (j), and (f) of the present invention, in the pellet 10 of the present invention, the first region 11 and the second region 12 may be arranged along the length direction (for example, up and down). In this case, the first region 11 and the second region 12 may be arranged alternately [ Figure 1 (d), (i)].

[0159] According to another example, Figure 1 As shown in (e), (j), and (k), in the pellet 10 of the present invention, the first region 11 and the second region 12 may be alternately arranged along the circumferential direction. In this case, the first region 11 and the second region 12 may be alternately arranged up and down.

[0160] According to another example, Figure 1 As shown in (l), in addition to the above-mentioned first region portion 11 and second region portion 12, the pellet 10 of the present invention may also include a third region portion 13 formed by pressing powder of a third organic compound different from the above-mentioned first organic compound and second organic compound, ..., and an nth region portion (not shown) (4≤n, specifically 4≤n≤6) formed by pressing powder of an nth organic compound.

[0161] The shape of the pellets is not particularly limited, and may be, for example, a polyhedron, a cylinder, a sphere, or the like.

[0162] The BET specific surface area of ​​the pellets of the present invention having the above-described predetermined morphology may be smaller than the BET specific surface area of ​​a simple mixture of the first organic compound powder and the second organic compound powder.

[0163] Furthermore, the surface resistance of the pellets of the present invention can be lower than the surface resistance of a simple mixture of the first organic compound powder and the second organic compound powder.

[0164] In addition, the pellets of the present invention are different from a mixture of a simple mixture of a first organic compound and a second organic compound. Even if a thin film is formed by a continuous process, the granules of the present invention are evaporated while the mixing ratio of the first organic compound and the second organic compound before and after the evaporation is constantly maintained. Therefore, the pellets of the present invention can form a thin film having a uniform mixing ratio characteristic when the thin film is evaporated by a continuous process. According to one example, when the thin film is evaporated by a continuous process, the time change rate of the pellets of the present invention before and after the evaporation can be less than about 1%, specifically about 0.01 to 0.8%.

[0165] The pellets of the present invention can be produced by a pellet forming method generally known in the art. However, since the pellets of the present invention are not subjected to heat treatment during pressurization and do not undergo chemical changes, the chemical and physical properties are the same as those of the first organic compound powder, the second organic compound powder, and a simple mixture thereof.

[0166] According to one example, the pellets of the present invention can be produced by injecting two or more organic compound powders including a first organic compound powder and a second organic compound powder into a mold, and applying a pressure of about 20,000 to 40,000 kgf / cm 2 pressure and injection molding without heat treatment.

[0167] <Organic electroluminescent element>

[0168] In another aspect, the present invention provides an organic electroluminescent element (hereinafter referred to as "organic EL element") using the above-mentioned pellets.

[0169] Specifically, Figures 2 to 4 As shown, the organic electroluminescent element of the present invention comprises an anode 100, a cathode 200 and one or more organic layers 300 between the anode and the cathode, wherein at least one of the one or more organic layers is a homogeneous thin film formed by the granules and containing the first organic compound and the second organic compound.

[0170] The above-mentioned one or more organic layers 300 may include any one or more of a hole injection layer 310, a hole transport layer 320, a light-emitting layer 330, an electron transport auxiliary layer 360, an electron transport layer 340 and an electron injection layer 350, wherein at least one organic layer 300 is a homogeneous thin film formed by the above-mentioned granules and containing the above-mentioned first organic compound and the second organic compound. In this case, the above-mentioned first organic compound may be a hole transporting organic compound, and the second organic compound may be an electron transporting organic compound.

[0171] According to one example, the homogeneous thin film may be the light-emitting layer 330. In this case, the first organic compound may be a hole-transporting host, and the second organic compound may be an electron-transporting host.

[0172] The mixing ratio of the first organic compound to the second organic compound may be 1:99 to 99:1 by weight, and specifically may be 20:80 to 80:20 by weight.

[0173] The light-emitting layer may further include a host and / or a dopant generally known in the art in addition to the first organic compound and the second organic compound. In this case, the total content of the first organic compound and the second organic compound may be 0 wt % to 100 wt % based on the total amount of all the hosts.

[0174] In addition, the total amount of all hosts may be about 70 to 99.9 wt % based on the total amount of the light-emitting layer, and the content of the dopant may be about 0.1 to 30 wt % based on the total amount of the light-emitting layer.

[0175] The structure of the organic electroluminescent element of the present invention is not particularly limited. For example, an anode 100, one or more organic layers 300, and a cathode 200 may be sequentially stacked on a substrate (see Figures 2 to 4 ). In addition, although not shown in the figure, an insulating layer or an adhesive layer may be inserted at the interface between the electrode and the organic layer.

[0176] According to one example, Figure 2 As shown, the organic electroluminescent element may have a structure in which an anode 100, a hole injection layer 310, a hole transport layer 320, a light emitting layer 330, an electron transport layer 340 and a cathode 200 are sequentially stacked on a substrate. Figure 3 As shown, an electron injection layer 350 may be provided between the electron transport layer 340 and the cathode 200. In addition, an electron transport auxiliary layer 360 (see Figure 4 ).

[0177] In addition to at least one layer of the organic layer 300 (for example, the light-emitting layer 330 ) being a uniform thin film formed of the above-mentioned granular material, the organic electroluminescent element of the present invention can form and manufacture the organic layer and the electrode by using materials and methods known in the technical field.

[0178] The organic layer can be formed by a dry film forming method such as vacuum evaporation, sputtering, plasma plating, ion plating, or the like.

[0179] The substrate that can be used in the present invention is not particularly limited, and non-limiting examples include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets, and the like.

[0180] In addition, examples of anode materials include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; 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 or SnO2:Sb; conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, or polyaniline; and carbon black, but are not limited to these.

[0181] In addition, examples of cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver (Ag), tin or lead, or alloys thereof; and multilayer structure materials such as LiF / Al or LiO2 / Al, but are not limited to these.

[0182] In addition, the hole injection layer, the hole transport layer, the light emitting layer, and the electron injection layer are not particularly limited, and common materials known in the art can be used.

[0183] Hereinafter, the present invention will be described in detail by way of examples, the contents of which are as follows. However, the following examples are merely illustrative of the present invention, and the present invention is not limited to the following examples.

[0184] <Preparation Example 1-1> Synthesis of Cz-D1

[0185]

[0186] Under a nitrogen flow, 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7 (134.3 g, 530.6 mmol), iodobenzene (130.0 g, 636.7 mmol), Cu (16.8 g, 265.3 mmol), K2CO3 (146.7 g, 1,061.3 mmol) and toluene (1000 ml) were mixed and stirred at 110°C for 12 hours.

[0187] After the reaction, the product was extracted with ethyl acetate, and then water was removed with MgSO 4 . The product was purified by column chromatography (hexane:EA=5:1 (v / v)) to obtain Cz-D1 (125.7 g, yield 72%).

[0188] Mass (theoretical value: 329.25, measured value: 329 g / mol)

[0189] <Preparation Example 1-2> Synthesis of Cz-D2

[0190]

[0191] The same process as Preparation Example 1-1 was carried out except that 4-iodo-1,1′-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene used in Preparation Example 1-1, thereby obtaining the target compound Cz-D2 (135.5 g, yield 63%).

[0192] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0193] <Preparation Example 1-3> Synthesis of Cz-D3

[0194]

[0195] The target compound Cz-D3 (148.4 g, yield 69%) was obtained by the same process as in Preparation Example 1-1 except that 3-iodo-1,1′-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene used in Preparation Example 1-1.

[0196] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0197] <Preparation Example 1-4> Synthesis of Cz-D4

[0198]

[0199] The same process as Preparation Example 1-1 was carried out except that 2-iodo-1,1′-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene used in Preparation Example 1-1, thereby obtaining the target compound Cz-D4 (96.8 g, yield 45%).

[0200] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0201] <Preparation Example 2-1> Synthesis of Cz-D5

[0202]

[0203] The target compound Cz-D5 (117.1 g, yield 67%) was obtained by carrying out the same process as 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.

[0204] Mass (theoretical value: 329.25, measured value: 329 g / mol)

[0205] <Preparation Example 2-2> Synthesis of Cz-D6

[0206]

[0207] The target compound Cz-D6 (139.8 g, yield 65%) was obtained by the same process as in Preparation Example 2-1 except that 4-iodo-1,1′-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene used in Preparation Example 2-1.

[0208] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0209] <Preparation Example 2-3> Synthesis of Cz-D7

[0210]

[0211] The target compound Cz-D7 (152.7 g, yield 71%) was obtained by the same process as in Preparation Example 2-1 except that 3-iodo-1,1′-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene used in Preparation Example 2-1.

[0212] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0213] <Preparation Example 2-4> Synthesis of Cz-D8

[0214]

[0215] The same process as in Preparation Example 2-1 was carried out except that 2-iodo-1,1′-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene, thereby obtaining the target compound Cz-D8 (75.2 g, yield 35%).

[0216] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0217] <Preparation Example 3-1> Synthesis of Cz-D9

[0218]

[0219] The target compound Cz-D9 (134.5 g, yield 77%) was obtained by carrying out the same process as 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.

[0220] Mass (theoretical value: 329.25, measured value: 329 g / mol)

[0221] <Preparation Example 3-2> Synthesis of Cz-D10

[0222]

[0223] The same process as in Preparation Example 3-1 was carried out except that 4-iodo-1,1′-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene used in Preparation Example 3-1, thereby obtaining the target compound Cz-D10 (159.1 g, yield 74%).

[0224] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0225] <Preparation Example 3-3> Synthesis of Cz-D11

[0226]

[0227] The same procedure as in Preparation Example 3-1 was carried out except that 3-iodo-1,1′-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene to obtain the target compound Cz-D11 (163.4 g, yield 76%).

[0228] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0229] <Preparation Example 3-4> Synthesis of Cz-D12

[0230]

[0231] The target compound Cz-D12 (92.4 g, yield 43%) was obtained by the same process as in Preparation Example 3-1 except that 2-iodo-1,1′-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene used in Preparation Example 3-1.

[0232] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0233] <Preparation Example 4-1> Synthesis of Cz-D13

[0234]

[0235] The target compound Cz-D13 (94.3 g, yield 54%) was obtained by carrying out the same process as Preparation Example 1-1, except that 1-bromo-9H-carbazole-2,3,4,5,6,7,8-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.

[0236] Mass (theoretical value: 329.25, measured value: 329 g / mol)

[0237] <Preparation Example 4-2> Synthesis of Cz-D14

[0238]

[0239] The same process as in Preparation Example 4-1 was carried out except that 4-iodo-1,1′-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene, thereby obtaining the target compound Cz-D14 (122.6 g, yield 57%).

[0240] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0241] <Preparation Example 4-3> Synthesis of Cz-D15

[0242]

[0243] The same process as in Preparation Example 4-1 was carried out except that 3-iodo-1,1′-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene used in Preparation Example 4-1, thereby obtaining the target compound Cz-D15 (111.8 g, yield 52%).

[0244] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0245] <Preparation Example 4-4> Synthesis of Cz-D16

[0246]

[0247] The same process as in Preparation Example 4-1 was carried out except that 2-iodo-1,1′-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene, thereby obtaining the target compound Cz-D16 (68.8 g, yield 32%).

[0248] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0249] <Preparation Example 5-1> Synthesis of BCz-D1

[0250] <Step 1> 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1, Synthesis of 2,4,5,6,7,8-d7

[0251]

[0252] Under a nitrogen flow, Cz-D1 (100.0 g, 303.7 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(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.

[0253] After the reaction, extraction was performed with ethyl acetate, water was removed with MgSO4, and purification was performed with column chromatography (hexane:EA=8:1 (v / v)) to obtain 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9H-carbazole-1,2,4,5,6,7,8-d7 (96.0 g, yield 84%).

[0254] Mass (theoretical value: 376.3, measured value: 376 g / mol)

[0255] <Step 2> Synthesis of BCz-D1

[0256]

[0257] Under a nitrogen flow, 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-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.

[0258] After the reaction was completed, the mixture was extracted with dichloromethane, and then MgSO4 was added and filtered. The solvent was removed from the obtained organic layer, and then the mixture was purified by column chromatography (hexane:EA=7:1 (v / v)) to obtain BCz-D1 (71.1 g, yield 66%).

[0259] Mass (theoretical value: 422.59, measured value: 422 g / mol)

[0260] <Preparation Example 5-2> Synthesis of BCz-D2

[0261]

[0262] The same process as in Preparation Example 5-1 was carried out except that Cz-D2 (100 g, 246.7 mmol) obtained in Preparation Example 1-2 was used instead of Cz-D1 used in Preparation Example 5-1, thereby obtaining the target compound BCz-D2 (66.4 g, final yield 54.0%).

[0263] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0264] <Preparation Example 5-3> Synthesis of BCz-D3

[0265]

[0266] The same process as in Preparation Example 5-1 was carried out except that Cz-D3 (100 g, 246.7 mmol) obtained in Preparation Example 1-3 was used instead of Cz-D1 used in Preparation Example 5-1, thereby obtaining the target compound BCz-D3 (59.7 g, final yield 48.5%).

[0267] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0268] <Preparation Example 5-4> Synthesis of BCz-D4

[0269]

[0270] The same process as in Preparation Example 5-1 was carried out except that Cz-D4 (100 g, 246.7 mmol) obtained in Preparation Example 1-4 was used instead of Cz-D1 used in Preparation Example 5-1, thereby obtaining the target compound BCz-D4 (59.4 g, final yield 48.3%).

[0271] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0272] [Synthesis Example 1] Synthesis of A-1

[0273]

[0274] Under nitrogen flow, 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, toluene was concentrated, and the solid salt was filtered and purified by recrystallization to obtain the target compound A-1 (13.0 g, yield 82%).

[0275] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0276] [Synthesis Example 2] Synthesis of A-2

[0277]

[0278] The same process as in Synthesis Example 1 was carried out 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, thereby obtaining the target compound A-2 (13.8 g, yield 78%).

[0279] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0280] [Synthesis Example 3] Synthesis of A-3

[0281]

[0282] The same process as Synthesis Example 1 was carried out 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, thereby obtaining the target compound A-3 (13.2 g, yield 75%).

[0283] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0284] [Synthesis Example 4] Synthesis of A-4

[0285]

[0286] The same process as Synthesis Example 1 was carried out 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, thereby obtaining the target compound A-4 (12.2 g, yield 69%).

[0287] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0288] [Synthesis Example 5] Synthesis of A-5

[0289]

[0290] The same process as Synthesis Example 1 was carried out 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, thereby obtaining the target compound A-5 (8.73 g, yield 55%).

[0291] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0292] [Synthesis Example 6] Synthesis of A-6

[0293]

[0294] The same process as Synthesis Example 1 was carried out 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, thereby obtaining the target compound A-6 (7.42 g, yield 42%).

[0295] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0296] [Synthesis Example 7] Synthesis of A-7

[0297]

[0298] The same process as Synthesis Example 1 was carried out except that Cz-D7 (10.0 g, 23.6 mmol) obtained in Preparation Example 2-3 was used instead of Cz-D1 used in Synthesis Example 1, thereby obtaining the target compound A-7 (8.83 g, yield 50%).

[0299] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0300] [Synthesis Example 8] Synthesis of A-8

[0301]

[0302] The same process as Synthesis Example 1 was carried out except that Cz-D8 (10.0 g, 23.6 mmol) obtained in Preparation Example 2-4 was used instead of Cz-D1 used in Synthesis Example 1, thereby obtaining the target compound A-8 (9.89 g, yield 56%).

[0303] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0304] [Synthesis Example 9] Synthesis of A-9

[0305]

[0306] The same process as Synthesis Example 1 was carried out except that Cz-D9 (9.3 g, 23.6 mmol) obtained in Preparation Example 3-1 was used instead of Cz-D1 used in Synthesis Example 1, thereby obtaining the target compound A-9 (8.41 g, yield 53%).

[0307] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0308] [Synthesis Example 10] Synthesis of A-10

[0309]

[0310] The same process as Synthesis Example 1 was carried out except that Cz-D10 (10.0 g, 23.6 mmol) obtained in Preparation Example 3-2 was used instead of Cz-D1 used in Synthesis Example 1, thereby obtaining the target compound A-10 (8.66 g, yield 49%).

[0311] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0312] [Synthesis Example 11] Synthesis of A-11

[0313]

[0314] The same process as Synthesis Example 1 was carried out 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, thereby obtaining the target compound A-11 (9.01 g, yield 51%).

[0315] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0316] [Synthesis Example 12] Synthesis of A-12

[0317]

[0318] The same process as Synthesis Example 1 was carried out 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, thereby obtaining the target compound A-12 (9.19 g, yield 52%).

[0319] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0320] [Synthesis Example 13] Synthesis of A-13

[0321]

[0322] The same process as Synthesis Example 1 was carried out 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, thereby obtaining the target compound A-13 (9.52 g, yield 60%).

[0323] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0324] [Synthesis Example 14] Synthesis of A-14

[0325]

[0326] The same process as Synthesis Example 1 was carried out 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, thereby obtaining the target compound A-14 (10.78 g, yield 61%).

[0327] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0328] [Synthesis Example 15] Synthesis of A-15

[0329]

[0330] The same process as Synthesis Example 1 was carried out except that Cz-D15 (10.0 g, 23.6 mmol) obtained in Preparation Example 4-3 was used instead of Cz-D1 used in Synthesis Example 1, thereby obtaining the target compound A-15 (11.13 g, yield 63%).

[0331] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0332] [Synthesis Example 16] Synthesis of A-16

[0333]

[0334] The same process as Synthesis Example 1 was carried out except that Cz-D16 (10.0 g, 23.6 mmol) obtained in Preparation Example 4-4 was used instead of Cz-D1 used in Synthesis Example 1, thereby obtaining the target compound A-16 (9.02 g, yield 51%).

[0335] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0336] [Synthesis Example 17] Synthesis of B-1

[0337]

[0338] Under nitrogen flow, BCz-D2 (10.0 g, 20.1 mmol) obtained in Preparation Example 5-2, 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, toluene was concentrated, and the solid salt was filtered and purified by recrystallization to obtain the target compound B-1 (10.2 g, yield 62%).

[0339] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0340] [Synthesis Example 18] Synthesis of B-2

[0341]

[0342] The same process as in Synthesis Example 17 was carried out 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, thereby obtaining the target compound B-2 (8.5 g, yield 48%).

[0343] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0344] [Synthesis Example 19] Synthesis of B-3

[0345]

[0346] The same process as in Synthesis Example 17 was carried out 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, thereby obtaining the target compound B-3 (11.1 g, yield 63%).

[0347] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0348] [Synthesis Example 20] Synthesis of B-4

[0349]

[0350] The same process as Synthesis Example 17 was carried out 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, thereby obtaining the target compound B-4 (7.42 g, yield 42%).

[0351] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0352] [Synthesis Example 21] Synthesis of C-1

[0353]

[0354] Under nitrogen flow, 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, toluene was concentrated, and the solid salt was filtered and purified by recrystallization to obtain the target compound C-1 (9.4 g, yield 63%).

[0355] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0356] [Synthesis Example 22] Synthesis of C-2

[0357]

[0358] The same process as Synthesis Example 21 was carried out 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, thereby obtaining the target compound C-2 (7.78 g, yield 44%).

[0359] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0360] [Synthesis Example 23] Synthesis of C-3

[0361]

[0362] The same process as Synthesis Example 21 was carried out 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, thereby obtaining the target compound C-3 (11.67 g, yield 66%).

[0363] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0364] [Synthesis Example 24] Synthesis of C-4

[0365]

[0366] The same process as Synthesis Example 21 was carried out 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, thereby obtaining the target compound C-4 (6.89 g, yield 39%).

[0367] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0368] [Synthesis Example 25] Synthesis of D-1

[0369]

[0370] Under nitrogen flow, 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, toluene was concentrated, and the solid salt was filtered and purified by recrystallization to obtain the target compound D-1 (8.1 g, yield 54%).

[0371] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0372] [Synthesis Example 26] Synthesis of D-2

[0373]

[0374] The same process as Synthesis Example 25 was carried out 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, thereby obtaining the target compound D-2 (7.24 g, yield 41%).

[0375] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0376] [Synthesis Example 27] Synthesis of D-3

[0377]

[0378] The same process as in Synthesis Example 25 was carried out 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, thereby obtaining the target compound D-3 (8.41 g, yield 51%).

[0379] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0380] [Synthesis Example 28] Synthesis of D-4

[0381]

[0382] The same process as Synthesis Example 25 was carried out 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, thereby obtaining the target compound D-4 (5.47 g, yield 31%).

[0383] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0384] [Preparation Example 6] Synthesis of DBF-1

[0385] <Step 1> Synthesis of 4-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan

[0386]

[0387] Under a nitrogen flow, 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.

[0388] After the reaction was completed, the mixture was extracted with dichloromethane, and then MgSO4 was added and filtered. Then, the solvent was removed from the obtained organic layer, and then purified by column chromatography (hexane:DCM=9:1 (v / v)) to obtain 4-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan (48.9 g, yield 51%).

[0389] Mass (theoretical value: 354.83, measured value: 354 g / mol)

[0390] <Step 2> Synthesis of DBF-1

[0391]

[0392] Under a nitrogen stream, 4-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan (48.9 g, 137.7 mmol) obtained in the above <Step 1>, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(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.

[0393] After the reaction, the product was extracted with ethyl acetate, and then water was removed with MgSO 4 , and purified by column chromatography (hexane:DCM=4:1 (v / v)) to obtain DBF-1 (26.4 g, yield 43%).

[0394] Mass (theoretical value: 446.35, measured value: 446 g / mol)

[0395] [Preparation Example 7] Synthesis of DBF-2

[0396] <Step 1> Synthesis of 4-(4-chlorophenyl)-6-phenyldibenzo[b,d]furan

[0397]

[0398] Under a nitrogen flow, 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.

[0399] After the reaction was completed, the mixture was extracted with dichloromethane, and then MgSO4 was added and filtered. Then, the solvent was removed from the obtained organic layer, and then 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%).

[0400] Mass (theoretical value: 354.83, measured value: 354 g / mol)

[0401] <Step 2> Synthesis of DBF-2

[0402]

[0403] Under a nitrogen stream, 4-(4-chlorophenyl)-6-phenyldibenzo[b,d]furan (60.4 g, 170.2 mmol) obtained in the above <Step 1>, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (47.5 g, 187.2 mmol), Pd(dppf)Cl2 (14.9 g, 17.0 mmol), KOAc (48.1 g, 510.4 mmol) and 1,4-dioxane (1000 ml) were mixed and stirred at 130°C for 12 hours.

[0404] After the reaction, the product was extracted with ethyl acetate, and then water was removed with MgSO 4 , and then purified by column chromatography (hexane:DCM=4:1 (v / v)) to obtain DBF-2 (36.5 g, yield 48%).

[0405] Mass (theoretical value: 446.35, measured value: 446 g / mol)

[0406] [Preparation Example 8] Synthesis of DBF-3

[0407] <Step 1> Synthesis of 3-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan

[0408]

[0409] Under a nitrogen flow, 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.

[0410] After the reaction was completed, the mixture was extracted with dichloromethane, and then MgSO4 was added and filtered. Then, the solvent was removed from the obtained organic layer, and then 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%).

[0411] Mass (theoretical value: 354.83, measured value: 354 g / mol)

[0412] <Step 2> Synthesis of DBF-3

[0413]

[0414] Under a nitrogen stream, 3-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan (68.0 g, 191.8 mmol) obtained in the above <Step 1>, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(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.

[0415] After the reaction, the product was extracted with ethyl acetate, and then water was removed with MgSO 4 , and then purified by column chromatography (hexane:DCM=4:1 (v / v)) to obtain DBF-3 (54.8 g, yield 64%).

[0416] Mass (theoretical value: 446.35, measured value: 446 g / mol)

[0417] [Preparation Example 9] Synthesis of DBF-4

[0418] <Step 1> Synthesis of 1-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan

[0419]

[0420] Under a nitrogen flow, 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.

[0421] After the reaction was completed, the mixture was extracted with dichloromethane, and then MgSO4 was added and filtered. Then, the solvent was removed from the obtained organic layer, and then purified by column chromatography (hexane:DCM=9:1 (v / v)) to obtain 1-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan (62.3 g, yield 65%).

[0422] Mass (theoretical value: 354.83, measured value: 354 g / mol)

[0423] <Step 2> Synthesis of DBF-4

[0424]

[0425] Under a nitrogen stream, 1-(3-chlorophenyl)-6-phenyldibenzo[b,d]furan (62.3 g, 175.6 mmol) obtained in the above <Step 1>, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (49.0 g, 193.1 mmol), Pd(dppf)Cl2 (15.4 g, 17.6 mmol), KOAc (49.6 g, 526.7 mmol) and 1,4-dioxane (1000 ml) were mixed and stirred at 130°C for 12 hours.

[0426] After the reaction, the product was extracted with ethyl acetate, and then water was removed with MgSO 4 , and then purified by column chromatography (hexane:DCM=4:1 (v / v)) to obtain DBF-4 (45.4 g, yield 58%).

[0427] Mass (theoretical value: 446.35, measured value: 446 g / mol)

[0428] [Preparation Example 10] Synthesis of DBF-5

[0429] <Step 1> Synthesis of 1-(3-chlorophenyl)-9-phenyldibenzo[b,d]furan

[0430]

[0431] Under a nitrogen flow, 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.

[0432] After the reaction was completed, the mixture was extracted with dichloromethane, and then MgSO4 was added and filtered. Then, the solvent was removed from the obtained organic layer, and then 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%).

[0433] Mass (theoretical value: 354.83, measured value: 354 g / mol)

[0434] <Step 2> Synthesis of DBF-5

[0435]

[0436] Under a nitrogen stream, 1-(3-chlorophenyl)-9-phenyldibenzo[b,d]furan (68.0 g, 191.8 mmol) obtained in the above <Step 1>, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(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.

[0437] After the reaction, the product was extracted with ethyl acetate, and then water was removed with MgSO 4 , and then purified by column chromatography (hexane:DCM=4:1 (v / v)) to obtain DBF-5 (41.9 g, yield 49%).

[0438] Mass (theoretical value: 446.35, measured value: 446 g / mol)

[0439] [Synthesis Example 29] Synthesis of E-1

[0440]

[0441] Under a nitrogen flow, 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.

[0442] After the reaction was completed, the mixture was extracted with dichloromethane, and then MgSO4 was added and filtered. Then, the solvent was removed from the obtained 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%).

[0443] Mass (theoretical value: 641.73, measured value: 641 g / mol)

[0444] [Synthesis Example 30] Synthesis of E-2

[0445]

[0446] 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. Except for this, the same process as Synthesis Example 29 was carried out to obtain the target compound E-2 (11.9 g, yield 74%).

[0447] Mass (theoretical value: 717.83, measured value: 717 g / mol)

[0448] [Synthesis Example 31] Synthesis of E-3

[0449]

[0450] 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. Except for this, the same process as Synthesis Example 29 was carried out to obtain the target compound E-3 (11.4 g, yield 71%).

[0451] Mass (theoretical value: 717.83, measured value: 717 g / mol)

[0452] [Synthesis Example 32] Synthesis of E-4

[0453]

[0454] 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. Except for this, the same process as Synthesis Example 29 was carried out to obtain the target compound E-4 (12.7 g, yield 79%).

[0455] Mass (theoretical value: 717.83, measured value: 717 g / mol)

[0456] [Synthesis Example 33] Synthesis of E-5

[0457]

[0458] The DBF-4 (10.0 g, 22.4 mmol) obtained in Preparation Example 9 was used instead of the 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. Except for this, the same process as Synthesis Example 29 was carried out to obtain the target compound E-5 (9.8 g, yield 61%).

[0459] Mass (theoretical value: 717.83, measured value: 717 g / mol)

[0460] [Synthesis Example 34] Synthesis of E-6

[0461]

[0462] Using 2-([1,1':3',1"-triphenyl]-5'-yl)-4-chloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine (13.7 g, 26.9 mmol) instead of 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine used in Synthesis Example 29, the same process as Synthesis Example 29 was carried out to obtain the target compound E-6 (9.6 g, yield 54%).

[0463] Mass (theoretical value: 793.93, measured value: 793 g / mol)

[0464] [Synthesis Example 35] Synthesis of E-7

[0465]

[0466] The DBF-4 (10.0 g, 22.4 mmol) obtained in Preparation Example 9 was used instead of the 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. Except for this, the same process as Synthesis Example 29 was carried out to obtain the target compound E-7 (9.8 g, yield 62%).

[0467] Mass (theoretical value: 703.85, measured value: 703 g / mol)

[0468] [Synthesis Example 36] Synthesis of E-8

[0469]

[0470] The DBF-3 (10.0 g, 22.4 mmol) obtained in Preparation Example 8 was used instead of the 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. Except for this, the same process as Synthesis Example 29 was carried out to obtain the target compound E-8 (10.8 g, yield 67%).

[0471] Mass (theoretical value: 717.83, measured value: 717 g / mol)

[0472] [Synthesis Example 37] Synthesis of E-9

[0473]

[0474] Using DBF-3 (10.0 g, 22.4 mmol) obtained in Preparation Example 8 instead of DBF-1 (10.0 g, 22.4 mmol) used in Synthesis Example 29, and using 2-([1,1'-biphenyl]-4-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, except for this, the same process as Synthesis Example 29 was carried out to obtain the target compound E-9 (11.4 g, yield 72%).

[0475] Mass (theoretical value: 703.85, measured value: 703 g / mol)

[0476] [Synthesis Example 38] Synthesis of E-10

[0477]

[0478] The DBF-5 (10.0 g, 22.4 mmol) obtained in Preparation Example 10 was used instead of the DBF-1 (10.0 g, 22.4 mmol) used in Synthesis Example 29, and 2-([1,1'-biphenyl]-3-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. Except for this, the same process as Synthesis Example 29 was carried out to obtain the target compound E-10 (10.4 g, yield 66%).

[0479] Mass (theoretical value: 703.85, measured value: 703 g / mol)

[0480] [Example 1] - Production of pellet P1 and fabrication of green organic EL element

[0481] Compound A-1 having hole properties and compound E-1 having electron properties were uniformly mixed in a weight ratio of 6:4, and then the mixture was heated at 20,000 kgf / cm 2 The pellets are formed under pressure of Figure 1 After the pellet P1 shown in (a) is prepared, a green organic EL element is produced according to the following process. At this time, the compound A-1 is a first organic compound having hole characteristics, which is synthesized in Synthesis Example 1, and the compound E-1 is a second organic compound having electron characteristics, which is synthesized in Synthesis Example 29.

[0482] First, we will The glass substrate coated with a thin film of indium tin oxide (ITO) was washed with distilled water ultrasonic. After the distilled water washing, it was ultrasonically cleaned with isopropyl alcohol, acetone, methanol and other solvents and dried, and then transferred to a UV OZONE cleaning machine (Power sonic 405, Hwashintech), and then the substrate was cleaned with UV for 5 minutes, and then the substrate was transferred to a vacuum evaporator.

[0483] On the ITO transparent electrode prepared in this way, the organic EL element is produced by stacking in the order of m-MTDATA (60nm) / TCTA (80nm) / 90wt% of granular material P1 + 10wt% of Ir(ppy)3 (300nm) / BCP (10nm) / Alq3 (30nm) / LiF (1nm) / Al (200nm).

[0484] The structures of m-MTDATA, TCTA, Ir(ppy)3 and BCP are as follows.

[0485]

[0486] [Example 2] to [Example 280] - Preparation of pellets P2 to P280 and green organic EL elements

[0487] In Example 1, except that the compounds A-2 to D-4 described in Table 2 were used instead of the compound A-1 used as the first organic compound, and the compounds E-2 to E-10 described in Table 2 were used instead of the compound E-1 used as the second organic compound, the same method as in Example 1 was carried out to produce pellets P2 to P280 and green organic EL elements using the same. At this time, the mixing ratio of the compound used as the first organic compound and the compound used as the second organic compound was the same as the mixing ratio of the compound A-1 and the compound E-1 described in Example 1.

[0488] [Example 281] - Preparation of pellet P281 and fabrication of green organic EL element

[0489] Pellets P281 and a green organic EL element using the same were prepared in the same manner as in Example 1, except that the compound A-1 and the compound E-1 used in Example 1 were mixed at a weight ratio of 5:5.

[0490] [Example 3] - Manufacture of pellet P282 and production of green organic EL element

[0491] Pellets P282 and a green organic EL element using the same were prepared in the same manner as in Example 1, except that the compound A-1 and the compound E-1 used in Example 1 were mixed at a weight ratio of 7:3.

[0492] [Comparative Example 1] - Preparation of Green Organic EL Element

[0493] A green organic EL element was produced by the same process as in Example 1 except that a simple mixture comA-1 of compound A-1 and compound E-1 (compound A-1: ​​compound E-1 = 6:4 weight ratio) was used instead of pellet P1 used as a luminescent host material when forming the luminescent layer. At this time, the simple mixture comA is different from pellet P1 in that compound A-1 and compound E-1 are uniformly mixed and not press-formed under high pressure. The above-mentioned compound A-1 and compound E-1 are the same as those described in Example 1.

[0494] [Comparative Example 2] - Preparation of Green Organic EL Element

[0495] A simple mixture comB and a green organic EL device using the same were prepared in the same manner as in Comparative Example 1 except that the compound A-1 and the compound E-1 used in Comparative Example 1 were mixed at a weight ratio of 5:5.

[0496] [Comparative Example 3] - Preparation of Green Organic EL Element

[0497] A simple mixture comC and a green organic EL device using the same were prepared in the same manner as in Comparative Example 1 except that the compound A-1 and the compound E-1 used in Comparative Example 1 were mixed at a weight ratio of 7:3.

[0498] [Experimental Example 1] - Determination of the maximum emission wavelength of pellets

[0499] The pellets P1 to P280 prepared by Examples 1 to 280 were formed into films, and their maximum emission wavelengths were measured. The results are shown in Table 1. At this time, the maximum emission wavelengths of the compounds A-1 to D-4 and E-1 to E-10, which were the raw materials of each pellet, were measured, and the maximum emission wavelength of the simple mixture comA of Comparative Example 1 was measured as a control group.

[0500] [Table 1]

[0501]

[0502]

[0503]

[0504]

[0505]

[0506]

[0507]

[0508]

[0509]

[0510]

[0511]

[0512]

[0513] As shown in Table 1 above, if compared with the raw material compounds (Compounds A-1 to D-4 and Compounds E-1 to E-10), it can be confirmed that the pellets P1 to P280 (Examples 1 to 280) of the present invention have the same maximum emission wavelength as the compounds with longer wavelengths.

[0514] [Experimental Example 2]-Performance evaluation of organic light-emitting elements

[0515] The current density of the green organic EL devices prepared in Examples 1 to 280 and Comparative Example 1 was measured at 10 mA / cm 2 Driving voltage, current efficiency and life T 97 , the results are shown in Table 2 below.

[0516] [Table 2]

[0517]

[0518]

[0519]

[0520]

[0521]

[0522]

[0523]

[0524]

[0525]

[0526]

[0527]

[0528]

[0529] As shown in Table 2, compared with the green organic EL element of Comparative Example 1 using the simple mixture comA, the green organic EL element of Example 1 using the pellet P1 of the present invention as the main material of the light-emitting layer has a low driving voltage, high current efficiency and a long life. It can be seen that when the pellet of the present invention is used as an organic material layer material (e.g., main material of the light-emitting layer) of OLED, the performance of the organic electroluminescent element can be improved.

[0530] [Experimental Example 3]

[0531] When manufacturing green organic EL elements in Examples 1, 281 to 282 and Comparative Examples 1 to 3, respectively, a thin film was formed through a continuous process, and the changes in the weight ratios of compound A-1 and compound E-1 in pellets P1, P281 to P282 and simple mixtures comA to ComC before and after the process were measured. The results are shown in Table 3 below.

[0532] [Table 3]

[0533]

[0534]

[0535] As shown in Table 3 above, it is confirmed that when the pellets P1, P281, and P282 (Example 1, Examples 281 to 282) of the present invention are formed into a light-emitting layer thin film of a green organic EL element through a continuous process, a thin film can be formed reproducibly and consistently, compared with the case where a simple mixture of compound A-1 and compound E-1 (Comparison Examples 1 to 3) is formed into a light-emitting layer thin film of a green organic EL element through a continuous process.

Claims

1. A pellet for an organic electroluminescent element, which is formed by pressing two or more organic compound powders including a first organic compound powder and a second organic compound powder, and has a maximum emission wavelength that is the same as the maximum emission wavelength of the organic compound having a longer emission wavelength among the first organic compound and the second organic compound. 2 . The pellet for an organic electroluminescent element according to claim 1 , which has a maximum emission wavelength which is the same as a maximum emission wavelength of a mixture powder of the first organic compound powder and the second organic compound powder.

3. The pellet for an organic electroluminescent element according to claim 1, comprising a first region and a second region. The first region is formed by pressing the first organic compound powder. The second region portion is integrally arranged with the first region portion and is formed by pressure-bonding the second organic compound powder.

4. The pellet for organic electroluminescent element according to claim 3, wherein: The first region portions and the second region portions are alternately arranged from the center toward the outside.

5. The pellet for organic electroluminescent element according to claim 3, wherein: The first region portion and the second region portion are arranged vertically.

6. The pellet for organic electroluminescent element according to claim 5, wherein: The first region portions and the second region portions are arranged alternately.

7. The pellet for organic electroluminescent element according to claim 3, wherein: The first region portions and the second region portions are alternately arranged along the circumferential direction.

8. The pellet for organic electroluminescent element according to claim 7, wherein: The first region portions and the second region portions are arranged alternately up and down.

9. The pellet for organic electroluminescent element according to claim 3, wherein: The pellets have a shape selected from the group consisting of a polyhedron, a cylinder, and a sphere. 10 . The pellet for an organic electroluminescent element according to claim 1 , comprising the first organic compound powder and the second organic compound powder in a weight ratio of 1:99 to 99:

1.

11. The pellet for organic electroluminescent element according to claim 1, wherein The first organic compound powder and the second organic compound powder are both sublimable powders.

12. The pellet for organic electroluminescent element according to claim 1, wherein The first organic compound is a hole-transporting organic compound, and the second organic compound is an electron-transporting organic compound.

13. The pellet for organic electroluminescent element according to claim 12, wherein: The hole-transporting organic compound is a hole-transporting host.

14. The pellet for organic electroluminescent element according to claim 12, wherein: The hole transporting host is a carbazole compound.

15. The pellet for organic electroluminescent element according to claim 12, wherein: The electron-transporting organic compound is an electron-transporting host.

16. The pellet for organic electroluminescent element according to claim 15, wherein The electron transporting host is an azine compound.

17. The pellet for an organic electroluminescent element according to claim 1, wherein the two or more organic compound powders are subjected to a pressure of 20,000 to 40,000 kgf / cm 2 A molded body formed by injection molding under pressure without heat treatment.

18. The pellet for organic electroluminescent element according to claim 1, wherein The first organic compound powder and the second organic compound powder are mixed at 10 -6 The evaporation temperature difference is 0 to 30°C under a pressure of 100 torr. 19 . The pellet for organic electroluminescent element according to claim 1 , wherein the BET specific surface area of ​​the pellet is smaller than the BET specific surface area of ​​a simple mixture of the first organic compound powder and the second organic compound powder. 20 . The pellet for organic electroluminescent element according to claim 1 , which has a surface resistance lower than that of a simple mixture of the first organic compound powder and the second organic compound powder.

21. An organic electroluminescent element comprising an anode, a cathode, and one or more organic layers between the anode and the cathode, At least one of the one or more organic layers is a homogeneous thin film containing the first organic compound and the second organic compound using the pellets according to any one of claims 1 to 20.

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