JP2016143879A - Organic electroluminescent element material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element material having a high triplet energy level.SOLUTION: In an organic electroluminescent element material, units Q having specific structures (charge transporting units) are linked through at least one unit A (divalent alicyclic group).SELECTED DRAWING: None

Description

  The present invention relates to a material for an organic electroluminescent element.

  Organic electroluminescent devices such as organic light emitting diodes (OLEDs) are self-emitting devices that emit light from organic materials in the light emitting layer by recombining holes and electrons injected from the anode and cathode in the light emitting layer. is there.

  For organic electroluminescent elements, materials for organic electroluminescent elements including charge transport materials such as hole transport materials are used. The charge transport material not only has the ability to transport charges to the light emitting layer, but also functions to prevent excitons formed by recombination of holes and electrons in the light emitting layer from entering the charge transport layer. . It is considered that the efficiency of the green and blue OLED elements can be improved particularly when the hole transport material has a high charge mobility and a high triplet energy level.

  For manufacturing an organic electroluminescent device for a coating process, a charge transport material having a polymer structure is useful from the viewpoint of processes such as residual film properties. For example, in Patent Document 1 and Non-Patent Document 1, a polymer material in which units having a fluorene structure and units having a triarylamine structure are alternately arranged on the main chain is used as a hole transport material. Is described.

International Publication No. 2013/018251

Synthetic Metals 160 (2010) 2393-2396

  However, the material of Patent Document 1 has a problem that the triplet energy level is low.

  Then, an object of this invention is to provide the material for organic electroluminescent elements which has a high triplet energy level.

  The present inventors have conducted intensive research to solve the above problems. As a result, it was found that a material for an organic electroluminescence device having a high triplet energy level can be obtained by arranging the charge transporting unit in the main chain of the polymer via an alicyclic group, and the present invention. It came to complete.

That is, the organic electroluminescent element material of the present invention is formed by connecting units Q via at least one unit A;
Unit A each independently represents a divalent alicyclic group having 3 to 22 carbon atoms,
Unit Q is represented by the following formula (1):

In formula (1),
Each of the units X ¹ is independently at least one partial structure selected from the group consisting of arylamines (except that the N atom of the arylamine is composed of only the N atom of carbazole). A monovalent or divalent group having two, and when p is 2, two X ¹ may be linked to each other to form a ring,
p independently represents 1 or 2,
Unit Y ¹ is each independently at least one partial structure selected from the group consisting of carbazole and fluorene (provided that at least one partial structure selected from the group consisting of arylamines (of the arylamine) Represents a p + divalent group having (excluding the case where the N atom has a case except that the N atom is composed only of the N atom of carbazole);
A group represented by
When the ionization potential of the unit X ¹ is IPX ¹ , the electron affinity is EAX ¹ , and the electron affinity of the unit Y ¹ is EAY ¹ , the maximum value of IPX ¹ (IPX _max ) in the entire organic electroluminescent element material, IPX ¹ The relationship between the minimum value (IPX _min ), the maximum value of EAX ¹ (EAX _max ), and the minimum value of EAY ¹ (EAY _min ) satisfies the following formulas 1 and 2.

  ADVANTAGE OF THE INVENTION According to this invention, the organic electroluminescent element material which has a high triplet energy level can be provided.

1 is a diagram illustrating a structure of an organic electroluminescence device according to an embodiment of the present invention.

  Embodiments of the present invention will be described below. In addition, this invention is not limited only to the following embodiment.

  In this specification, “x to y” indicating a range means “x or more and y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

<Material for organic electroluminescence device>
[First form]
The organic electroluminescent element material according to one embodiment of the present invention is formed by connecting units Q via at least one unit A.

  In the organic electroluminescent element material of the present embodiment, the unit A has a function of cutting the conjugation between the charge transporting units (units Q) present on the main chain. Thereby, the triplet energy level of the organic electroluminescent element material can be increased.

  Each unit A independently represents a divalent alicyclic group having 3 to 22 carbon atoms. Specific examples (A-1 to A-22) of unit A are shown below.

  Among the groups shown above, 1,3-adamantanediyl group, 1,4-diamantanediyl group, 4,9-diamantanediyl group, and 3,9-triamantanediyl group are preferable, An adamantanediyl group and a 4,9-diamantanediyl group are more preferable. Since these alicyclic groups have a cage-type molecular structure and are rigid, they can increase the glass transition temperature of the organic electroluminescent element material. As a result, an organic electroluminescent element using the material for an organic electroluminescent element can have excellent heat resistance.

  At least one unit A needs to be present between the charge transporting units (unit Q) in order to break the conjugate between the charge transporting units (unit Q). The number of units A existing between one charge transporting unit (unit Q) is not particularly limited, but is preferably 1 to 3, and more preferably one. When the number of units A is 3 or less, an organic electroluminescent element material having sufficient charge transportability can be obtained.

  In the organic electroluminescent element material of this embodiment, the unit Q has a function of imparting charge transportability. Unit Q is represented by the following formula (1).

In the formula (1), each of the units X ¹ is independently at least one partial structure selected from the group consisting of arylamines (provided that the N atom of the arylamine is composed of only the N atom of carbazole). Represents a monovalent or divalent group. When there are two X ¹ bonded to the unit Y ¹ (when p = 2), the two X ¹ may be connected to each other to form a ring. Specific examples of the unit ^{X 1} a ^{(X 1 -1~X} 1 -18) are shown below.

Among X ¹ -1~X ¹ -18, R each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Here, specific examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl, neopentyl, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n -Linear or branched alkyl groups such as octadecyl group. Of these, n-octyl group and n-hexyl group are preferable from the viewpoint of solubility.

Among X ¹ -1~X ¹ -18, n are each independently an integer of 0 to 5.

  In formula (1), p represents 1 or 2 each independently.

In the formula (1), each of the units Y ¹ is independently at least one partial structure selected from the group consisting of carbazole and fluorene (however, at least one type selected from the group consisting of arylamines) P + divalent group having a partial structure (excluding the case where the N atom of the arylamine has a case where the N atom of the arylamine is composed only of the N atom of carbazole). Specific examples of the unit ^{Y 1} a ^{(Y 1 -1~Y} 1 -10) are shown below.

Among Y ¹ -1~Y ¹ -10, ^{R 1} each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Here, specific examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl, neopentyl, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n -Linear or branched alkyl groups such as octadecyl group. Of these, a methyl group, an ethyl group, and a propyl group are preferable from the viewpoint of charge mobility.

Among Y ¹ -1~Y ¹ -10, ^{R 2} is a phenyl group, bicyclo [4.2.0] octa-1,3,5-trien-7-yl group, a vinyl group, hexenyl group, a styryl group, Or, it represents a (3-ethoxyethane-3-yl) methoxy group. Of these, a phenyl group, a bicyclo [4.2.0] octa-1,3,5-trien-7-yl group, a vinyl group, a hexenyl group, and a styryl group are preferable from the viewpoint of film formability.

Among ^{Y 1 -1~Y 1 -10, - (} X) represents a bond to the unit X. Further,-(A) represents a bond with unit A.

Among Y ¹ -1~Y ¹ -10, n are each independently an integer of 0 to 5.

In the organic electroluminescent element material of the present embodiment, the unit X ¹ and the unit Y ¹ constituting the unit Q satisfy the following relationship. That is, when the ionization potential of the unit X ¹ is IPX ¹ , the electron affinity is EAX ¹ , and the electron affinity of the unit Y ¹ is EAY ¹ , the maximum value of IPX ^{1 in} the whole organic electroluminescent element material (IPX _max ), The minimum value of IPX ¹ (IPX _min ), the maximum value of EAX ¹ (EAX _max ), and the minimum value of EAY ¹ (EAY _min ) satisfy the following Equation 1 and Equation 2.

In the organic electroluminescent element material of this embodiment, the unit Y ¹ having a relatively high electron affinity is disposed on the main chain, and the unit X ¹ having a relatively low electron affinity is disposed as a side chain of the unit Y ¹ . It has the unit Q. Since the conjugation is separated between the unit X and the unit Y by the unit A, the radical anion generated in the material is localized in the unit Y by having such a configuration. Compared to unit Y, unit X tends to cause chemical decomposition and degradation of the molecular structure due to localization of anion radicals, but the material of this embodiment can prevent localization of anion radicals to unit X. Thereby, it becomes possible to improve the durability (electron resistance) against deterioration and chemical decomposition due to radical anionization of the organic electroluminescent element material of this embodiment, and it is possible to suppress deterioration of the material. In addition, by configuring the unit X and the unit Y in this embodiment, the charge mobility of the organic electroluminescent element material can be increased, and higher luminous efficiency can be achieved in the organic electroluminescent element. It becomes possible. The reason why such an effect is obtained is not clear, but the present inventors presume as follows. That is, the unit Q has a smaller rearrangement energy λ ⁺ than a unit in which both the unit X ¹ and the unit Y ¹ are arranged adjacent to each other in a straight line. By having the unit Q having such a small rearrangement energy λ ^+, it is considered that an organic electroluminescent element material having high charge mobility can be obtained. In addition, the said mechanism is a guess to the last, and this invention is not restrict | limited to the said mechanism at all. For reference, in the examples described later, the rearrangement energy λ between an example of the unit Q and the unit when the unit X ¹ and the unit Y ¹ constituting the unit Q are both arranged adjacent to each other in a linear shape. ^{+ Is} shown.

  In the present specification, the ionization potential, the electron affinity, and the rearrangement energy can be calculated by the methods described in the examples.

  In the first embodiment, preferred combinations of units are as follows.

That is, at least one of the units A is a group represented by the following A-16 or A-17,
At least one of the units X ¹ is a group represented by the following X ¹ -1, X ¹ -8, or X ¹ '-14,
At least one of the units Y ¹ is a group represented by the following Y ¹ -1 or Y ¹ -6.

In the above formula, R, R ^a , R ^b , and R ¹ each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and n is each independently an integer of 0 to 5 Represents.

At this time, in X ¹ -1, R represents a hydrogen atom or a hexyl group, n represents 0,
Among X ¹ -8, R represents an octyl group, n represents 0,
In X ¹ ′ -14, R ^a represents an octyl group, R ^b represents a hydrogen atom, n represents 0,
In Y ¹ -1, R ¹ represents a hydrogen atom, n represents 0,
Among Y ¹ -6, ^{R 1} represents a hydrogen atom, n represents represents 0; more preferably.

  By making each unit into the above combination, a material for an organic electroluminescence device having high triplet excitation energy and high hole transportability can be obtained.

[Second form]
The material for an organic electroluminescent element according to another embodiment of the present invention is connected via a charge transporting unit (unit Q and unit X ² ) and at least one unit A. The organic electroluminescent device material according to the present second embodiment, in that the unit X ² is present on the main chain, different from the material for an organic electroluminescent element according to the first embodiment described above.

In the second embodiment, the definition and preferred form of the unit A and the unit Q (unit X ¹ , unit Y ¹ ) are the same as those in the first form described above, and detailed description thereof is omitted here.

In this embodiment, each of the units X ² is independently at least one partial structure selected from the group consisting of arylamines (provided that the N atom of the arylamine is composed of only the N atom of carbazole) Represents a divalent group. Specific examples of the unit ^{X 2} a ^{(X 2 -1~X} 2 -28) are shown below.

Among X ² -1~X ² -28, R each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

Among X ² -1~X ² -28, R each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Here, specific examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl, neopentyl, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n -Linear or branched alkyl groups such as octadecyl group. Of these, a methyl group, an ethyl group, and a propyl group are preferable from the viewpoint of charge mobility.

Among X ² -1~X ² -28, n are each independently an integer of 0 to 5.

In the organic electroluminescent element material of the present embodiment, the unit X ¹ and the unit Y ¹ and the unit X ² constituting the unit Q satisfy the following relationship. That is, when the ionization potential of the unit X ¹ is IPX ¹ , the electron affinity is EAX ¹ , the ionization potential of the unit X ² is IPX ² , the electron affinity is EAX ² , and the electron affinity of the unit Y ¹ is EY ¹ , the organic electric field Maximum value of IPX ¹ and IPX ² (IPX _max ), minimum value of IPX ¹ and IPX ² (IPX _min ), maximum value of EAX ¹ and EAX ² (EAX _max ), and minimum of EY ^{1 in} the entire light emitting device material The relationship between the values (EAY _min ) satisfies the following formula 3 and the following formula 4.

In the organic electroluminescent element material of the present embodiment, the unit Y ¹ having a relatively high electron affinity is disposed on the main chain, and the unit X ¹ having a relatively low electron affinity is a unit as in the first embodiment. It is characterized by having arranged unit Q as a side chain of Y ^1. By having such a configuration, the charge mobility of the organic electroluminescent element material can be increased, and higher luminous efficiency can be achieved in the organic electroluminescent element.

Further, the unit Y ¹ having a relatively high electron affinity and the unit X ² having a relatively low electron affinity are both arranged on the main chain via the unit A. Since the conjugation is separated between the unit X ² and the unit Y ¹ by the unit A, the radical anion generated in the material is localized in the unit Y ¹ by having such a configuration. Compared to unit Y, unit X tends to cause chemical decomposition and degradation of the molecular structure due to localization of anion radicals, but the material of this embodiment can prevent localization of anion radicals to unit X. Thereby, it becomes possible to improve the durability (electron resistance) against deterioration and chemical decomposition due to radical anionization of the organic electroluminescent element material of this embodiment, and it is possible to suppress deterioration of the material.

  In the second embodiment, preferable unit combinations are as follows.

That is, at least one of the units A is a group represented by the following A-16 or A-17,
At least one of the units X ¹ is a group represented by the following X ¹ -1, X ¹ -8, or X ¹ '-14,
At least one of the unit X ² is a group represented by the following X ² -27,
At least one of the units Y ¹ is a group represented by the following Y ¹ -1 or Y ¹ -6.

In the above formula, R, R ^a , R ^b , and R ¹ each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and n is each independently an integer of 0 to 5 Represents.

At this time, in X ¹ -1, R represents a hydrogen atom or a hexyl group, n represents 0,
Among X ¹ -8, R represents an octyl group, n represents 0,
In X ¹ ′ -14, R ^a represents an octyl group, R ^b represents a hydrogen atom, n represents 0,
In X ² -27, R represents a hydrogen atom, n represents 0,
In Y ¹ -1, R ¹ represents a hydrogen atom, n represents 0,
Among Y ¹ -6, ^{R 1} represents a hydrogen atom, n represents represents 0; more preferably.

  By making each unit into the above combination, a material for an organic electroluminescence device having high triplet excitation energy and high hole transportability can be obtained.

[Third form]
The material for an organic electroluminescent element according to still another embodiment of the present invention is connected via a charge transporting unit (unit Q and unit Y ² ) and at least one unit A. The organic electroluminescent device material according to the present third embodiment, in that there are units Y ² on the main chain, different from the material for an organic electroluminescent element according to the first embodiment described above.

In the third embodiment, the definition and preferred form of the unit A and the unit Q (unit X ¹ , unit Y ¹ ) are the same as those in the first form described above, and detailed description thereof is omitted here.

In this embodiment, each of the units Y ² is independently selected from at least one partial structure selected from the group consisting of carbazole, fluorene, dibenzofuran, dibenzothiophene, and triazine (however, selected from the group consisting of arylamines) Represents a divalent group having at least one partial structure (excluding the case where the N atom of the arylamine is composed only of the N atom of carbazole). Specific examples of the unit ^{Y 2} a ^{(Y 2 -1~Y} 2 -13) are shown below.

Among Y ² -1~Y ² -13, R each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, n is independently an integer of 0 to 5.

Among Y ² -1~Y ² -13, R each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Here, specific examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl, neopentyl, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n -Linear or branched alkyl groups such as octadecyl group. Of these, a methyl group, an ethyl group, and a propyl group are preferable from the viewpoint of charge mobility.

Among Y ² -1~Y ² -13, n are each independently an integer of 0 to 5.

In the organic electroluminescent element material of the present embodiment, the unit X ^{1, the} unit Y ¹ , and the unit Y ² constituting the unit Q satisfy the following relationship. That, IPX ¹ the ionization potential of the unit ^{X 1,} EAX ¹ electron affinity, electron affinity of the unit ^{Y 1} EAY ^1, the ionization potential of the unit ^{Y 2} IPY ^2, when the electron affinity EAY ^2, and the organic The maximum value of IPX ¹ (IPX _max ), the minimum value of IPX ¹ (IPX _min ), the maximum value of EAX ¹ (EAX _max ), and the minimum value of EAY ¹ and EAY ² (EAY _min ) in the entire electroluminescent element material Satisfies the following formula 5 and the following formula 6.

In the organic electroluminescent element material of the present embodiment, the unit Y ¹ having a relatively high electron affinity is disposed on the main chain, and the unit X ¹ having a relatively low electron affinity is a unit as in the first embodiment. It is characterized by having arranged unit Q as a side chain of Y ^1. By having such a configuration, the charge mobility of the organic electroluminescent element material can be increased, and higher luminous efficiency can be achieved in the organic electroluminescent element.

Further, by arranging both the unit Y ¹ and the unit Y ² having relatively large electron affinity on the main chain, the number of units Y in the material is relatively increased as compared with the first embodiment, When an organic electroluminescent device emits light, more anion radicals generated in the material can be localized in the unit Y, thereby improving the electron resistance of the material for the organic electroluminescent device compared to the first embodiment. In addition, the deterioration of the material can be further suppressed. On the other hand, there is a possibility that the charge mobility may be lower than that in the first mode by increasing the number of Y units that do not have the charge transporting property as compared with the first mode. In this mode, Y ² is arranged on the main chain. By doing so, it becomes possible to suppress the fall of the relative charge mobility compared with the first form as much as possible.

  In the second embodiment, preferable unit combinations are as follows.

That is, at least one of the units A is a group represented by the following A-16 or A-17,
At least one of the units X ¹ is a group represented by the following X ¹ -1, X ¹ -8, or X ¹ '-14,
At least one of the units Y ¹ is a group represented by the following Y ¹ -1 or Y ¹ -6,
At least one of the units Y ² is a group represented by the following Y ² '-1 or Y ² -12.

In the above formula, R, R ^a , R ^b , and R ¹ each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and n is each independently an integer of 0 to 5 Represents.

At this time, in X ¹ -1, R represents a hydrogen atom or a hexyl group, n represents 0,
Among X ¹ -8, R represents an octyl group, n represents 0,
In X ¹ ′ -14, R ^a represents an octyl group, R ^b represents a hydrogen atom, n represents 0,
In Y ² '-1, R ^a represents ^a hexyl group, R ^b represents a hydrogen atom, n represents 0,
Among Y ² -12, n represents 0,
In Y ¹ -1, R ¹ represents a hydrogen atom, n represents 0,
Among Y ¹ -6, ^{R 1} represents a hydrogen atom, n represents represents 0; more preferably.

  By making each unit the above combination, the number of units X that are charge transport units included in the material is relatively increased as compared with the first embodiment. Thereby, the charge mobility of the organic electroluminescent element material can be improved as compared with the first embodiment. From the above, a material for an organic electroluminescence device having high triplet excitation energy and high charge mobility can be obtained.

[Common features in the first, second, and third embodiments]
The organic electroluminescent element material of the present embodiment is composed of the unit X ¹ and the unit Y ¹ (in the second embodiment, the unit X ¹ , the unit X ² , and the unit Y ¹ ; in the third embodiment, the unit X ¹ , the unit It is preferable that at least one unit of Y ¹ and unit Y ² ) has at least one crosslinking group. In the present specification, the “crosslinking group” means a group that reacts (crosslinks) with the same or different group of structural units located in the vicinity by heating or irradiation with active energy rays to form a new bond. By including a unit having a cross-linking group, a cross-linking reaction occurs by heating or irradiation with an active energy ray, so that it becomes insoluble in a solvent and a stronger film can be formed. As a result, the productivity and durability of the organic electroluminescent element can be further improved.

  The cross-linking group is not particularly limited as long as it can induce a cross-linking reaction by heat or active energy rays. For example, bicyclo [4.2.0] octa-1,3,5-trienyl group, vinyl group, hexenyl group , A styryl group, a (3-ethoxyethane-3-yl) methoxy group, and the like.

  In the organic electroluminescent element material, the ratio of the unit having at least one crosslinking group is not particularly limited, but is preferably 1 to 20 mol%, and preferably 5 to 15 mol%, based on the total number of all units. Is more preferable, and it is further more preferable that it is 8-10 mol%. When the proportion of the unit having at least one crosslinking group is 1 mol% or more, the solubility of the film can be lowered, and when it is 8 mol% or more, it can be completely insolubilized.

In the organic electroluminescent element material of the present embodiment, the above unit A and unit Q (in the second embodiment, unit A, unit Q, and unit X ² ; In the main chain, other units that can be used in the technical field other than the unit A, the unit Q, and the unit Y ² ) may be included. However, from the viewpoint of sufficiently exerting the effects of the present invention, the proportion of other units is preferably 0 to 50 mol% with respect to the total number of all units contained in the organic electroluminescent element material. It is more preferably 10%, and further preferably 0%.

  The terminal of the organic electroluminescent element material of the present invention is not particularly limited and is appropriately defined depending on the type of raw material (monomer) used, but is usually a hydrogen atom.

Unit A and unit Q (in the second embodiment, unit A, unit Q, and unit X ² ; unit A, unit Q, and unit Y ² ) included in the organic electroluminescent element material of this embodiment are respectively Only one type may be used, or two or more types may be combined.

  The number average molecular weight (Mn) of the organic electroluminescent element material of the present embodiment is not particularly limited, but is, for example, 10,000 to 1,000,000, preferably 20,000 to 500,000. It is. When the number average molecular weight (Mn) is 10,000 or more, film formability can be improved. On the other hand, when the number average molecular weight (Mn) is 1,000,000 or less, there is an advantage that embrittlement of the material can be prevented. In this specification, the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

  The manufacturing method of the organic electroluminescent element material of this embodiment is not particularly limited. For example, a monomer having each unit can be easily synthesized by appropriately combining known reactions such as a coupling reaction that can be used in the present technical field after appropriately combining known synthesis reactions. For example, Suzuki-Miyaura coupling (Japanese Patent Laid-Open No. 2008-106241), Buchwald-Hartwig reaction (Japanese Patent Laid-Open No. 2009-287000), Kumada / Tamao / Colleu coupling (Japanese Patent Laid-Open No. 2008-150355). No. Publication), Negishi Coupling (T.-A. Chen and R. D. Rieke, J. Am. Chem. Soc., 114, 10087, (1992)), Yamamoto Coupling (C. Ego, A. C.). (Grimsdale, F. Uckert, G. Yu, G. Srdanov and K. Mullen) can be used.

<Organic electroluminescent device>
The organic electroluminescent element material according to the present invention is used for an organic electroluminescent element. In one aspect of the present invention, an organic electroluminescent device comprising a first electrode, a second electrode, and an organic film disposed between the first electrode and the second electrode, wherein the organic film The organic electroluminescent element in which at least 1 layer of contains said organic electroluminescent element material is provided. From the viewpoint of increasing the efficiency of the device, in a preferred embodiment of the present invention, the organic film containing the material for an organic electroluminescent device according to the present invention is a hole injection layer or a hole transport layer.

  FIG. 1 is a cross-sectional view of an organic electroluminescent device 100 according to an embodiment of the present invention. FIG. 1 shows the first electrode 120 / the hole injection layer 130 / the hole transport layer 140 / the light emitting layer 150 / the electron transport layer 160 / the electron injection layer 170 / the second electrode 180. It is not limited to a simple structure. The organic electroluminescent device has a first electrode / single film having a hole injection function and a hole transport function / a light emitting layer / electron transport layer / second electrode or a first electrode / a hole injection function and a hole transport function. It may have a structure such as a single film / light emitting layer / electron transport layer / electron injection layer / second electrode.

  The organic electroluminescent element according to the present invention may be either a front light emitting type or a back light emitting type.

  With reference to FIG. 1, an organic light emitting device according to an embodiment of the present invention will be described. FIG. 1 is a schematic diagram illustrating an example of the structure of an organic light emitting device according to an embodiment of the present invention.

  As shown in FIG. 1, the organic light emitting device 100 according to an embodiment of the present invention includes a substrate 110, a first electrode 120 disposed on the substrate 110, and a hole injection disposed on the first electrode 120. A layer 130, a hole transport layer 140 disposed on the hole injection layer 130, a light emitting layer 150 disposed on the hole transport layer 140, an electron transport layer 160 disposed on the light emitting layer 150, The electron injection layer 170 arrange | positioned on the electron carrying layer 160 and the 2nd electrode 180 arrange | positioned on the electron injection layer 170 are provided.

  As the substrate 110, a substrate used in a general organic light emitting device can be used. For example, the substrate 110 may be a glass substrate, a semiconductor substrate, or a transparent plastic substrate.

The first electrode 120 is, for example, an anode, and is formed on the substrate 110 using a vacuum deposition method or a sputtering method. Specifically, the first electrode 120 is formed as a transmission electrode using a metal, an alloy, a conductive compound, or the like having a high work function. The first electrode 120 is, for example, transparent and may be formed of indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) or the like having excellent conductivity. . The first electrode 120 may be formed as a reflective electrode using magnesium (Mg), aluminum (Al), or the like.

  The hole injection layer 130 is a layer having a function of facilitating the injection of holes from the first electrode 120, and uses a vacuum deposition method, a spin coating method, an ink jet method, or the like. Formed on the first electrode 120. Further, the hole injection layer 130 may be specifically formed with a thickness of about 10 nm to about 500 nm, more specifically about 20 nm to about 200 nm. The hole injection layer 130 can be formed using a known material in addition to the material for an organic electroluminescence device of the present invention. For example, N, N′-diphenyl-N, N′-bis- [ 4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl-4,4′-diamine (DNTPD), phthalocyanine compounds such as copper phthalocyanine, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino ) Triphenylamine (m-MTDATA), N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (NPB), 4,4 ′, 4 ″ -tris {N, N diphenylamino} tri Phenylamine (TDATA), 4,4 ′, 4 ″ -tris (N, N-2-naphthylphenylamino) triphenylamine (2-TNATA), polyaniline / dodecylben Sulfonic acid (PANI / DBSA), poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (PANI / CSA), or polyaniline / poly (4 -Styrene sulfonate) (PANI / PSS) or the like.

  When the organic electroluminescent element material according to the present invention is used for the hole injection layer, the content of the whole layer is 50 to 100% by mass (dry mass), preferably 90 to 100% by mass (dry mass). It is.

  The hole transport layer 140 is a layer containing a hole transport material having a function of transporting holes, and is formed on the hole injection layer 130 using a vacuum deposition method, a spin coating method, an ink jet method, or the like. In addition, the hole transport layer 140 may be specifically formed with a thickness of about 5 nm to about 500 nm, more specifically about 100 nm to about 250 nm. The hole transport layer 140 can be formed using a known hole transport material in addition to the organic electroluminescent element material of the present invention. For example, N-phenyl carbazole (N-phenyl carbazole), Carbazole derivatives such as polyvinylcarbazole, N, N′-bis (3-methylphenyl) -N, N′-diphenyl- [1,1-biphenyl] -4,4′-diamine (TPD), 4 , 4 ′, 4 ″ -tris (N-carbazolyl) triphenylamine (TCTA), N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (NPB). .

  When the organic electroluminescent element material according to the present invention is used for the hole transport layer, the content of the whole layer is 50 to 100% by mass (dry mass), preferably 90 to 100% by mass (dry mass). It is.

  The light emitting layer 150 is a layer that emits light by phosphorescence, fluorescence, or the like, and is formed on the hole transport layer 140 using a vacuum deposition method, a spin coating method, an ink jet method, or the like. Further, the light emitting layer 150 includes a host material and a dopant material, and may include the organic electroluminescent element material of the present invention. In addition, the light emitting layer 150 may be specifically formed with a thickness of about 10 nm to about 100 nm, more specifically about 20 nm to about 60 nm.

  In addition, the light emitting layer 150 may include other host materials, for example, tris (8-quinolinolato) aluminum (Alq3), 4,4′-N, N′-dicabazole-biphenyl (CBP), poly (n— Vinylcarbazole) (PVK), 9,10-di (naphthalen-2-yl) anthracene (ADN), 4,4 ′, 4 ″ -tris (N-carbazolyl) triphenylamine (TCTA), 1,3,5 -Tris (N-phenylbenzimidazol-2-yl) benzene (TPBI), 3-tert-butyl-9,10-di (naphth-2-yl) anthracene (TBADN), distyrylarylene (DSA), 4, 4'-bis (9-carbazole) -2,2'-dimethyl-biphenyl (dmCBP) may also be included.

  The light emitting layer 150 may be formed as a light emitting layer that emits light of a specific color. For example, the light emitting layer 150 may be formed as a red light emitting layer, a green light emitting layer, and a blue light emitting layer.

  When the light emitting layer 150 is a blue light emitting layer, a known material can be used as the blue dopant. For example, perlene and its derivatives, bis [2- (4,6-difluorophenyl) pyridinate] picoline, for example. An iridium (Ir) complex such as iridium (III) (FIrpic) can be used.

When the light emitting layer 150 is a red light emitting layer, a known material can be used as the red dopant. For example, rubrene and its derivatives, 4-dicyanomethylene-2- (p-dimethylaminostyryl) ) -6-methyl-4H-pyran (DCM) and its derivatives, iridium complexes such as bis (1-phenylisoquinoline) (acetylacetonate) iridium (III) (Ir (piq) ₂ (acac)), osmium (Os ) Complexes, platinum complexes and the like can be used.

When the light emitting layer 150 is a green light emitting layer, a known material can be used as the green dopant. For example, coumarin and its derivatives, tris (2-phenylpyridine) iridium (III) (Ir An iridium complex such as (ppy) ₃ ) or the like can be used.

  When the organic electroluminescent element material according to the present invention is used for the light emitting layer, the content of the light emitting layer with respect to the entire host is 50 to 100% by mass (dry mass), preferably 90 to 100% by mass (dry mass). ).

  The electron transport layer 160 is a layer containing an electron transport material having a function of transporting electrons, and is formed on the light emitting layer 150 by using a vacuum deposition method, a spin coating method, an ink jet method, or the like. In addition, the electron transport layer 160 may be specifically formed with a thickness of about 10 nm to about 100 nm, more specifically about 15 nm to about 50 nm. Note that the electron-transport layer 160 can be formed using a known electron-transport material. For example, a Li complex such as lithium quinolate (Liq), or a quinoline such as tris (8-quinolinolato) aluminum (Alq3) ( quinoline) derivatives, 1,2,4-triazole derivatives (TAZ), bis (2-methyl-8-quinolinolato)-(p-phenylphenolate) -aluminum (BAlq), beryllium bis (benzoquinoline-10-olate) (BeBq2) or the like can be used.

The electron injection layer 170 is a layer having a function of facilitating injection of electrons from the second electrode 180, and is formed on the electron transport layer 160 using a vacuum deposition method or the like. Further, the electron injection layer 170 may be specifically formed with a thickness of about 0.1 nm to about 10 nm, more specifically about 0.3 nm to about 9 nm. Note that the electron injection layer 170 can be formed using a known material. For example, lithium fluoride (LiF), sodium chloride (NaCl), cesium fluoride (CsF), and lithium oxide (Li ₂ O) can be used. , Barium oxide (BaO), lithium chelate (Liq), and the like.

  The second electrode 180 is, for example, a cathode, and is formed on the electron injection layer 170 by vapor deposition or sputtering. Specifically, the second electrode 180 is formed as a reflective electrode using a metal, an alloy, a conductive compound, or the like having a low work function. The second electrode 180 is made of, for example, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( (Mg—Ag) or the like. The second electrode 180 may be formed as a transmissive electrode using indium tin oxide (ITO), indium zinc oxide (IZO), or the like.

  The example of the structure of the organic light emitting device 100 according to one embodiment of the present invention has been described above, but the structure of the organic light emitting device 100 according to one embodiment of the present invention is not limited to the above example. The organic light emitting device 100 according to an embodiment of the present invention may be formed using other known structures of various organic light emitting devices. For example, the organic light emitting device 100 may not include one or more of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, and the electron injection layer 170. In addition, each layer of the organic light emitting device 100 may be formed of a single layer or a plurality of layers.

  Further, the organic light emitting device 100 includes a hole blocking layer between the hole transport layer 140 and the light emitting layer 150 in order to prevent the phenomenon of triplet excitons or holes diffusing into the electron transport layer 160. May be. Note that the hole blocking layer can be formed using, for example, an oxadiazole derivative, a triazole derivative, or a phenanthroline derivative.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

<Measurement methods for various data>
[Ionization potential, electron affinity, and rearrangement energy]
The theoretically calculated values of ionization potential, electron affinity, and rearrangement energy were calculated by the methods shown below.

(Initial molecular structure creation)
The monomer molecular structure was created using a free modeling tool of a molecular modeling visualization application (Perkin Elmer, trade name: ChemBioOffice), and the molecular structure was stored in the Tripos MOL2 format.

(Stable conformation molecular structure creation)
Using the conformational search application (Schrödinger, trade name: MacroModel) for the created initial molecular structure, the stable conformational calculation of the molecular structure was performed, and the most of the obtained conformational structures. An energetically stable structure (stable conformational molecular structure) was obtained. At this time, for the initial molecular structure, the structure optimization calculation was performed in advance using the OPLS2005 molecular force field (chloroform dielectric Born model). The conformational search algorithm was implemented by OPLS2005 molecular force field (chloroform dielectric Born model) using Monte Carlo multiple optimization / low frequency normal mode weighted hybrid method. A structure optimization calculation was performed on the most stable conformational structure obtained by the conformational calculation using an OPLS 2005 molecular force field (chloroform dielectric Born model) to obtain a stable conformational molecular structure.

(Quantum chemical calculation (ionization potential))
Using the quantum chemistry calculation application (Gaussian 09, Rev. D.01), the structure optimization calculation and energy calculation by quantum chemistry theory are performed on the created stable conformation molecular structure, and the molecular structure electron Sought state. The electronic states to be calculated are a molecular state (neutral state) where the charge of the entire monomer molecule is 0 and the spin multiplicity is 1, and a molecular state (cation radical) where the overall charge of the monomer molecule is +1 and the spin multiplicity is 2. Two electronic states were assumed. For both the structure optimization calculation and the energy calculation, a hybrid functional B3LYP using a Beck3 parameter functional based on a density functional theory and a Lee-Yang-Parr functional was used as a computational chemistry model. As the basis function, a Gaussian orbit function linearly coupled basis 6-31G (D) was used for the structural optimization calculation, and a Gaussian orbit function linearly coupled basis 6-31 + G (D, P) was used for the energy calculation. The structure optimization calculation was performed using the Berny algorithm. At the time of energy calculation, quantum chemical calculation was performed using the optimized molecular structure obtained by structure optimization calculation, and at that time, a polarization continuum model (model solvent: toluene) was added as a solvent effect. The neutral state and cation radical energies obtained by quantum chemistry calculations were determined as E _neutral and E _tionalradial , respectively.

(Calculation of ionization potential)
The ionization potential (IP) is obtained by using the neutral state and cation radical energy obtained from the quantum chemical calculation.
IP ₌ was determined as _{E cationradical} -E _neutral.

(Quantum chemical calculation (electron affinity))
Using the quantum chemistry calculation application (Gaussian 09, Rev. D.01), the structure optimization calculation and energy calculation by quantum chemistry theory are performed on the created stable conformation molecular structure, and the molecular structure electron Sought state. The electronic states to be calculated are a molecular state where the charge of the entire monomer molecule is 0 and the spin multiplicity is 1 (neutral state), and a molecular state where the charge of the entire monomer molecule is -1 and the spin multiplicity is 2 (anion radical) These two electronic states were used. For both the structure optimization calculation and the energy calculation, a hybrid functional B3LYP using a Beck3 parameter functional based on a density functional theory and a Lee-Yang-Parr functional was used as a computational chemistry model. As the basis function, a Gaussian orbit function linearly coupled basis 6-31G (D) was used for the structural optimization calculation, and a Gaussian orbit function linearly coupled basis 6-31 + G (D, P) was used for the energy calculation. The structure optimization calculation was performed using the Berny algorithm. At the time of energy calculation, quantum chemical calculation was performed using the optimized molecular structure obtained by structure optimization calculation, and at that time, a polarization continuum model (model solvent: toluene) was added as a solvent effect. The energy of the neutral state and anion radicals obtained by quantum chemical calculation respectively obtained as _{E neutral} and _{E anionradical.}

(Calculation of electron affinity)
The electron affinity (EA) is obtained by using the energy of the neutral state and anion radical obtained from the quantum chemical calculation,
It was determined as EA = E _{neutral −E anionic} .

(Quantum chemical calculation (rearrangement energy))
Using the quantum chemistry calculation application (Gaussian 09, Rev. D.01), the structure optimization calculation and energy calculation by quantum chemistry theory are performed on the created stable conformation molecular structure, and the molecular structure electron Sought state. The electronic states to be calculated are a molecular state (neutral state) where the charge of the entire monomer molecule is 0 and the spin multiplicity is 1, and a molecular state (cation radical) where the overall charge of the monomer molecule is +1 and the spin multiplicity is 2. Two electronic states were assumed. For both the structure optimization calculation and the energy calculation, a hybrid functional B3LYP using a Beck3 parameter functional based on a density functional theory and a Lee-Yang-Parr functional was used as a computational chemistry model. As the basis function, a Gaussian orbit function linearly coupled basis 6-31G (D) was used for the structural optimization calculation, and a Gaussian orbit function linearly coupled basis 6-31 + G (D, P) was used for the energy calculation. The structure optimization calculation was performed using the Berny algorithm. At the time of energy calculation, neutral state and cation radical state quantum chemical calculations were performed for each using the neutral state and the optimized molecular structure in the cation radical obtained by the structure optimization calculation. At that time, a polarization continuum model (model solvent: toluene) was added as a solvent effect. The neutral state and cation radical energy in the optimized structure of the neutral state obtained by the quantum chemical calculation are respectively represented as E _neutral and _cationradial ^* , and the neutral state and cation radical energy in the optimized structure of the cation radical state, respectively. It was determined as E _neutral ^* _, E _{nationalradical} .

(Calculation of rearrangement energy)
The rearrangement energy λ ⁺ for the hole mobility is obtained by using the energy of the neutral state and the cation state obtained from the quantum chemical calculation,
λ ⁺ = E _{nationalradial} ^* −E _{nationalradial +} E _neutral ^* −E _neutral
As sought.

(MacroModel reference)
Schrodinger Release 2014-1: MacroModel, version 10.3, Schrodinger, LLC, New York, NY, 2014.
(Gaussian 09 cited document)
Gaussian 09, Revision D. 01, M.M. J. et al. Frisch, G.M. W. Trucks, H.M. B. Schlegel, G.M. E. Scuseria, M.M. A. Robb, J.M. R. Cheeseman, G.C. Scalmani, V.M. Barone, B.M. Mennucci, G.M. A. Petersson, H.C. Nakatsuji, M .; Caricato, X. Li, H.M. P. Hratchian, A.H. F. Izmaylov, J.M. Bloino, G.M. Zheng, J. et al. L. Sonnenberg, M.M. Hada, M.M. Ehara, K .; Toyota, R.A. Fukuda, J. et al. Hasegawa, M.M. Ishida, T .; Nakajima, Y .; Honda, O .; Kitao, H.M. Nakai, T .; Vreven, J.M. A. Montgomery, Jr. , J. et al. E. Peralta, F.A. Ogliaro, M.M. Bearpark, J.A. J. et al. Heyd, E .; Brothers, K.M. N. Kudin, V.M. N. Staroverov, T .; Keith, R.A. Kobayashi, J. et al. Normand, K.M. Raghavachari, A.R. Rendell, J.M. C. Burant, S.M. S. Iyengar, J.A. Tomasi, M.M. Cossi, N .; Rega, J .; M.M. Millam, M.M. Klene, J .; E. Knox, J .; B. Cross, V.D. Bakken, C.I. Adamo, J .; Jaramillo, R.A. Gomperts, R.A. E. Stratmann, O.M. Yazyev, A.M. J. et al. Austin, R .; Cammi, C.I. Pomelli, J.M. W. Ochterski, R.M. L. Martin, K.M. Morokuma, V.M. G. Zakrzewski, G.M. A. Voth, P.M. Salvador, J.M. J. et al. Dannenberg, S.M. Dapprich, A.D. D. Daniels, O.D. Farkas, J .; B. Foresman, J.M. V. Ortiz, J.A. Cioslowski, and D.C. J. et al. Fox, Gaussian, Inc. , Wallingford CT, 2013.

The values of ionization potential, electron affinity, and rearrangement energy λ ⁺ of the main molecular structure are shown below.

[Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw)]
The number average molecular weight (Mn) and dispersity (Mw / Mn) in terms of polystyrene were determined by GPC (manufactured by Shimadzu Corporation, trade name: LC-20AD). At this time, each organic electroluminescent element material to be measured was dissolved in tetrahydrofuran so as to have a concentration of about 0.05% by mass, and 20 μL was injected into GPC. Tetrahydrofuran (THF) was used for the mobile phase of GPC, and it was allowed to flow at a flow rate of 1.0 mL / min. As the column, PLgel MIXED-B (manufactured by Polymer Laboratories) was used. A UV-VIS detector (manufactured by Shimadzu Corporation, trade name: SPD-10AV) was used as the detector.

[NMR measurement]
NMR measurement was performed by dissolving 5 to 20 mg of a measurement sample in about 0.5 mL of deuterated chloroform, and using NMR (BRUKER, Inc., trade name: AVANCE III 300).

[Measurement of glass transition temperature (Tg)]
The glass transition temperature (Tg) was measured by DSC (manufactured by Seiko Instruments Inc., trade name: DSC6000). Each organic electroluminescent element material was heated to a heating rate of 250 ° C. at 10 ° C. per minute, and then rapidly cooled to 50 ° C. And it measured to 250 degreeC with the temperature increase rate of 10 degreeC / min.

[Measurement of triplet energy levels]
Each organic electroluminescent element material was dissolved in toluene at a concentration of 3.2% by mass, applied by spin coating at a rotational speed of 1600 rpm, dried on a hot plate at 250 ° C. for 60 minutes, and having a thickness of about 70 nm. A membrane was obtained. The sample was cooled to 77 K, and a light emission (Photo Luminescence: PL) spectrum was measured using a known measuring apparatus. The triplet energy level was calculated from the peak value on the shortest wavelength side of the PL spectrum.

[Measurement of charge mobility]
Poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonate) diluted with ethanol to a glass substrate with a 150 nm thick indium-tin oxide (ITO) transparent conductive film by sputtering. Baytron PH510 (manufactured by HC Syarck), which is a dispersion of (PEDOT / PSS) = 1: 1.25, is formed to a thickness of 20 nm by spin coating, and is dried on a hot plate at 220 ° C. for 3 minutes. did. Thereafter, each organic electroluminescent element material was dissolved in toluene at a concentration of 3.2% by mass, applied by spin coating at a rotational speed of 1600 rpm, and dried on a hot plate at 250 ° C. for 60 minutes to obtain a film. . The thickness of this film was about 70 nm. Subsequently, molybdenum oxide with a thickness of 5 nm, gold with a thickness of 10 nm, and aluminum with a thickness of 80 nm were laminated. The charge mobility of the charge mobility measurement sample thus prepared was measured by a known impedance spectroscopy.

<Synthesis of materials for organic electroluminescent elements>
[Synthesis Example 1: Synthesis of Compound 1]
The synthesis process of Compound 1 is shown below.

  Into a nitrogen-substituted three-necked flask, 2,7-dibromofluorenone (3.00 g), triphenylamine (10.9 g), toluene (44 mL) and methanesulfonic acid (1.71 g) were added and refluxed for 6 hours. . Chloroform was added to the reaction solution cooled to room temperature, and insoluble matters were filtered off. The eluate was distilled off under reduced pressure, and the obtained residue was purified by column chromatography packed with silica gel, and 4,4 ′-(2,7-dibromo-9H-fluorene-9,9-diylbis (N, N-diphenylaniline) was obtained (3.90 g).

  To a nitrogen-substituted three-necked flask, 4,4 ′-(2,7-dibromo-9H-fluorene-9,9-diyl) bis (N, N-diphenylaniline) (1.50 g), 4,4, 5,5-tetramethyl-1,3,2-dioxaborolane (2.04 g), potassium acetate (1.11 g), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (0.025 g) and dioxane (36 mL) were added, and the mixture was refluxed for 5 hours and cooled to room temperature. The reaction solution was filtered through celite, and the solvent was distilled off under reduced pressure. The obtained residue was purified by column chromatography packed with silica gel to obtain Compound 1 (1.30 g).

¹ H-NMR (300 MHz / CDCl ₃ ): δ [ppm] 7.85-7.76 (m, 6H), 7.21-7.19 (m, 8H), 7.10-7.05 (m 8H), 7.00-6.95 (m, 4H), 6.91-6.88 (m, 4H), 1.34 (s, 24H).

[Synthesis Example 2: Synthesis of Compound 2]
The synthesis process of Compound 2 is shown below.

  3M-phenylmagnesium bromide-diethyl ether solution (550 mL) is placed in a four-necked flask purged with argon, the solvent is distilled off under reduced pressure, 1-bromoadamantane (118 g) and dichloromethane (1380 mL) are added, and the mixture is refluxed for 1 day. did. After cooling to room temperature, ice-cooled, 2N-HCl (1320 mL) was added, extracted with dichloromethane, the organic phase was washed with saturated brine, dried over sodium sulfate, the solvent was distilled off under reduced pressure, and column chromatography was performed. To obtain 1-phenyladamantane (118 g).

  Acetic acid (1100 mL), acetic anhydride (1100 mL), and chromium trioxide (157 g) were added to a four-necked flask replaced with argon, and the mixture was ice-cooled. 1-Phenyladamantane (118 g) was added and ice-cooled for 1 day. Water (650 mL) and saturated brine (650 mL) were added, and the mixture was extracted with pentane and ethyl acetate. The organic phase was washed with saturated brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid was dissolved in methanol (2000 mL), 2M-NaOH aqueous solution (600 mL) was added, and the mixture was stirred for 1 hour. The solvent was distilled off from the organic phase under reduced pressure, and the resulting solid was purified by column chromatography to obtain 1-phenyl-3-hydroadamantane (81.1 g).

  To a four-necked flask purged with argon, 1-phenyl-3-hydroadamantane (81.1 g), acetic acid (2250 mL), 48% -hydrobromic acid (1500 mL) were added, and the internal temperature was kept at 60 ° C. Stir for minutes. The mixture was further stirred at room temperature for 40 minutes, and water (1500 mL) was added. The mixture was extracted with diethyl ether and dichloromethane and dried over sodium sulfate. The solvent was distilled off under reduced pressure until the solvent was only acetic acid, and the solid was filtered off and washed with hexane to obtain crude 1-phenyl-3-bromoadamantane (98.1 g).

  To a four-necked flask substituted with argon, crude 1-phenyl-3-bromoadamantane (98.1 g) and water (461 g) were added, bromine (256 g) was added dropwise, stirred at room temperature for 10 minutes, and chloroform (2000 mL). ) And an aqueous sodium sulfite solution (2000 mL) was added. The mixture was extracted with chloroform, washed with saturated brine, and dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1-bromophenyl-3-bromoadamantane (101 g).

  Iron (III) chloride (3.85 g), carbon disulfide (2200 ml), and 9,9-dihexylfluorene (40.9 g) were added to a four-necked flask replaced with argon. 1-Bromophenyl-3-bromoadamantane (101 g) dissolved in carbon disulfide (400 mL) was added dropwise, and the internal temperature was kept at 46 ° C. and stirred for 24 hours. Water (2000 mL) was added, and the mixture was extracted with dichloromethane and saturated. Washed with brine and dried over sodium sulfate. The solvent was distilled off under reduced pressure and purified by column chromatography to obtain Compound 2 (48.1 g).

¹ H-NMR (300 MHz / CDCl ₃ ): δ [ppm] 7.58 (d, 2H), 7.46-7.43 (m, 4H), 7.32-7, 25 (m, 8H), 2.34 (s, 4H), 2.03-1.81 (m, 28H), 1.09-1.03 (m, 12H), 0.76-0.62 (m, 10H).

[Synthesis Example 3: Synthesis of Compound 3]
The synthesis process of Compound 3 is shown below.

  A four-necked flask purged with argon was charged with iron (III) chloride (450 mg) and bromobenzene (108 g), and heated at 60 ° C. for 10 minutes. 1,3-dibromoadamantane (40.2 g) was dissolved in bromobenzene (215 g) and added dropwise thereto, and the mixture was stirred at 60 ° C. for 4 hours. The mixture was allowed to cool to room temperature, water (300 mL) was added, extracted with toluene, and the organic phase was washed with saturated brine. After drying with sodium sulfate, the solvent was distilled off to obtain a crude product. The crude product was recrystallized to obtain compound 3 (32.3 g).

¹ H-NMR (300 MHz / CDCl ₃ ): δ [ppm] 7.44 (d, 4H), 7.43 (d, 4H), 2.45 to 2.22 (br, 2H), 2.10 1.82 (br, 10H), 1.82-1.70 (br, 2H).

  [Example 1: Synthesis of material 1 for organic electroluminescent element]

Compound 1 (0.734 g), Compound 2 (0.519 g), palladium acetate (1.81 mg), tris (2-methoxyphenyl) phosphine (11.3 mg), toluene (20 mL) in a four-necked flask substituted with argon 20% by mass of tetraethylammonium hydroxide aqueous solution (2.96 g) was added and refluxed for 7 hours. Compound 1 (73.4 mg) dissolved in toluene (2 mL) was added dropwise and heated at 105 ° C. for 3 hours, and phenylboric acid (0.100 g) diluted with toluene (2 mL) was added dropwise and heated at 105 ° C. for 3 hours. The temperature was lowered to 85 ° C., sodium N, N-diethyldithiocarbamate trihydrate (0.907 g) dissolved in ion-exchanged water (14 mL) was added dropwise, and the mixture was stirred for 6 hours. After separating the organic phase from the aqueous phase, the organic phase was washed with water, a 3% by mass acetic acid aqueous solution and ion-exchanged water. The organic phase was added dropwise to a large excess of methanol / acetone (1/1 (v / v)), and the precipitated solid was filtered off. The solid was passed through column chromatography packed with silica gel / alumina, and the solvent was distilled off under reduced pressure. Reprecipitation was performed using THF as a good solvent and methanol / acetone (1/1, v / v) as a poor solvent, and the precipitated solid was separated by filtration and dried to obtain an organic electroluminescent element material 1 (0.689 g). . The number average molecular weight (Mn) of the material 1 for organic electroluminescent elements was 64,300, and the degree of dispersion (Mw / Mn) was 2.42. The glass transition temperature (Tg) was 162 ° C., the relative triplet energy level was 1.2 with Comparative Example 1 being 1.0, and the relative charge mobility was 10 with Comparative Example 1 being 1.0. In addition, the material 1 for organic electroluminescent elements includes unit A (unit A-16), unit X ¹ (unit 1-1; IP = 5.59 [eV], EA = 0.43 [eV]), unit Y ¹ (unit 4-4; IP = 5.78 [eV], EA = 1.26 [eV]), unit Y ² (unit 2-78; IP = 6.09 [eV], EA = 0.63 [ eV]). The results are shown in Table A below.

  [Example 2: Synthesis of organic electroluminescent element material 2]

Compound 1 (0.971 g), compound 3 (0.477 g), palladium acetate (2.39 mg), tris (2-methoxyphenyl) phosphine (15.0 mg), toluene (27 mL) in a four-necked flask substituted with argon 20% by mass of tetraethylammonium hydroxide aqueous solution (3.92 g) was added and refluxed for 7 hours. Compound 1 (97.1 mg) dissolved in toluene (2 mL) was added dropwise and heated at 105 ° C. for 3 hours, and phenylboric acid (0.500 g) diluted with toluene (2 mL) was added dropwise and heated at 105 ° C. for 3 hours. The temperature was lowered to 85 ° C., sodium N, N-diethyldithiocarbamate trihydrate (1.20 g) dissolved in ion-exchanged water (19 mL) was added dropwise, and the mixture was stirred for 6 hours. After separating the organic phase from the aqueous phase, the organic phase was washed with water, a 3% by mass acetic acid aqueous solution and ion-exchanged water. The organic phase was added dropwise to a large excess of methanol / acetone (1/1, v / v), and the precipitated solid was filtered off. The solid was passed through column chromatography packed with silica gel / alumina, and the solvent was distilled off under reduced pressure. Reprecipitation was performed using THF as a good solvent and methanol / acetone (1/1, v / v) as a poor solvent, and the precipitated solid was separated by filtration and dried to obtain an organic electroluminescent element material 2 (0.732 g). . The number average molecular weight (Mn) of the material 2 for organic electroluminescent elements was 53,800, and the degree of dispersion (Mw / Mn) was 2.12. The glass transition temperature (Tg) was 153 ° C., the relative triplet energy level was 1.2 with Comparative Example 1 being 1.0, and the relative charge mobility was 9.3 with Comparative Example 1 being 1.0. . Note that the organic electroluminescent element material 2, unit A (unit A-16), unit ^{X 1} (unit 1-1; IP = 5.59 [eV] , EA = 0.43 [eV]), units Y ¹ (unit 4-4; IP = 5.78 [eV], EA = 1.26 [eV]). The results are shown in Table A below.

[Comparative Example 1]
As the organic electroluminescent element material 3 of Comparative Example 1, commercially available poly [(9,9-dioctylfluorenyl) 2,7-diyl] -co-4,4 ′-(N- (4-sec-butyl) Phenyl) diphenylamine] (TFB) was used as is.

The number average molecular weight (Mn) of the organic electroluminescent element material 3 was 28,300, and the degree of dispersion (Mw / Mn) was 2.64. The glass transition temperature (Tg) was 121 ° C. The triplet energy level of the organic electroluminescent element material 3 was set to 100 (reference value). In addition, the organic electroluminescent element material 3 does not have the unit A and the unit Q, but the unit Y ² (unit 2-78; IP = 6.09 [eV], EA = 0.63 [eV]), unit X ² (unit 2-83; IP = 5.37 [eV], EA = 0.36 [eV]). The results are shown in Table A below.

  From the results shown in Table A, it was shown that the organic photoelectric conversion material according to the present invention has a high triplet energy level.

  Moreover, it turned out that the organic photoelectric conversion material of Example 1 and 2 has a high glass transition temperature by having the divalent group which has an adamantane structure as the unit A.

  Moreover, it turned out that the organic photoelectric conversion material of Example 1 and 2 has a high charge mobility by having the unit Q which has a specific structure.

100 organic electroluminescent device,
110 substrates,
120 first electrode;
130 hole injection layer,
140 hole transport layer,
150 light emitting layer,
160 electron transport layer,
170 electron injection layer,
180 Second electrode.

Claims (12)

A material for an organic electroluminescence device, wherein the unit Q is connected via at least one unit A;
Each of the units A independently represents a divalent alicyclic group having 3 to 22 carbon atoms,
The unit Q has the following formula (1):
In formula (1),
Each of the units X ¹ is independently at least one partial structure selected from the group consisting of arylamines (except that the N atom of the arylamine is composed of only the N atom of carbazole). A monovalent or divalent group having two, and when p is 2, two X ¹ may be linked to each other to form a ring,
p independently represents 1 or 2,
Unit Y ¹ is each independently at least one partial structure selected from the group consisting of carbazole and fluorene (provided that at least one partial structure selected from the group consisting of arylamines (of the arylamine) Represents a p + divalent group having (excluding the case where the N atom has a case except that the N atom is composed only of the N atom of carbazole);
A group represented by
When the ionization potential of the unit X ¹ is IPX ¹ , the electron affinity is EAX ¹ , and the electron affinity of the unit Y ¹ is EAY ¹ , the maximum value (IPX _max ) of IPX ^{1 in} the whole organic electroluminescent element material , IPX ¹ minimum value (IPX _min ), EAX ¹ maximum value (EAX _max ), and EAY ¹ minimum value (EAY _min ) satisfy the following Equation 1 and Equation 2.
It said unit X ¹ are each independently any group among the groups represented by the following X ¹ -1～X 1 ^-18, material for an organic electroluminescent element according to claim 1.
Among X ¹ -1~X ¹ -18, R each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, n is independently an integer of 0 to 5. Unit Q and unit X ² is an organic electroluminescence element material formed by connected via at least one unit A;
Each of the units A independently represents a divalent alicyclic group having 3 to 22 carbon atoms,
The unit Q has the following formula (1):
In formula (1),
Each of the units X ¹ is independently at least one partial structure selected from the group consisting of arylamines (except that the N atom of the arylamine is composed of only the N atom of carbazole). A monovalent or divalent group having two, and when p is 2, two X ¹ may be linked to each other to form a ring,
p independently represents 1 or 2,
Unit Y ¹ is each independently at least one partial structure selected from the group consisting of carbazole and fluorene (provided that at least one partial structure selected from the group consisting of arylamines (of the arylamine) Represents a p + divalent group having a (excluding the case where the N atom has a case except that the N atom is composed only of the N atom of carbazole),
Each of the units X ² is independently at least one partial structure selected from the group consisting of arylamines (except that the N atom of the arylamine is composed of only the N atom of carbazole). Represents a divalent group having;
A group represented by
When the ionization potential of the unit X ¹ is IPX ¹ , the electron affinity is EAX ¹ , the ionization potential of the unit X ² is IPX ² , the electron affinity is EAX ² , and the electron affinity of the unit Y ¹ is EAY ¹ , Maximum value of IPX ¹ and IPX ² (IPX _max ), minimum value of IPX ¹ and IPX ² (IPX _min ), maximum value of EAX ¹ and EAX ² (EAX _max ), and EY ^{1 in the} entire organic electroluminescent device material The relationship of the minimum value (EAY _min ) satisfies the following formula 3 and the following formula 4.
It said unit ^{X 1} are each independently any group among the groups represented by the following ^{X 1 -1~X} 1 -18,
It said unit X ² are each independently any group among the groups represented by the following X ² -1~X ^{2 -28,} material for an organic electroluminescent element according to claim 3;
Among X ¹ -1~X ¹ -18, R each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, n is independently an integer of 0 to 5.
Among X ² -1~X ² -28, R each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, n is independently an integer of 0 to 5. Unit Q and the unit Y ² is an organic electroluminescence element material formed by connected via at least one unit A;
Each of the units A independently represents a divalent alicyclic group having 3 to 22 carbon atoms,
The unit Q has the following formula (1):
In formula (1),
Each of the units X ¹ is independently at least one partial structure selected from the group consisting of arylamines (except that the N atom of the arylamine is composed of only the N atom of carbazole). A monovalent or divalent group having two, and when p is 2, two X ¹ may be linked to each other to form a ring,
p independently represents 1 or 2,
Unit Y ¹ is each independently at least one partial structure selected from the group consisting of carbazole and fluorene (provided that at least one partial structure selected from the group consisting of arylamines (of the arylamine) Represents a p + divalent group having a (excluding the case where the N atom has a case except that the N atom is composed only of the N atom of carbazole),
Each of the units Y ² independently has at least one partial structure selected from the group consisting of carbazole, fluorene, dibenzofuran, dibenzothiophene, and triazine (provided that the arylamine is not a partial structure). Represents a divalent group having at least one partial structure selected from the group consisting of amines (excluding the case where the N atom of the arylamine has only the N atom of carbazole). ;
A group represented by
IPX ¹ an ionization potential of the unit ^{X 1,} EAX ¹ electron affinity, electron affinity of the unit ^{Y 1} EAY ^1, the ionization potential of the unit ^{Y 2} IPY ^2, when the electron affinity EAY ^2, and, The maximum value of IPX ¹ (IPX _max ), the minimum value of IPX ¹ (IPX _min ), the maximum value of EAX ¹ (EAX _max ), and the minimum value of EAY ¹ and EAY ² (EAY) in the entire organic electroluminescent element material _min )) satisfies the following formulas 5 and 6.
It said unit ^{X 1} are each independently any group among the groups represented by the following ^{X 1 -1~X} 1 -18,
The unit Y ² are each independently any group among the groups represented by the following Y ² -1~Y ^{2 -13,} material for an organic electroluminescent element according to claim 5;
Among X ¹ -1~X ¹ -18, R each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, n is independently an integer of 0 to 5.
Among Y ² -1~Y ² -13, R each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, n is independently an integer of 0 to 5. The units A are each independently any one of groups represented by the following A-1 to A-22,
Said unit ^{Y 1} are each independently any group among the groups represented by the following ^Y 1 -1～Y ¹ -10, organic electroluminescent according to any one of claims 1 to 6 Materials for light-emitting elements;
Among Y ¹ -1~Y ¹ -10, ^{R 1} each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, ^{R 2} are each independently phenyl group, bicyclo [4 .2.0] represents an octa-1,3,5-trien-7-yl group, a vinyl group, a hexenyl group, a styryl group, or a (3-ethoxyethane-3-yl) methoxy group, and-(X) represents , Represents a bond with unit X,-(A) represents a bond with unit A, and n independently represents an integer of 0 to 5. At least one of the units A is a group represented by the following A-16 or A-17,
At least one of the units X ¹ is a group represented by the following X ¹ -1, X ¹ -8, or X ¹ '-14,
The organic electroluminescent element material according to claim 1, wherein at least one of the units Y ¹ is a group represented by the following Y ¹ -1 or Y ¹ -6.
In the above formula, R, R ^a , R ^b , and R ¹ each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and n is each independently an integer of 0 to 5 Represents. At least one of the units A is a group represented by the following A-16 or A-17,
At least one of the units X ¹ is a group represented by the following X ¹ -1, X ¹ -8, or X ¹ '-14,
At least one of the units X ² is a group represented by the following X ² -27,
At least one of the unit Y ¹ is a group represented by the following Y ¹ -1 or Y ¹ -6, material for an organic electroluminescent element according to claim 3.
In the above formula, R, R ^a , R ^b , and R ¹ each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and n is each independently an integer of 0 to 5 Represents. At least one of the units A is a group represented by the following A-16 or A-17,
At least one of the units X ¹ is a group represented by the following X ¹ -1, X ¹ -8, or X ¹ '-14,
At least one of the units Y ¹ is a group represented by the following Y ¹ -1 or Y ¹ -6,
At least one of the unit ^{Y 2} is a group represented by the following ^{Y 2} '-1 or ^Y 2 -12, material for an organic electroluminescent element according to claim 5.
In the above formula, R, R ^a , R ^b , and R ¹ each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and n is each independently an integer of 0 to 5 Represents. A first electrode;
A second electrode;
An organic film disposed between the first electrode and the second electrode;
An organic electroluminescent device comprising:
At least 1 layer of the said organic film is an organic electroluminescent element containing the organic electroluminescent element material of any one of Claims 1-10.   The organic electroluminescent element according to claim 11, wherein the organic film containing the material for an organic electroluminescent element is a hole injection layer or a hole transport layer.