JPWO2020171190A1 - Polymers, organic electroluminescent devices, organic EL display devices and organic EL lighting - Google Patents

Abstract

An object of the present invention is to provide a polymer having high hole injection transport ability and high durability and a composition for an organic electroluminescent device containing the polymer, and an organic having high brightness and a long drive life. An object of the present invention is to provide an electroluminescent element, and an object of the present invention is to provide an organic electroluminescent element having a low drive voltage and a long life. A polymer containing a repeating unit represented by the following formula (1). In the formula, G represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a C atom, an N atom, a B atom or a P atom. , Ar2 to Ar4 each independently have a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. Ar5 represents a divalent group in which a plurality of aromatic heterocyclic groups which may have a optionally aromatic hydrocarbon group or a substituent are directly linked or via a linking group, and Ar5 has a substituent. May have an aromatic hydrocarbon group, an aromatic heterocyclic group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent and an aromatic which may have a substituent. A group selected from the group heterocyclic groups represents a monovalent group in which a plurality of groups are directly linked or linked via a linking group, and Ar6 represents a hydrogen atom or a substituent. "-*" In Ar1 is the connection position with G in the formula (1).

Description

The present invention relates to a polymer, an organic electroluminescent element, and an organic EL display device and organic EL lighting having the organic electroluminescent element.

Various electronic devices that utilize organic EL elements, such as organic EL lighting and organic EL displays, have been put into practical use. Since the applied voltage of the organic electroluminescent element is low, the power consumption is low and it is possible to emit three primary colors. Therefore, it has begun to be applied not only to large display monitors but also to small and medium-sized displays such as mobile phones and smartphones. ..
The organic electroluminescent device is manufactured by stacking a plurality of layers such as a light emitting layer, a charge injection layer, and a charge transport layer. Currently, most organic electroluminescent devices are manufactured by vapor-filming an organic material under vacuum, but the vacuum-film deposition method complicates the vapor deposition process and is inferior in productivity. It is extremely difficult to increase the size of lighting and display panels with organic electroluminescent devices manufactured by the vacuum vapor deposition method.

In recent years, a wet film forming method (coating method) has been studied as a process for efficiently manufacturing an organic electroluminescent device that can be used for a large-scale display or lighting. The wet film forming method has an advantage that a stable layer can be easily formed as compared with the vacuum film deposition method, and is expected to be applied to mass production of displays and lighting devices and to large devices.
The advantage of the wet film deposition method over the vacuum film deposition method is that more material types can be used in one layer. In the vacuum vapor deposition method, it becomes difficult to control the vapor deposition rate to a constant level as the number of material types increases, whereas in the wet film deposition method, even if the material types increase, as long as each material is dissolved in an organic solvent, it is sufficient. It is possible to produce ink with a constant component ratio.

However, since the wet film formation method is difficult to stack, the drive stability is inferior to that of the device by the vacuum vapor deposition method, and the current situation is that the drive stability has not reached the practical level except for a part.

Therefore, a charge-transporting polymer having a crosslinkable group is desired and is being developed for laminating by a wet film forming method. For example, Patent Documents 1 to 3 disclose an organic electroluminescent device containing a polymer having a specific repeating unit and laminated by a wet film forming method.

Patent Documents 4 and 5 disclose a hole injection transporting material having a structure in which a fluorene ring or a carbazole ring and a phenylene ring having no substituent are bonded to the main chain of the polymer.

Patent Document 6 describes that it is preferable that the polymer having a triarylamine repeating unit contains a fluorene ring in the main chain, and further, the polymer main chain is twisted by containing a phenylene group having a substituent. Is described to increase the triple term energy of the polymer.
Patent Document 7 discloses a compound in which a phenylene group having a substituent is linked between nitrogen atoms of the main chain amine of an arylamine polymer or oligomer.
Patent Document 8 discloses that a mixed layer containing an arylamine polymer or oligomer having a polymerizable substituent is used as a hole transport layer. Further, it is described as an effect that the thermal stability of the layer can be improved by polymerizing the polymer or the oligomer, and that the polymerized layer is not dissolved when the light emitting layer is further applied thereto.

Further, Patent Documents 9 to 12 disclose a polymer having a carbazole structure in a side chain structure of a polymer having an arylamine structure. Patent Documents 9 to 11 have only one side-chain structure carbazole, and Patent Documents 9 and 12 indicate that the side-chain structure carbazole is directly bonded to the nitrogen atom of the main chain amine. Discloses a structure in which there are two side chain carbazoles.

International Publication No. 2009/123269 Japanese Unexamined Patent Publication No. 2013-045986 International Publication No. 2013/191088 Japanese Unexamined Patent Publication No. 2016-08437 Japanese Unexamined Patent Publication No. 2017-002287 Special table 2007-520858 Special table 2013-513658 JP-A-2010-034496 International Publication No. 2011/099531 International Publication No. 2016/031639 International Publication No. 2009/11360 International Publication No. 2008/126393

However, the conventional technology is not sufficient in terms of the performance of the organic electroluminescent element for lighting and display applications, and further reduction of the drive voltage and improvement of the drive life have been required.

These elements described in Patent Documents 1 to 3 have problems that the brightness is low and the drive life is short. Therefore, it is required to improve the charge injection transport ability and durability of the charge transport material.

_{The polymers described in Patent Documents 4 and 5 have low excited singlet energy levels (S 1} ) and excited triplet energy levels (T ₁ ) due to the spread of the π-conjugated system in the main chain, and are light-emitting materials. There is a problem that quenching occurs due to energy transfer from the luminescence exciter and the luminescence efficiency is lowered. Therefore, a charge-transporting material having a high S1 level and T1 level is required.

Although F8-TFB (fluorene + triphenylamine system) is described in Examples as an arylamine polymer containing a fluorene ring in the main chain in Patent Document 6, F8-TFB is between fluorene and the nitrogen atom of amine. Since phenylene does not have a substituent, it is not twisted, and LUMO spreads to the vicinity of the nitrogen atom of the amine, so that there is a problem that the electron durability is inferior.
Since the compound disclosed in Patent Document 7 does not contain a fluorene ring or a carbazole structure in the main chain, there is a problem that the electron durability is inferior.
Patent Document 8 discloses an arylamine polymer or oligomer having a fluorenyl group or a carbazole group in the main chain, but the durability of the device is insufficient.

Further, since the polymers disclosed in Patent Documents 9 to 12 are not copolymers containing a twisted aromatic ring in the main chain, fluorene or carbazole, and a twist-free aromatic ring, the durability of the device will be described later. The sex was insufficient.

The present invention provides a polymer having high hole injection transport ability and high durability and a composition for an organic electroluminescent element containing the polymer, and has a low drive voltage and high brightness, that is, luminous efficiency. The first object is to provide an organic electroluminescent element having a high drive life and a long drive life.
A second object of the present invention is to provide an organic electroluminescent device having a low drive voltage and a long life.

The present inventor has studied diligently and has completed the present invention. That is, the first gist of the present invention is that the first problem can be solved by using a polymer having a specific structure including a carbazole structure in the side chain. A second gist of the present invention is an organic electroluminescent device having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate, wherein the organic layer becomes a hole transport layer and a hole transport layer. A polymer having an adjacent light emitting layer and the hole transport layer having a specific structure including the carbazole structure in the side chain is contained, and further, the material contained in the hole transport layer and the material contained in the light emitting layer are contained. By including a material having a specific structure having a carbazole ring as a partial structure, the performance of the organic electroluminescent element can be improved, and the first problem can be solved. A third gist of the present invention is an organic electroluminescent device having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate, wherein the organic layer becomes a hole transport layer and a hole transport layer. The material contained in the hole transport layer and the material contained in the light emitting layer comprises yet another polymer having an adjacent light emitting layer and the hole transport layer having a specific structure including a carbazole structure in the side chain. By including a material having a specific structure having a carbazole ring as a partial structure, the performance of the organic electroluminescent element is improved, and the above-mentioned second problem can be solved.

（式（１）中、
Ｇは置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又はＣ原子、Ｎ原子、Ｂ原子若しくはＰ原子を表し、
Ａｒ^２〜Ａｒ^４は、それぞれ独立に、置換基を有していてもよい二価の芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した二価の基を表し、
Ａｒ^５は置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される基が直接若しくは連結基を介して複数個連結した一価の基を表し、
Ａｒ^６は水素原子又は置換基を表す。Ａｒ^１中の“−＊”が式（１）中Ｇとの結合位置を表す。）That is, the gist of the present invention is as follows [1] to [22].
[1] A polymer containing a repeating unit represented by the following formula (1).

(In equation (1),
G represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a C atom, an N atom, a B atom or a P atom.
Ar ^{2 to} Ar ⁴ each independently have a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. Represents a divalent group in which a plurality of aromatic heterocyclic groups, which may have an aromatic hydrocarbon group or a substituent which may have a substituent, are directly linked or are linked via a linking group.
Ar ⁵ is an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aromatic hydrocarbon group and a substituent which may have a substituent. A monovalent group in which a plurality of groups selected from aromatic heterocyclic groups which may have a group are directly linked or linked via a linking group is represented.
Ar ⁶ represents a hydrogen atom or a substituent. "-*" In Ar ¹ represents the bonding position with G in the formula (1). )

（ａ−１〜ｅ−４において、“−＊”はＡｒ^４との結合位置を表わし、“−＊”が複数ある場合はいずれか一つがＡｒ^４との結合位置を表す。）[2] The polymer according to [1], wherein G is an N atom.
[3] Ar ⁵ is the polymer according to [1] or [2], which is represented by any of the following a-1 to e-4.

(In a-1 to e-4, "-*" ^{represents the bonding position with Ar 4,} and when there are a plurality of "-*", any one of them represents the bonding position with ^{Ar 4.)}

（式（２）−１〜式（２）−３中、
Ａｒ^１は前記式（１）のＡｒ^１と同じであり、
Ｘは、−Ｃ（Ｒ^５）（Ｒ^６）−、−Ｎ（Ｒ^７）−または−Ｃ（Ｒ^１１）（Ｒ^１２）−Ｃ（Ｒ^１３）（Ｒ^１４）−を表し、
Ｒ^１〜Ｒ^４は、各々独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、又は置換基を有していてもよいアラルキル基を表し、
Ｒ^５〜Ｒ^７及びＲ^１１〜Ｒ^１４は、各々独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアラルキル基、または置換基を有していてもよい芳香族炭化水素基を表し、
ａ、ｂは、各々独立に、０〜４の整数であり、
ｃ１、ｃ２は、各々独立に、１〜３の整数であり、
ｄ１、ｄ２は、各々独立に、０〜４の整数であり、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４が該繰り返し単位中に複数ある場合は、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は同一であっても異なっていてもよい。）[4] The polymer according to [1] or [2], wherein the formula (1) is a repeating unit represented by any of the following formulas (2) -1 to (2) -3.

(In equation (2) -1 to equation (2) -3,
Ar ¹ is the same as Ar ¹ in the formula (1),
X represents −C (R ⁵ ) (R ⁶ ) −, −N (R ⁷ ) − or −C (R ¹¹ ) (R ¹² ) −C (R ¹³ ) (R ¹⁴ ) −.
R ^{1 to} R ⁴ each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aralkyl group which may have a substituent.
R ^{5 to} R ⁷ and R ^{11 to} R ¹⁴ may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Represents an aromatic hydrocarbon group, or aromatic hydrocarbon group which may have a substituent,
a and b are independently integers of 0 to 4, respectively.
c1 and c2 are independently integers of 1 to 3, respectively.
d1 and d2 are independently integers of 0 to 4, respectively.
When ^{there are a plurality of R 1} , R ² , R ³ , and R ⁴ in the repeating unit, R ¹ , R ² , R ³ , and R ⁴ may be the same or different. )

（式（３）−１〜（３）−３中、
Ａｒ^７は、それぞれの繰り返し単位において独立に、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した二価の基を表し、
Ｘ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ａ、ｂ、ｃ１、ｃ２、ｄ１、ｄ２は、それぞれ前記式（２）−１〜（２）−３と同じである。）[5] The polymer according to any one of [1] to [4], further comprising a repeating unit represented by any of the following (3) -1 to (3) -3.

(In equations (3) -1 to (3) -3,
Ar ⁷ has an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent independently in each repeating unit. It represents a divalent group in which a plurality of aromatic heterocyclic groups which may have a good aromatic hydrocarbon group or a substituent are directly or via a linking group are linked.
X, R ¹ , R ² , R ³ , R ⁴ , a, b, c1, c2, d1, and d2 are the same as those in the above formulas (2) -1 to (2) -3, respectively. )

[6] The polymer according to any one of [1] to [5], wherein the polymer has a crosslinkable group as a substituent.
[7] Described in any one of [1] to [6], wherein the polymer has a weight average molecular weight (Mw) of 10,000 or more and a dispersity (Mw / Mn) of 3.5 or less. Polymer.
[8] A composition for an organic electroluminescent device containing the polymer according to any one of [1] to [7].
[9] A method for manufacturing an organic electroluminescent device having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate.
Production of an organic electroluminescent device including a film forming step of forming at least one of the layers constituting the organic layer by a wet film forming method using the composition for an organic electroluminescent device according to [8]. Method.
[10] The organic layer has a hole injection layer and a hole transport layer, and at least one of the hole injection layer and the hole transport layer is a layer formed in the film forming step. , [9] The method for manufacturing an organic electroluminescent device.
[11] The organic layer further has a light emitting layer, and the organic layer has a light emitting layer.
The method for manufacturing an organic electroluminescent device according to [9] or [10], wherein the hole injection layer, the hole transport layer, and the light emitting layer are layers formed in the film forming step.
[12] The polymer or the polymer according to any one of [1] to [7], which has an anode, a cathode, and an organic layer between the anode and the cathode on the substrate. An organic electroluminescent device having a layer containing a crosslinked polymer.

[13] The layer containing the polymer or the polymer crosslinked with the polymer is a hole transport layer, the organic layer further has a light emitting layer, and the light emitting layer is in contact with the hole transport layer. The organic electroluminescent element according to [12], wherein at least one of the materials contained in the light emitting layer contains a compound having a partial structure represented by the following formula (CzP).

[14] The material contained in the light emitting layer containing the compound having a partial structure represented by the formula (CzP) is a host material having at least one of hole transporting property and electron transporting property, or a light emitting material. , [13]. The organic electroluminescent element.

[15] The skeleton of the host material includes an aromatic structure, an aromatic amine structure, a triarylamine structure, a dibenzofuran structure, a naphthalene structure, a phenanthrene structure, a phthalocyanine structure, a porphyrin structure, a thiophene structure, a benzylphenyl structure, a fluorene structure, and a quinacridone. Structure, triphenylene structure, carbazole structure, pyrene structure, anthracene structure, phenanthroline structure, quinoline structure, pyridine structure, pyrimidine structure, triazine structure, oxadiazole structure or imidazole structure, carbazole structure, dibenzofuran structure, triarylamine structure, naphthalene structure The organic electric field light emitting element according to [14], which has any of a phenanthrene structure and a pyrene structure.

（式（１４）〜（１６）中、
Ａは前記式（ＣｚＰ）で表される部分構造であり、置換基を有していてもよい。
Ｂは単結合または任意の部分構造を表す。
Ａが複数存在する場合、同一であっても互いに異なっていてもよい。
Ｂが複数存在する場合、同一であっても互いに異なっていてもよい。
ｎａ、ｎｂ及びｎｃは、それぞれ独立に、１以上、５以下の整数を表す。）[16] The compound having a partial structure represented by the formula (CzP) contained in the light emitting layer is a low molecular weight compound represented by any of the following formulas (14) to (16) and is The organic electroluminescent element according to any one of [13] to [15], wherein the low molecular weight compound has a molecular weight of 5,000 or less.

(In equations (14) to (16),
A is a partial structure represented by the above formula (CzP) and may have a substituent.
B represents a single bond or any partial structure.
When there are a plurality of A's, they may be the same or different from each other.
When there are a plurality of B's, they may be the same or different from each other.
na, nb and nc independently represent integers of 1 or more and 5 or less. )

（上記式（１７）において、
Ｑは、窒素原子または、下記構造式（１８−１）〜（１８−３）のいずれかで表される３価の置換基のいずれかを表し、
Ｘｂ^１、Ｙｂ^１、及びＺｂ^１は、各々独立に、置換基を有していてもよい炭素数６〜３０の二価の炭化水素芳香環基、又は置換基を有していてもよい炭素数３〜３０の二価の複素芳香環基を表し、Ｘｂ^１、Ｙｂ^１、及びＺｂ^１のそれぞれはが複数存在する場合は同一であっても異なっていてもよく、
Ａは、前記式（ＣｚＰ）で表される部分構造であり、置換基を有していてもよく、かつ、複数存在するＡは互いに同一であっても異なっていてもよく、
ｐ１２、ｑ１２、及びｒ１２は、各々独立に、０以上６以下の整数を表し、
ｑ１３、ｒ１３は、各々独立に、０または１を表し、
ｑ１３が０の場合のＹｂ^２及び、ｒ１３が０の場合のＺｂ^２は各々独立に、水素原子、置換基を有していてもよい炭素数６〜３０の一価の炭化水素芳香環基、又は置換基を有していてもよい炭素数３〜３０の一価の複素芳香環基を表し、
ｑ１３が１の場合のＹｂ２は直接結合であり、
ｒ１３が１の場合のＺｂ２は直接結合であり
式（１８−１）〜（１８−３）において、一つの構造式中の３つの＊は、それぞれＸｂ^１、Ｙｂ^１、又はＺｂ^１のいずれか基との結合位置を表す。）

[17] The organic electroluminescent device according to [16], wherein the low molecular weight compound represented by the formula (14) is a low molecular weight compound represented by the following formula (17).

(In the above formula (17)
Q represents either a nitrogen atom or a trivalent substituent represented by any of the following structural formulas (18-1) to (18-3).
Xb ¹ , Yb ¹ , and Zb ¹ each independently have a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms, which may have a substituent, or a carbon which may have a substituent. It represents a divalent heteroaromatic ring group of the number 3 to 30 ^{, and each of Xb 1} , Yb ¹ , and Zb ¹ may be the same or different when a plurality of them are present.
A is a partial structure represented by the above formula (CzP), may have a substituent, and a plurality of A may be the same or different from each other.
p12, q12, and r12 each independently represent an integer of 0 or more and 6 or less.
q13 and r13 independently represent 0 or 1, respectively.
^{Yb 2} when q13 is 0 ^{and Zb 2} when r13 is 0 independently have a hydrogen atom and a monovalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent. Alternatively, it represents a monovalent heteroaromatic ring group having 3 to 30 carbon atoms which may have a substituent.
When q13 is 1, Yb2 is a direct bond and is a direct bond.
When r13 is 1, Zb2 is a direct bond, and in the formulas (18-1) to (18-3), three * in one structural formula ^{are either Xb 1} , Yb ¹ , or Zb ¹ , respectively. Represents the bond position with the group. )

（上記式（１９）中、
Ｘｃ^１及びＹｃ^１は、各々独立に、置換基を有していてもよい炭素数６〜３０の二価の炭化水素芳香環基、又は置換基を有していてもよい炭素数３〜３０の二価の複素芳香環基を表し、
Ｘｃ^２及びＹｃ^２は、各々独立に、水素原子、置換基を有していてもよい一価の炭素数６〜３０の炭化水素芳香環基、又は置換基を有していてもよい炭素数３〜３０の一価の複素芳香環基を表し、
Ｘｃ^１及びＹｃ^１のそれぞれは複数存在する場合は同一であっても異なっていてもよく、
Ａは前記式（ＣｚＰ）で表される部分構造であり、置換基を有していてもよく、
ｓ１１及びｔ１１は、各々独立に、０以上６以下の整数を表し、
ｎｃは、１以上、５以下の整数を表す。）[18] The organic electroluminescent device according to [16], wherein the low molecular weight compound represented by the formula (16) is a low molecular weight compound represented by the following formula (19).

(In the above formula (19),
Each of Xc ¹ and Yc ¹ independently has a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent, or 3 to 30 carbon atoms which may have a substituent. Represents a divalent heteroaromatic ring group of
Each of Xc ² and Yc ² independently has a hydrogen atom and a hydrocarbon aromatic ring group having a monovalent number of 6 to 30 carbon atoms which may have a substituent, or a carbon number which may have a substituent. Represents a monovalent heteroaromatic ring group of 3 to 30
If there are a plurality of Xc ¹ and Yc ¹ , they may be the same or different.
A is a partial structure represented by the above formula (CzP) and may have a substituent.
s11 and t11 each independently represent an integer of 0 or more and 6 or less.
nc represents an integer of 1 or more and 5 or less. )

（上記一般式（１７−１）〜（１７−６）中、
ｐ１２’は、１以上５以下の整数を表し、
ｑ１２’及びｒ１２’は、各々独立に、０以上５以下の整数を表し、
ｐ１４は１２であり、
ｑ１４はｑ１３が１の場合は１２であり、ｑ１３が０の場合は存在せず、
ｒ１４はｒ１３が１の場合は１２であり、ｒ１３が０の場合は存在せず、
ｑ１５及びｒ１５は、各々独立に、４又は５であり、
Ｒ^３１及びＲ^３２は、各々独立に、水素原子または置換基であり、
Ｘｂ^１、Ｙｂ^１、Ｚｂ^１、ｑ１３、ｒ１３は、それぞれ前記式（１７）と同じである。）[19] The organic electroluminescence according to [17], wherein the low molecular weight compound represented by the formula (17) is a compound represented by any of the following formulas (17-1) to (17-6). element.

(In the above general formulas (17-1) to (17-6),
p12'represents an integer of 1 or more and 5 or less.
q12'and r12'independently represent integers of 0 or more and 5 or less.
p14 is 12,
q14 is 12 when q13 is 1, and does not exist when q13 is 0.
r14 is 12 when r13 is 1, and does not exist when r13 is 0.
q15 and r15 are 4 or 5 independently, respectively.
R ³¹ and R ³² are independent hydrogen atoms or substituents, respectively.
Xb ¹ , Yb ¹ , Zb ¹ , q13, and r13 are the same as those in the above equation (17), respectively. )

（上記一般式（１９−１）において、
Ｒ^３１は、水素原子または置換基であり、
ｕ１１は、１１を表し、
Ｘｃ^１、Ｙｃ^１、Ｘｃ^１、Ｙｃ^１、ｔ１１、及びｓ１１は、それぞれ前記式（１９）と同じである。）[20] The organic electroluminescent device according to [18], wherein the low molecular weight compound represented by the formula (19) is a compound represented by the following formula (19-1).

(In the above general formula (19-1),
R ³¹ is a hydrogen atom or a substituent and is
u11 represents 11 and represents
Xc ¹ , Yc ¹ , Xc ¹ , Yc ¹ , t11, and s11 are the same as those in the above formula (19), respectively. )

[21] An organic EL display device including the organic electroluminescent device according to any one of [12] to [20].
[22] An organic EL lighting comprising the organic electroluminescent element according to any one of [12] to [20].

According to the present invention, it is possible to provide a polymer having high hole injection transport ability and high durability and a composition for an organic electroluminescent device containing the polymer. Further, it is possible to provide an organic electroluminescent device having a low drive voltage, high luminous efficiency, and a long drive life.

The reason why the polymer according to the embodiment of the present invention exerts the above effect will be considered as follows.

The polymer contained in the hole transport layer transports the holes injected from the anode to the light emitting layer. On the other hand, a small amount of electrons that did not recombine with holes in the light emitting layer from the cathode side, which is the opposite electrode, seeps into the hole transport layer. Since many hole-transporting materials have low electron durability, these electrons cause decomposition of the polymer. In particular, in a polymer in which the main chain transports holes, such as a polymer having an arylamine in the main chain, the electron durability of the main chain is low, and there is room for improvement.

It is considered that the side chain and the main chain are close to each other as one of the factors that hinder the improvement of the electron durability of the polymer. In the present invention, an attempt is made to solve the above problem by making the main chain that transports holes difficult to receive electrons. ^{In the structure having two or more aromatic rings or aromatic heterocycles (Ar 4} , Ar ⁵ ) at the 9-position of carbazole as in the above formula (1), the electron-withdrawal of the conjugated group extended from the 9-position of carbazole. Due to its high attractiveness, electrons are distributed on the terminal side of the side chain. In the polymer according to the following embodiment, the carbazole structure of the side chain is appropriately separated from the main chain in the vicinity of the amine, which is inferior in electron durability, so that it is easier to receive electrons in the side chain than in the main chain. Since the carbazole structure of the chain has high electron durability, it is considered that the electron durability as a polymer is improved. It is considered that this effect is further ^{enhanced by having an aromatic ring or an aromatic heterocycle (Ar 3} ) between the main chain and the side chain carbazole.

In addition, by distributing electrons on the terminal side of the side chain, it is possible to reduce the rate at which holes transported via the main chain hop to the side chain side, and the hole injection transport capacity is high. Conceivable.

The main chain of the polymer of the present embodiment preferably contains a fluorene ring or a carbazole ring, and in this case, it is preferable that a phenylene group is bonded to the 2nd and 7th positions of these fluorene ring or carbazole ring. The phenylene group attached to the 2nd and 7th positions of the fluorene ring or the carbazole ring makes the fluorene ring or the carbazole ring electrically more stable. In particular, it is considered that the electronic durability is improved and the device drive life is extended. At this time, when the phenylene ring has a substituent, the surface of the phenylene group having the substituent has a more twisted arrangement with respect to the surface of the adjacent fluorene ring or carbazole ring due to the steric hindrance due to the substituent. Become. In this case, since it has a main chain structure in which the spread of the π-conjugated system is hindered by the steric hindrance of the substituent, the excited singlet energy level (S ₁ ) and the excited triplet energy level (T ₁ ) are high. Therefore, the extinction due to the energy transfer from the luminescence exciter is suppressed, so that the luminescence efficiency is excellent.

Further, when the phenylene group of the main chain of the polymer of the present embodiment has a substituent, the surface of the phenylene group having the substituent may be an adjacent phenylene group, a divalent fluorene group, or a divalent fluorene group due to the steric disorder of the substituent. It has a more twisted arrangement with respect to the plane of the divalent carbazole group, is less likely to crystallize due to steric damage due to substituents, and has excited single-term energy levels (S ₁ ) and excited triple-term energies. It is preferable because it has a high level (T _1).
Further, since the main chain of the polymer of the present embodiment has a main chain structure in which the spread of the π-conjugated system is hindered by including a structure in which phenylene and oxygen atoms are alternately bonded, the excited single-term energy level (S _1). ) And the excited triple-term energy level (T ₁ ) are high, and quenching due to energy transfer from the luminescence exciter is suppressed, so that the luminescence efficiency is excellent.

In an organic electroluminescent device, if the energy level difference between each organic layer is not appropriate, it becomes difficult to inject carriers into the light emitting layer, and the drive voltage rises. Alternatively, it is considered that carrier leakage from the light emitting layer to the adjacent layer is likely to occur, and the device efficiency is lowered.
On the other hand, a charge transport material having an energy level higher than the energy level of the excitons of the light emitting material in the light emitting layer as in the present embodiment is preferable because it has a high effect of confining the excitons of the light emitting material.

Further, the layer obtained by wet film formation using the composition for an organic electroluminescent device containing the polymer of the present embodiment is flat without cracks or the like. As a result, the organic electroluminescent device, which is one of the embodiments of the present invention having the layer, has high brightness and a long drive life.

Further, since the polymer of the present embodiment has excellent electrochemical stability, the element including the layer formed by using the polymer is a flat panel display (for example, for an OA computer or a wall-mounted television) or an in-vehicle display. It is considered to be applied to elements, mobile phone displays, light sources that make the best use of its characteristics as surface emitters (for example, light sources for copying machines, backlight sources for liquid crystal displays and instruments), display boards, and indicator lights. The value is great.

Further, since the organic electroluminescent device in the second gist and the third gist contains a material having a specific structure having carbazole as a partial structure in both the hole transport layer and the light emitting layer, the hole transport layer and the light emitting layer are included. It is easy to transfer and receive charges at the interface between the two, and it is possible to drive with a lower voltage than before. Further, since it is easy to transfer and receive electric charges at the interface between the two layers and it is difficult for electric charges to be accumulated, quenching is suppressed, and an element having higher efficiency and longer drive life than the conventional one is possible.

Further, the organic electroluminescent device according to the embodiment of the present invention can be manufactured by a wet film forming method.
Further, since the organic electroluminescent element according to the embodiment of the present invention has excellent electrochemical stability, the element including a layer formed by using the above polymer is a flat panel display (for example, for an OA computer or the like). Applications for wall-mounted TVs), in-vehicle display elements, light sources that take advantage of the characteristics of mobile phone displays and surface emitters (for example, light sources for copying machines, backlight sources for liquid crystal displays and instruments), display boards, and indicator lights. It is conceivable and its technical value is great.

It is a schematic diagram of the cross section which shows the structural example of the organic electroluminescent element which concerns on this embodiment. It is a figure which shows the electronic state of the electronic polymerization unit 1 in an Example (halftone image). It is a figure which shows the electronic state of the electronic polymerization unit 2 in an Example (halftone image). It is a figure which shows the electronic state of the electronic polymerization unit 3-5 in an Example (halftone image).

Hereinafter, embodiments of the organic electroluminescent element according to the embodiment of the present invention, the organic EL display device having the organic electroluminescent element, and the organic EL lighting will be described in detail. It is an example (representative example) of an embodiment, and the present invention is not specified in these contents unless the gist thereof is exceeded.
Further, in the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value, and "A to B" means. It means that it is A or more and B or less.
Further, in the present specification, "independently" used when two or more objects are described together is used in the sense that the two or more objects may be the same or different. Will be done.

式（１）中、
Ｇは置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又はＣ原子、Ｎ原子、Ｂ原子若しくはＰ原子を表し、
Ａｒ^２〜Ａｒ^４は、それぞれ独立に、置換基を有していてもよい二価の芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した二価の基を表し、
Ａｒ^５は置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは芳香族複素環基が直接若しくは連結基を介して複数個連結した一価の基を表し、
Ａｒ^６は水素原子又は置換基を表す。
なお、Ａｒ^１中の“−＊”が式（１）中Ｇと結合する部位（結合位置）である。<Embodiment pertaining to the first gist>
<Polymer>
The polymer of the embodiment according to the first gist is a polymer containing a structure represented by the following formula (1). In the present specification, this polymer is also referred to as polymer 1.

In equation (1),
G represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a C atom, an N atom, a B atom or a P atom.
Ar ^{2 to} Ar ⁴ each independently have a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. Represents a divalent group in which a plurality of aromatic heterocyclic groups, which may have an aromatic hydrocarbon group or a substituent which may have a substituent, are directly linked or via a linking group.
Ar ⁵ is an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aromatic hydrocarbon group or an aromatic which may have a substituent. Represents a monovalent group in which a plurality of group heterocyclic groups are directly linked or linked via a linking group.
Ar ⁶ represents a hydrogen atom or a substituent.
In addition, ^{"-*" in Ar 1} is a site (bonding position) to be bonded to G in the formula (1).

(G)
In the repeating unit represented by the above formula (1), G is an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a C atom. Represents an N atom, a B atom or a P atom. From the viewpoint of excellent charge transportability and localization of LUMO distributed at the 9-position of the carbazole ring and HOMO distributed in the main chain, G is a benzene ring or a substituent which may have a substituent. A triazine ring which may have a substituent, a fluorene ring which may have a substituent, a spirofluorene ring which may have a substituent, and a carbazole ring which may have a substituent are preferable, and the following scheme is preferable. The structure shown in 1 is more preferable. The following structure may have a substituent. Further, in the figure, "-*" indicates the connection position with ^{Ar 3.}

As the substituent which may be possessed, any one of the substituent group Z described later, the aralkyl group having 7 to 40 carbon atoms, the aralkyl group having a heterocycle having 4 to 37 carbon atoms, or a combination thereof shall be used. Is preferable. Among them, in terms of electron durability (also simply referred to as "durability"), the alkyl group having 1 to 24 carbon atoms and the aralkyl group having 7 to 40 carbon atoms are the same or different each time they appear. A heterocyclic aralkyl group having 3 to 37 carbon atoms, an arylamino group having 10 to 24 carbon atoms, an aromatic hydrocarbon group having 6 to 36 carbon atoms, or an aromatic heterocyclic group having 3 to 36 carbon atoms. Is preferable
An alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aralkyl group having a heterocycle having 3 to 27 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, or an aromatic hydrocarbon group having 3 to 24 carbon atoms. More preferably, it is an aromatic heterocyclic group.
It is more preferably an aryl group having 6 to 24 carbon atoms.
From the viewpoint of charge transportability, it is preferable to be an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic heterocyclic group having 3 to 24 carbon atoms, which is the same or different each time it appears, preferably phenyl. More preferably, it is a group, a naphthyl group, a fluorenyl group, a carbazolyl group, an indolocarbazolyl group, an indenocarbazolyl group, or an indenofluorenyl group.

Further, G is preferably an N atom (nitrogen atom) from the viewpoint of excellent charge transportability.

(Ar ² , Ar ³ , Ar ⁴ )
In the repeating unit represented by the above formula (1), Ar ^{2 to} Ar ⁴ each independently have a divalent aromatic hydrocarbon group and a substituent which may have a substituent. A plurality of aromatic heterocyclic groups which may have a divalent aromatic heterocyclic group, or an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, either directly or via a linking group. Represents a concatenated divalent group.
The aromatic hydrocarbon group preferably has 6 or more and 60 or less carbon atoms, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, and a chrysene ring. , Triphenylene ring, anthracene ring, fluorantene ring, fluorene ring and the like, a bivalent group of a 6-membered monocyclic ring or a 2-5 fused ring, or a divalent group in which a plurality of these are linked.
When a plurality of the above divalent groups are linked, 2 to 10 linked divalent groups are mentioned, and 2 to 5 linked divalent groups are preferable.

The aromatic heterocyclic group preferably has 3 or more carbon atoms and 60 or less carbon atoms, and specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and an oxadiazole ring. , Indole ring, carbazole ring, pyroloymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, flofuran ring, thienofran ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine 5 such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxalin ring, phenanthridine ring, benzoimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. Examples thereof include a divalent group of a monocycle having a ~ 6-membered ring or a 2-4 condensed ring, or a divalent group in which a plurality of these are linked.
When a plurality of the above divalent groups are linked, 2 to 10 linked divalent groups are mentioned, and 2 to 5 linked divalent groups are preferable.

The same group is used as a divalent group in which a plurality of aromatic hydrocarbon groups which may have a substituent or an aromatic heterocyclic group which may have a substituent are directly linked or linked via a linking group. May be a group in which a plurality of different groups are linked, or a group in which a plurality of different groups are linked may be used.
When a plurality of the above divalent groups are linked, 2 to 10 linked divalent groups are mentioned, and 2 to 5 linked divalent groups are preferable.

Ar ² has a divalent aromatic hydrocarbon group which may have a substituent and a divalent aromatic complex which may have a substituent because of its excellent charge transportability and durability. It is preferable that one or a plurality of groups selected from the ring groups are divalent groups bonded directly or via a linking group, and the linking group is preferably an oxygen atom or a carbonyl group. As the group directly bonded to the nitrogen atom, an aromatic hydrocarbon group which may have a substituent is preferable, and a phenylene group or a substituent which may have a substituent is preferable because the hole transport property is improved. A divalent fluorene group which may have a group is more preferable, and a phenylene group which may have a substituent is particularly preferable. It is preferable that a fluorene ring or a carbazole ring is bonded to the phenylene ring directly bonded to the nitrogen atom, and one or more phenylene groups are further between the fluorene ring directly bonded to the nitrogen atom and the fluorene ring or the carbazole ring. A structure in which fluorene is connected is also preferable. Further, a structure in which the phenylene rings are linked by an oxygen atom or a carbonyl group is also preferable.

The ^{substituent that Ar 2} may have is the same as the substituent that may have when G is an aromatic hydrocarbon group or an aromatic heterocyclic group.

Ar ³ has 1 to 6 divalent aromatic hydrocarbon groups which may have a substituent from the viewpoint of localization with LUMO distributed at the 9-position of the carbazole ring and HOMO distributed in the main chain. A linked group is preferable, a group in which 2 to 4 divalent aromatic hydrocarbon groups which may have a substituent are linked are more preferable, and a phenylene ring which may have a substituent is 1 to 1 to. A group in which four are linked is more preferable, and biphenylene in which two phenylene rings which may have a substituent are linked are particularly preferable.

The ^{substituents that Ar 3} may have are the same as those of Ar ² described above.

Ar ⁴ is preferably a group in which one or a plurality of divalent aromatic hydrocarbon groups which may be the same or different are linked, from the viewpoint of excellent charge transportability and durability, and the divalent aromatic group is preferable. The group hydrocarbon group may have a substituent. As described above, it is preferable that the number of linkages is large from the viewpoint of distribution of LUMO in the structure represented by ^{−Ar 4} −Ar ^{5, but it is preferable that the number of linkages is small from the viewpoint of charge transportability and film stability.} preferable. In the case of ligation, 2 or more and 10 or less are preferable, 6 or less is more preferable, and 3 or less is particularly preferable from the viewpoint of film stability. Preferred aromatic hydrocarbon structures are a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring, and more preferably a benzene ring and a fluorene ring. The plurality of linked groups may be a group in which 1 to 4 phenylene rings which may have a substituent are linked, or a group which may have a phenylene ring and a substituent which may have a substituent. A group to which a fluorene ring is linked is preferable. From the viewpoint of spreading LUMO, biphenylene in which two phenylene rings which may have a substituent are linked is particularly preferable.

As the ^{substituent that Ar 4} may have, any one of the substituent group Z described later or a combination thereof can be used. From the viewpoint of inhibiting the spread of LUMO, it is preferable that the group is other than N-carbazolyl group, indolocarbazolyl group and indenocarbazolyl group, and more preferable substituents are phenyl group, naphthyl group and fluorenyl group. be. It is also preferable that it does not have a substituent.

(Ar ⁵ )
Ar ⁵ includes an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. A monovalent group in which a plurality of groups selected from the aromatic heterocyclic groups which may have the substituent are directly or via a linking group are linked. When a plurality of groups are linked, 2 to 10 linked divalent groups are mentioned, and 2 to 5 linked divalent groups are preferable. As the aromatic hydrocarbon and the aromatic heterocycle, the aromatic hydrocarbon structure and the aromatic heterocyclic structure mentioned in Ar2 to Ar4, which are monovalent, can be used. It is preferable to have a structure represented by any of the following scheme 2 at the 9-position of the carbazole ring specified in ^{Ar 1} of the formula (1). Furthermore, from the viewpoint of distributing the LUMO of the molecule, it is selected from a-1 to a-4, b-1 to b-9, c-1 to c-5, d-1 to d-16, and e1 to e4. Structure is preferable. Furthermore, from the viewpoint of promoting the spread of LUMO of the molecule by having an electron-withdrawing group, a-1 to a-4, b-1 to b-9, d-1 to d-13, and e1 to e4. The structure selected from is preferred. Further, from the viewpoint of the effect of confining excitons formed in the light emitting layer having a high triplet level, a structure selected from a-1 to a-4, d-1 to d-13, and e1 to e4 is preferable. .. It is also preferable that it is a phenyl group. Further, these structures may have a substituent. In the figure, "-*" indicates ^{the connection position with Ar 4,} and when there are a plurality of "-*", any one of them indicates the connection position with ^{Ar 4.}

As the ^{substituent that Ar 5} may have, any one of the substituent group Z described later or a combination thereof can be used. From the viewpoint of durability and charge transportability, it is preferable to select from the same substituents that ^{Ar 4 may have.}

(Ar ⁶ )
Ar ⁶ represents a hydrogen atom or a substituent. When Ar ⁶ is a substituent, it is not particularly limited, but is preferably an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. The preferred structure is a structure similar to the aromatic hydrocarbon structure and the aromatic heterocyclic structure mentioned in ^{Ar 2 to} Ar ^{4 and having a monovalent value.}
When Ar ⁶ is a substituent, it is preferable that it is bonded to the 3-position of carbazole from the viewpoint of improving durability. Ar ⁶ is preferably a hydrogen atom from the viewpoint of ease of synthesis and charge transportability. From the viewpoint of improving durability and charge transportability, Ar ⁶ is preferably an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. , It is more preferable that it is an aromatic hydrocarbon group which may have a substituent.

Examples of the substituent when Ar ⁶ is an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent are listed in Substituent Group Z described later. The same is true for the substituents or the crosslinkable groups described below, the preferred substituents are the same, and so are the substituents that these substituents may further have. Further, from the viewpoint of insolubilization, it is preferable to contain at least one crosslinkable group described later as the substituent.

[Preferable repeating unit structure]
Above all, the formula (1) is more preferably a repeating unit represented by any of the following formulas (2) -1 to (2) -3.

In equations (2) -1 to (2) -3,
Ar ¹ is the same as Ar ¹ in formula (1),
X represents −C (R ⁵ ) (R ⁶ ) −, −N (R ⁷ ) − or −C (R ¹¹ ) (R ¹² ) −C (R ¹³ ) (R ¹⁴ ) −.
R ^{1 to} R ⁴ each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aralkyl group which may have a substituent.
R ^{5 to} R ⁷ and R ^{11 to} R ¹⁴ may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Represents an aromatic hydrocarbon group, or aromatic hydrocarbon group which may have a substituent,
a and b are independently integers of 0 to 4, respectively.
c1 and c2 are independently integers of 1 to 3, respectively.
d1 and d2 are independently integers of 0 to 4, respectively.
When ^{there are a plurality of R 1} , R ² , R ³ , and R ⁴ in the repeating unit, R ¹ , R ² , R ³ , and R ⁴ may be the same or different.

(X)
X is either −C (R ⁵ ) (R ⁶ ) −, −N (R ⁷ ) − or −C (R ¹¹ ) (R ¹² ) −C (R ¹³ ) (R ¹⁴ ) −. Preferably ^-C terms of durability ^{(R 5) (R 6)} -, - N (R 7) - is.

(R ¹ and R ² )
^{R 1} and R ² in the repeating unit represented by the above formulas (2) -1 to (2) -3 are linear, branched or cyclic alkyls which may independently have a substituent. It is preferably a group. The number of carbon atoms of the alkyl group is not particularly limited, but in order to maintain the solubility of the polymer, the number of carbon atoms is preferably 1 or more and 6 or less, more preferably 3 or less, and further preferably a methyl group or an ethyl group. ..
When ^{there are a plurality of R 1} and R ² in the repeating unit, R ¹ and R ² may be the same or different, but the charge can be uniformly distributed around the nitrogen atom. Further, since synthesis is easy, ^{it is preferable that all R 1} and R ² are the same group.

(R ³ and R ⁴ )
^{R 3} and R ⁴ in the repeating unit represented by the above formulas (2) -1 to (2) -3 are linear, branched or cyclic alkyls which may independently have a substituent. It is preferably a group. The number of carbon atoms of the alkyl group is not particularly limited, but in order to maintain the solubility of the polymer, the number of carbon atoms is preferably 1 or more, more preferably 4 or more, preferably 12 or less, and further preferably 8. It is the following, and it is particularly preferable that it is a hexyl group.

(R ^{5 to} R ⁷ and R ^{11 to} R ¹⁴ )
R ^{5 to} R ⁷ and R ^{11 to} R ¹⁴ may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. It is preferably an aromatic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent.

The alkyl group is not particularly limited, but a long one is preferable because it tends to improve the solubility of the polymer, and a short one is preferable in order to improve the stability of the membrane and the charge transportability. Preferably, the number of carbon atoms is 1 or more and 24 or less, more preferably 12 or less, further preferably 8 or less, particularly preferably 6 or less, more preferably 2 or more, still more preferably 3 or more, and particularly preferably 4 or more. Further, each structure may be linear, branched or cyclic.
Specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, and an n-octyl group. , Cyclohexyl group, dodecyl group and the like.

The alkoxy group is not particularly limited, but since it tends to improve the solubility of the polymer, the number of carbon atoms is preferably 1 or more and 24 or less, more preferably 12 or less, further preferably 8 or less, and particularly preferably 6 or less. 2 or more is more preferable, 3 or more is further preferable, and 4 or more is particularly preferable.
Specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a tert-butoxy group, a hexyloxy group and the like.

The aralkyl group is not particularly limited, but since it tends to improve the solubility of the polymer, the number of carbon atoms is preferably 5 or more and 60 or less, more preferably 40 or less, more preferably 7 or more, still more preferably 10 or more. 12 or more is particularly preferable.
Specifically, 1,1-dimethyl-1-phenylmethyl group, 1,1-di (n-butyl) -1-phenylmethyl group, 1,1-di (n-hexyl) -1-phenylmethyl group. , 1,1-di (n-octyl) -1-phenylmethyl group, phenylmethyl group, phenylethyl group, 3-phenyl-1-propyl group, 4-phenyl-1-n-butyl group, 1-methyl- 1-Phenylethyl group, 5-Phenyl-1-n-propyl group, 6-Phenyl-1-n-hexyl group, 6-naphthyl-1-n-hexyl group, 7-Phenyl-1-n-heptyl group, Examples thereof include 8-phenyl-1-n-octyl group and 4-phenylcyclohexyl group.

The aromatic hydrocarbon group is not particularly limited, but the solubility of the polymer tends to be improved, so that the number of carbon atoms is preferably 6 or more and 60 or less, more preferably 30 or less, still more preferably 24 or less, and 14 or less. The following are particularly preferred.
Specifically, 6-membered rings such as benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc. Examples thereof include monovalent groups of monocyclic or 2-5 fused rings, or groups in which 2 to 8 linked ring structures are selected from these, preferably monocyclic or 2 to 4 or less linked groups.

From the viewpoint of improving charge transportability and durability, R ^{5 to} R ⁷ are preferably an alkyl group or an aromatic hydrocarbon group, R ⁵ and R ⁶ are more preferably an alkyl group, and R ⁷ is an aromatic hydrocarbon. It is more preferably a group, and the preferred number of carbon atoms is as described above.
From the viewpoint of excellent charge transportability while improving solubility, R ⁵ and R ⁶ are preferably an alkyl group or an aralkyl group having 9 or more 40 or less carbon atoms 3 to 8 carbon atoms.

The alkyl groups of R ^{1 to} R ^4, the alkyl groups of R ^{5 to} R ⁷ and R ^{11 to} R ¹⁴ , the alkoxy group, the aralkyl group and the aromatic hydrocarbon group may have a substituent. Substituent which may have an alkyl group of the R ⁵ to R ⁷ and R ¹¹ to R ^14, alkoxy groups, groups exemplified as the preferable groups of the aralkyl group and an aromatic hydrocarbon group, or below described crosslinkable The group is mentioned.
The alkyl groups of R ^{1 to} R ^4, the alkyl groups of R ^{5 to} R ⁷ and R ^{11 to} R ¹⁴ , the alkoxy group, the aralkyl group and the aromatic hydrocarbon group have substituents from the viewpoint of lowering the voltage. Most preferably not.

Further, the ^{substituents that R 5 to} R ⁷ and R ^{11 to} R ¹⁴ may have are a solvent when the polymer of the present embodiment is formed into a film and then another layer is applied to form a film and laminated. From the viewpoint of improving insolubility with respect to, a crosslinkable group described later is preferable. ^{Among them, it is preferable that any one of R 5} , R ⁶ and R ^{11 to} R ¹⁴ has a crosslinkable group described later as a substituent because it does not hinder the charge transport property, and at least one of ^{R 5} and R ^{6 has.} It is more preferable to have a crosslinkable group described later as a further substituent.

(A, b, c1, c2, d1 and d2)
In the repeating unit represented by the above equations (2) -1 to (2) -3, a and b are independently integers of 0 to 4. Further, it is preferable that a + b is 1 or more. Further, a and b are preferably 2 or less, respectively, and both a and b are more preferably 1.

In the repeating unit represented by the above equations (2) -1 to (2) -3, c1 and c2 are independently integers 1 to 3, and d1 and d2 are independently 0 to 4, respectively. Is an integer of. c1, c2, d1 and d2 are preferably 2 or less, respectively, c1, c2, d1 and d2 are more preferably equal, and all of c1, c2, d1 and d2 are 1 or 2. Is more preferable, and it is particularly preferable that all of c1, c2, d1, and d2 are 1.

All of c1, c2, d1 and d2 in the repeating unit represented by the above equations (2) -1 to (2) -3 are 1, or all of c1, c2, d1 and d2 are 2. And when both a and b are 2 or 1, ^{it is most preferable that R 1} and R ² are coupled to each other at symmetrical positions.
Here, the fact that R ¹ and R ² are coupled to each other at symmetrical positions will be described by the following equation, taking the case where X = C in the equation (2) -1 as an example. That is, it means that the bonding position of ^{R 1} and R ² is the target for the fluorene ring of the main chain in the following equation. At this time, 180 degree rotation about the main chain is regarded as the same structure. For example, in the equation (1a), R ^a and R ^b are objects, R ^a'and R ^b'are objects, and the equation (1a) and the equation (1b) are regarded as having the same structure.

From the viewpoint of durability or lowering the voltage of the device when used in an organic electroluminescent device, it is preferable to include a repeating unit represented by the formula (2) -1 or the formula (2) -2.

[Substituent group Z]
Examples of the substituent group Z include the following structures.
For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl group and the like. , A linear, branched, or cyclic alkyl group usually having 1 or more carbon atoms, preferably 4 or more, usually 24 or less, preferably 12 or less;
For example, an alkenyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as a vinyl group;
For example, an alkynyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as an ethynyl group;
For example, an alkoxy group such as a methoxy group or an ethoxy group having a carbon number of usually 1 or more, usually 24 or less, preferably 12 or less;
For example, an aryloxy group or a heteroaryloxy group having a carbon number of usually 4 or more, preferably 5 or more, usually 36 or less, preferably 24, such as a phenoxy group, a naphthoxy group, and a pyridyloxy group;
For example, an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, which usually has 2 or more carbon atoms and usually has 24 or less, preferably 12 or less carbon atoms;
For example, a dialkylamino group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as a dimethylamino group and a diethylamino group;
For example, a diarylamino group having a carbon number of usually 10 or more, preferably 12 or more, usually 36 or less, preferably 24 or less, such as a diphenylamino group, a ditrilamino group, and an N-carbazolyl group;
For example, an arylalkylamino group having a carbon number of 7 or more, usually 36 or less, preferably 24 or less, such as a phenylmethylamino group;
For example, an acyl group such as an acetyl group or a benzoyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less;
For example, halogen atoms such as fluorine atoms and chlorine atoms;
For example, a haloalkyl group having a carbon number of usually 1 or more, usually 12 or less, preferably 6 or less, such as a trifluoromethyl group;
For example, an alkylthio group having a carbon number of usually 1 or more, usually 24 or less, preferably 12 or less, such as a methylthio group and an ethylthio group;
For example, an arylthio group having a carbon number of usually 4 or more, preferably 5 or more, usually 36 or less, preferably 24 or less, such as a phenylthio group, a naphthylthio group, and a pyridylthio group;
For example, a silyl group having a carbon number of usually 2 or more, preferably 3 or more, usually 36 or less, preferably 24 or less, such as a trimethylsilyl group and a triphenylsilyl group;
For example, a syroxy group having a carbon number of usually 2 or more, preferably 3 or more, usually 36 or less, preferably 24 or less, such as a trimethylsiloxy group and a triphenylsiloxy group;
Cyano group;
For example, an aromatic hydrocarbon group having a carbon number of 6 or more, usually 36 or less, preferably 24 or less, such as a phenyl group and a naphthyl group;
For example, an aromatic heterocyclic group having a carbon number of usually 3 or more, preferably 4 or more, and usually 36 or less, preferably 24 or less, such as a thienyl group and a pyridyl group.
Among the above-mentioned substituent group Z, the above-mentioned alkyl group, alkoxy group, aromatic hydrocarbon group and aromatic heterocyclic group are preferable. From the viewpoint of charge transportability, it is more preferable to have no substituent.

Moreover, each substituent of the above-mentioned substituent group Z may further have a substituent. Examples of these substituents include the same substituents as the above-mentioned substituents (substituent group Z) or crosslinkable groups described later. Preferably, it has no additional substituent or is an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, a phenyl group or a crosslinkable group described later. From the viewpoint of charge transportability, it is more preferable to have no additional substituent.

[Terminal group]
In the present embodiment, the terminal group refers to the structure of the terminal portion of the polymer formed by the end cap agent used at the end of the polymerization of the polymer. The terminal group of the polymer of this embodiment is usually a hydrocarbon group. From the viewpoint of charge transportability, the hydrocarbon group preferably has 1 or more and 60 or less carbon atoms, more preferably 1 or more and 40 or less, and further preferably 1 or more and 30 or less.

Preferably,
For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl group and the like. , A linear, branched, or cyclic alkyl group usually having 1 or more carbon atoms, preferably 4 or more, usually 24 or less, preferably 12 or less;
For example, an alkenyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as a vinyl group;
For example, an alkynyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as an ethynyl group;
For example, an aromatic hydrocarbon ring group having a carbon number of usually 6 or more, usually 36 or less, preferably 24 or less, such as a phenyl group and a naphthyl group;
Can be mentioned.
These hydrocarbon groups may further have a substituent, and the substituent which may further have is preferably an alkyl group or an aromatic hydrocarbon group, and there are a plurality of these substituents which may further have. In some cases, they may be bonded to each other to form a ring.
From the viewpoint of charge transportability and durability, an alkyl group or an aromatic hydrocarbon group is preferable, and an aromatic hydrocarbon group is more preferable.

[Soluble group]
The polymer of the present embodiment preferably has a soluble group for soluble expression in a solvent. The soluble group in the present embodiment is a group having a linear or branched alkyl group or alkylene group having 3 or more and 24 or less carbon atoms, preferably 12 or less carbon atoms. Among these, an alkyl group, an alkoxy group, or an aralkyl group is preferable, and for example, an n-propyl group, a 2-propyl group, an n-butyl group, an isobutyl group, and the like. More preferably, it is an n-hexyl group or an n-octyl group. The soluble group may have a substituent. When one or more of the above R ^{1 to} R ⁷ and R ^{11 to} R ¹⁴ have these structures, those groups are considered to be soluble groups. Further, when the substituents in the present embodiment satisfy the conditions of the soluble group, those substituents are considered to be soluble groups.

(Number of soluble groups)
It is preferable that the amount of the soluble group contained in the polymer of the present embodiment is large in that it is easy to obtain a polymer solution that can be used in the wet film forming method. On the other hand, a small amount is preferable in that the film thickness decrease due to the layer being dissolved in the solvent when another layer is formed on the formed layer by the wet film forming method is small.

The number of soluble groups contained in the polymer of the present embodiment can be expressed by the number of moles per 1 g of the polymer.
When the number of soluble groups contained in the polymer of the present embodiment is expressed in terms of the number of moles per 1 g of the polymer, it is usually 4.0 mmol or less, preferably 3.0 mmol or less, more preferably 3.0 mmol or less per 1 g of the polymer. It is 2.0 mmol or less, and usually 0.1 mmol or more, preferably 0.5 mmol or more.
When the number of soluble groups is within the above range, the polymer is easily dissolved in a solvent, and a composition containing a polymer suitable for a wet film forming method can be easily obtained. Further, since the soluble group density is appropriate, the solubility in an organic solvent after drying with a heated solvent is sufficient, so that a multi-layer laminated structure can be formed by a wet film forming method.

Here, the number of soluble groups per 1 g of the polymer can be calculated from the molar ratio of the charged monomer at the time of synthesis and the structural formula, excluding the terminal groups from the polymer.
Explaining the case of the polymer 1 synthesized in Example 1 described later, the molecular weight of the repeating unit excluding the terminal group in the polymer 1 is 767 on average, and the hexyl group which is a soluble group is a soluble group. The average is 2 per repeating unit. When this is calculated by simple proportionality, the number of soluble groups per 1 g of molecular weight is calculated to be 2.09 mmol.

[Crosslinkable group]
The polymer of this embodiment may have a crosslinkable group as a substituent. The crosslinkable group in the polymer of the present embodiment may be present in the repeating unit represented by the formula (1), or may be present in a repeating unit different from the repeating unit represented by the formula (1). You may be doing it. In particular, it is preferable to have a crosslinkable group in ^{Ar 1} which is a side chain because the crosslinkable reaction can easily proceed.
By having a crosslinkable group, it is possible to make a large difference in solubility in an organic solvent before and after a reaction (poor solubility reaction) caused by irradiation with heat and / or active energy rays.

A crosslinkable group is a group that forms a new chemical bond by reacting with a group constituting another molecule located in the vicinity of the crosslinkable group by irradiation with heat and / or active energy rays. To say. In this case, the reacting group may be the same group as the crosslinkable group or a different group.
As the crosslinkable group, a cyclobutene ring fused to the aromatic ring and a group containing an alkenyl group bonded to the aromatic ring are preferable, and a group selected from the following crosslinkable group group T is more preferable. The crosslinkable group is preferably further substituted with a substituent having each of the above structures.

(Crosslinkable group T)
The crosslinkable group T has the structure shown below.

In the crosslinkable group T,
R ^{21 to} R ²³ each independently represent a hydrogen atom or an alkyl group.
R ^{24 to} R ²⁶ each independently represent an alkyl group or an alkoxy group. p is an integer of 1 to 4, q is an integer of 1 to 5, and r is an integer of 1 to 7.
When p is 2 or more, the plurality of R ^24s may be the same or different, and adjacent R ^24s may be bonded to each other to form a ring.
When q is 2 or more, the plurality of R ^25s may be the same or different, and adjacent R ^25s may be bonded to each other to form a ring.
When r is 2 or more, the plurality of R ^26s may be the same or different.
Ar ²¹ and Ar ²² represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent.

Examples of the alkyl group of R ^{21 to R 26} include a linear or branched chain alkyl group having 6 or less carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, an n-butyl group, an isobutyl group and the like. More preferably, it is a methyl group or an ethyl group. Since ^{the carbon number of R 21 to} R ²⁶ is 6 or less, the cross-linking reaction is not sterically inhibited, and the insolubilization of the membrane tends to occur easily.

Examples of the alkoxy group of R ^{24 to} R ²⁶ include a linear or branched chain alkoxy group having 6 or less carbon atoms, for example, a methoxy group, an ethoxy group, an n-propoxy group, a 2-propoxy group, and the like. It is an n-butoxy group or the like. More preferably, it is a methoxy group or an ethoxy group. When the ^{number of carbon atoms of R 24 to} R ²⁶ is 6 or less, the cross-linking reaction is not sterically inhibited, and the insolubilization of the membrane tends to occur easily.

Further, ^{as the aromatic hydrocarbon group which may have a substituent of Ar 21} and Ar ²² , for example, a single ring of a 6-membered ring such as a benzene ring or a naphthalene ring having one free valence, or a single ring. Examples thereof include 2 to 5 fused rings. In particular, a benzene ring having one free valence is preferable.
Ar ²² may be a group in which two or more aromatic hydrocarbon groups which may have a substituent are bonded. Examples of such a group include a biphenylene group and a terphenylene group, and a 4,4'-biphenylene group is preferable.
The ^{substituents that Ar 21} and Ar ²² may have are the same as those of the above-mentioned substituent group Z.

As a crosslinkable group, cyclization of an arylvinylcarbonyl group such as a cinnamoyle group, a benzocyclobutene ring having a monovalent free valence, and a 1,2-dihydrocyclobuta [a] naphthalene ring having a monovalent free valence. Additive reacting groups are preferred in that they further improve the electrochemical stability of the device.
Among the crosslinkable groups, the cyclobutene ring condensed into an aromatic ring having a monovalent free valence and 1,2-dihydro having a monovalent free valence are particularly stable in the structure after cross-linking. A group containing a cyclobutane [a] naphthalene ring is preferable, and a benzocyclobutene ring or a 1,2-dihydrocyclobutane [a] naphthalene ring having a monovalent free valence is more preferable, and the cross-linking reaction temperature is low. A 1,2-dihydrocyclobuta [a] naphthalene ring having a monovalent free valence is particularly preferred.

(Number of crosslinkable groups)
The crosslinkable group of the polymer of the present embodiment is preferably sufficiently insolubilized by crosslinking, and it is easy to form another layer on the crosslinkable group by a wet film forming method. On the other hand, it is preferable that the number of crosslinkable groups is small in that cracks are unlikely to occur in the formed layer, unreacted crosslinkable groups are unlikely to remain, and the organic electroluminescent device tends to have a long life.

In the polymer of the present embodiment, the number of crosslinkable groups present in one polymer chain is preferably 1 or more, more preferably 2 or more, and preferably 200 or less, more preferably 100 or less.
Further, the number of crosslinkable groups contained in the polymer of the present embodiment can be expressed by the number per 1000 molecular weight of the polymer.
When the number of crosslinkable groups contained in the polymer of the present embodiment is expressed by the number per 1000 molecular weight of the polymer, it is usually 3.0 or less, preferably 2.0 or less, more preferably 2.0 or less per 1000 molecular weight. The number is 1.0 or less, and usually 0.01 or more, preferably 0.05 or more.
When the number of crosslinkable groups is within the above range, cracks and the like are unlikely to occur, and a flat film can be easily obtained. Further, since the cross-linking density is appropriate, there are few unreacted cross-linking groups remaining in the layer after the cross-linking reaction, which does not easily affect the life of the obtained device.
Further, since the poor solubility in the organic solvent after the crosslinking reaction is sufficient, it is easy to form a multilayer laminated structure by the wet film forming method.

Here, the number of crosslinkable groups per 1000 molecular weight of the polymer can be calculated from the molar ratio of the charged monomer at the time of synthesis and the structural formula, excluding the terminal groups from the polymer.
For example, in the case of the polymer 3 synthesized in Examples described later, in the polymer 3, the molecular weight of the repeating unit excluding the terminal group is 816 on average, and the crosslinkable group is 0. There are 138 pieces. When this is calculated by simple proportionality, the number of crosslinkable groups per 1000 molecular weight is calculated to be 0.15.

[Content of repeating unit]
In the polymer of the present embodiment, the content of the repeating unit represented by the formula (1) is not particularly limited, but is usually contained in the polymer in an amount of 50 mol% or more, preferably 60 mol% or more, preferably 70. It is more preferably contained in an amount of mol% or more, and particularly preferably contained in an amount of 80 mol% or more. In the polymer of the present embodiment, the repeating unit may be composed of only the repeating unit represented by the formula (1), but the formula (1) is used for the purpose of balancing various performances when the organic electroluminescent element is used. It may have a repeating unit different from 1), in which case the content of the repeating unit represented by the formula (1) in the polymer is usually 95 mol% or more, preferably 99 mol%. That is all.

[Preferable repeating unit that may be included elsewhere]
It is also preferable that the polymer of the present embodiment further contains a repeating unit represented by any of the following (3) -1 to formula (3) -3.

In equations (3) -1 to (3) -3,
Ar ⁷ has an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent independently in each repeating unit. It represents a divalent group in which a plurality of aromatic heterocyclic groups which may have a good aromatic hydrocarbon group or a substituent are directly or via a linking group are linked.
X represents −C (R ⁵ ) (R ⁶ ) −, −N (R ⁷ ) − or −C (R ¹¹ ) (R ¹² ) −C (R ¹³ ) (R ¹⁴ ) −.
R ^{1 to} R ⁴ each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aralkyl group which may have a substituent.
R ^{5 to} R ⁷ and R ^{11 to} R ¹⁴ may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Represents an aromatic hydrocarbon group, or aromatic hydrocarbon group which may have a substituent,
a and b are independently integers of 0 to 4, respectively.
c1 and c2 are independently integers of 1 to 3, respectively.
d1 and d2 are independently integers of 0 to 4, respectively.
When ^{there are a plurality of R 1} , R ² , R ³ , and R ⁴ in the repeating unit, R ¹ , R ² , R ³ , and R ⁴ may be the same or different.

(Ar ⁷ )
In the repeating units represented by the formulas (3) -1 to (3) -3, Ar ⁷ is an aromatic hydrocarbon group or a substituent which may have a substituent independently in each repeating unit. Represents an aromatic heterocyclic group which may have a group.
The aromatic hydrocarbon group preferably has 6 or more and 60 or less carbon atoms, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, and a chrysene ring. , Triphenylene ring, anthracene ring, fluorene ring, fluorene ring and the like, a 6-membered monocyclic ring or a 2-5 fused ring, or a monovalent group in which a plurality of these are linked is mentioned.
When a plurality of the above divalent groups are linked, 2 to 10 linked divalent groups are mentioned, and 2 to 5 linked divalent groups are preferable.

The aromatic heterocyclic group preferably has 3 or more carbon atoms and 60 or less carbon atoms, and specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, and an oxadiazole ring. , Indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, flofran ring, thienoflan ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine 5 such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxalin ring, phenanthridine ring, benzoimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. Examples thereof include a monocycle having a ~ 6-membered ring, a 2-4 fused ring, or a monovalent group in which a plurality of these are linked.
When a plurality of the above divalent groups are linked, 2 to 10 linked divalent groups are mentioned, and 2 to 5 linked divalent groups are preferable.

Ar ⁷ is preferably an aromatic hydrocarbon group which may have a substituent, and above all, a benzene ring or a fluorene ring which may have a substituent from the viewpoints of excellent charge transportability and durability. A monovalent group, that is, a phenyl group or a fluorenyl group which may have a substituent is more preferable, a fluorenyl group which may have a substituent is further preferable, and a fluorenyl group which may have a substituent may be possessed. A 2-fluorenyl group is particularly preferred.

The ^{substituent that the aromatic hydrocarbon group and the aromatic heterocyclic group of Ar 7} may have is not particularly limited as long as it does not significantly reduce the characteristics of the polymer of the present embodiment. Preferred are the substituent group Z or a group selected from the crosslinkable groups, preferably an alkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group or the crosslinkable group, with the alkyl group being more preferred. preferable.

From ^{the viewpoint of solubility in the coating solvent, Ar 7} is preferably a fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms, and particularly a 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms. preferable. Further, a 9-alkyl-2-fluorenyl group in which the alkyl group is substituted at the 9-position of the 2-fluorenyl group is preferable, and a 9,9-dialkyl-2-fluorenyl group in which the alkyl group is 2-substituted is particularly preferable. When at least one of the 9-position and the 9'-position is a fluorenyl group substituted with an alkyl group, the solubility in a solvent and the durability of the fluorene ring tend to be improved. Furthermore, since both the 9-position and the 9'-position are fluorenyl groups substituted with an alkyl group, the solubility in a solvent and the durability of the fluorene ring tend to be further improved.
Further, ^{it is preferable that Ar 7} contains the above-mentioned crosslinkable group because the insolubility in the solvent is improved when the film is laminated and coated after the film formation.

From the viewpoint of insolubilization, the polymer preferably contains a repeating unit represented by the formula (3) -1 to the formula (3) -3, which comprises at least one of the above-mentioned crosslinkable groups as a further substituent. It is preferable that the crosslinkable group is further substituted with a substituent which may be possessed by an aromatic hydrocarbon group represented by Ar ^{7 or an aromatic heterocyclic group.}
From the viewpoint of durability or lowering the voltage of the device when used in an organic electroluminescent device, it is preferable to include a repeating unit represented by the formula (3) -1 or the formula (3) -2.

[Molecular weight of polymer]
The weight average molecular weight (Mw) of the polymer of the present embodiment is usually 3,000,000 or less, preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 200,000 or less, and particularly preferably. Is 100,000 or less. Further, it is usually 10,000 or more, preferably 20,000 or more, and more preferably 30,000 or more.

When the weight average molecular weight of the polymer is not more than the above upper limit value, solubility in a solvent is obtained, and the film forming property tends to be excellent. Further, when the weight average molecular weight of the polymer is at least the above lower limit value, the decrease in the glass transition temperature, the melting point and the vaporization temperature of the polymer may be suppressed, and the heat resistance may be improved. In addition, the coating film after the cross-linking reaction may be sufficiently insoluble in the organic solvent.

The number average molecular weight (Mn) of the polymer of the present embodiment is usually 2,500,000 or less, preferably 750,000 or less, more preferably 400,000 or less, and particularly preferably 100,000 or less. Further, it is usually 2,000 or more, preferably 4,000 or more, more preferably 8,000 or more, still more preferably 20,000 or more.

Further, the dispersity (Mw / Mn) in the polymer of the present embodiment is preferably 3.5 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. Since the smaller the value of the dispersion, the better, the lower limit is ideally 1. When the dispersity of the polymer is not more than the above upper limit, purification is easy, and solubility in a solvent and charge transporting ability are good.

Usually, the weight average molecular weight and the number average molecular weight of the polymer are determined by SEC (Size Exclusion Chromatography) measurement. In the SEC measurement, the higher the molecular weight component, the shorter the elution time, and the lower the molecular weight component, the longer the elution time. By conversion, the weight average molecular weight and the number average molecular weight are calculated.

[Other repeating units]
The polymer of the present embodiment may further contain a repeating unit represented by the formula (4) or the formula (5) in terms of charge transportability and durability. The repeating unit represented by the following formula (4) is the repeating unit represented by the above formulas (1), formula (2) -1 to formula (2) -3 and formula (3) -1 to formula (3) -3. It may coincide with some structural parts in the unit, but it is a structure of another repeating unit.

In equation (4),
Ar ⁸ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
Ar ⁹ may have a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or the substituent. Represents a divalent group in which a plurality of groups selected from a good aromatic hydrocarbon group and an aromatic heterocyclic group which may have the substituent are linked directly or via a linking group.

In equation (5),
Ar ¹⁰ may have a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or the substituent. Represents a divalent group in which a plurality of groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group which may have the substituent are linked directly or via a linking group.

(Ar ⁸ , Ar ⁹ and Ar ¹⁰ )
As the aromatic hydrocarbon group and aromatic heterocyclic group in ^{Ar 8} , Ar ⁹ and Ar ^{10 , Ar 8} is an aromatic hydrocarbon group and an aromatic heterocyclic group that can be taken ^{by Ar 6} of the formula (1). ^{Ar 9} and Ar ¹⁰ are groups selected from similar groups, and Ar 9 and Ar 10 are groups selected from the same groups as the aromatic hydrocarbon group and the aromatic heterocyclic group that can be taken by the formula (1) Ar ^2. Represents a divalent group. Similarly, when a plurality of these divalent groups are linked, 2 to 10 are preferable, and 2 to 5 are more preferable. As the substituent which may be possessed, the substituent group Z or a group similar to the crosslinkable group is preferable.

[Preferable polymer]
The polymer of the present embodiment is most preferably a repeating unit represented by any of the following formulas (6).

In each polymer of formula (6),
Ar ^T represents the Ar ¹ or the Ar ^7, and the plurality of Ar ^Ts in each polymer may be the same or different, and at least one ^{of the Ar Ts in each polymer is the Ar 1} . Represent,
X, R ¹ , R ² , R ³ , and R ⁴ are the same as those in the above equations (2) -1 to (2) -3.
n and m represent the number of repetitions.

The polymer of another embodiment of the first gist of the present invention is a polymer containing a structure represented by the following formula (12) or the following formula (13).

In equation (12),
G, Ar ² , Ar ⁴ , and Ar ⁶ are the same as G, Ar ² , and Ar ⁴ in the equation (1), respectively.
Ar ⁵⁵ is selected from a-1 to a-4, b-1 to b-9, c-1 to c-5, d-1 to d-16, and e1 to e4 shown in Scheme 2 below. Represents either structure.
In addition, ^{"-*" in Ar 12} is a site (bonding position) to be bonded to G in the formula (12).

In the formula (12), the preferred range of G, Ar ² , Ar ⁴ , Ar ⁶ and the ^{substituents that may be possessed are G, Ar 2} , Ar ⁴ , Ar ^{6 in the above formula (1), respectively.} The same is true.

In the formula (12), ^{the preferable range of Ar 55 is} the preferable range of Ar ^{5 in} the above formula (1), and the substituent which may be possessed is the same as that of Ar ^{5 in the above formula (1).} Is.

In equation (13),
^G, Ar 2, Ar ^4, and Ar ⁶ are each similar to G, and Ar ^2, and Ar ⁴ in the above equation (1),
Ar ³³ and Ar ³⁴ each independently have a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. Represents a divalent group in which a plurality of aromatic heterocyclic groups, which may have an aromatic hydrocarbon group or a substituent which may have a substituent, are directly linked or are linked via a linking group.
Ar ⁵⁵⁵ has a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aromatic hydrocarbon which may have a substituent. Represents a monovalent group in which a plurality of hydrogen groups or aromatic heterocyclic groups are directly linked or linked via a linking group.
In addition, ^{"-*" in Ar 13} is a site (bonding position) to be bonded to G in the formula (13).

In formula (13), ^{the preferred ranges of G, Ar 2} , Ar ⁴ and Ar ⁶ and the substituents that they may have are G, Ar ² , Ar ⁴ and Ar 4 in the above formula (1), respectively. It is the same as Ar ⁶ .

In the formula (13), ^{the preferable range of Ar 33} and Ar ³⁴ , and the substituents that may be possessed are the same as those of Ar ² and Ar ^{4 in} the above formula (1), and a plurality of the substituents are linked. The same applies to the preferred range of the case.

The preferred range of Ar ^{555 is the same as} the preferred range of Ar ^{5 in} the above formula (1). The substituent which may be possessed is the same as that of Ar ⁵ in the formula (1).

The preferred repeating unit structure of the formula (12) and the formula (13), the terminal group thereof, the soluble group, the crosslinkable group, the content of the repeating unit, the preferred repeating unit which may be contained elsewhere, the molecular weight of the polymer, and the like. The other repeating units, etc. that may be used are the same as those of the polymer of the above formula (1).

In the formula (12), since Ar ⁵⁵ can distribute the LUMO of the molecule on the terminal side of the side chain, the hole injection transport ability is high and the durability can be increased. Further, in the formula (13), HOMO and LUMO can be separated by taking a distance between the main chain and carbazole by ^{Ar 33} and Ar ^{34, so that the hole injection transport capacity and durability are improved.} can do. Since the formula (1) has Ar ³ and Ar ⁵ , the LUMO of the molecule can be distributed on the terminal side of the side chain, and the HOMO of the main chain and the LUMO of the side chain can be separated, which is more preferable.

[Concrete example]
Specific examples of the polymer of this embodiment are shown below, but the present invention is not limited thereto. The numbers in the chemical formula represent the molar ratio of the repeating unit.
These polymers may be random copolymers, alternate copolymers, block copolymers, graft copolymers, or the like, and the order of arrangement of the monomers is not limited.

[Method for producing polymer]
The method for producing the polymer of the present embodiment is not particularly limited. For example, it can be produced by a polymerization method by Suzuki reaction, a polymerization method by Grignard reaction, a polymerization method by Yamamoto reaction, a polymerization method by Ullmanne reaction, a polymerization method by Buchwald-Hartwig reaction, or the like.

In the case of the polymerization method by the Ullmann reaction and the polymerization method by the Buchwald-Hartwig reaction, for example, the dial halide represented by the formula (1a) (Y represents a halogen atom such as I, Br, Cl, F) and the formula ( By reacting with the primary aminoaryl represented by 1b) and further reacting with 2a, the polymer of the present embodiment is synthesized.

In the above formula, Ar ¹ , R ^{1 to} R ² , X, a, and b are synonymous with the above formulas (2) -1 to (2) -3, respectively. c and d are synonymous with c1 or c2 and d1 or d2 in the above formulas (2) -1 to (2) -3, respectively. n and m represent the number of repetitions.
In the above polymerization method, the reaction for forming an N-aryl bond is usually carried out in the presence of a base such as potassium carbonate, tert-butoxysodium or triethylamine. It can also be carried out in the presence of a transition metal catalyst such as copper or palladium complex.

<Embodiment pertaining to the second gist>
<Same partial structure>
The organic electric field light emitting element according to the second gist of the present invention is an organic electric field light emitting element having an anode, a cathode, and an organic layer between the anode and the cathode, and the organic layer is a hole. It has a transport layer and a light emitting layer adjacent to the hole transport layer, and the hole transport layer contains a polymer 1 represented by the formula (1) or a polymer cross-linked with the polymer 1 and has a weight thereof. A material having a partial structure represented by the following formula (CzP) in which the coalescence 1 or the polymer crosslinked with the polymer 1 and at least one of the materials contained in the light emitting layer both have a carbazole ring (the following formula (CzP)). It is preferable that the organic electric field light emitting element contains a compound having a partial structure represented by. Regarding the description of "material" in the present specification, the description that can be replaced with "compound" may be replaced with "compound".

More preferably, the material contained in the hole transport layer and the material contained in the light emitting layer both contain a material having a partial structure represented by the formula (CzP), and the material contained in the hole transport layer or the above. One of the materials contained in the light emitting layer includes a material having two or more partial structures represented by the formula (CzP), and more preferably, the material contained in the light emitting layer is represented by the formula (CzP). It is to contain a material (compound) having two or more partial structures, and it is particularly preferable that the material contained in the hole transport layer and the material contained in the light emitting layer are both represented by the formula (CzP). Is to include a material (compound) having 2 or more. With such a combination, it is expected that the battery will be driven at a lower voltage, emit light with high efficiency, and have a long life. Further, it is also preferable that at least one of the hole transport layer or the light emitting layer contains two or more kinds of materials having a partial structure represented by the formula (CzP), and in particular, the light emitting layer is represented by the formula (CzP). It is preferable to contain two or more kinds of materials having a partial structure. Even in such a combination, it is expected that the battery will be driven at a lower voltage, emit light with high efficiency, and have a long life.

The material contained in the hole transport layer having a partial structure represented by the formula (CzP) is not particularly limited, but is preferably a polymer compound. The polymer compound is preferably a polymer compound having an arylamine structure. The arylamine polymer compound is more preferably a polymer having a repeating unit represented by the following formula (20).

The material contained in the light emitting layer having a partial structure represented by the formula (CzP) is not particularly limited, but is preferably a low molecular weight compound.
When the material having a partial structure represented by the formula (CzP) is a polymer compound, the number of formulas (CzP) contained in the polymer compound is the number of the formula (CzP) contained in the repeating unit of the polymer compound. It is preferably a number or more. When two formulas (CzP) are present in the repeating unit, the number of formulas (CzP) contained in the polymer compound is twice that of the repeating unit of the polymer compound. When the polymer compound has a plurality of repeating units, at least one repeating unit may have the formula (CzP). The formula (CzP) may have a substituent.

Further, the bonding method between the material contained in the hole transport layer or the material contained in the light emitting layer and the formula (CzP) is not particularly limited. For example, the carbazole moiety may be bonded to the material contained in the hole transport layer or the material contained in the light emitting layer, and the benzene moiety and the material contained in the hole transport layer or the material contained in the light emitting layer may be bonded. It may be combined.

<Low molecular weight compound>
Next, a case where the material having a partial structure represented by the formula (CzP) included in the device of the present embodiment is a low molecular weight compound will be described. The formula (CzP) can be used for the light emitting material used for the light emitting layer or the low molecular weight compound used as the host material, and in the case of the host material, for example, it is as follows.

It is a host material having the following formula (CzP-2) as the formula (CzP).

In the above formula (CzP-2), * 1, * 2, and * 3 are bonding positions of the host material with the skeleton, and it is sufficient that at least one of * 1, * 2, and * 3 is bonded. It may be directly bonded to the skeleton of the host material or may be bonded via another structure. The formula (CzP-2) may have a substituent. The other structure that may be interposed is not particularly limited, but is preferably an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or a substituent. Examples thereof include a structure in which a plurality of two or more groups selected from an aromatic hydrocarbon group which may have a substituent and an aromatic heterocyclic group which may have a substituent are linked, and specific examples thereof will be described later. An aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent which can be used as B in the formulas (14) to (16). It is possible to use and have a structure in which a plurality of two or more groups selected from an aromatic hydrocarbon group which may have a substituent and an aromatic heterocyclic group which may have a substituent are linked. The same applies to substituents and preferred ranges.
As the substituent, a group selected from the above-mentioned substituent group Z can be used.
Since the transfer of electric charge between the hole transport layer and the light emitting layer adjacent to the hole transport layer is mainly performed between the material forming the hole transport layer and the host material in the light emitting layer, the light emitting layer When the host material used has the formula (CzP) and / or the formula (CzP-2), the hole transport property can be improved particularly at the interface.

The skeleton of the host material is preferably selected from those having electron transporting property, hole transporting property, and both electron transporting property and hole transporting property.
Specific examples of the skeleton having excellent charge transport properties include an aromatic structure, an aromatic amine structure, a triarylamine structure, a dibenzofuran structure, a naphthalene structure, a phenanthrene structure, a phthalocyanine structure, a porphyrin structure, a thiophene structure, and a benzylphenyl structure. Examples thereof include those having a fluorene structure, a quinacridone structure, a triphenylene structure, a carbazole structure, a pyrene structure, an anthracene structure, a phenanthrene structure, a quinoline structure, a pyridine structure, a pyrimidine structure, a triazine structure, an oxadiazole structure, an imidazole structure and the like.

As the electron transporting material, a compound having a pyridine structure, a pyrimidine structure and a triazine structure is more preferable, and a compound having a pyrimidine structure and a triazine structure is preferable from the viewpoint of being a material having excellent electron transporting property and a relatively stable structure. It is more preferable to have.
The hole transporting material is a compound having a structure excellent in hole transporting property, and examples of the skeleton having excellent charge transporting property include a carbazole structure, a dibenzofuran structure, a triarylamine structure, a naphthalene structure, a phenanthrene structure or pyrene. Those having a structure can be used, and among them, those having a carbazole structure, a dibenzofuran structure or a triarylamine structure are particularly preferable.

The host material of the light emitting layer preferably has a condensed ring structure of 3 or more rings, and is further preferably a compound having 2 or more condensed ring structures of 3 or more rings or a compound having at least one condensed ring structure of 5 or more rings. preferable. By using these compounds, the rigidity of the molecule is increased, and the effect of suppressing the degree of molecular motion in response to heat can be easily obtained. Further, it is preferable that the condensed ring having 3 or more rings and the condensed ring having 5 or more rings have an aromatic hydrocarbon ring or an aromatic heterocycle in terms of charge transportability and durability of the material.

Specific examples of the fused ring structure having three or more rings include anthracene structure, phenanthrene structure, pyrene structure, chrysen structure, naphthacene structure, triphenylene structure, fluorene structure, benzofluorene structure, indenofluorene structure, and indolofluorene structure. Examples thereof include a carbazole structure, an indenocarbazole structure, an indrocarbazole structure, a dibenzofuran structure, and a dibenzothiophene structure. From the viewpoint of charge transportability and solubility, at least one selected from the group consisting of a phenanthrene structure, a fluorene structure, an indenofluorene structure, a carbazole structure, an indenocarbazole structure, an indolocarbazole structure, a dibenzofuran structure and a dibenzothiophene structure is selected. Preferably, a carbazole structure or an indolocarbazole structure is more preferable from the viewpoint of durability against charge.

From the viewpoint of durability against electric charge of the organic electroluminescent element, at least one of the host materials of the light emitting layer is preferably a material having a pyrimidine skeleton or a triazine skeleton.
As the structure used between the skeleton of the host material and the formula (CzP-2), for example, an arylene group can be used. Examples of the arylene group include phenylene, biphenylene, and triphenylene, which may have a branch.

The host material of the light emitting layer is preferably a polymer material from the viewpoint of excellent flexibility. A light emitting layer formed by using a material having excellent flexibility is preferable as a light emitting layer of an organic electroluminescent element formed on a flexible substrate. When the host material contained in the light emitting layer is a polymer material, the molecular weight is preferably 5,000 or more and 1,000,000 or less, more preferably 10,000 or more, 500,000 or less, and more preferably 10,000. It is 100,000 or less.

[Preferable low molecular weight compound]
The compound having a partial structure represented by the formula (CzP) contained in the light emitting layer, particularly a low molecular weight compound, is represented by any of the following formula (14), the following formula (15), or the following formula (16). It is preferably a compound.

In the above formulas (14) to (16),
A is a partial structure represented by the above formula (CzP) and may have a substituent.
B represents a single bond or any partial structure.
When there are a plurality of A's, they may be the same or different from each other.
When there are a plurality of B's, they may be the same or different from each other.
na, nb and nc independently represent integers of 1 or more and 5 or less, respectively.
The molecular weight of the compounds represented by the formulas (14) to (16) is 5,000 or less.

(A)
The substituent which may be possessed in A is preferably selected from the substituent group Z, and the same applies to the preferred group and the substituent which may be further possessed.

(B)
B in the formulas (14) to (16) is not particularly limited, but is preferably a functional group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a substituent. Two or more groups selected from an aromatic heterocyclic group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent and an aromatic heterocyclic group which may have a substituent. Represents a structure in which a plurality of are connected. As the substituents that may be possessed, any one of the above-mentioned substituent group Z or a combination thereof can be used.
Functional groups include a structure having hole transportability, a structure having electron transportability, a structure that suppresses charge transport, a structure that imparts solubility to an organic solvent, a structure that inhibits crystallization and improves amorphousness, and a structure. Alternatively, a structure having light emission is preferable.
As a monovalent group in which a plurality of two or more groups selected from an aromatic hydrocarbon group, an aromatic heterocyclic group, an aromatic hydrocarbon group and an aromatic heterocyclic group are linked, Ar in the above formula (1) is used. The same structure as in ^{2 is preferable.} Similarly, when connecting a plurality of pieces, it is preferable to connect 2 to 10 and more preferably 2 to 5 are connected.
The position of A to which B is bonded is preferably a benzene ring bonded to a carbon atom of the carbazole ring or a nitrogen atom of the carbazole ring, and at least one B is bonded to N of the carbazole ring in the partial structure A. It is more preferable that it is a benzene ring.
The low molecular weight compound having a partial structure represented by the formula (CzP) is preferably a charge transport material in the light emitting layer.
The low molecular weight compound having a partial structure represented by the formula (CzP) contained in the light emitting layer is preferably the above formula (14) or the above formula (16).
Further, the compound represented by the formula (14) is preferably a compound represented by the following formula (17), and the compound represented by the formula (16) is represented by the formula (19) described later. It is preferably the compound represented.

In the above formula (17)
Q represents either a nitrogen atom or a trivalent substituent represented by the following structural formulas (18-1), (18-2) and (18-3).
Xb ¹ , Yb ¹ , and Zb ¹ each independently have a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms, which may have a substituent, or a carbon which may have a substituent. It represents a divalent heteroaromatic ring group of the number 3 to 30 ^{, and each of Xb 1} , Yb ¹ , and Zb ¹ may be the same or different when a plurality of them are present.
A is a partial structure represented by the above formula (CzP), may have a substituent, and a plurality of A may be the same or different from each other.
p12, q12, and r12 each independently represent an integer of 0 or more and 6 or less.
q13 and r13 independently represent 0 or 1, respectively.
^{Yb 2} when q13 is 0 ^{and Zb 2} when r13 is 0 independently have a hydrogen atom and a monovalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent. Alternatively, it represents a monovalent heteroaromatic ring group having 3 to 30 carbon atoms which may have a substituent.
When q13 is 1, Yb2 is a direct bond and is a direct bond.
When r13 is 1, Zb2 is a direct bond.

In the formulas (18-1) to (18-3), * in one structural formula represents the bonding position with any group of ^{Xb 1} , Yb ¹ , or Zb ^{1, respectively.}

In the above formula (19)
Each of Xc ¹ and Yc ¹ independently has a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent, or 3 to 30 carbon atoms which may have a substituent. Represents a divalent heteroaromatic ring group of
Each of Xc ² and Yc ² independently has a hydrogen atom and a hydrocarbon aromatic ring group having a monovalent number of 6 to 30 carbon atoms which may have a substituent, or a carbon number which may have a substituent. Represents a monovalent heteroaromatic ring group of 3 to 30
Each of Xc ¹ and Yc ¹ may be the same or different when there are a plurality of them.
A is a partial structure represented by the above formula (CzP) and may have a substituent.
s11 and t11 each independently represent an integer of 0 or more and 6 or less.
nc represents an integer of 1 or more and 5 or less.

In the formula (17) and the formula (19), the hydrocarbon aromatic ring having 6 to 30 carbon atoms is preferably a 6-membered single ring or a 2-5 condensed ring. Specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, and a fluoranthene ring. More preferably, it is a monocyclic ring or a 2-3 fused ring, and specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Of these, a benzene ring, a naphthalene ring, a phenanthrene ring, and a fluorene ring are preferable, and a benzene ring or a fluorene ring is more preferable.

In the formula (17) and the formula (19), the heteroaromatic ring having 3 to 30 carbon atoms is preferably a single ring having 5 or 6 members, or a 2-5 condensed ring thereof. Specifically, furan ring, benzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, pyrol ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, indolocarbazole ring, Pyroloymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, flopyrol ring, flofran ring, thienofran ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring , Pyrazole ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, perimidine ring, quinazoline ring, quinazorinone ring and the like.
Of these, the thiophene ring, pyrrole ring, imidazole ring, pyridine ring, pyrimidine ring, triazine ring, quinoline ring, quinazoline ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring, indolocarbazole ring, phenanthroline ring, or indolocarbazole ring are preferable. And
More preferably, it is a pyridine ring, a pyrimidine ring, a triazine ring, a quinoline ring, a quinazoline ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, or an indolocarbazole ring.
More preferably, it is a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, or an indolocarbazole ring.

^{Further, Yb 2} when q13 = 0 ^{and Zb 2} when r13 = 0 in the above formula (17), Xc ² and Yc ² in the above formula (19) are particularly preferable aromatic hydrocarbon rings. , Benzene ring, naphthalene ring or phenanthrene ring, and a particularly preferable aromatic heterocycle is a dibenzofuran ring, a dibenzothiophene ring, or an indolocarbazole ring.

The substituent which may be contained in the formula (CzP) represented by A is preferably an aromatic hydrocarbon group or a substituent having 6 to 30 carbon atoms which may have a substituent. It is an aromatic heterocyclic group having 3 to 30 carbon atoms which may be used. From the viewpoint of improving durability and charge transportability, it is more preferable to use an aromatic hydrocarbon group which may have a substituent. Further, it is preferable that a substituent is bonded to the 3-position or 6-position of carbazole in the partial structure A from the viewpoint of improving durability.

Substituents that Xb ¹ , Yb ¹ , Zb ¹ , Yb ² , Zb ² , Xc ¹ , Xc ² , Yc ¹ , and Yc ² may have, the above-mentioned hydrocarbon aromatic ring having 6 to 30 carbon atoms. The substituents which may be possessed by, the substituents which may be possessed by the heteroaromatic ring having 3 to 30 carbon atoms, and the substituents which may be further possessed by A may be. The same is true for the substituents listed in the substituent group Z or the crosslinkable group in the polymer represented by the above formula (1), and the same applies to the preferred substituents and the substituents which may be further possessed. be.

The compound represented by the formula (17) is more preferably a compound represented by any of the following formulas (17-1) to (17-6).

In the above general formulas (17-1) to (17-6),
p12'represents an integer of 1 or more and 5 or less.
q12'and r12'independently represent integers of 0 or more and 5 or less.
p14 is 12,
q14 is 12 when q13 is 1, and does not exist when q13 is 0.
r14 is 12 when r13 is 1, does not exist when r13 is 0, and does not exist.
q15 and r15 are independently 4 or 5, respectively.
R ³¹ and R ³² are independently hydrogen atoms or substituents, respectively.
Xb ¹ , Yb ¹ , Zb ¹ , q13, and r13 are the same as those in the above equation (17), respectively.
The substituent R ³¹ is the same as the hydrogen atom or the substituent that A may have, the same is true as the preferred substituent, and the same is true for the substituent that may be further contained.
The substituent R ³² is the same as the hydrogen atom or the substituent listed in the substituent group Z in the polymer represented by the formula (1) or the crosslinkable group, and is preferable as a substituent and a preferred substituent. The same applies to the substituents that may be further possessed.

The compound represented by the formula (19) is more preferably a compound represented by the following general formula (19-1).

In the above general formula (19-1),
R ³¹ is a hydrogen atom or a substituent and is
u11 represents 11 and represents
Xc ¹ , Yc ¹ , Xc ¹ , Yc ¹ , t11, and s11 are the same as those in the above formula (19), respectively.
In the case of a substituent, R ³¹ is the same as the substituent or the crosslinkable group listed in the substituent group Z in the polymer represented by the above formula (1), and is a preferable substituent and further present. The same applies to the substituents that may be used.

In addition, the host material (compound) of the light emitting layer is easy to synthesize and purify, easy to design electron transport performance and hole transport performance, and easy to adjust the viscosity when dissolved in a solvent. , Preferably small molecules. When the host material contained in the light emitting layer is a low molecular weight material, the molecular weight is preferably 5,000 or less, more preferably 4,000 or less, particularly preferably 3,000 or less, and most preferably 2,. It is 000 or less, usually 300 or more, preferably 350 or more, and more preferably 400 or more.
Examples of the host material having the above formula (CzP-2) include the following compounds.

Examples of the low molecular weight compound include a light emitting material, and a light emitting material having a formula (CzP) can be used. As the light emitting material, a phosphorescent light emitting material described later can be used, and a material having a formula (CzP) in these structures can be used.

<Embodiment pertaining to the third gist>
An embodiment of the third gist of the present invention is an organic electroluminescent device having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate, wherein the organic layer is a hole transport layer. And a light emitting layer adjacent to the hole transport layer, and the material contained in the hole transport layer and the material contained in the light emitting layer both have a partial structure represented by the following formula (CzP) having a carbazole ring. An organic electroluminescent device containing a material.

More preferably, the material contained in the hole transport layer and the material contained in the light emitting layer both contain a material having a partial structure represented by the formula (CzP), and the material contained in the hole transport layer or the light emitting layer. One of the materials contained in the layer includes a material having two or more partial structures represented by the formula (CzP), and particularly preferably contained in the material contained in the hole transport layer and the light emitting layer. Both materials include materials having two or more partial structures represented by the formula (CzP). With such a combination, it is expected that the battery will be driven at a lower voltage and the life will be extended.

The material contained in the hole transport layer having a partial structure represented by the formula (CzP) is not particularly limited, but is preferably a polymer compound. The polymer compound is preferably a polymer compound having an arylamine structure. The arylamine polymer compound is more preferably a polymer having a repeating unit represented by the following formula (20) or a polymer having a repeating unit represented by the following formula (30). For convenience, the polymer having the repeating unit represented by the following formula (20) is referred to as polymer 2, and the polymer having the formula (30) described later in the side chain is referred to as polymer 3.

The material contained in the light emitting layer having a partial structure represented by the formula (CzP) is not particularly limited, but is preferably a low molecular weight compound.
When the material having a partial structure represented by the formula (CzP) is a polymer compound, the number of formulas (CzP) contained in the polymer compound is the number of the formula (CzP) contained in the repeating unit of the polymer compound. It is preferably a number or more. When two formulas (CzP) are present in the repeating unit, the number of formulas (CzP) contained in the polymer compound is the repeating unit of the polymer compound × 2. When the polymer compound has a plurality of repeating units, at least one repeating unit may have the formula (CzP). The formula (CzP) may have a substituent.

Further, the bonding method between the material contained in the hole transport layer or the material contained in the light emitting layer and the formula (CzP) is not particularly limited. For example, the carbazole moiety may be bonded to the material contained in the hole transport layer or the material contained in the light emitting layer, and the benzene moiety and the material contained in the hole transport layer or the material contained in the light emitting layer may be bonded. It may be combined.

<Polymer 2>

In equation (20),
Ar 1 ^'is have a which may have aromatic hydrocarbon group or an optionally substituted a substituent an aromatic heterocyclic group, Ar ^1', at least one formula of (21) Represented by
X is -C (R ³ ') (R ⁴ ')-, -N (R ⁵ ')-or -C (R ¹¹ ') (R ¹² ')-C (R ¹³ '), (R ¹⁴ '). )-Represents
R 1 ^'and R ^2' each independently represents an alkyl group which may have a substituent,
R ³ ′ to R ⁵ ′ and R ¹¹ ′ to R ¹⁴ ′ each independently have an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. Represents an aromatic hydrocarbon group that may be present
a and b are each independently an integer of 0 to 4, and a + b is 1 or more.
c is an integer from 1 to 3 and
d is an integer from 0 to 4 and
If R 1 ^'and R ^2' is located more in the repeating unit, R 1 ^'and R ^2' may or may not be the same.

In equation (21),
Ar 11 ^'and Ar ^12' each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic radical of the dihydric may have a substituent group,
^{Ar 13} '~Ar ^15' each independently represent a hydrogen atom or a substituent.
* Represents the bond position.
At least one of ^{Ar 11} '~Ar ^15' as equation (CZP) in addition to the equation (21), it may have the formula (CZP-1).

In the above formula (CzP-1), * 1, * 2, and * 3 are bonding positions with the skeleton of the polymer, and at least one of * 1, * 2, and * 3 may be bonded. It may be directly bonded to the skeleton of the polymer or may be bonded via another structure. The formula (CzP-1) may have a substituent.
As the substituent, for example, it can be the same as the above-described ^{Ar 13 '~Ar 15'.}

^{(R 1} 'and ^{R 2')}
R ¹ in the repeating unit represented by formula (20) 'and R ^2' each independently represents an alkyl group which may have a substituent. The number of carbon atoms of the alkyl group is not particularly limited, but in order to maintain the solubility of the polymer, the number of carbon atoms is preferably 1 or more and 6 or less, more preferably 3 or less, and further preferably a methyl group or an ethyl group. .. Further, the alkyl group may have a linear, branched or cyclic structure.

If R 1 ^'and R ^2' is located more in the repeating unit, that R ¹ and R ² may be independently identical or different, but distributed around homogeneously nitrogen atom charge It is preferable that ^{all R 1} and R ² have the same group because they can be synthesized and can be easily synthesized.

^{(R 3} '~R ^5' and ^{R 11 '~R 14')}
R ^{3 '~R} 5' and R ¹¹ 'to R ¹⁴ each independently optionally substituted alkyl group, an optionally substituted aralkyl group, or substituted Represents an aromatic hydrocarbon group that may be present.

The alkyl group is not particularly limited, but the solubility of the polymer tends to be improved, so that the number of carbon atoms is preferably 1 or more and 24 or less, and more preferably 6 or less. Further, each structure may be linear, branched or cyclic.
Specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, and an n-octyl group. , Cyclohexyl group, dodecyl group and the like.

The aralkyl group is not particularly limited, but the solubility of the polymer tends to be improved, so that the number of carbon atoms is 5 or more and 60 or less, and more preferably 40 or less.
Specifically, 1,1-dimethyl-1-phenylmethyl group, 1,1-di (n-butyl) -1-phenylmethyl group, 1,1-di (n-hexyl) -1-phenylmethyl group. , 1,1-di (n-octyl) -1-phenylmethyl group, phenylmethyl group, phenylethyl group, 3-phenyl-1-propyl group, 4-phenyl-1-n-butyl group, 1-methyl- 1-Phenylethyl group, 5-Phenyl-1-n-propyl group, 6-Phenyl-1-n-hexyl group, 6-naphthyl-1-n-hexyl group, 7-Phenyl-1-n-heptyl group, Examples thereof include 8-phenyl-1-n-octyl group and 4-phenylcyclohexyl group.

The aromatic hydrocarbon ring group is not particularly limited, but the number of carbon atoms is preferably 6 or more and 60 or less, and more preferably 30 or less because the solubility of the polymer tends to be improved.
Specifically, 6-membered rings such as benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc. Examples thereof include monovalent groups of monocyclic or 2-5 fused rings, or groups in which a plurality of these are linked.

From the viewpoint of charge transporting property and durability, R ³ 'to R ^5' is preferably a methyl group or an aromatic hydrocarbon group, more preferably R 3 ^'and R ^4' is a methyl group, R ⁵ ' Is more preferably a phenyl group.
From the viewpoint of excellent charge transportability while improving solubility, R 3 ^'and R ^4' is preferably an aralkyl group having 3 to 6 alkyl group or a carbon number of 9 or more 40 or less carbon atoms.

The alkyl group of ^{R 1} 'and ^{R 2',} alkyl group, aralkyl group and an aromatic hydrocarbon group ^{R 3 '~R 5'} and ^{R 11 '~R 14'} may have a substituent .. Have optionally substituent group, the R ^{3 '~R} 5' and R ¹¹ alkyl group 'to R ^14', preferred groups mentioned as groups of the aralkyl group and an aromatic hydrocarbon group, or a later crosslinking Sexual groups are mentioned.
Alkyl group, an alkyl group, an aralkyl group and an aromatic hydrocarbon group ^{R 3 '~R 5'} and ^{R 11 '~R 14'} of the ^{R 1} 'and ^{R 2',} from the viewpoint of low voltage, substituted Most preferably, it has no group.

The alkyl group of the R ^{3 '~R} 5' and R ^{11 '~R} 14', an aralkyl group and an aromatic hydrocarbon group, from the viewpoint of immobilization, as substituents, at least one of the later-described crosslinking group It is preferable to include a repeating unit represented by the above formula (20), which comprises.

(A', b', c'and d')
In the repeating unit represented by the above formula (20), a'and b'are independently integers of 0 to 4, and a'+ b'is 1 or more. Further, a'and b'are preferably 2 or less, and more preferably both a'and b'are 1.
In the repeating unit represented by the above equation (20), c'is an integer of 1 to 3 and d'is an integer of 0 to 4. c'and d'are preferably 2 or less, respectively, c'and d'are more preferably equal, both c'and d'are 1, or both c'and d'are 1. It is more preferably 2.

Both c'and d'in the repeating unit represented by the above formula (20) are 1, or both c'and d'are 2, and both a'and b'are 2 or. If 1 is, R 1 ^'and R ^2' is most preferably bonded to each other symmetrical positions.
Here, "R ^{1 'and} R ^2' and are attached to the positions symmetrical with each other", binding position of relative fluorene ring or carbazole ring in Formula (20), R 1 ^'and R ^2' are symmetrical It means that it is. For example, it can be said in the following formula (20a) included in the equation ^(20), 'and ^{R 2a' R 1a} and the position of the ^subject, 'and ^{R 2b' R 1b} and the the object position. At this time, the 180-degree rotation about the main chain is regarded as the same structure. For example, hereinafter, the formula (20a) and the formula (20b) can be regarded as having the same structure.

(Ar ¹ ')
In the repeating unit represented by the formula (20), Ar 1 ^'is an optionally substituted aromatic hydrocarbon group which may have a substituent aromatic heterocyclic group or the following It represents a group represented by the formula (21).
The aromatic hydrocarbon ring group preferably has 6 or more carbon atoms and 60 or less carbon atoms, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, and a chrysene ring. Examples thereof include monovalent groups of 6-membered monocyclic rings or 2-5 fused rings such as rings, triphenylene rings, acenaphthene rings, fluorentene rings, and fluorene rings, or groups in which a plurality of these are linked.

The aromatic heterocyclic group preferably has 3 or more carbon atoms and 60 or less carbon atoms, and specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, and an oxadiazole ring. , Indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, flofran ring, thienoflan ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine 5 such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxalin ring, phenanthridine ring, benzoimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. Alternatively, a monovalent group of a 6-membered monocyclic ring or a 2-4 condensed ring, or a group in which a plurality of these are linked may be mentioned.

Ar 1 ^', the charge transporting excellent point, from the viewpoint of excellent durability, is preferably an aromatic hydrocarbon ring group which may have a substituent, among them may have a substituent benzene ring or A monovalent group of a fluorene ring, that is, a phenyl group or a fluorenyl group which may have a substituent is more preferable, and a fluorenyl group which may have a substituent is further preferable, and a fluorenyl group which may have a substituent is more preferable. A good 2-fluorenyl group is particularly preferred.

The aromatic hydrocarbon ring group, substituents which may be possessed by the aromatic heterocyclic group of Ar 1 ^', so long as it does not significantly reduce the characteristics of the polymer are not particularly limited. Preferably, a group selected from the following substituent group Z'or a crosslinkable group described below is mentioned, and an alkyl group, a good lucoxy group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group or a crosslinkable group described below can be mentioned. Preferably, an alkyl group is more preferred.

Ar 1 ^', from the viewpoint of solubility in coating solvent, preferably fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms, in particular, 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms Is preferable. Further, a 9-alkyl-2-fluorenyl group in which the alkyl group is substituted at the 9-position of the 2-fluorenyl group is preferable, and a 9,9-dialkyl-2-fluorenyl group in which the alkyl group is 2-substituted is particularly preferable. When at least one of the 9-position and the 9'-position is a fluorenyl group substituted with an alkyl group, the solubility in a solvent and the durability of the fluorene ring tend to be improved. Furthermore, since both the 9-position and the 9'-position are fluorenyl groups substituted with an alkyl group, the solubility in a solvent and the durability of the fluorene ring tend to be further improved.

(Ar ¹ is a formula (21) ')
At least one of Ar 1 ^'in the repeating unit represented by the formula (20) is a group represented by the following formula (21).

In equation (21),
Ar 11 ^'and Ar ^12' each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic radical of the dihydric may have a substituent group,
^{Ar 13} '~Ar ^15' each independently represent a hydrogen atom or a substituent.

[Substituent group Z']
As the substituent, for example, a substituent selected from the following substituent group Z'can be used. The following structure can be mentioned as the substituent group Z'.

For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl group and the like. , A linear, branched, or cyclic alkyl group usually having 1 or more carbon atoms, preferably 4 or more, usually 24 or less, preferably 12 or less;
For example, an alkenyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as a vinyl group;
For example, an alkynyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as an ethynyl group;
For example, an alkoxy group such as a methoxy group or an ethoxy group having a carbon number of usually 1 or more, usually 24 or less, preferably 12 or less;
For example, an aryloxy group having a carbon number of usually 4 or more, preferably 5 or more, usually 36 or less, preferably 24, such as a phenoxy group, a naphthoxy group, and a pyridyloxy group;
For example, an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, which usually has 2 or more carbon atoms and usually has 24 or less, preferably 12 or less carbon atoms;
For example, a dialkylamino group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as a dimethylamino group and a diethylamino group;
For example, a diarylamino group having a carbon number of usually 10 or more, preferably 12 or more, usually 36 or less, preferably 24 or less, such as a diphenylamino group, a ditrilamino group, and an N-carbazolyl group;
For example, an arylalkylamino group having 7 carbon atoms, usually 36 or less, preferably 24 or less, such as a phenylmethylamino group;
For example, an acyl group such as an acetyl group or a benzoyl group, which usually has 2 carbon atoms and usually has 24 or less carbon atoms, preferably 12 carbon atoms;
For example, halogen atoms such as fluorine atoms and chlorine atoms;
For example, a haloalkyl group having a carbon number of usually 1 or more, usually 12 or less, preferably 6 or less, such as a trifluoromethyl group;
For example, an alkylthio group having a carbon number of usually 1 or more, usually 24 or less, preferably 12 or less, such as a methylthio group and an ethylthio group;
For example, an arylthio group having a carbon number of usually 4 or more, preferably 5 or more, usually 36 or less, preferably 24 or less, such as a phenylthio group, a naphthylthio group, and a pyridylthio group;
For example, a silyl group having a carbon number of usually 2 or more, preferably 3 or more, usually 36 or less, preferably 24 or less, such as a trimethylsilyl group and a triphenylsilyl group;
For example, a syroxy group having a carbon number of usually 2 or more, preferably 3 or more, usually 36 or less, preferably 24 or less, such as a trimethylsiloxy group and a triphenylsiloxy group;
Cyano group;
For example, an aromatic hydrocarbon ring group having a carbon number of usually 6 or more, usually 36 or less, preferably 24 or less, such as a phenyl group and a naphthyl group;
For example, an aromatic heterocyclic group having a carbon number of usually 3 or more, preferably 4 or more, and usually 36 or less, preferably 24 or less, such as a thienyl group and a pyridyl group.

Among the above-mentioned substituent group Z', the above-mentioned alkyl group, alkoxy group, aromatic hydrocarbon ring group and aromatic heterocyclic group are preferable. From the viewpoint of charge transportability, it is more preferable to have no substituent.
Further, each substituent of the above-mentioned substituent group Z'may further have a substituent. Examples of these substituents include the same substituents as the above-mentioned substituents (substituent group Z') or crosslinkable groups described later. Preferably, it has no additional substituent or is an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, a phenyl group or a crosslinkable group described later. From the viewpoint of charge transportability, it is more preferable to have no additional substituent.

From the viewpoint of insolubilization, the further substituent preferably contains a repeating unit represented by the formula (20) containing at least one crosslinkable group described below, and the crosslinkable group is represented by Ar ¹ '. It is preferable that the aromatic hydrocarbon ring group or the aromatic heterocyclic group is further substituted with a substituent which may be possessed.

(Ar ¹³ '~ ^{Ar 15} ')
^{Ar 13} '~Ar ^15' each independently represents a hydrogen atom or a substituent. When Ar ^{13 '~Ar} 15' is a substituent, it is not particularly limited, preferably aromatic substituted hydrocarbon group or optionally substituted aromatic heterocyclic It is a group. The preferred structure is the same as the group mentioned in ^{Ar 1'.}

When Ar ^{13 '~Ar} 15' is a substituent, it is bonded to the 3-position or 6-position of the carbazole is preferable from the viewpoint of durability.
^{Ar 13} '~Ar ^15' from the viewpoint of ease of synthesis and charge transport property, preferably a hydrogen atom.
Ar ^{13 '~Ar} 15' is, in view of the durability and charge transportability, which may have a which may have aromatic hydrocarbon group or an optionally substituted a substituent aromatic heterocyclic group Is preferable, and it is more preferable that it is an aromatic hydrocarbon group which may have a substituent.

Ar ¹³ As the substituent if 'to Ar ^15' are aromatic optionally substituted hydrocarbon group or optionally substituted aromatic heterocyclic group, the substituent group The same is true for the substituents listed in Z'or the crosslinkable groups described below, the preferred substituents are the same, and so are the substituents that these substituents may further have.
From the viewpoint of insolubilization, it is preferable that the substituent contains a group represented by the formula (21) containing at least one crosslinkable group described later.
On the other hand, from the viewpoint that the uncrosslinked residue after the film formation does not adversely affect the light emitting layer, it is preferable that the substituent is not contained as a substituent.

(Ar ¹² ')
Ar 12 ^'are aromatic or divalent optionally substituted hydrocarbon group, or, have a an aromatic hydrocarbon group which may divalent be substituted substituent A good divalent aromatic heterocyclic group is arbitrarily linked to a divalent group, and the structure bonded to N of at least one of the two carbazole rings constituting the formula (21) is phenylene. It is a group.

The aromatic hydrocarbon group preferably has 6 or more and 60 or less carbon atoms, more preferably 10 or more and 50 or less carbon atoms, and particularly preferably 12 or more and 40 or less carbon atoms. Specifically, 6-membered rings such as benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc. Examples thereof include a divalent group of a monocyclic ring or a 2-5 fused ring, or a group in which a plurality of these are linked. When a plurality of these are linked, it is preferably a group to which a plurality of linked divalent aromatic hydrocarbon groups are conjugated.

The aromatic heterocyclic group preferably has 3 or more carbon atoms and 60 or less carbon atoms, and specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, and an oxadiazole ring. , Indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, flofran ring, thienoflan ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine 5 such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxalin ring, phenanthridine ring, benzoimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. Alternatively, a monocyclic ring of a 6-membered ring, a divalent group of a 2-4 condensed ring, or a group in which a plurality of these are linked may be mentioned.

These aromatic hydrocarbon group or an aromatic heterocyclic group substituents which may be possessed, the mentioned R ^{3 '~R} 5' and R ^{11 '~R} 14', an alkyl group, an aralkyl group and an aromatic Group hydrocarbon groups are mentioned, and the preferred range is the same. If the steric effect ^{of the substituent causes a twist in the structure of Ar 12} ', it is preferable that there is no substituent, and if the steric effect of the substituent does not cause a twist in the structure of ^{Ar 12', it should have a substituent.} Is preferable.

A specific preferred structure is a divalent group of a benzene ring, a naphthalene ring, an anthracene ring, or a fluorene ring or a group in which a plurality of these are linked, and more preferably, a divalent group of a benzene ring or a plurality of linked groups thereof. It is a group, and particularly preferably, a 1,4 phenylene group in which a benzene ring is linked at a divalent position at the 1,4 position, a 2,7 fluorenylene group linked at a divalent position at the 2,7 position of a fluorene ring, or a plurality of these. It is a linked group, and most preferably a group containing 1,4 phenylene group-2,7 fluorenylene group-1,4 phenylene group-. In these preferable structures, it is preferable that the phenylene group has no substituent other than the linking position, because the steric effect of the substituent does not cause twisting ^{of Ar 12'.} Further, it is preferable that the fluorene group has a substituent at the 9,9'position from the viewpoint of improving the solubility and the durability of the fluorene structure.

Ar 12 ^'is that it is a structure as described above, it is an aromatic hydrocarbon group between the nitrogen atoms of the two carbazole structures conjugated structure, LUMO is easily distributed on the aromatic hydrocarbon groups this conjugate .. Therefore, LUMO does not easily spread around the nitrogen atom of the main chain, which is vulnerable to electrons and excitons, and it is considered that the durability is improved.
Further, when an aromatic heterocyclic group is contained, the electron attraction is improved and LUMO is easily distributed. Therefore, it is considered that LUMO is difficult to spread around the nitrogen atom of the main chain, which is weak against electrons and excitons, and the durability is improved. ..

(Ar ¹¹ ')
Ar 11 ^'is a divalent group linking the nitrogen atom of the amine in the main chain in the formula (20). Although Ar 11 ^'is not particularly limited, aromatic heterocyclic group of the aromatic hydrocarbon group or may have a substituent divalent or bivalent may have a substituent is preferable.
The aromatic hydrocarbon group of Ar ¹¹ 's preferably has 6 or more and 60 or less carbon atoms, more preferably 10 or more and 50 or less carbon atoms, and particularly preferably 12 or more and 40 or less carbon atoms. Specifically, 6-membered rings such as benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc. Examples thereof include a divalent group of a monocyclic ring or a 2-5 fused ring, or a group in which a plurality of these are linked.

The aromatic heterocyclic group of Ar ¹¹ ', three or more carbon atoms, preferably 60 or less. Specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrol ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloymidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, Thienopyrrole ring, thienothiophene ring, flopyrol ring, furan ring, thienofran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring , Cinnoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. Examples thereof include a group in which a plurality of these are linked.

These aromatic hydrocarbon group or an aromatic heterocyclic group substituents which may be possessed are mentioned in R ^{3 '~R} 5' and R ^{11 '~R} 14', an alkyl group, an aralkyl group and an aromatic Groups similar to the hydrocarbon group are mentioned, and the preferred range is also the same.
When a plurality of these divalent aromatic hydrocarbon groups or divalent aromatic heterocyclic groups are linked, it is preferable that the plurality of linked divalent aromatic hydrocarbon groups are bonded so as not to be conjugated. Specifically, it is preferable to include a 1,3 phenylene group or a group having a substituent and having a twisted structure due to the steric effect of the substituent. By containing such linking groups, LUMO distributed on Ar 12 ^'is less likely to spread to the main chain, electronic or LUMO around the nitrogen atom of the weak backbone excitons hardly distributed and improved durability Conceivable.

Further, in the polymer having the repeating unit represented by the above formula (20) of the present embodiment, ^{when there are a plurality of Ar 1} ', R ¹ ', R ² ', and X', they are different even if they are the same. May be. Preferably, the polymer contains a plurality of repeating units having the same structure as the repeating unit represented by the formula (20). In this case, by including a plurality of repeating units having the same structure, the repeating unit HOMO, Since the LUMOs are the same, it is considered that the charges do not concentrate on a specific shallow level and become a trap, the charge transportability is excellent, and the durability is also improved.

[Preferable repeating unit]
The repeating unit represented by the formula (20) is most preferably the repeating unit represented by any of the following formulas (20-I).

In the above formula ^{(20-I), R 1} ' and ^{R 2'} are the same, and, ^{'R 2} and' ^{R 1} is attached to each other symmetrical positions.

[Terminal group]
In the present embodiment, the terminal group refers to the structure of the terminal portion of the polymer formed by the end cap agent used at the end of the polymerization of the polymer. The terminal group of the polymer having the repeating unit represented by the formula (20) is preferably a hydrocarbon group. From the viewpoint of charge transportability, the hydrocarbon group preferably has 1 or more and 60 or less carbon atoms, more preferably 1 or more and 40 or less, and further preferably 1 or more and 30 or less.

Preferably,
For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl group and the like. , A linear, branched, or cyclic alkyl group usually having 1 or more carbon atoms, preferably 4 or more, usually 24 or less, preferably 12 or less;
For example, an alkenyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as a vinyl group;
For example, an alkynyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as an ethynyl group;
For example, an aromatic hydrocarbon ring group having a carbon number of usually 6 or more, usually 36 or less, preferably 24 or less, such as a phenyl group and a naphthyl group;
Can be mentioned.

These hydrocarbon groups may further have a substituent, and the substituent which may further have is preferably an alkyl group or an aromatic hydrocarbon ring group, and there are a plurality of these substituents which may further have. In some cases, they may be combined with each other to form a ring.
From the viewpoint of charge transportability and durability, an alkyl group or an aromatic hydrocarbon ring group is preferable, and an aromatic hydrocarbon ring group is more preferable.

[Another repeating unit]
The polymer having the repeating unit represented by the above formula (20) may further contain a repeating unit different from the repeating unit represented by the above formula (20).
As another repeating unit, a repeating unit represented by the following formula (22) is preferable in terms of charge transportability and durability. Here, the repeating unit represented by the following formula (22) may coincide with a part of the structural part in the repeating unit of the above formula (20), but here, it is only represented by the formula (20). It means that the structure is other than the repeating unit to be used.

In equation (22),
Ar 3 ^'represents which may have aromatic hydrocarbon group or an aromatic heterocyclic group substituents,
Ar 4 ^', the double may have a substituent monovalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, or an aromatic hydrocarbon group and aromatic heterocyclic group directly or linking group Represents a plurality of divalent groups linked via.

(Ar ³ 'and Ar ^4')
The aromatic hydrocarbon group and an aromatic hydrocarbon ring group for Ar ³ 'and Ar ^4', Ar ³ 'is Ar ¹ of formula (20)' group similar to, Ar ⁴ 'is Ar in formula (20) a group similar to ^{1 'represents} a divalent and a group. Further, the substituent which may be possessed is preferably the same as the substituent group Z'or the crosslinkable group described later, and the substituent which may be further possessed is the same as the same as the substituent group Z'. be.
Charge transport, other durable, from the viewpoint of excellent hole injection from the anode side, the formula (22) Ar 4 ^'in is further preferably a group represented by the following formula (23).

In formula (23),
k'and n'independently represent an integer of 0 to 3, and k'+ n'is 1 or more.
m'represents an integer of 0 or 1.
X'is the same as the equation (20), and * 1 and * 2 represent the bonding position with the adjacent structure.

(K', n'and m')
In the formula (23), k'+ n'is preferably 2 and more preferably 3 in terms of excellent electronic durability.

Further, k'is preferably 1 or more, and is preferably bonded to N in the above formula (22) in * 1. Further, it is more preferable that both k'and n'are 1 or both k'and n'are 2 or more.
It is more preferable that m'is 1 in that the polymer has excellent solubility in a solvent.
In the above formula (22), when a plurality of aromatic hydrocarbon groups and aromatic heterocyclic groups are linked via a linking group, the linking group is specifically, for example, an −O— group. _{, -C (= O) -groups, and groups selected from -CH 2} -groups, which may be substituted with a hydrogen atom, are arranged in any order from 1 to 30, preferably 1 to 5, and even more preferably 1. Examples thereof include a divalent linking group formed by linking up to three groups.

Among these, from the viewpoint of excellent hole injection into the light emitting layer, wherein (22) Ar ⁴ 'in were plurality linked via a linking group represented by the following formula (24), an aromatic hydrocarbon group Alternatively, it is preferably an aromatic heterocyclic group.

In equation (24),
p'represents an integer from 1 to 10 and represents
R 8 ^'and R ^9' are each independently, represent a hydrogen atom or an optionally substituted alkyl group, an aromatic hydrocarbon group, or an aromatic heterocyclic group.
If R 8 ^'and R ^9' there are a plurality, it may be different even in the same.

^{(R 8} 'and ^{R 9')}
The alkyl group for R 8 ^'and R ^9', the ^'have the same group as the alkyl groups listed, aromatic hydrocarbon group and aromatic heterocyclic group, wherein Ar ^1' R ¹ aromatic mentioned in It is a group similar to the hydrocarbon group and the aromatic heterocyclic group. Further, the substituent which these groups may have is preferably the same group as the substituent group Z'or the crosslinkable group described later, and the substituent which may further have is also the substituent group Z'. Is similar to.

As another repeating unit included in the polymer having the repeating unit represented by the formula (20), the repeating unit represented by the following formula (25) is preferable. In the repeating unit represented by the formula (25), the excited singlet energy level and the excited triplet energy level tend to be high due to the twist of the aromatic ring. Further, due to the steric hindrance of the twist of the aromatic ring, the polymer tends to have excellent solubility in a solvent, and the coating film formed by a wet film forming method and heat-treated tends to have excellent insolubility in a solvent.

In equation (25),
Ar 2 ^'represents which may have aromatic hydrocarbon group or an aromatic heterocyclic group substituents,
R ^{17 '~R} 19' represent each independently an optionally substituted alkyl group, an alkoxy group, an aralkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group,
f', g', h'independently represent an integer of 0 to 4, and f'+ g'+ h'is 1 or more.
e'represents an integer from 0 to 3.

(Ar ² 'and ^{R 17' ~R 19} ')
Ar 2 ^'and R ^17' ~R 19 'aromatic hydrocarbon group in the aromatic heterocyclic group are each independently, the Ar ^1' is the same groups as those mentioned, also, these groups As the substituent which may be possessed, the substituent group Z'or the same group as the crosslinkable group described later is preferable.
Alkyl group and aralkyl group in R ¹⁷ 'to R ^19', the R ⁷ the same groups as ^'preferably the same groups as those mentioned further substituent which may have the R ^7' preferably ..
Alkoxy group in R ¹⁷ 'to R ^19', the substituent group Z is the same as the 'alkoxy groups listed are preferred, have also substituent group optionally the substituent group Z'.

(H'~ j')
Each of f', g', and h'independently represents an integer of 0 to 4, and f'+ g'+ h'is 1 or more.
It is preferable that f'+ h'is 1 or more.
It is more preferable that f'+ h'is 1 or more and f', g'and h'are 2 or less.
It is more preferable that f'+ h'is 1 or more and f'and h'are 1 or less.
It is most preferable that both f'and h'are 1.
If f 'and h' are both 1, ^'and R ^19' R ¹⁷ are preferably bonded to each other symmetrical positions.

It ^is preferable that the ^{'R 19} and' ^{R 17} are the same,
It is more preferable that g'is 2.
When g'is 2, ^{it is most preferable that the two R 18} 's are bonded to each other in a para position.
When g'is 2, it is most preferable that the ^{two R 18's are the same.}
Here, ^'and R ^19' R ¹⁷ and are attached at positions symmetrical to each other, it refers to the binding position below. However, in the notation, 180 degree rotation around the main chain is regarded as the same structure.

Further, the repeating unit represented by the formula (22) is preferably a repeating unit represented by the following formula (26).

In the case of the repeating unit represented by the above formula (26), g'= 0 or 2 is preferable. When g'= 2, the bonding positions are the 2nd and 5th positions. When g'= 0, there is ^{no steric hindrance due to R 18} ', and when g'= 2 and the bond positions are the 2nd and 5th positions, the steric hindrance is the benzene ring to which ^{two R 18' are bonded.} It becomes diagonal positions of, it is possible ^{to 'and} R ^19' R ¹⁷ and are attached to the positions symmetrical with each other.
Further, the repeating unit represented by the formula (26) is more preferably the repeating unit represented by the following formula (27).

In the case of the repeating unit represented by the formula (27), g'= 0 or 2 is preferable. When g'= 2, the bonding positions are the 2nd and 5th positions. When g'= 0, there is ^{no steric hindrance due to R 18} ', and when g'= 2 and the bond positions are the 2nd and 5th positions, the steric hindrance is a benzene ring to which ^{two R 18' are bonded.} becomes diagonal positions of, it is possible ^{to 'and} R ^9' R 7 and are attached to the positions symmetrical with each other.

[Content of repeating unit]
In the polymer having the repeating unit represented by the formula (20), the content of the repeating unit represented by the formula (20) is not particularly limited, but is usually contained in the polymer in an amount of 10 mol% or more and 30 mol%. It is preferably contained in an amount of 40 mol% or more, more preferably 40 mol% or more, and particularly preferably 50 mol% or more. In the polymer having the repeating unit represented by the formula (20), the repeating unit may be composed of only the repeating unit represented by the formula (20), but various performances when the organic electric field light emitting element is used. For the purpose of balancing the above, it may have a repeating unit different from the formula (20), in which case the content of the repeating unit represented by the formula (20) in the polymer is usually 99 mol. % Or less, preferably 95 mol% or less.

When the repeating unit represented by the formula (25) is included, the ratio of the repeating unit represented by the formula (20) to the repeating unit represented by (25) is the repeating unit represented by (25). The number of moles) / (the number of moles of the repeating unit represented by the formula (20)) is preferably 0.1 or more, more preferably 0.3 or more, further preferably 0.5 or more, and more preferably 0.9 or more. Further preferred, 1.0 is particularly preferred. Further, 2.0 or less is preferable, 1.5 or less is more preferable, and 1.2 or less is further preferable.

[Preferable combination of repeating units]
The combination of the repeating unit of the polymer is not particularly limited, but the following ^{formula (28) includes the repeating unit represented by the formula (20) and the repeating unit in which Ar 4 of the} formula (22) is the formula (23). It is preferable to have the represented repeating unit from the viewpoint of improving charge transportability and durability.

In equation (28),
Ar ¹ ', Ar ³ ', X', R ¹ ', R ² ', a', b', c', d', k', m'and n'are equations (20) and (22). And the same as those in the formula (23).
The preferable structure, range, etc. are the same as those in the formula (20), the formula (22), and the formula (23).
More preferably, c'= d'= k'= n'and m'= 1.

In formula (28), a biphenyl skeleton linked with a fluorene ring, a carbazole ring, or an ethylene group close to phenylene having a substituent is linked with A, a fluorene ring, a carbazole ring, or an ethylene group close to phenylene without a substituent. When the biphenyl skeleton is B, A having a bond not conjugated with an amine is not conjugated with an amine, so that LUMO is difficult to distribute and the durability tends to be improved. Further, since B conjugated with an amine has a wider conjugation, the hole transport property tends to be improved and stable.

Further, more preferably, X'of A and X'of B are -C (R ³ ') (R ⁴ ')-, or X'of A and X'of B are -N (R ⁵ '. )-Or X'of A and X'of B are-C (R ¹¹ ') (R ¹² ')-C (R ¹³ ') (R ¹⁴ ')-. In this case, A and ^{B, R 3 ', R 4} ', R 5 ', R 11', R 12 ', R 13' and ^{R 14} 'may be be the same or different.
A of X 'and B of X' is ^{-C (R 3 ') (R} 4') - a either, 'X of and B' X of A is -NR ⁵ '- or is, or A X of Since'and B's X'are −C (R ¹¹ ′) (R ¹² ′) −C (R ¹³ ′) (R ¹⁴ ′) −, the repeating basic skeleton contained in the polymer is the same. Therefore, it is considered that a level that acts as a charge trap is not easily formed, the charge transport property is excellent, and the durability is excellent.

More preferably, A and B are the same, and even more preferably, X'of A and B is -C (R ³ ') (R ⁴ ')-, and particularly preferably X'of A. And B X'is −C (R ³ ′) (R ⁴ ′) − and is the same.

<Polymer 3>
The polymer 3 that can be used for the hole transport layer in the present embodiment has a structure represented by the following formula (30) in the side chain.

In formula (30),
Ar 31 ^'represents a divalent group linking the main chain,
Ar 12 ^'represents an aromatic or divalent optionally substituted hydrocarbon group or a may have a substituent monovalent aromatic heterocyclic group,
^{Ar 13} '~Ar ^15' each independently represents a hydrogen atom or a substituent.
* Represents the bond position.

Ar 31 ^'represents a divalent group linking the main chain. Is not particularly limited, preferably the same as Ar 11 ^'of formula (21), a preferred range is also the same, such as the substituent which may have. ^{Ar 12} '~Ar ^15' is the same as ^{Ar 12 '~Ar 15'} of formula (21), a preferred range is also the same, such as the substituent which may have.

In equation (21),
Ar 11 ^'and Ar ^12' each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic radical of the dihydric may have a substituent group,
^{Ar 13} '~Ar ^15' each independently represent a hydrogen atom or a substituent.
The polymer having the structure represented by the formula (21) in the side chain preferably has the structure represented by the following formula (31).

In equation (31),
^{Ar 13 '~Ar 15', Ar} 31 ' is the same as equation (21),
Ar 16 ^'represents the structure constituting the main chain of the polymer.

In structural polymer having a structure represented by the formula (21) in the side chain, the formula (22) a polymer containing a repeating unit represented by the Ar 3 ^'is represented by the formula (20) some polymers or it is also preferable that the formula be a polymer containing a repeating unit represented by formula (25) Ar 3 ^'is a polymer has a structure represented by formula (20).

[Soluble group]
The polymer of the present embodiment having a partial structure represented by the formula (CzP) preferably has a soluble group for soluble expression in a solvent. The soluble group in the present embodiment is a group having a linear or branched alkyl group or alkylene group having 3 or more and 24 or less carbon atoms, preferably 12 or less carbon atoms. Among these, an alkyl group, an alkoxy group, or an aralkyl group is preferable, and for example, an n-propyl group, a 2-propyl group, an n-butyl group, an isobutyl group, and the like. More preferably, it is an n-hexyl group or an n-octyl group. The soluble group may have a substituent.

(Number of soluble groups)
It is preferable that the amount of the soluble group contained in the polymer of the present embodiment having a partial structure represented by the formula (CzP) is large in that it is easy to obtain a polymer solution that can be used in a wet film forming method. On the other hand, a small amount is preferable in that the film thickness decrease due to the layer being dissolved in the solvent when another layer is formed on the formed layer by the wet film forming method is small.

The number of soluble groups of the polymer of the present embodiment having a partial structure represented by the formula (CzP) can be expressed by the number of moles per gram of the polymer.
When the number of soluble groups of the polymer of the present embodiment having a partial structure represented by the formula (CzP) is expressed in the number of moles per 1 g of the polymer, it is usually 4.0 mmol or less per 1 g of the polymer. It is preferably 3.0 mmol or less, more preferably 2.0 mmol or less, and usually 0.1 mmol or more, preferably 0.5 mmol or more.

When the number of soluble groups is within the above range, the polymer is easily dissolved in a solvent, and a composition containing a polymer suitable for a wet film forming method can be easily obtained. Further, since the soluble group density is appropriate, the solubility in an organic solvent after drying with a heated solvent is sufficient, so that a multi-layer laminated structure can be formed by a wet film forming method.
Here, the number of soluble groups per 1 g of the polymer can be calculated from the molar ratio of the charged monomer at the time of synthesis and the structural formula, excluding the terminal groups from the polymer.

For example, in the case of the polymer 1 synthesized in Example 1 described later, in the polymer 1, the molecular weight of the repeating unit excluding the terminal group is 650 on average, and the soluble group is 1 on average per repeating unit. It is an individual. When this is calculated by simple proportionality, the number of soluble groups per 1 g of molecular weight is calculated to be 1.54 mmol.

[Crosslinkable group]
The polymer of the present embodiment having a partial structure represented by the formula (CzP) may have a crosslinkable group. The crosslinkable group that the polymer of the present embodiment having a partial structure represented by the formula (CzP) may have may be present in the repeating unit represented by the formula (20), and may be present in the repeating unit represented by the formula (20). It may exist in a repeating unit different from the repeating unit represented by). In particular, it is preferable to have a crosslinkable group in ^{Ar 1} ', which is a side chain, because the crosslinkable reaction can easily proceed.

By having a crosslinkable group, it is possible to make a large difference in solubility in an organic solvent before and after a reaction (poor solubility reaction) caused by irradiation with heat and / or active energy rays.
A crosslinkable group is a group that forms a new chemical bond by reacting with a group constituting another molecule located in the vicinity of the crosslinkable group by irradiation with heat and / or active energy rays. To say. In this case, the reacting group may be the same group as the crosslinkable group or a different group.
As the crosslinkable group, a cyclobutene ring fused to the aromatic ring and a group containing an alkenyl group bonded to the aromatic ring are preferable, and a group selected from the following crosslinkable group group T'is more preferable.
The crosslinkable group is preferably further substituted with a substituent having each of the above structures.

(Crosslinkable group T')
The crosslinkable group T'has a structure shown below.

^{'In, R 21'} crosslinkable group & T ^{to R 23} 'each independently represent a hydrogen atom or an alkyl group. ^{R 24 ',} R ^25', and ^{R 26} 'each independently represent a hydrogen atom, an alkyl group or an alkoxy group. p'represents an integer of 1 to 4, q'represents an integer of 1 to 5, and r'represents an integer of 1 to 7.
When p'is 2 or more, a plurality of R ^24's may be the same or different, and adjacent R ^24's may be combined to form a ring.

When q'is 2 or more, a plurality of R ^25's may be the same or different, and adjacent R ^25's may be combined to form a ring.
When r'is 2 or more, a plurality of R ²⁶ 's may be the same or different.
Ar ^{21 ',} Ar 22' may have a substituent, an aromatic hydrocarbon group or an aromatic heterocyclic group.

As the alkyl group for R ^{21 '~R} 26', it includes straight chain or branched chain alkyl group having carbon atoms is 6 or less. For example, a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, an n-butyl group, an isobutyl group and the like. More preferably, it is a methyl group or an ethyl group. By carbon number of R ^{21 '~R} 26' is 6 or less, without sterically inhibit the crosslinking reaction, in the prone tendency insolubilized film.

The alkoxy group of R ^{25 'and} R ^26', include straight chain or branched chain alkoxy group having carbon atoms is 6 or less, for example, a methoxy group, an ethoxy group, n- propoxy group, 2-propoxy , N-butoxy group and the like. More preferably, it is a methoxy group or an ethoxy group. When the number of carbon atoms in the R ^{25 'and} R ^26' is 6 or less, without sterically inhibit the crosslinking reaction, insolubilization of the film is in the prone tendency.

As the aromatic hydrocarbon ring group which may have a substituent group R ^{21 'and} R ^22', for example, having one free valence, a benzene ring, a 6-membered ring such as a naphthalene ring Examples thereof include a monocyclic ring or a 2-5 fused ring. In particular, a benzene ring having one free valence is preferable.
Ar 22 ^'is an aromatic hydrocarbon ring group which may have a substituent may be two or more coupled to form groups. Examples of such a group include a biphenylene group and a terphenylene group, and a 4,4'-biphenylene group is preferable.

Ar ^{21 ',} Ar 22' substituent which may be possessed are the same as previously described in the substituent group Z '.
As a crosslinkable group, cyclization of an arylvinylcarbonyl group such as a cinnamoyle group, a benzocyclobutene ring having a monovalent free valence, and a 1,2-dihydrocyclobuta [a] naphthalene ring having a monovalent free valence. Additive reacting groups are preferred in that they further improve the electrochemical stability of the device.

Among the crosslinkable groups, the cyclobutene ring condensed into an aromatic ring having a monovalent free valence and 1,2-dihydro having a monovalent free valence are particularly stable in the structure after cross-linking. A group containing a cyclobutane [a] naphthalene ring is preferable, and a benzocyclobutene ring or a 1,2-dihydrocyclobutane [a] naphthalene ring having a monovalent free valence is more preferable, and the cross-linking reaction temperature is low. A 1,2-dihydrocyclobutane [a] naphthalene ring having a monovalent free valence is particularly preferred.

(Number of crosslinkable groups)
The crosslinkable group of the polymer of the present embodiment having a partial structure represented by the formula (CzP) is sufficiently insolubilized by crosslinking, and another layer can be easily formed on the crosslinkable group by a wet film forming method. Then, the larger the number, the better. On the other hand, it is preferable that the number of crosslinkable groups is small in that cracks are unlikely to occur in the formed layer, unreacted crosslinkable groups are unlikely to remain, and the organic electroluminescent device tends to have a long life.

In the polymer of the present embodiment having a partial structure represented by the formula (CzP), the number of crosslinkable groups present in one polymer chain is preferably 1 or more, more preferably 2 or more, and preferably 200. Below, it is more preferably 100 or less.
Further, the number of crosslinkable groups of the polymer having a partial structure represented by the formula (CzP) can be expressed by the number per 1000 molecular weight of the polymer.

When the number of crosslinkable groups of the polymer of the present embodiment having a partial structure represented by the formula (CzP) is expressed by the number per 1000 molecular weight of the polymer, it is usually 3.0 or less per 1000 molecular weight. The number is preferably 2.0 or less, more preferably 1.0 or less, and usually 0.01 or more, preferably 0.05 or more.
When the number of crosslinkable groups is within the above range, cracks and the like are unlikely to occur, and a flat film can be easily obtained. Further, since the cross-linking density is appropriate, there are few unreacted cross-linking groups remaining in the layer after the cross-linking reaction, which does not easily affect the life of the obtained device.

Further, since the poor solubility in the organic solvent after the crosslinking reaction is sufficient, it is easy to form a multilayer laminated structure by the wet film forming method.
Here, the number of crosslinkable groups per 1000 molecular weight of the polymer can be calculated from the molar ratio of the charged monomer at the time of synthesis and the structural formula, excluding the terminal groups from the polymer.
For example, in the case of the polymer 3 synthesized in Examples described later, in the polymer 3, the molecular weight of the repeating unit excluding the terminal group is 868 on average, and the crosslinkable group is 0. There are 114 pieces. When this is calculated by simple proportionality, the number of crosslinkable groups per 1000 molecular weight is calculated to be 0.132.

[Molecular weight of polymer]
The weight average molecular weight of the polymer having a partial structure represented by the formula (CzP) is usually 3,000,000 or less, preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 200,000. Below, it is particularly preferably 100,000 or less. Further, it is usually 2,500 or more, preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more.

When the weight average molecular weight of the polymer is not more than the above upper limit value, solubility in a solvent is obtained, and the film forming property tends to be excellent. Further, when the weight average molecular weight of the polymer is at least the above lower limit value, the decrease in the glass transition temperature, the melting point and the vaporization temperature of the polymer may be suppressed, and the heat resistance may be improved. In addition, the coating film after the cross-linking reaction may be sufficiently insoluble in the organic solvent.

The number average molecular weight (Mn) of the polymer having a partial structure represented by the formula (CzP) is usually 2.5 million or less, preferably 750,000 or less, more preferably 400,000 or less, and particularly preferably. It is 100,000 or less. Further, it is usually 2,000 or more, preferably 4,000 or more, more preferably 8,000 or more, still more preferably 20,000 or more.

Further, the dispersity (Mw / Mn) in the polymer having a partial structure represented by the formula (CzP) is preferably 3.5 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. be. Since the smaller the value of the dispersion, the better, the lower limit is ideally 1. When the dispersity of the polymer is not more than the above upper limit, purification is easy, and solubility in a solvent and charge transporting ability are good.

Usually, the weight average molecular weight of a polymer is determined by SEC (Size Exclusion Chromatography) measurement. In the SEC measurement, the higher the molecular weight component, the shorter the elution time, and the lower the molecular weight component, the longer the elution time. By conversion, the weight average molecular weight is calculated.

[Concrete example]
Specific examples of the polymer having a partial structure represented by the formula (CzP) are shown below, but the polymer having a partial structure represented by the formula (CzP) is not limited thereto. The numbers in the chemical formula represent the molar ratio of the repeating unit.
These polymers may be random copolymers, alternate copolymers, block copolymers, graft copolymers, or the like, and the order of arrangement of the monomers is not limited.

[Method for producing polymer]
The method for producing a polymer having a partial structure represented by the formula (CzP) is not particularly limited, and is arbitrary as long as a polymer having a partial structure represented by the formula (CzP) can be obtained. For example, it can be produced by a polymerization method by Suzuki reaction, a polymerization method by Grignard reaction, a polymerization method by Yamamoto reaction, a polymerization method by Ullmanne reaction, a polymerization method by Buchwald-Hartwig reaction, or the like.

In the case of the polymerization method by the Ullmann reaction and the polymerization method by the Buchwald-Hartwig reaction, for example, the aryl halide represented by the formula (1a') (X'indicates a halogen atom such as I, Br, Cl, F) and By reacting with the primary aminoaryl represented by the formula (1b'), a polymer having a partial structure represented by the formula (CzP) is synthesized.

In the above formula, Y represents a halogen ^{atom, Ar 1 ', R 1'} ~R 4 ', X are as defined in the formula (20).
In the above polymerization method, the reaction for forming an N-aryl bond is usually carried out in the presence of a base such as potassium carbonate, tert-butoxysodium or triethylamine. It can also be carried out in the presence of a transition metal catalyst such as copper or palladium complex.

<Low molecular weight compound>
In the third gist of the present invention, when the material containing the above formula (CzP) as a partial structure, which is a specific structure having a carbazole ring contained in the light emitting layer, is a low molecular weight material, in the second gist of the present invention. It is the same as the above-mentioned low molecular weight compound contained in a light emitting layer. That is, it is preferable that the host material has the above formula (CzP-2), and the preferable range is also the same.

<Composition for organic electroluminescent device>
The hole transport layer of the organic electroluminescent device and the light emitting layer adjacent to the hole transport layer according to the second gist and the third gist of the present invention are made of a material having the formula (CzP) as a partial structure as a solvent. A wet film can be formed by using the composition dissolved in.
The composition for an organic electroluminescent element for forming the hole transport layer preferably contains any one of the above-mentioned polymers 1 to 3, and is a composition for an organic electroluminescent element for forming a light emitting layer. The substance preferably contains the above-mentioned electroluminescent compound.

[Content of material having formula (CzP) as a partial structure]
The content of the material having the formula (CzP) as a partial structure in the composition is usually 0.01 to 70% by mass, preferably 0.1 to 60% by mass, and more preferably 0.5 to 50% by mass. be.
Within the above range, defects are less likely to occur in the formed organic layer, and uneven film thickness is less likely to occur, which is preferable.

[solvent]
The composition usually contains a solvent. The solvent is preferably one that dissolves a material having the formula (CzP) as a partial structure. Specifically, a solvent that dissolves a material having the formula (CzP) as a partial structure at room temperature in an amount of usually 0.05% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more is preferable. ..

Specific examples of the solvent include aromatic solvents such as toluene, xylene, mesityrene and cyclohexylbenzene; halogen-containing solvents such as 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene; ethylene glycol dimethyl ether, ethylene glycol diethyl ether and propylene. Aliper ethers such as glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetol, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, Ether-based solvents such as aromatic ethers such as 2,3-dimethylanisole and 2,4-dimethylanisole; aliphatic ester-based solvents such as ethyl acetate, n-butyl acetate, ethyl lactate and n-butyl lactate; phenyl acetate, Ester-based solvents such as phenyl propionate, methyl benzoate, ethyl benzoate, isopropyl benzoate, propyl benzoate, n-butyl benzoate and other aromatic esters; organic solvents such as, and other hole injection layer formation described later. Examples thereof include organic solvents used in the composition for forming a hole transport layer and the composition for forming a hole transport layer.

As the solvent, one type may be used, or two or more types may be used in any combination and in any ratio.
Among them, as the solvent contained in the composition for an organic electroluminescent device, a solvent having a surface tension at 20 ° C. of usually less than 40 dyn / cm, preferably 36 dyn / cm or less, more preferably 33 dyn / cm or less is preferable.

The composition used in the wet film forming method is required to have a low surface tension so that a uniform coating film having higher leveling property can be formed. Therefore, by using a solvent having a low surface tension as described above, it is possible to form a uniform layer containing a material having the formula (CzP) as a partial structure, which is preferable.
Specific examples of the low surface tension solvent include the above-mentioned aromatic solvents such as toluene, xylene, mesitylene and cyclohexylbenzene, ester solvents such as ethyl benzoate, ether solvents such as anisole, trifluoromethoxyanisole and penta. Fluoromethoxybenzene, 3- (trifluoromethyl) anisole, ethyl (pentafluorobenzoate) and the like can be mentioned.

On the other hand, as the solvent contained in the composition, it is preferable that the vapor pressure at 25 ° C. is usually 10 mmHg or less, preferably 5 mmHg or less, and usually 0.1 mmHg or more. By using such a solvent, a composition for an organic electroluminescent device suitable for a process of manufacturing an organic electroluminescent device by a wet film forming method and suitable for the properties of a material having a formula (CzP) as a partial structure can be obtained. Can be prepared.

Specific examples of such a solvent include the above-mentioned aromatic solvents such as toluene, xylene and mesitylene, ether solvents and ester solvents.
By the way, moisture may cause performance deterioration of the organic electroluminescent device, and in particular, it may promote a decrease in brightness during continuous driving. Therefore, in order to reduce the water content remaining during the wet film formation as much as possible, among the above-mentioned solvents, those having a water solubility at 25 ° C. of 1% by mass or less are preferable, and those having a solubility of 0.1% by mass or less are preferable. Is more preferable.

The content of the solvent contained in the composition for an organic electroluminescent device is usually 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 80% by mass or more. When the content of the solvent is at least the above lower limit, the flatness and uniformity of the formed layer can be improved.

[Electron accepting compound]
The composition for an organic electroluminescent device preferably further contains an electron-accepting compound in terms of lowering the resistance. In particular, when the composition for an organic electroluminescent device is used to form a hole injection layer, it is preferable to contain an electron accepting compound.
As the electron-accepting compound, a compound having an oxidizing power and an ability to accept one electron from the above-mentioned polymer is preferable. Specifically, a compound having an electron affinity of 4 eV or more is preferable, and a compound having an electron affinity of 5 eV or more is more preferable.
Examples of such an electron-accepting compound include a triarylboron compound, a metal halide, a Lewis acid, an organic acid, an onium salt, a salt of an arylamine and a metal halide, and a salt of an arylamine and a Lewis acid. Examples thereof include one kind or two or more kinds of compounds selected from the group consisting of.

Specifically, an onium salt substituted with an organic group such as 4-isopropyl-4'-methyldiphenyliodonium tetrakis (pentafluorophenyl) boronate and triphenylsulfonium tetrafluoroborate (International Publication No. 2005/089024), ( International Publication No. 2017/164268); high valence inorganic compounds such as iron chloride (III) (Japanese Patent Laid-Open No. 11-251067), ammonium peroxodisulfate; cyano compounds such as tetracyanoethylene; tris (pentafluorophenyl) Examples include aromatic boron compounds such as borane (Japanese Patent Laid-Open No. 2003-31365); fullerene derivatives, iodine and the like.

The composition for an organic electroluminescent device may contain one kind of the above-mentioned electron-accepting compound alone, or may contain two or more kinds in any combination and ratio.
When the composition for an organic electroluminescent element contains an electron-accepting compound, the content of the electron-accepting compound in the composition for an organic electroluminescent element is usually 0.0005% by mass or more, preferably 0.001% by mass or more. It is usually 20% by mass or less, preferably 10% by mass or less. The ratio of the electron-accepting compound to the polymer in the composition for an organic electroluminescent element is usually 0.5% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and usually 80% by mass. % Or less, preferably 60% by mass or less, more preferably 40% by mass or less.
When the content of the electron-accepting compound in the composition for an organic electroluminescent element is at least the above lower limit, the electron acceptor receives electrons from the polymer and the formed organic layer has a low resistance, which is preferable. This is preferable because defects are less likely to occur in the formed organic layer and uneven film thickness is less likely to occur.

[Cation radical compound]
The composition for an organic electroluminescent device may further contain a cationic radical compound.
As the cation radical compound, an ionic compound composed of a cation radical, which is a chemical species obtained by removing one electron from a hole transporting compound, and a counter anion is preferable. However, when the cation radical is derived from a hole-transporting polymer compound, the cation radical has a structure in which one electron is removed from the repeating unit of the polymer compound.
Further, the cation radical is preferably a chemical species obtained by removing one electron from the hole transporting compound described later. A chemical species obtained by removing one electron from a preferable compound as a hole transporting compound is preferable in terms of amorphousness, visible light transmittance, heat resistance, solubility and the like.

Here, the cationic radical compound can be produced by mixing the hole transporting compound described later and the electron accepting compound described above. That is, by mixing the hole transporting compound and the electron accepting compound, electron transfer occurs from the hole transporting compound to the electron accepting compound, and the hole transporting compound is composed of a cation radical and a counter anion. A cationic ion compound is produced.

When the composition for an organic electroluminescent element contains a cation radical compound, the content of the cation radical compound in the composition for an organic electroluminescent element is usually 0.0005% by mass or more, preferably 0.001% by mass or more. It is usually 40% by mass or less, preferably 20% by mass or less. When the content of the cationic radical compound is not less than the lower limit, the formed organic layer has a low resistance, which is preferable, and when it is not more than the upper limit, the formed organic layer is less likely to have defects and uneven film thickness is less likely to occur.
In addition to the above components, the composition for an organic electroluminescent device contains the components contained in the hole injection layer forming composition and the hole transport layer forming composition described later in the content described below. May be.

<Organic electroluminescent device>
The organic electroluminescent element in the present invention is an organic electroluminescent element having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate. The organic electroluminescent device according to the first embodiment of the present invention has a layer in which the organic layer contains the above-mentioned polymer 1 or a polymer crosslinked with the polymer 1. In the organic electroluminescent device according to the second gist of the present invention, the organic layer has a hole transport layer and a light emitting layer adjacent to the hole transport layer, and the hole transport layer is described above. It contains a polymer 1 or a polymer in which the polymer 1 is crosslinked, and the light emitting layer contains a material having a partial structure represented by the above formula (CzP). The organic electroluminescent device according to the third gist of the present invention has a hole transport layer and a light emitting layer adjacent to the hole transport layer, and is included in the hole transport layer and the light emitting layer. A material (compound) having a partial structure represented by the above formula (CzP) in which at least one of the materials has a carbazole ring is included. In the embodiment of the third gist, the material having a partial structure represented by the formula (CzP) contained in the hole transport layer is the polymer 2 or the polymer crosslinked with the polymer 2, or the weight. It is preferable that the combined product 3 or the polymer 3 is a crosslinked polymer.
The conditions and embodiments of the organic electroluminescent device according to each of the above embodiments can be arbitrarily combined. Specific explanations of manufacturing methods and characteristics applicable to these organic electroluminescent devices are shown below.

The method for manufacturing the organic electroluminescent device according to the embodiment of the present invention is not particularly limited, but at least one of the layers constituting the organic layer is wet-formed by using the above-mentioned composition for an organic electroluminescent device. It is preferably manufactured by a method including a film forming step formed by the method. When the organic layer is composed of a plurality of layers, a known method can be used as a method for laminating the plurality of layers.

In an organic electroluminescent element, the organic layer has a hole injection layer and a hole transport layer, and at least one of the hole injection layer and the hole transport layer is a layer formed by a wet film forming method (a layer (). It is preferably an organic layer formed in the film forming step), and in particular, the organic layer has a hole injection layer, a hole transport layer, and a light emitting layer, and these hole injection layers, hole transport layers, and light emitting layers are used. It is preferable that all of the layers are layers formed by a wet film forming method.

The wet film forming method in the present embodiment is a film forming method, that is, as a coating method, for example, a spin coating method, a dip coating method, a die coating method, a bar coating method, a blade coating method, a roll coating method, a spray coating method, and the like. It refers to a method of forming a film by adopting a wet film forming method such as a capillary coating method, an inkjet method, a nozzle printing method, a screen printing method, a gravure printing method, and a flexographic printing method, and drying the coating film. Among these film forming methods, a spin coating method, a spray coating method, an inkjet method, a nozzle printing method and the like are preferable.

As an example of the structure of the organic electroluminescent device, FIG. 1 shows a schematic diagram (cross section) of a structural example of the organic electroluminescent device 10. In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is a hole blocking layer, 7 is an electron transport layer, and 8 is an electron injection layer. 9 represents each cathode.
Hereinafter, an example of an embodiment such as a layer structure of an organic electroluminescent device and a general forming method thereof will be described with reference to FIG. 1.

[substrate]
The substrate 1 serves as a support for an organic electroluminescent element, and usually a quartz or glass plate, a metal plate, a metal foil, a plastic film, a sheet, or the like is used. Of these, a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polysulfone is preferable. The substrate is preferably made of a material having a high gas barrier property because the organic electroluminescent device is unlikely to be deteriorated by the outside air. Therefore, particularly when a material having a low gas barrier property such as a substrate made of synthetic resin is used, it is preferable to provide a dense silicon oxide film or the like on at least one side of the substrate to improve the gas barrier property.

[anode]
The anode 2 has a function of injecting holes into the layer on the light emitting layer 5 side.
The anode 2 is usually a metal such as aluminum, gold, silver, nickel, palladium, platinum; a metal oxide such as an oxide of indium and / or tin; a halide metal such as copper iodide; carbon black and poly (3). -Methylthiophene), polypyrrole, polyaniline and other conductive polymers.

The anode 2 is usually formed by a dry method such as a sputtering method or a vacuum vapor deposition method. When forming an anode using metal fine particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, conductive polymer fine powder, etc., use an appropriate binder resin solution. It can also be formed by dispersing and applying it on a substrate. Further, in the case of a conductive polymer, a thin film can be formed directly on the substrate by electrolytic polymerization, or an anode can be formed by applying the conductive polymer on the substrate (Appl. Phys. Lett., 60). Volume, p. 2711, 1992).

The anode 2 usually has a single-layer structure, but may have a laminated structure as appropriate. When the anode 2 has a laminated structure, different conductive materials may be laminated on the first-layer anode.
The thickness of the anode 2 may be determined according to the required transparency, material and the like. When particularly high transparency is required, a thickness having a visible light transmittance of 60% or more is preferable, and a thickness having a visible light transmittance of 80% or more is more preferable. The thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less. On the other hand, when transparency is not required, the thickness of the anode 2 may be arbitrarily set according to the required strength and the like, and in this case, the anode 2 may have the same thickness as the substrate.
When another layer is formed on the surface of the anode 2, impurities on the anode 2 are removed by treating with ultraviolet rays / ozone, oxygen plasma, argon plasma, etc. before the film formation, and the ionization potential thereof is formed. It is preferable to improve the hole injection property.

[Hole injection layer]
The layer having a function of transporting holes from the anode 2 side to the light emitting layer 5 side is usually called a hole injection transport layer or a hole transport layer. When there are two or more layers having a function of transporting holes from the anode 2 side to the light emitting layer 5, the layer closer to the anode side may be referred to as the hole injection layer 3. The hole injection layer 3 is preferably formed in that it enhances the function of transporting holes from the anode 2 to the light emitting layer 5 side. When forming the hole injection layer 3, the hole injection layer 3 is usually formed on the anode 2.

The film thickness of the hole injection layer 3 is usually 1 nm or more, preferably 5 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
The hole injection layer may be formed by either a vacuum vapor deposition method or a wet film deposition method. From the viewpoint of excellent film forming property, it is preferable to form by a wet film forming method.
The hole injection layer 3 preferably contains a hole transporting compound, and more preferably contains a hole transporting compound and an electron accepting compound. Further, it is preferable to contain a cationic radical compound in the hole injection layer, and it is particularly preferable to contain a cationic radical compound and a hole transporting compound.
Hereinafter, a general method for forming the hole injection layer will be described. In the organic electroluminescent device, the hole injection layer may be formed by a wet film forming method using a composition for an organic electroluminescent device. preferable.

[Hole-transporting compound]
The composition for forming a hole injection layer usually contains a hole transporting compound that becomes the hole injection layer 3. Further, in the case of the wet film forming method, a solvent is usually further contained. It is preferable that the composition for forming a hole injection layer has high hole transportability and can efficiently transport the injected holes. Therefore, it is preferable that the hole mobility is high and impurities that serve as traps are unlikely to be generated during manufacturing or use. Further, it is preferable that the stability is excellent, the ionization potential is small, and the transparency to visible light is high. In particular, when the hole injection layer is in contact with the light emitting layer, those that do not quench the light emitted from the light emitting layer or those that form an exciplex with the light emitting layer and do not reduce the luminous efficiency are preferable.

As the hole transporting compound, a compound having an ionization potential of 4.5 eV to 6.0 eV is preferable from the viewpoint of a charge injection barrier from the anode to the hole injection layer. Examples of hole transporting compounds include aromatic amine compounds, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzylphenyl compounds, compounds in which a tertiary amine is linked with a fluorene group, and hydrazone. Examples thereof include system compounds, silazane compounds, quinacridone compounds and the like.

Among the above-mentioned exemplary compounds, aromatic amine compounds are preferable, and aromatic tertiary amine compounds are particularly preferable, from the viewpoint of amorphousness and visible light transmission. Here, the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and also includes a compound having a group derived from the aromatic tertiary amine.
The type of the aromatic tertiary amine compound is not particularly limited, but is a polymer compound having a weight average molecular weight of 1000 or more and 1,000,000 or less (a polymerized compound having a series of repeating units) because it is easy to obtain uniform light emission due to the surface smoothing effect. ) Is preferably used.

Since the hole injection layer 3 can improve the conductivity of the hole injection layer by oxidizing the hole transporting compound, the hole injection layer 3 contains the above-mentioned electron accepting compound and the above-mentioned cationic radical compound. Is preferable.
Cationic radical compounds derived from polymer compounds such as PEDOT / PSS (Adv. Mater., 2000, Vol. 12, p. 481) and emeraldine hydrochloride (J. Phys. Chem., 1990, Vol. 94, p. 7716) It is also produced by oxidative polymerization (dehydropolymerization).

The oxidative polymerization referred to here is to chemically or electrochemically oxidize the monomer in an acidic solution using peroxodisulfate or the like. In the case of this oxidative polymerization (dehydropolymerization), a cation radical obtained by removing one electron from a repeating unit of a polymer, which is polymerized by oxidizing a monomer and has an anion derived from an acidic solution as a counter anion, is used. Generate.

[Formation of hole injection layer by wet film formation method]
When the hole injection layer 3 is formed by the wet film formation method, the material to be the hole injection layer is usually mixed with a soluble solvent (solvent for the hole injection layer) to form a composition for film formation (holes). A composition for forming an injection layer) is prepared, and this composition for forming a hole injection layer is applied onto a layer (usually an anode) corresponding to the lower layer of the hole injection layer to form a film, which is then dried. Form.

The concentration of the hole transporting compound in the composition for forming a hole injection layer is arbitrary as long as the effect of the present invention is not significantly impaired, but it is preferable that the concentration is low in terms of film thickness uniformity. , Higher is preferable in that defects are less likely to occur in the hole injection layer. Specifically, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and on the other hand, 70% by mass. It is preferably less than or equal to, more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

Examples of the solvent include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents and the like.
Examples of the ether solvent include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and propylene glycol-1-monomethyl ether acetate (PGMEA), and 1,2-dimethoxybenzene, 1,3-dimethoxybenzene and anisole. , Fenetol, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and other aromatic ethers.

Examples of the ester-based solvent include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.
Examples of the aromatic hydrocarbon solvent include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, methylnaphthalene and the like. Be done.

Examples of the amide-based solvent include N, N-dimethylformamide, N, N-dimethylacetamide and the like.
In addition to these, dimethyl sulfoxide and the like can also be used.
The formation of the hole injection layer 3 by the wet film formation method is usually performed on the layer corresponding to the lower layer of the hole injection layer 3 (usually, the anode 2) after preparing the composition for forming the hole injection layer. It is carried out by applying a film to the film and drying it.
In the hole injection layer 3, the coating film is usually dried by heating, vacuum drying, or the like after the film formation.

[Formation of hole injection layer by vacuum vapor deposition method]
When the hole injection layer 3 is formed by the vacuum vapor deposition method, usually one or more of the constituent materials of the hole injection layer 3 (the above-mentioned hole transporting compound, electron accepting compound, etc.) are evacuated. Put it in a crucible installed in the container (when using two or more materials, usually put each in a separate crucible), ^{exhaust the inside of the vacuum container to about 10 -4} Pa with a vacuum pump, and then heat the crucible. (When using two or more types of materials, usually heat each crucible) and evaporate while controlling the amount of evaporation of the materials in the crucible (when using two or more types of materials, each is usually independent). Evaporate while controlling the amount of evaporation) to form a hole injection layer on the anode on the substrate placed facing the crucible. When two or more kinds of materials are used, a mixture thereof can be placed in a crucible and heated and evaporated to form a hole injection layer.

The degree of vacuum at the time of vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 × 10 ^-6 Torr (0.13 × 10 ^-4 Pa) or more, 9.0 × 10 ^-6 Torr ( It is 12.0 × 10 ^-4 Pa) or less. The vapor deposition rate is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 Å / sec or more and 5.0 Å / sec or less. The film formation temperature at the time of vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is preferably 10 ° C. or higher and 50 ° C. or lower.
The hole injection layer 3 may be crosslinked in the same manner as the hole transport layer 4 described later.

[Hole transport layer]
The hole transport layer 4 is a layer having a function of transporting holes from the anode 2 side to the light emitting layer 5 side. In the present embodiment, the hole transport layer 4 and the light emitting layer 5 are in contact with each other, and the hole transport layer 4 is a layer containing a material having a partial structure represented by the formula (CzP). When forming the hole transport layer 4, the hole transport layer 4 is usually formed between the anode 2 and the light emitting layer 5. Further, when the hole injection layer 3 described above is present, it is formed between the hole injection layer 3 and the light emitting layer 5.

The film thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, and on the other hand, usually 300 nm or less, preferably 100 nm or less.
The hole transport layer 4 may be formed by either a vacuum vapor deposition method or a wet film deposition method. From the viewpoint of excellent film forming property, it is preferable to form by a wet film forming method.
A general method for forming the hole transport layer will be described below. In the organic electroluminescent device, the hole transport layer is preferably formed by a wet film forming method using a composition for an organic electroluminescent device. ..

The hole transport layer containing the material having the partial structure represented by the formula (CzP) in the organic electroluminescent device may contain a hole transporting compound other than the material having the partial structure represented by the formula (CzP).
The hole transport layer 4 usually contains a hole transport compound. As the hole-transporting compound contained in the hole-transporting layer 4, the above-mentioned polymer or, when the above-mentioned polymer has a crosslinkable group, a polymer in which the polymer is crosslinked is preferable. Further, in addition to the polymer, it contains two or more tertiary amines represented by the hole transporting compound, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl. Stars such as aromatic diamine (Japanese Patent Laid-Open No. 5-234681) in which two or more condensed aromatic rings are substituted with nitrogen atoms, 4,4', 4''-tris (1-naphthylphenylamino) triphenylamine and the like. Aromatic amine compounds with a burst structure (J. Lumin., 72-74, pp. 985, 1997), aromatic amine compounds consisting of triphenylamine tetramers (Chem. Commun., 2175, 1996). ), 2,2', 7,7'-tetrakis- (diphenylamino) -9,9'-spirobifluorene and other spiro compounds (Synth. Metalls, Vol. 91, p. 209, 1997), 4, 4'. Carbazole derivatives such as -N, N'-dicarbazole biphenyl and the like are preferable. Further, for example, polyvinylcarbazole, polyvinyltriphenylamine (Japanese Patent Laid-Open No. 7-53953), polyarylene ether sulfone containing tetraphenylbenzidine (Polym. Adv. Tech., Vol. 7, p. 33, 1996) and the like can be used. It may be included.

[Formation of hole transport layer by wet film formation method]
When the hole transport layer is formed by the wet film forming method, holes are usually formed instead of the hole injection layer forming composition in the same manner as in the case where the hole injection layer is formed by the wet film forming method. It is formed using a composition for forming a transport layer.
When the hole transport layer is formed by the wet film forming method, the composition for forming the hole transport layer usually further contains a solvent. As the solvent used in the composition for forming a hole transport layer, the same solvent as the solvent used in the composition for forming a hole injection layer described above can be used.
The concentration of the hole-transporting compound in the composition for forming the hole-transporting layer can be in the same range as the concentration of the hole-transporting compound in the composition for forming the hole-injecting layer.
The hole transport layer can be formed by the wet film formation method in the same manner as the hole injection layer film formation method described above.

[Formation of hole transport layer by vacuum deposition method]
Also in the case of forming the hole transport layer by the vacuum vapor deposition method, the hole transport is usually performed instead of the composition for forming the hole injection layer in the same manner as in the case of forming the hole injection layer by the vacuum vapor deposition method. It can be formed using a layer-forming composition. The film formation conditions such as the degree of vacuum, the vapor deposition rate, and the temperature at the time of vapor deposition can be the same as those at the time of vacuum deposition of the hole injection layer.

[Light emitting layer]
The light emitting layer 5 is a layer having a function of emitting light by being excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 9 when an electric field is applied between the pair of electrodes. .. The light emitting layer 5 is a layer formed between the anode 2 and the cathode 9, and the light emitting layer is formed between the hole injection layer and the cathode when there is a hole injection layer on the anode, and the anode. If there is a hole transport layer on top of it, it is formed between the hole transport layer and the cathode.

The film thickness of the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired. .. Therefore, it is preferably 3 nm or more, more preferably 5 nm or more, and usually 200 nm or less, further preferably 100 nm or less.

The light emitting layer 5 preferably contains a light emitting material described later, or a host material having at least one of hole transporting property or electron transporting property such as a compound having a partial structure represented by the above-mentioned formal (CzP). In particular, it is preferable to contain at least a material having a light emitting property (light emitting material) and preferably a material having a charge transport property (host material).
As the light emitting material, a phosphorescent light emitting material or a fluorescent light emitting material can be used.
In the organic electroluminescent device according to the second and third gist of the present invention, the light emitting layer includes a material having a partial structure represented by the formula (CzP). The light emitting layer may contain a material other than the material having a partial structure represented by the formula (CzP).
When the light emitting layer is a phosphorescent light emitting layer, the following materials are preferable as the phosphorescent light emitting material.

<Phosphorescent material>
The phosphorescent material is a material that emits light from an excited triplet state. For example, a metal complex compound having Ir, Pt, Eu, etc. is a typical example, and a material containing a metal complex is preferable as the structure of the material.

Among the metal complexes, as a phosphorescent organic metal complex that emits light via a triplet state, it is a long-periodic periodic table (hereinafter, unless otherwise specified, the term "periodic table" refers to a long-periodic table. A Werner-type complex or an organic metal complex compound containing a metal selected from Groups 7 to 11 as a central metal can be mentioned. As such a phosphorescent material, a compound represented by the following formula (201) or a compound represented by the formula (205) is preferable, and a compound represented by the formula (201) is more preferable.

Ring A1 represents an aromatic hydrocarbon ring structure which may have a substituent or an aromatic heterocyclic structure which may have a substituent.
Ring A2 represents an aromatic heterocyclic structure which may have a substituent.
R ²⁰¹ and R ²⁰² are structures independently represented by the formula (202), and “*” in the formula (202) represents a bond with the ring A1 or the ring A2. R ²⁰¹ and R ²⁰² may be the same or different, and ^{when a plurality of R 201} and R ²⁰² are present, they may be the same or different.

Ar ²⁰¹ and Ar ²⁰³ each independently represent an aromatic hydrocarbon ring structure which may have a substituent or an aromatic heterocyclic structure which may have a substituent.
Ar ²⁰² has an aromatic hydrocarbon ring structure which may have a substituent, an aromatic heterocyclic structure which may have a substituent, or an aliphatic hydrocarbon structure which may have a substituent. Represents.
Each other substituents attached to the ring A ^201, each other substituents attached to the ring A ^2, or each other substituent bonded to a substituent and the ring A ² which binds to the ring A1 is also bonded to each other to form a ring good.

B ^201- L ^200- B ²⁰² represents an anionic bidentate ligand. B ²⁰¹ and B ²⁰² each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring. L ²⁰⁰ represents a single bond, ^or, together with ^{B 201} and ^{B 202} an atomic group necessary to form a bidentate ligand. When ^{there are a plurality of B 201-} L ^200- B ²⁰² , they may be the same or different.

i1 and i2 independently represent integers of 0 or more and 12 or less.
i3 is an integer of 0 or more up to a number substitutable for ^{Ar 202.}
j is an integer of 0 or more up to a number substitutable for ^{Ar 201.}
k1 and k2 are independently integers of 0 or more, up to a number substitutable for rings A1 and A2, respectively.
v is an integer of 1-3.
Unless otherwise specified, for each group in the formulas (201) and (202), a group selected from the following substituent group Z2 is preferable as the substituent which may be possessed.

<Substituent group Z2>
An alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 6 carbon atoms. ..
An alkoxy group, preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and further preferably an alkoxy group having 1 to 6 carbon atoms.
An aryloxy group, preferably an aryloxy group having 6 to 20 carbon atoms, more preferably an aryloxy group having 6 to 14 carbon atoms, still more preferably an aryloxy group having 6 to 12 carbon atoms, particularly preferably 6 carbon atoms. Aryloxy group.
A heteroaryloxy group, preferably a heteroaryloxy group having 3 to 20 carbon atoms, more preferably a heteroaryloxy group having 3 to 12 carbon atoms.
-Alkylamino group, preferably an alkylamino group having 1 to 20 carbon atoms, more preferably an alkylamino group having 1 to 12 carbon atoms.
An arylamino group, preferably an arylamino group having 6 to 36 carbon atoms, and more preferably an arylamino group having 6 to 24 carbon atoms.
An aralkyl group, preferably an aralkyl group having 7 to 40 carbon atoms, more preferably an aralkyl group having 7 to 18 carbon atoms, and further preferably an aralkyl group having 7 to 12 carbon atoms.
A heteroaralkyl group, preferably a heteroaralkyl group having 7 to 40 carbon atoms, more preferably a heteroaralkyl group having 7 to 18 carbon atoms.
An alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms, further preferably an alkenyl group having 2 to 8 carbon atoms, and particularly preferably an alkenyl group having 2 to 6 carbon atoms. ..
An alkynyl group, preferably an alkynyl group having 2 to 20 carbon atoms, and more preferably an alkynyl group having 2 to 12 carbon atoms.
An aryl group, preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, further preferably an aryl group having 6 to 18 carbon atoms, and particularly preferably an aryl group having 6 to 14 carbon atoms. ..
A heteroaryl group, preferably a heteroaryl group having 3 to 30 carbon atoms, more preferably a heteroaryl group having 3 to 24 carbon atoms, still more preferably a heteroaryl group having 3 to 18 carbon atoms, and particularly preferably 3 to 18 carbon atoms. 14 heteroaryl groups.
An alkylsilyl group, preferably an alkylsilyl group having 1 to 20 carbon atoms, more preferably an alkylsilyl group having 1 to 12 carbon atoms.
An arylsilyl group, preferably an arylsilyl group having 6 to 20 carbon atoms, more preferably an arylsilyl group having 6 to 14 carbon atoms.
-Alkylcarbonyl group, preferably an alkylcarbonyl group having 2 to 20 carbon atoms.
An arylcarbonyl group, preferably an arylcarbonyl group having 7 to 20 carbon atoms.

In the above group, one or more hydrogen atoms may be replaced with a fluorine atom, or one or more hydrogen atoms may be replaced with a deuterium atom.
Unless otherwise specified, aryl is an aromatic hydrocarbon and heteroaryl is an aromatic heterocycle.
-Hydrogen atom, deuterium atom, fluorine atom, cyano group, or -SF5.

(Preferable group in substituent group Z2)
Of these substituents Z2, preferred are alkyl groups, alkoxy groups, aryloxy groups, arylamino groups, aralkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkylsilyl groups, arylsilyl groups, and groups thereof. One or more hydrogen atoms of the group are replaced with a fluorine atom, a fluorine atom, a cyano group, or -SF5, and more preferably an alkyl group, an arylamino group, an aralkyl group, an alkenyl group, an aryl group, or a hetero. Aryl groups, and groups in which one or more hydrogen atoms of these groups are replaced with fluorine atoms, fluorine atoms, cyano groups, or -SF5, more preferably alkyl groups, alkoxy groups, aryls. Oxy group, arylamino group, aralkyl group, alkenyl group, aryl group, heteroaryl group, alkylsilyl group, arylsilyl group, and particularly preferably alkyl group, arylamino group, aralkyl group, alkenyl group, aryl group, hetero. It is an aryl group, most preferably an alkyl group, an arylamino group, an aralkyl group, an aryl group, or a heteroaryl group.

The substituent group Z2 may further have a substituent selected from the substituent group Z2 as a substituent. Preferred groups, more preferred groups, more preferred groups, particularly preferred groups, and most preferred groups of the substituents which may be possessed are the same as the preferred groups in the substituent group Z2.
Ring A1 represents an aromatic hydrocarbon ring structure which may have a substituent or an aromatic heterocyclic structure which may have a substituent.

The aromatic hydrocarbon ring is preferably an aromatic hydrocarbon ring having 6 to 30 carbon atoms, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a triphenylyl ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. preferable.
As the aromatic heterocycle, an aromatic heterocycle having 3 to 30 carbon atoms, which contains any of a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, is preferable, and a furan ring, a benzofuran ring, and a thiophene ring are more preferable. , Benzothiophene ring.

The ring A1 is more preferably a benzene ring, a naphthalene ring, or a fluorene ring, particularly preferably a benzene ring or a fluorene ring, and most preferably a benzene ring.
Ring A2 represents an aromatic heterocyclic structure which may have a substituent.
The aromatic heterocycle is preferably an aromatic heterocycle having 3 to 30 carbon atoms, preferably containing either a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, and specifically, a pyridine ring or a pyrimidine ring. , Pyrazine ring, triazine ring, imidazole ring, oxazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzoimidazole ring, quinoline ring, isoquinoline ring, quinoxalin ring, quinazoline ring, naphthylidine ring, phenanthridin ring. , More preferably, a pyridine ring, a pyrazine ring, a pyrimidine ring, an imidazole ring, a benzothiazole ring, a benzoxazole ring, a quinoline ring, an isoquinoline ring, a quinoxalin ring, a quinazoline ring, and more preferably a pyridine ring, an imidazole ring, a benzo. It is a thiazole ring, a quinoline ring, an isoquinoline ring, a quinoxalin ring, a quinazoline ring, and most preferably a pyridine ring, an imidazole ring, a benzothiazole ring, a quinoline ring, a quinoxalin ring, or a quinazoline ring.

As a preferable combination of ring A1 and ring A2, when expressed as (ring A1-ring A2), (benzene ring-pyridine ring), (benzene ring-quinoline ring), (benzene ring-quinoxaline ring), (benzene ring-) Quinazoline ring), (benzene ring-imidazole ring), (benzene ring-benzothiazole ring).
The substituents that the rings A1 and A2 may have can be arbitrarily selected, but are preferably one or a plurality of substituents selected from the substituent group Z2.

Ar ²⁰¹ and Ar ²⁰³ each independently represent an aromatic hydrocarbon ring structure which may have a substituent or an aromatic heterocyclic structure which may have a substituent.
Ar ²⁰² has an aromatic hydrocarbon ring structure which may have a substituent, an aromatic heterocyclic structure which may have a substituent, or an aliphatic hydrocarbon structure which may have a substituent. Represents.
When ^{any one of Ar 201} , Ar ²⁰² , and Ar ²⁰³ has an aromatic hydrocarbon ring structure which may have a substituent, the aromatic hydrocarbon ring structure is preferably an aromatic having 6 to 30 carbon atoms. It is a hydrocarbon ring, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a triphenylyl ring, an acenaphthene ring, a fluorantene ring, and a fluorene ring are preferable, more preferably a benzene ring, a naphthalene ring, and a fluorene ring, and most preferably. A benzene ring is preferable.

When any of Ar ²⁰¹ , Ar ²⁰² , and Ar ^{203 is} a fluorene ring which may have a substituent, the 9-position and 9'-position of the fluorene ring have a substituent or are bonded to an adjacent structure. Is preferable.
When any of Ar ²⁰¹ , Ar ²⁰² , and Ar ^{203 is} a benzene ring which may have a substituent, it is preferable that at least one benzene ring is bonded to an adjacent structure at the ortho-position or the meta-position. It is more preferable that at least one benzene ring is bonded to an adjacent structure at the meta position.

When ^{any one of Ar 201} , Ar ²⁰² , and Ar ^{203 is} an aromatic heterocyclic structure which may have a substituent, the aromatic heterocyclic structure is preferably a nitrogen atom, an oxygen atom, or a heteroatom as a heteroatom. An aromatic heterocycle containing any of sulfur atoms and having 3 to 30 carbon atoms, specifically, a pyridine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a benzothiazole ring. , Benzoxazole ring, benzoimidazole ring, quinoline ring, isoquinoline ring, quinoxalin ring, quinazoline ring, naphthylidine ring, phenanthridine ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring, and more preferably pyridine ring and pyrimidine. It is a ring, a triazine ring, a carbazole ring, a dibenzofuran ring, and a dibenzothiophene ring.

If any of Ar ²⁰¹ , Ar ²⁰² , and Ar ^{203 is} a carbazole ring that may have a substituent, the N-position of the carbazole ring may have a substituent or be attached to an adjacent structure. preferable.
When Ar ² is an aliphatic hydrocarbon structure which may have a substituent, it is an aliphatic hydrocarbon structure having a linear, branched or cyclic structure, preferably having 1 or more and 24 or less carbon atoms. Yes, more preferably the carbon number is 1 or more and 12 or less, and more preferably the carbon number is 1 or more and 8 or less.

i1 represents an integer of 0 to 12, preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 6. Within this range, improvement in solubility and charge transportability is expected.
i3 preferably represents an integer of 0-5, more preferably 0-2, more preferably 0 or 1.

j preferably represents an integer of 0 to 2, and is more preferably 0 or 1.
k1 and k2 preferably represent an integer of 0 to 3, more preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.
The ^{substituents that Ar 201} , Ar ²⁰² , and Ar ²⁰³ may have can be arbitrarily selected, but are preferably one or more substituents selected from the substituent group Z2, and the preferred group is also the above-mentioned substitution. It is the same as the group Z2, but more preferably a hydrogen atom, an alkyl group, or an aryl group, particularly preferably a hydrogen atom or an alkyl group, and most preferably an unsubstituted (hydrogen atom).

Among the structures represented by the above formula (202), a material having the following structure is preferable. A structure having a group in which benzene rings are linked. That is, Ar ²⁰¹ is bonded to a benzene ring structure, i1 is 1 to 6, and at least one of the benzene rings is bonded to an adjacent structure at the ortho-position or the meta-position. With this structure, it is expected that the solubility is improved and the charge transportability is improved.

A structure having an aromatic hydrocarbon group or an aromatic heterocyclic group in which an alkyl group or an aralkyl group is bonded to ring A1 or ring A2, that is, Ar ²⁰¹ is an aromatic hydrocarbon structure or an aromatic heterocyclic structure, and i1 is 1. ~ 6, Ar ²⁰² is an aliphatic hydrocarbon structure, i2 is 1 to 12, preferably 3 to 8, Ar ²⁰³ is a benzene ring structure, and i3 is 0 or 1. Ar ²⁰¹ is preferably the aromatic hydrocarbon structure, more preferably a structure in which 1 to 5 benzene rings are linked, and more preferably one benzene ring. With this structure, it is expected that the solubility is improved and the charge transportability is improved.

A structure in which dendron is bound to ring A1 or ring A2. For example, Ar ²⁰¹ and Ar ²⁰² have a benzene ring structure, Ar ²⁰³ has a biphenyl or terphenyl structure, i1 and i2 have 1 to 6, i3 has 2, and j has 2. With this structure, it is expected that the solubility is improved and the charge transportability is improved.
B ^201- L ^200- B ²⁰² represents an anionic bidentate ligand. B ²⁰¹ and B ²⁰² each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring. L ²⁰⁰ represents a single bond, ^or, together with ^{B 201} and ^{B 202} an atomic group necessary to form a bidentate ligand. When ^{there are a plurality of B 201-} L ^200- B ²⁰² , they may be the same or different.
Of the structures represented by B ^201- L ^200- B ²⁰² , the structure is preferably represented by the following formula (203) or (204).

In formula (203), R ²¹¹ , R ²¹² , and R ²¹³ represent substituents. As the substituent, a group selected from the above-mentioned substituent group Z2 is preferable.

In formula (204), ring B3 represents an aromatic heterocyclic structure containing a nitrogen atom, which may have a substituent. Ring B3 is preferably a pyridine ring. As the substituent which may be possessed, a group selected from the above-mentioned substituent group Z2 is preferable.

The phosphorescent material represented by the formula (201) is not particularly limited, and specific examples thereof include the following structures.

As the phosphorescent material, a compound represented by the formula (205) can be used in addition to the formula (201).

In formula (205), M ² represents a metal and T represents a carbon atom or a nitrogen atom. R ^{92 to} R ⁹⁵ each independently represent a substituent. However, when T is a nitrogen atom, there are no R94 and R95.
In formula (205), M ² represents a metal. As a specific example, the above-mentioned metal can be mentioned as a metal selected from the 7th to 11th groups of the periodic table. Of these, ruthenium, rhodium, palladium, silver, renium, osmium, iridium, platinum or gold are preferred, and divalent metals such as platinum and palladium are particularly preferred.

Further, in the formula (205), R ⁹² and R ⁹³ are independently hydrogen atom, halogen atom, alkyl group, aralkyl group, alkenyl group, cyano group, amino group, acyl group, alkoxycarbonyl group and carboxyl group, respectively. Represents an alkoxy group, an alkylamino group, an aralkylamino group, a haloalkyl group, a hydroxyl group, an aryloxy group, an aromatic hydrocarbon group or an aromatic heterocyclic group.

Further, when T is a carbon atom, R ⁹⁴ and R ⁹⁵ independently represent substituents represented by the same examples as ^{R 92} and R ^{93, respectively.} Further, when T is a nitrogen atom, there is no ^{R 94} or R ^{95 directly bonded to the T.} Further, R ^{92 to} R ⁹⁵ may further have a substituent. As the substituent, the above-mentioned substituent can be used. Further, ^{any two or more groups of R 92 to} R ⁹⁵ may be connected to each other to form a ring.

The molecular weight of the phosphorescent material is preferably 5000 or less, more preferably 4000 or less, and particularly preferably 3000 or less. The molecular weight of the phosphorescent material is usually 800 or more, preferably 1000 or more, and more preferably 1200 or more. It is considered that within this molecular weight range, the phosphorescent materials do not aggregate and are uniformly mixed with the charge transport material, so that a light emitting layer having high luminous efficiency can be obtained.

The molecular weight of the phosphorescent material is high in Tg, melting point, decomposition temperature, etc., and the phosphorescent material and the formed light emitting layer are excellent in heat resistance, and the film quality due to gas generation, recrystallization, molecular migration, etc. It is preferable that the amount is large in that the decrease in the amount of impurities and the increase in the concentration of impurities due to the thermal decomposition of the material are unlikely to occur. On the other hand, the molecular weight of the phosphorescent light emitting material is preferably small in that the organic compound can be easily purified.
In an organic electroluminescent device in which a polymer is used as a charge-transporting material that forms at least one of a hole injection layer and a hole transport layer, when the light emitting layer is a phosphorescent light emitting material, the following materials are used as host materials. preferable.

<Host material (compound)>
As the host material (compound) of the light emitting layer, those having the above-mentioned formula (CzP) and formula (CzP-2) can be used. Further, when the light emitting material or another host material has the formula (CzP), a host material having no formula (CzP) or formula (CzP-2) can be used as appropriate. In this case, the skeleton, molecular weight, substituents and the like are the same as described above.

In an organic electroluminescent device in which a polymer is used as a charge-transporting material that forms at least one of a hole injection layer and a hole transport layer, when the light emitting layer is a fluorescent light emitting material, it is the following blue fluorescent light emitting material. Is preferable.
The light emitting material for the blue fluorescent light emitting layer is not particularly limited, but a compound represented by the following formula (211) is preferable.

In the above formula (211)
Ar ²⁴¹ represents an aromatic hydrocarbon condensed ring structure which may have a substituent.
Ar ²⁴² and Ar ²⁴³ each independently represent an alkyl group which may have a substituent, an aromatic hydrocarbon group, or a group to which these are bonded.
n41 is 1 to 4.

Ar ²⁴¹ preferably represents an aromatic hydrocarbon condensed ring structure having 10 to 30 carbon atoms, and specific structures include naphthalene, acenaphthene, fluorene, anthracene, phenatren, fluoranthene, pyrene, tetracene, chrysene, perylene and the like. Be done.
More preferably, it is an aromatic hydrocarbon fused ring structure having 12 to 20 carbon atoms, and specific structures include acenaphthene, fluorene, anthracene, phenatren, fluoranthene, pyrene, tetracene, chrysene, and perylene. More preferably, it is an aromatic hydrocarbon condensed ring structure having 16 to 18 carbon atoms, and specific structures include fluoranthene, pyrene, and chrysene.

n41 is 1 to 4, preferably 1 to 3, more preferably 1 to 2, and most preferably 2.
The ^{substituent that Ar 241} , Ar ²⁴² , and Ar ²⁴³ may have is preferably a group selected from the substituent group Z2, more preferably a hydrocarbon group contained in the substituent group Z2, and further preferably. Is a hydrocarbon group among the preferred groups as the substituent group Z2.

In an organic electroluminescent device in which a polymer is used as a charge-transporting material that forms at least one of a hole injection layer and a hole transport layer, when the light emitting layer is a phosphorescent light emitting material, the following materials are used as host materials. preferable.
The host material for the blue fluorescent light emitting layer is not particularly limited, but a compound represented by the following formula (212) is preferable.

[In the above formula (212),
R ²⁴¹ and R 242 have structures independently represented by the equation (213), respectively.
R ²⁴³ represents a substituent, and ^{if there are a plurality of R 243} , they may be the same or different.
n43 is 0 to 8. ]

Ar ²⁴⁴ and Ar ²⁴⁵ each independently represent an aromatic hydrocarbon structure which may have a substituent or a heteroaromatic ring structure which may have a substituent.
When ^{a plurality of Ar 244} and Ar ²⁴⁵ exist, they may be the same or different.
n44 is 1 to 5, and n45 is 0 to 5.

Ar ²⁴⁴ is preferably an aromatic hydrocarbon structure which is a monocyclic or condensed ring having 6 to 30 carbon atoms, which may have a substituent, and more preferably may have a substituent. , An aromatic hydrocarbon structure which is a monocyclic or condensed ring having 6 to 12 carbon atoms.
Ar ²⁴⁵ preferably has an aromatic hydrocarbon structure which is a monocyclic or fused ring having 6 to 30 carbon atoms, which may have a substituent, or may have a substituent, which may have 6 carbon atoms. It is an aromatic heterocyclic structure which is a fused ring of about 30 and more preferably an aromatic hydrocarbon structure which is a monocyclic or condensed ring having 6 to 12 carbon atoms or which may have a substituent. It is an aromatic heterocyclic structure which is a fused ring having 12 carbon atoms which may have a substituent.

n44 is preferably 1-3, more preferably 1 or 2.
n45 is preferably 0 to 3, more preferably 0 to 2.
The substituents R ²⁴³ and Ar ²⁴⁴ and Ar ²⁴⁵ may have a substituent preferably selected from the above-mentioned Substituent Group Z, and more preferably a hydrocarbon group contained in the Substituent Group Z. It is a hydrocarbon group among the groups preferable as the substituent group Z.

The molecular weight of the light emitting material for the blue fluorescent light emitting layer and the host material is preferably 5,000 or less, more preferably 4,000 or less, particularly preferably 3,000 or less, and most preferably 2,000 or less. It is usually 300 or more, preferably 350 or more, and more preferably 400 or more.

[Formation of light emitting layer by wet film formation method]
The light emitting layer may be formed by either a vacuum vapor deposition method or a wet film forming method, but the wet film forming method is preferable, and the spin coating method and the inkjet method are more preferable because of the excellent film forming property. In particular, when a hole injection layer or a hole transport layer to be a lower layer of the light emitting layer is formed by using a composition for an organic electroluminescent device, laminating by a wet film forming method is easy, so a wet film forming method is used. It is preferable to adopt it. When the light emitting layer is formed by the wet film forming method, usually, in the same manner as when the hole injection layer is formed by the wet film forming method, instead of the composition for forming the hole injection layer, a light emitting layer is used. The material is formed by using a composition for forming a light emitting layer prepared by mixing a soluble solvent (solvent for a light emitting layer).

Examples of the solvent include ether-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents, amide-based solvents, alcan-based solvents, halogenated aromatic hydrocarbon-based solvents, and fats mentioned for the formation of the hole injection layer. Examples thereof include a group alcohol solvent, an alicyclic alcohol solvent, an aliphatic ketone solvent, an alicyclic ketone solvent and the like. Specific examples of the solvent are given below, but the present invention is not limited thereto as long as the effect of the present invention is not impaired.

For example, aliphatic ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetol, 2 -Aromatic ether solvents such as methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole, diphenyl ether; phenyl acetate, phenyl propionate, methyl benzoate, benzoic acid Aromatic ester solvents such as ethyl, propyl benzoate, n-butyl benzoate; toluene, xylene, mesitylen, cyclohexylbenzene, tetralin, 3-iropropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1, Aromatic hydrocarbon solvents such as 4-diisopropylbenzene, cyclohexylbenzene and methylnaphthalene; amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; n-decane, cyclohexane, ethylcyclohexane, decalin, bi Alcan solvents such as cyclohexane; halogenated aromatic hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene; aliphatic alcohol solvents such as butanol and hexanol; alicyclic alcohol solvents such as cyclohexanol and cyclooctanol; An aliphatic ketone solvent such as methyl ethyl ketone and dibutyl ketone; an alicyclic ketone solvent such as cyclohexanone, cyclooctanone and fencon can be mentioned. Of these, alkane-based solvents and aromatic hydrocarbon-based solvents are particularly preferable.

[Hole blocking layer]
A hole blocking layer 6 may be provided between the light emitting layer 5 and the electron injection layer 8 described later. The hole blocking layer 6 is a layer laminated on the light emitting layer 5 so as to be in contact with the interface on the cathode 9 side of the light emitting layer 5.
The hole blocking layer 6 has a role of blocking holes moving from the anode 2 from reaching the cathode 9 and a role of efficiently transporting electrons injected from the cathode 9 toward the light emitting layer 5. Has. The physical properties required for the material constituting the hole blocking layer 6 are high electron mobility and low hole mobility, a large energy gap (difference between HOMO and LUMO), and an excited triplet level (T1). Is high.

Examples of the material of the hole blocking layer satisfying such conditions include bis (2-methyl-8-quinolinolat) (phenorato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanorat) aluminum and the like. Mixed ligand complex, bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolilato) aluminum dinuclear metal complex and other metal complexes, distyrylbiphenyl derivative and the like. Triazole derivatives such as styryl compounds (Japanese Patent Laid-Open No. 11-242996), 3- (4-biphenylyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole (Japanese Patent Laid-Open No. 11-24296). 7-41759A), a phenylanthroline derivative such as bathocuproine (Japanese Patent Laid-Open No. 10-79297), and the like. Further, a compound having at least one pyridine ring substituted at the 2, 4, and 6 positions described in International Publication No. 2005/022962 is also preferable as a material for the hole blocking layer.

There is no limitation on the method of forming the hole blocking layer 6. Therefore, it can be formed by a wet film forming method, a thin film deposition method, or another method.
The film thickness of the hole blocking layer 6 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less. be.

[Electron transport layer]
The electron transport layer 7 is provided between the light emitting layer 5 and the electron injection layer 8 for the purpose of further improving the current efficiency of the device.
The electron transport layer 7 is formed of a compound capable of efficiently transporting electrons injected from the cathode 9 between electrodes to which an electric field is applied in the direction of the light emitting layer 5. The electron transporting compound used in the electron transporting layer 7 has high electron injection efficiency from the cathode 9 or the electron injection layer 8 and high electron mobility, and efficiently transports the injected electrons. It needs to be a capable compound.

Specific examples of the electron-transporting compound used in the electron-transporting layer include metal complexes such as an aluminum complex of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), 10-hydroxybenzo [h] quinoline. Metal complex, oxadiazole derivative, distyrylbiphenyl derivative, silol derivative, 3-hydroxyflavon metal complex, 5-hydroxyflavon metal complex, benzoxazole metal complex, benzothiazole metal complex, trisbenzimidazolylbenzene (US Patent No. 5645948) Specified specification), quinoxalin compound (Japanese Patent Laid-Open No. 6-207169), phenanthroline derivative (Japanese Patent Laid-Open No. 5-331459), 2-t-butyl-9,10-N, N'-dicyanoanthraquinonediimine, n-type. Examples thereof include hydrided amorphous silicon carbide, n-type zinc sulfide, and n-type zinc selenium.
The film thickness of the electron transport layer 7 is usually 1 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less.
The electron transport layer 7 is formed by laminating on the hole blocking layer 6 by a wet film forming method or a vacuum vapor deposition method in the same manner as described above. Usually, a vacuum deposition method is used.

[Electron injection layer]
The electron injection layer 8 serves to efficiently inject the electrons injected from the cathode 9 into the electron transport layer 7 or the light emitting layer 5.
In order to efficiently perform electron injection, the material forming the electron injection layer 8 is preferably a metal having a low work function. As an example, alkali metals such as sodium and cesium, alkaline earth metals such as barium and calcium, and the like are used. The film thickness is usually preferably 0.1 nm or more and 5 nm or less.
Furthermore, alkali metals such as sodium, potassium, cesium, lithium, and rubidium are doped into organic electron transport materials represented by metal complexes such as nitrogen-containing heterocyclic compounds such as vasophenantroline and aluminum complexes of 8-hydroxyquinoline (). Also described in JP-A No. 10-270171, JP-A-2002-100478, JP-A-2002-1000482, etc.), because electron injection and transportability are improved and excellent film quality can be achieved at the same time. preferable.

The film thickness of the electron injection layer 8 is usually 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.
The electron injection layer 8 is formed by laminating on the light emitting layer 5 or the hole blocking layer 6 or the electron transport layer 7 on the light emitting layer 5 by a wet film forming method or a vacuum vapor deposition method.
The details of the wet film forming method are the same as those of the above-mentioned light emitting layer.

[cathode]
The cathode 9 serves to inject electrons into a layer on the light emitting layer 5 side (electron injection layer, light emitting layer, or the like).
As the material of the cathode 9, the material used for the anode 2 can be used, but in order to efficiently inject electrons, it is preferable to use a metal having a low work function, for example, tin and magnesium. , Indium, calcium, aluminum, metals such as silver or alloys thereof are used. Specific examples include alloy electrodes having a low work function such as magnesium-silver alloys, magnesium-indium alloys, and aluminum-lithium alloys.

From the viewpoint of device stability, it is preferable to laminate a metal layer having a high work function and stable to the atmosphere on the cathode to protect the cathode made of a metal having a low work function. Examples of the metal to be laminated include metals such as aluminum, silver, copper, nickel, chromium, gold, and platinum.
The film thickness of the cathode is usually the same as that of the anode.

[Other layers]
The organic electroluminescent device may further have another layer as long as the effect of the present invention is not significantly impaired. That is, any of the above-mentioned other layers may be provided between the anode and the cathode.

[Other element configurations]
The organic electroluminescent device has a structure opposite to that described above, that is, a cathode, an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer, a hole transport layer, a hole injection layer, and an anode on a substrate. It is also possible to stack them in order.
When an organic electroluminescent device is applied to an organic electroluminescent device, whether it is used as a single organic electroluminescent device or in a configuration in which a plurality of organic electroluminescent devices are arranged in an array, an anode and a cathode are used. May be used in a configuration arranged in an XY matrix.

<Organic EL display device>
The organic EL display device (organic electroluminescent element display device) according to still another embodiment of the present invention includes the above-mentioned organic electroluminescent element. The model and structure of the organic EL display device are not particularly limited, and can be assembled according to a conventional method using an organic electroluminescent element.
For example, forming an organic EL display device by the method described in "Organic EL Display" (Ohmsha, published on August 20, 2004, by Shizushi Tokito, Chihaya Adachi, Hideyuki Murata). Can be done.

<Organic EL lighting>
The organic EL lighting (organic electroluminescent element lighting) according to still another embodiment of the present invention includes the above-mentioned organic electroluminescent element. The type and structure of the organic EL lighting are not particularly limited, and can be assembled according to a conventional method using an organic electroluminescent element.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and the present invention can be arbitrarily modified and carried out without departing from the gist thereof.

<Experiment I>
<Synthesis of intermediates>
[Synthesis of compound 3]

Under nitrogen stream, compound 1 (10.3 g, 36.58 mmol), compound 2 (5.2 g, 24.39 mmol), potassium phosphate (13.0 g, 60.98 mmol), toluene (60 ml), ethanol (30 ml) And water (30 ml) was placed in a flask, and the inside of the system was sufficiently replaced with nitrogen and heated to 60 ° C.
Bis (triphenylphosphine) palladium (II) dichloride (0.086 g, 0.122 mmol) was added, and the mixture was stirred at 60 ° C. for 3 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 85/15) to obtain Compound 3 (4.4 g, yield 55.8%).

[Synthesis of compound 4]

Under a nitrogen stream, 50 ml of dimethylsulfonate, compound 3 (4.4 g, 13.6 mmol), bis (pinacolato) diboron (4.2 g, 16.34 mmol), potassium acetate (4.0 g, 40.) in a 200 ml flask. 83 mmol) was added, and the mixture was stirred at 60 ° C. for 30 minutes. Then, 1,1'-bis (diphenylphosphino) ferrocene-palladium (II) dichloride-dichloromethane [PdCl ₂ (dppf) CH ₂ Cl ₂ ] (0.56 g, 0.68 mmol) was added, and the temperature was 85 ° C. for 4 hours. Reacted.
Pure water was added dropwise, the reaction solution was filtered under reduced pressure, the filtrate was extracted with toluene, dried over anhydrous magnesium sulfate, and roughly purified with activated clay. Further, the crude product was purified by column chromatography (developing solution: hexane / ethyl acetate = 90/10) to obtain Compound 4 (5.0 g, yield 98%).

[Synthesis of compound 6]

Under nitrogen stream, compound 4 (5.0 g, 13.5 mmol), compound 5 (6.48 g, 14.46 mmol), potassium phosphate (8.8 g, 41.31 mmol), toluene (40 ml), ethanol (20 ml). And water (20 ml) was placed in a flask, and the inside of the system was sufficiently replaced with nitrogen and heated to 60 ° C.
Bis (triphenylphosphine) palladium (II) dichloride (0.048 g, 0.069 mmol) was added, and the mixture was stirred at 60 ° C. for 2 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 85/15) to obtain Compound 6 (6.3 g, yield 81.0%).

[Synthesis of compound 7]

3-Nitrophenylboronic acid (30.1 g, 180.3 mmol), 1-bromo-3-iodobenzene (56.0 g, 197.94 mmol), potassium phosphate (95.5 g, 450 mmol), and toluene (350 ml), Ethanol (150 ml) and water (225 ml) were placed in a flask, and the inside of the system was sufficiently replaced with nitrogen and heated to 60 ° C. Tetrakis (triphenylphosphine) palladium (0) (5.2 g, 4.5 mmol) was added, and the mixture was stirred at 85 ° C. for 5 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 3/1) to obtain Compound 7 (20.3 g, yield 41%).

[Synthesis of Compound 8]

260 ml of 1,4-dioxane, compound 7 (20.3 g, 72.9 mmol), bis (pinacolato) diboron (22.2 g, 89.6 mmol), potassium acetate (35.9 g,) in a 500 ml flask under a nitrogen stream. 365.8 mmol) was added, and the mixture was stirred at 60 ° C. for 30 minutes. Then, 1,1'-bis (diphenylphosphino) ferrocene-palladium (II) dichloride-dichloromethane [PdCl ₂ (dppf) CH ₂ Cl ₂ ] (1.8 g, 2.19 mmol) was added, and the temperature was 85 ° C. Reacted for 5 hours.
Pure water was added dropwise, the reaction solution was filtered under reduced pressure, the filtrate was extracted with toluene, dried over anhydrous magnesium sulfate, and roughly purified with activated clay. Further, the crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 1/1) to obtain Compound 8 (19.1 g, yield 84%).

[Synthesis of compound 9]

Compound 6 (3.6 g, 6.4 mmol), Compound 8 (2.3 g, 7.03 mmol), potassium phosphate (4.1 g, 19.21 mmol), and toluene (40 ml), ethanol (20 ml), water ( 10 ml) was placed in a flask, the inside of the system was sufficiently replaced with nitrogen, and the mixture was heated to 60 ° C. Tetrakis (triphenylphosphine) palladium (0) (0.2 g, 0.19 mmol) was added, and the mixture was stirred at 85 ° C. for 3.5 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 1/1) to obtain Compound 9 (3.5 g, yield 80.2%).

[Synthesis of compound 10]

Under a nitrogen stream, 350 ml of tetrahydrofuran, 20 ml of ethanol, compound 9 (3.5 g, 5.13 mmol), palladium / carbon (10%, about 55% wet product, 0.4 g) were placed in a 500 ml flask, and 50 The mixture was stirred at ° C for 10 minutes. Then, human razin monohydrate (1.8 g) was added dropwise, and the reaction was carried out at this temperature for 3 hours.
The reaction mixture was filtered under reduced pressure with water-moist Celite, the filtrate was concentrated, washed with methanol and purified to give compound 10 (3.0 g, yield 91%).

[Synthesis of compound 12]

Under nitrogen stream, compound 11 (5.0 g, 9.27 mmol), phenylboronic acid (1.2 g, 9.46 mmol), potassium phosphate (5.9 g, 27.8 mmol), toluene (30 ml), ethanol (15 ml). ) And water (14 ml) were placed in a flask, and the inside of the system was sufficiently replaced with nitrogen and heated to 65 ° C.
Bis (triphenylphosphine) palladium (II) dichloride (0.033 g, 0.046 mmol) was added, and the mixture was stirred at 65 ° C. for 3 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 85/15) to obtain Compound 12 (4.1 g, yield 90.3%).

[Synthesis of compound 13]

Under a nitrogen stream, 35 ml of dimethylsulfonic acid, compound 12 (4.1 g, 8.38 mmol), bis (pinacolato) diboron (3.2 g, 12.6 mmol), potassium acetate (2.5 g, 25 mmol) in a 200 ml flask. 1 mmol) was added, and the mixture was stirred at 60 ° C. for 30 minutes. Then, 1,1'-bis (diphenylphosphino) ferrocene-palladium (II) dichloride-dichloromethane [PdCl ₂ (dppf) CH ₂ Cl ₂ ] (0.34 g, 0.42 mmol) was added, and the temperature was 85 ° C. for 3 hours. Reacted.
The reaction mixture was filtered under reduced pressure, the filtrate was extracted with toluene, dried over anhydrous magnesium sulfate, and roughly purified with activated clay. Further, the crude product was purified by column chromatography (developing solution: hexane / ethyl acetate = 90/10) to obtain Compound 13 (4.5 g, yield 97%).

[Synthesis of compound 14]

Under nitrogen stream, compound 13 (4.5 g, 8.39 mmol), 3-bromo-9- (4-iodophenyl) -9H-carbazole (3.95 g, 8.81 mmol), potassium phosphate (4.5 g, 20.98 mmol), toluene (30 ml), ethanol (10 ml) and water (10.5 ml) were placed in a flask, and the inside of the system was sufficiently replaced with nitrogen and heated to 65 ° C.
Bis (triphenylphosphine) palladium (II) dichloride (0.030 g, 0.042 mmol) was added, and the mixture was stirred at 65 ° C. for 3 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 75/25) to obtain Compound 14 (2.2 g, yield 35.9%).

[Synthesis of compound 15]

Then, compound 14 (2.2 g, 3.01 mmol), compound 8 (1.2 g, 3.61 mmol), potassium phosphate (1.6 g, 7.5 mmol), and toluene (10 ml), ethanol (5 ml),. Water (4 ml) was placed in a flask, the inside of the system was sufficiently replaced with nitrogen, and the mixture was heated to 60 ° C. Tetrakis (triphenylphosphine) palladium (0) (0.1 g, 0.09 mmol) was added, and the mixture was stirred at 85 ° C. for 4 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 50/50) to obtain Compound 15 (1.75 g, yield 68.5%).

[Synthesis of compound 16]

Under a nitrogen stream, 20 ml of tetrahydrofuran, 10 ml of ethanol, compound 15 (1.75 g, 2.06 mmol), palladium / carbon (10%, about 55% wet product, 0.18 g) were placed in a 100 ml flask, 52. The mixture was stirred at ° C for 10 minutes. Then, human razin monohydrate (0.7 g) was added dropwise, and the reaction was carried out at this temperature for 8 hours.
The reaction mixture was filtered under reduced pressure with water-moist Celite, the filtrate was concentrated, and purified by recrystallization with ethanol to give compound 16 (0.9 g, yield 53.3%).

[Synthesis of compound 17]

4-bromophenol (11.6 g, 67.21 mmol), 4,4'-difluorobenzophenone (6.67 g, 30.55 mmol), 100 ml N, N'-dimethylformamide, carbonate in a 300 ml flask under a nitrogen stream. Potassium (16.9 g, 122.29 mmol) was added and stirred at 140 ° C. for 3 hours. Then, the reaction solution at 40 ° C. was put into 500 ml of pure water, stirred for 10 minutes, filtered under reduced pressure, and the filtrate was washed in the order of ethanol and methanol, filtered, dried, and compound 17 (12.6 g) was dried. , Yield 78.6%) was obtained.

[Synthesis of compound 19]

270 ml of toluene, 135 ml of ethanol, compound 18 (20.0 g, 44.8 mmol), 50.72 g (179.3 mmol) of 5-bromo-2-iodotoluene, potassium phosphate aqueous solution (2M, i.e. 2) in a 1 L flask. The solution containing 191 ml (molar / liter concentration) was degassed in vacuum and then replaced with nitrogen. It was heated under a nitrogen stream and stirred for 30 minutes. Then, 0.63 g (0.90 mmol) of bis (triphenylphosphine) palladium (II) dichloride was added, and the mixture was refluxed for 6 hours. Water was added to the reaction mixture, the mixture was extracted with toluene, and treated with 00544 and activated clay. After heating and refluxing the toluene solution, the insoluble material was filtered and recrystallized to obtain compound 19 as a colorless solid (yield 14.2 g, yield 60.2%).

[Synthesis of compound 20]

Compound 20 was synthesized using 1-bromo-4-iodobenzene instead of 5-bromo-2-iodotoluene in the same manner as in the synthesis of compound 19.

窒素気流下、化合物２１（１７．８ｇ、３３．０ｍｍｏｌ）、４−（９Ｈ−カルバゾール−９−イル）フェニルボロン酸（９．５ｇ、３３．０ｍｍｏｌ）、リン酸カリウム（２１．０ｇ、９９．０ｍｍｏｌ）、トルエン（１００ｍｌ）、エタノール（５０ｍｌ）及び水（５０ｍｌ）をフラスコに仕込み、系内を十分に窒素置換して６５℃まで加温した。
ビス(トリフェニルホスフィン)パラジウム(II)ジクロリド（０．１２ｇ、０．１７ｍｍｏｌ）を加え、６５℃で３時間攪拌した。反応液に水を加え、トルエンで抽出を行った。有機層を無水硫酸マグネシウムで乾燥して活性白土より粗精製した。粗精製品をカラムクロマトグラフィー（展開液：ヘキサン／塩化メチレン＝８０／２０）により精製し、化合物２２（１８．４ｇ、収率８５．２％）を得た。[Synthesis of compound 22]

Under nitrogen stream, compound 21 (17.8 g, 33.0 mmol), 4- (9H-carbazole-9-yl) phenylboronic acid (9.5 g, 33.0 mmol), potassium phosphate (21.0 g, 99. 0 mmol), toluene (100 ml), ethanol (50 ml) and water (50 ml) were placed in a flask, and the inside of the system was sufficiently replaced with nitrogen and heated to 65 ° C.
Bis (triphenylphosphine) palladium (II) dichloride (0.12 g, 0.17 mmol) was added, and the mixture was stirred at 65 ° C. for 3 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 80/20) to obtain Compound 22 (18.4 g, yield 85.2%).

[Synthesis of compound 23]

Under a nitrogen stream, 100 ml of dimethylsulfonate, compound 22 (18.2 g, 27.8 mmol), bis (pinacolato) diboron (10.6 g, 41.7 mmol), potassium acetate (8.2 g, 83. mmol) in a 300 ml flask. 4 mmol) was added, and the mixture was stirred at 60 ° C. for 30 minutes. Then, 1,1'-bis (diphenylphosphino) ferrocene-palladium (II) dichloride-dichloromethane [PdCl ₂ (dppf) CH ₂ Cl ₂ ] (2.3 g, 2.78 mmol) was added, and the temperature was 85 ° C. Reacted for 5 hours.
The reaction mixture was filtered under reduced pressure, the filtrate was extracted with toluene, dried over anhydrous magnesium sulfate, and roughly purified with activated clay. Further, the crude product was purified by column chromatography (developing solution: hexane / ethyl acetate = 90/10) to obtain Compound 23 (17.7 g, yield 90.7%).

[Synthesis of compound 24]

Then, compound 23 (5.3 g, 7.49 mmol), 3-bromo-9- (4-iodophenyl) -9H-carbazole (3.3 g, 7.34 mmol), potassium phosphate (4.2 g, 19.). 82 mmol), toluene (30 ml), ethanol (15 ml) and water (10 ml) were placed in a flask, and the inside of the system was sufficiently replaced with nitrogen and heated to 65 ° C.
Bis (triphenylphosphine) palladium (II) dichloride (0.052 g, 0.073 mmol) was added, and the mixture was stirred at 65 ° C. for 3 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 75/25) to obtain compound 24 (4.8 g, yield 76.0%).

[Synthesis of compound 26]

Then, compound 24 (4.6 g, 5.13 mmol), compound 25 (2.2 g, 6.67 mmol), potassium carbonate (2.1 g, 15.4 mmol), and toluene (24 ml), ethanol (8 ml), water. (8 ml) was placed in a flask, the inside of the system was sufficiently substituted with nitrogen, and the mixture was heated to 60 ° C. Tetrakis (triphenylphosphine) palladium (0) (0.18 g, 0.154 mmol) was added, and the mixture was stirred at 85 ° C. for 3.5 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 60/40) to obtain compound 26'(3.9 g, yield 74.9%).

Under a nitrogen stream, 40 ml of tetrahydrofuran, 40 ml of ethanol, compound 26'(3.9 g, 3.84 mmol) and palladium / carbon (10%, about 55% wet product, 0.29 g) were placed in a 300 ml flask. The mixture was stirred at 52 ° C. for 10 minutes. Then, human razin monohydrate (1.3 g) was added dropwise, and the reaction was carried out at this temperature for 5 hours.
The reaction mixture was filtered under reduced pressure with water-moist Celite, the filtrate was concentrated, and purified by recrystallization with ethanol to give compound 26 (3.3 g, yield 87.2%).

[Synthesis of compound 27]

Then, compound 3-bromo-3'-iod-1,1-biphenyl (29.4 g, 81.9 mmol), commercially available compound 26 (20.0 g, 81.9 mmol), potassium phosphate (2M aqueous solution, 103 g), 205 mmol), toluene (200 ml) and ethanol (100 ml) were placed in a flask, and the inside of the system was sufficiently replaced with nitrogen and heated to 60 ° C. Tetrakis (triphenylphosphine) palladium (0) (2.37 g, 2.05 mmol) was added, and the mixture was stirred at 85 ° C. for 6 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 950/50) to obtain compound 27 (23.1 g, yield 81%).

[Synthesis of compound 28]

Compound 27 (23.1 g, 66.1 mmol), commercially available 3-aminophenylboronic acid (9.8 g, 63.0 mmol), potassium phosphate (2M aqueous solution, 79 g, 158 mmol), and toluene (160 ml), ethanol ( 80 ml) was placed in a flask, and the inside of the system was sufficiently replaced with nitrogen and heated to 60 ° C. Tetrakis (triphenylphosphine) palladium (0) (1.85 g, 1.6 mmol) was added, and the mixture was stirred at 85 ° C. for 4 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / ethyl acetate = 8/2) to obtain compound 28 (22.2 g, yield 92.9%).

[Synthesis of compound 30]

Compound 30 was synthesized in the same manner as in the synthesis of compound 27, using compound 29 instead of compound 26.

[Synthesis of compound 31]

Compound 31 was synthesized in the same manner as in the synthesis of compound 28, using compound 30 instead of compound 27.

[Synthesis of compound 32]

2- (9,9-dimethyl-9H-fluorene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.5 g,) commercially available from Tokyo Kasei under a nitrogen stream. 8.39 mmol), 3-bromo-9- (4-iodophenyl) -9H-carbazole (3.95 g, 8.81 mmol), potassium phosphate (4.5 g, 20.98 mmol), toluene (30 ml), ethanol (10 ml) and water (10.5 ml) were placed in a flask, and the inside of the system was sufficiently replaced with nitrogen and heated to 65 ° C.
Bis (triphenylphosphine) palladium (II) dichloride (0.030 g, 0.042 mmol) was added, and the mixture was stirred at 65 ° C. for 3 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 75/25) to obtain compound 32 (2.2 g, yield 35.9%).

[Synthesis of compound 33]

Then, compound 32 (2.2 g, 3.01 mmol), compound 8 (1.2 g, 3.61 mmol), potassium phosphate (1.6 g, 7.5 mmol), and toluene (10 ml), ethanol (5 ml),. Water (4 ml) was placed in a flask, the inside of the system was sufficiently replaced with nitrogen, and the mixture was heated to 60 ° C. Tetrakis (triphenylphosphine) palladium (0) (0.1 g, 0.09 mmol) was added, and the mixture was stirred at 85 ° C. for 4 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 50/50) to obtain compound 33 (1.75 g, yield 68.5%).

[Synthesis of compound 34]

Under a nitrogen stream, 20 ml of tetrahydrofuran, 10 ml of ethanol, compound 33 (1.75 g, 2.06 mmol), palladium / carbon (10%, about 55% wet product, 0.18 g) were placed in a 100 ml flask, 52. The mixture was stirred at ° C for 10 minutes. Then, human razin monohydrate (0.7 g) was added dropwise, and the reaction was carried out at this temperature for 8 hours.
The reaction mixture was filtered under reduced pressure with water-moist Celite, the filtrate was concentrated, and purified by recrystallization with ethanol to give compound 34 (0.9 g, yield 53.3%).

[Synthesis of compound 35]

3-bromo-9-phenyl-9H-carbazole (3.6 g, 6.4 mmol), compound 8 (2.3 g, 7.03 mmol), potassium phosphate (4.1 g, 19.21 mmol), and toluene (40 ml). , Ethanol (20 ml) and water (10 ml) were placed in a flask, and the inside of the system was sufficiently replaced with nitrogen and heated to 60 ° C. Tetrakis (triphenylphosphine) palladium (0) (0.2 g, 0.19 mmol) was added, and the mixture was stirred at 85 ° C. for 3.5 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified from activated clay. The crude product was purified by column chromatography (developing solution: hexane / methylene chloride = 1/1) to obtain compound 35 (3.5 g, yield 80.2%).

[Synthesis of compound 36]

Under a nitrogen stream, 350 ml of tetrahydrofuran, 20 ml of ethanol, compound 35 (3.5 g, 5.13 mmol), palladium / carbon (10%, about 55% wet product, 0.4 g) were placed in a 500 ml flask, and 50 The mixture was stirred at ° C for 10 minutes. Then, human razin monohydrate (1.8 g) was added dropwise, and the reaction was carried out at this temperature for 3 hours.
The reaction mixture was filtered under reduced pressure with water-moist Celite, the filtrate was concentrated, washed with methanol and purified to give compound 36 (3.0 g, yield 91%).

<Example 1>
[Synthesis of Polymer 1]
Polymer 1 was synthesized according to the following reaction formula.

Compound 19 (1.8 g, 3.4 mmol), 2-amino-9,9-dihexylfluorene (1.89 g, 5.4 mmol), Compound 10 (0.883 g, 1.4 mmol), tert-butoxysodium (2). .51 g, 26.1 mmol) and toluene (32 g, 37 ml) were charged, the inside of the system was sufficiently replaced with nitrogen, and the mixture was heated to 60 ° C. (solution A1).
[4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine (Amphos) (0.14 g) in a solution of tris (dibenzylideneacetone) dipalladium complex (0.062 g, 0.07 mmol) in 11 ml of toluene. , 0.5 mmol) and heated to 60 ° C. (solution B1).

Solution B1 was added to solution A1 in a nitrogen stream, and a heating reflux reaction was carried out for 1.0 hour. After confirming that compound 19 had disappeared, compound 20 (1.49 g, 2.95 mmol) was added. After heating and refluxing for 2 hours, bromobenzene (0.66 g, 4.2 mmol) was added, and a heating and reflux reaction was carried out for 2 hours. The reaction mixture was allowed to cool, 73 ml of toluene was added, and the mixture was added dropwise to an ethanol / water (500 ml / 90 ml) solution to obtain an end-capped crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered off. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer 1 (2.2 g). The molecular weight and the like of the obtained polymer 1 were as follows.
Weight average molecular weight (Mw) = 40,000
Number average molecular weight (Mn) = 29850
Dispersity (Mw / Mn) = 1.34

<Example 2>
[Synthesis of polymer 2]
Polymer 2 was synthesized according to the following reaction formula.

Compound 19 (1.8 g, 3.4 mmol), 2-amino-9,9-dihexylfluorene (1.3 g, 3.7 mmol), Compound 10 (1.99 g, 3.0 mmol), tert-butoxysodium (2). .51 g, 26.1 mmol) and toluene (32 g, 37 ml) were charged, the inside of the system was sufficiently replaced with nitrogen, and the mixture was heated to 60 ° C. (solution A2).

[4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine (Amphos) (0.14 g) in a solution of tris (dibenzylideneacetone) dipalladium complex (0.062 g, 0.07 mmol) in 11 ml of toluene. , 0.5 mmol) and heated to 60 ° C. (solution B2).

Solution B2 was added to solution A2 in a nitrogen stream, and a heating reflux reaction was carried out for 1.0 hour. After confirming that compound 19 had disappeared, compound 20 (1.51 g, 2.99 mmol) was added. After heating and refluxing for 2 hours, bromobenzene (0.66 g, 4.2 mmol) was added, and a heating and reflux reaction was carried out for 2 hours. The reaction mixture was allowed to cool, 73 ml of toluene was added, and the mixture was added dropwise to an ethanol / water (500 ml / 90 ml) solution to obtain an end-capped crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered off. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer 2 (2.6 g). The molecular weight and the like of the obtained polymer 2 were as follows.
Weight average molecular weight (Mw) = 39000
Number average molecular weight (Mn) = 27080
Dispersity (Mw / Mn) = 1.44

<Example 3>
[Synthesis of Polymer 3]
Polymer 3 was synthesized according to the following reaction formula.

Compound 19 (1.2 g, 2.25 mmol), 2-amino-9,9-dihexylfluorene (1.056 g, 3.02 mmol), Compound 16 (0.739 g, 0.90 mmol), Compound 31 (0.233 g). , 0.59 mmol), tert-butoxysodium (1.67 g, 17.4 mmol) and toluene (30 g, 35 ml) were charged, the inside of the system was sufficiently substituted with nitrogen, and the mixture was heated to 60 ° C. (solution A3).

[4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine (0.096 g) in a solution of tris (dibenzylideneacetone) dipalladium complex (0.041 g, 0.045 mmol) in 11 ml of toluene. , 0.36 mmol) and heated to 60 ° C. (solution B3).

Solution B3 was added to solution A3 in a nitrogen stream, and a heating reflux reaction was carried out for 1.0 hour. After confirming that compound 19 had disappeared, compound 17 (0.91 g, 1.74 mmol) was added. After heating under reflux for 2 hours, bromobenzene (0.83 g, 5.3 mmol) was added, and the mixture was heated under reflux for 2 hours. The reaction mixture was allowed to cool and dropped into an ethanol / water (200 ml / 20 ml) solution to obtain an end-capped crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered off. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer 3 (1.2 g). The molecular weight and the like of the obtained polymer 3 were as follows.
Weight average molecular weight (Mw) = 19500
Number average molecular weight (Mn) = 14770
Dispersity (Mw / Mn) = 1.32

<Example 4>
[Synthesis of polymer 4]
Polymer 4 was synthesized according to the following reaction formula.

Compound 19 (2.0 g, 3.76 mmol), 2-amino-9,9-dihexylfluorene (1.79 g, 5.12 mmol), Compound 28 (0.60 g, 1.66 mmol), Compound 34 (0.45 g). , 0.75 mmol), tert-butoxysodium (2.78 g, 28.93 mmol) and toluene (52 g, 60 ml) were charged, the inside of the system was sufficiently replaced with nitrogen, and the mixture was heated to 60 ° C. (solution A4).
[4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine (Amphos) (0) in a 11.9 ml solution of tris (dibenzylideneacetone) dipalladium complex (0.069 g, 0.075 mmol) in toluene. .16 g, 0.6 mmol) was added and heated to 60 ° C. (solution B4).

Solution B4 was added to solution A4 in a nitrogen stream, and a heating reflux reaction was carried out for 1.0 hour. After confirming that compound 19 had disappeared, compound 20 (1.33 g, 2.6 mmol) was added. After heating and refluxing for 2 hours, bromobenzene (1.77 g, 11.3 mmol) was added, and the mixture was heated under reflux for 2 hours. The reaction solution was allowed to cool and dropped into an ethanol / water (315 ml / 50 ml) solution to obtain an end-capped crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered off. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer 4 (2.8 g). The molecular weight and the like of the obtained polymer 4 were as follows.

Weight average molecular weight (Mw) = 15100
Number average molecular weight (Mn) = 11100
Dispersity (Mw / Mn) = 1.36

<Example 5>
[Synthesis of Polymer 5]
Polymer 5 was synthesized according to the following reaction formula.

Compound 19 (1.7 g, 3.19 mmol), 2-amino-9,9-dihexylfluorene (1.12 g, 3.20 mmol), Compound 34 (1.93 g, 3.19 mmol), tert-butoxysodium (2). .37 g, 24.66 mmol) and toluene (34 g, 39 ml) were charged, the inside of the system was sufficiently replaced with nitrogen, and the mixture was heated to 60 ° C. (solution A5).
[4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine (Amphos) (0.136 g) in a 10 ml solution of tris (dibenzylideneacetone) dipalladium complex (0.059 g, 0.06 mmol) in toluene. , 0.51 mmol) and heated to 60 ° C. (solution B5).

Solution B5 was added to solution A5 in a nitrogen stream, and a heating reflux reaction was carried out for 1.0 hour. After confirming that compound 19 had disappeared, compound 20 (0.81 g, 1.61 mmol) was added, and after heating under reflux for 1.5 hours, compound 19 (0.63 g, 1.18 mmol) was added. After heating and refluxing for 2 hours, bromobenzene (0.65 g, 4.14 mmol) was added, and a heating and reflux reaction was carried out for 2 hours. After allowing the reaction solution to cool, 58 ml of toluene was added, and the mixture was added dropwise to an ethanol / water (270 ml / 43 ml) solution to obtain an end-capped crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered off. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer 5 (2.7 g). The molecular weight and the like of the obtained polymer 5 were as follows.
Weight average molecular weight (Mw) = 38840
Number average molecular weight (Mn) = 28990
Dispersity (Mw / Mn) = 1.34

[Insolubilization experiment]
Using the polymer prepared in the example, an insolubilization experiment with cyclohexylbenzene and butyl benzoate was performed. Polymers 1, 2 and 5 were dissolved in anisole to prepare a coating composition. A film having a diameter of 110 nm to 130 nm was prepared by spin coating on a slide glass substrate using the coating composition. Further, the membrane was heat-treated at 230 ° C. for 30 minutes. Then, the thickness of each film was measured at room temperature.
In addition, each membrane was rinsed with cyclohexylbenzene or butyl benzoate. The rinsing treatment was carried out by dropping 130 μl of the solvent onto the coating film and allowing it to stand for 90 seconds, and then spinning the substrate. The rinsed film was heat-treated together with the slide glass substrate, and the film thickness of the residual film on the slide glass substrate was measured. Table 1 shows the ratio of the film thickness (insolubilization rate) before and after the rinsing treatment.

As shown in Table 1, it was shown that the organic films of the polymers 1, 2 and 5 after the heat treatment were not dissolved in cyclohexylbenzene or butyl benzoate and could be wet-formed.

<Experiment II>
<Example 6>
[Synthesis of polymer 6]
Polymer 6 was synthesized according to the following reaction formula.

Compound 19 (1.3 g, 2.44 mmol), 2-amino-9,9-dihexylfluorene (0.79 g, 2.25 mmol), Compound 36 (1.08 g, 2.64 mmol), tert-butoxysodium (1). .81 g, 18.83 mmol) and toluene (23 g, 27 ml) were charged, the inside of the system was sufficiently replaced with nitrogen, and the mixture was heated to 60 ° C. (solution A6).
[4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine (Amphos) (0.11 g) in a 7 ml solution of tris (dibenzylideneacetone) dipalladium complex (0.045 g, 0.05 mmol) in toluene. , 0.42 mmol) and heated to 60 ° C. (solution B6).

Solution B6 was added to solution A6 in a nitrogen stream, and a heating reflux reaction was carried out for 1.0 hour. After confirming that compound 19 had disappeared, compound 20 (1.12 g, 2.22 mmol) was added. After heating and refluxing for 2 hours, bromobenzene (0.35 g, 2.23 mmol) was added, and a heating and reflux reaction was carried out for 2 hours. The reaction mixture was allowed to cool, 57 ml of toluene was added, and the mixture was added dropwise to an ethanol / water (240 ml / 50 ml) solution to obtain an end-capped crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered off. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer 6 (1.8 g). The molecular weight and the like of the obtained polymer 6 were as follows.
Weight average molecular weight (Mw) = 41300
Number average molecular weight (Mn) = 30150
Dispersity (Mw / Mn) = 1.37

<Example 7>
[Synthesis of polymer 7]
Polymer 7 was synthesized according to the following reaction formula.

Compound 19 (1.5 g, 2.8 mmol), 2-amino-9,9-dihexylfluorene (0.59 g, 1.7 mmol), 2-amino-9,9-dimethylfluorene (0.59 g, 2.8 mmol) ), Compound 28 (1.11 g, 1.1 mmol), tert-butoxysodium (2.09 g, 21.7 mmol) and toluene (24 g, 27.7 ml) were charged, and the inside of the system was sufficiently nitrogen-substituted to 60. It was heated to ° C (solution A3).
[4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine (Amphos) (0) in a 3.3 ml solution of tris (dibenzylideneacetone) dipalladium complex (0.052 g, 0.06 mmol) in toluene. .12 g, 0.5 mmol) was added and heated to 60 ° C. (solution B3).
Solution B3 was added to solution A3 in a nitrogen stream, and a heating reflux reaction was carried out for 1.0 hour. After confirming that compound 19 had disappeared, compound 20 (1.30 g, 2.6 mmol) was added. After heating and refluxing for 2 hours, bromobenzene (0.44 g, 2.8 mmol) was added, and a heating and reflux reaction was carried out for 2 hours. The reaction mixture was allowed to cool, 40 ml of toluene was added, and the mixture was added dropwise to an ethanol / water (500 ml / 90 ml) solution to obtain an end-capped crude polymer.
The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered off. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer 7 (1.7 g). The molecular weight and the like of the obtained polymer 7 were as follows.

Weight average molecular weight (Mw) = 40,000
Number average molecular weight (Mn) = 29600
Dispersity (Mw / Mn) = 1.35

[Element example]
Hereinafter, the results of producing an element using the polymers 1, 5, 6 and 7 and the polymer HT-1 and evaluating their performance will be shown. The present invention is not limited to the following examples, and the present invention can be arbitrarily modified and carried out without departing from the gist thereof.

<Example 8>
An organic electroluminescent device was manufactured by the following method.
A transparent conductive film of indium tin oxide (ITO) deposited on a glass substrate to a thickness of 50 nm (manufactured by Sanyo Vacuum Co., Ltd., sputter-deposited product) is 2 mm wide using ordinary photolithography technology and hydrochloric acid etching. The stripes were patterned to form an anode. The substrate on which the ITO pattern is formed is washed in the order of ultrasonic cleaning with an aqueous solution of a surfactant, water washing with ultrapure water, ultrasonic cleaning with ultrapure water, and water washing with ultrapure water, and then dried with compressed air. Finally, UV ozone cleaning was performed.

As a composition for forming a hole injection layer, 3.0% by weight of a hole-transporting polymer compound having a repeating structure of the following formula (P1) and 0.6% by weight of an oxidizing agent (HI-1) are added as benzoic acid. A composition dissolved in ethyl acid acid was prepared.

This solution was spin-coated on the substrate in the atmosphere and dried at an atmospheric hot plate at 240 ° C. for 30 minutes to form a uniform thin film having a film thickness of 40 nm to form a hole injection layer.
Next, 100 parts by mass of the charge-transporting polymer compound having the following polymer 5 was dissolved in cyclohexylbenzene to prepare a 1.5 wt% solution.

This solution is spin-coated in a nitrogen glove box on a substrate coated with the hole injection layer and dried at 230 ° C. for 30 minutes on a hot plate in the nitrogen glove box to form a uniform thin film having a film thickness of 25 nm. It was formed and used as a hole transport layer.

Subsequently, as the material of the light emitting layer, 95 parts by mass of the following structural formula (H-1) and 5 parts by mass of (D-1) were weighed and dissolved in cyclohexylbenzene to prepare a 4.0 wt% solution.

This solution is spin-coated on a substrate coated with the hole transport layer in a nitrogen glove box and dried on a hot plate in the nitrogen glove box at 120 ° C. for 20 minutes to form a uniform thin film having a film thickness of 40 nm. It was formed and used as a light emitting layer.
The substrate on which the film was formed up to the light emitting layer was installed in a vacuum vapor deposition apparatus, and the inside of the apparatus was exhausted until it became ^{2 × 10 -4 Pa or less.}
Next, the following structural formula (HB-1) and 8-hydroxyquinolinolatrithium are co-deposited on the light emitting layer at a film thickness ratio of 2: 3 by a vacuum vapor deposition method at a rate of 1 Å / sec to form a film. A hole blocking layer having a thickness of 30 nm was formed.

Subsequently, a striped shadow mask having a width of 2 mm was brought into close contact with the substrate so as to be orthogonal to the ITO stripe of the anode as a mask for cathode vapor deposition, and installed in another vacuum vapor deposition apparatus. Then, as a cathode, aluminum was heated by a molybdenum boat to form an aluminum layer having a film thickness of 80 nm at a vapor deposition rate of 1 to 8.6 Å / sec to form a cathode. As described above, an organic electroluminescent device having a light emitting area portion having a size of 2 mm × 2 mm was obtained.

<Example 9>
The device was manufactured in the same manner as in Example 1 except that the hole transport layer was the polymer 1.

<Comparative Example 1>
The device was manufactured in the same manner as in Example 1 except that the hole transport layer was (HT-1).

[Evaluation of element]
The characteristics of the obtained organic electroluminescent devices of Example 1-2 and Comparative Example 1 are summarized in Table 1. For the relative luminous efficiency, the current luminous efficiency (cd / A) when emitting light at a brightness of 1000 cd / m ² was measured, and the current luminous efficiency of the comparative example was divided by the current luminous efficiency of the example to obtain a relative value. The relative value was used when the comparative example was set to 100. If it exceeds 100, it indicates that the current luminous efficiency is high. The relative voltage is a difference (V) when the voltage (V) when light is emitted at a current density of 10 mA / cm ^{2 is measured and the voltage of Comparative Example 1 is used as a reference.} A negative value indicates that the voltage is low. It was found that the organic electric field device having the hole transport layer containing the polymer of the present invention 1 has higher efficiency and lower voltage than the organic electric field device of the comparative example.

<Example 10>
This was carried out except that the hole transport layer was the polymer 5 and the light emitting layer composition was a thin film having a film thickness of (H-2) :( H-3) :( D-2) = 60:40:15 and a film thickness of 75 nm. The element was manufactured in the same manner as in Example 1. (H-2), (H-3) and (D-2) are shown below.

<Comparative Example 2>
The device was manufactured in the same manner as in Example 3 except that the hole transport layer was (HT-1).

[Evaluation of element]
Table 2 summarizes the characteristics of the obtained organic electroluminescent devices of Example 10 and Comparative Example 2. Relative current efficiency and relative voltage are synonymous with Table 1. As shown in the results of Table 2, the organic electric field element having the hole transport layer and the light emitting layer composition of the present invention, which is the second gist, has higher efficiency and lower voltage than the organic electric field element of the comparative example. It turned out to be.

<Example 11>
The hole injection layer is a thin film having a film thickness of (P1) :( HI-1) = 100: 20 and a film thickness of 60 nm, the hole transport layer is a thin film having a film thickness of 25 nm of the polymer 5, and the light emitting layer composition is (H-4). ): (H-5): (D-2) = 60:40:15 The device was manufactured in the same manner as in Example 1 except that the thin film had a film thickness of 70 nm. (H-4) and (H-5) are shown below.

<Comparative Example 3>
The hole transport layer was polymer 6, and the light emitting layer composition was (H-6) :( H-7) :( D-2) = 60: 40: 15, except that the film thickness was 70 nm. The element was manufactured in the same manner as in Example 4. (H-6) and (H-7) are shown below.

<Reference example 1>
The device was manufactured in the same manner as in Example 4 except that the hole transport layer was the polymer 6 and the light emitting layer composition was the same as in Example 4.

<Reference example 2>
The device was manufactured in the same manner as in Example 4 except that the hole transport layer was the polymer 5 and the light emitting layer composition was the same as in Comparative Example 3.

[Evaluation of element]
The characteristics of the obtained organic electroluminescent devices of Example 10 and Reference Example 1 are summarized in Table 3. The relative current efficiency was taken as a relative value when the current efficiency (cd / A) when light was emitted at ^{a brightness of 1000 cd / m 2 was measured and Reference Example 1 was set to 100.} As the relative voltage, the voltage (V) when light was emitted at a current density of 10 mA / cm ² was measured, and the difference (V) when the voltage of Reference Example 1 was used as a reference was used. As shown in the results of Table 3, it was found that the efficiency of the organic electric field device containing the polymer, which is the first gist of the present invention, in the hole transport layer is improved.

Table 4 summarizes the characteristics of the obtained organic electroluminescent devices of Reference Example 2 and Comparative Example 3. The relative current efficiency was taken as a relative value when the current efficiency (cd / A) when light was emitted at ^{a brightness of 1000 cd / m 2 was measured and Comparative Example 3 was set to 100.} As the relative voltage, the voltage (V) when light was emitted at a current density of 10 mA / cm ² was measured, and the difference (V) when the voltage of Comparative Example 3 was used as a reference was used. As shown in the results of Table 3, it was found that the efficiency of the organic electric field device containing the polymer, which is the first gist of the present invention, in the hole transport layer is improved.

The characteristics of the obtained organic electroluminescent devices of Example 10 and Reference Example 2 are summarized in Table 5. The relative current efficiency was taken as a relative value when the current efficiency (cd / A) when light was emitted at ^{a brightness of 1000 cd / m 2 was measured and Reference Example 2 was set to 100.} As the relative voltage, the voltage (V) when light was emitted at a current density of 10 mA / cm ² was measured, and the difference (V) when the voltage of Reference Example 2 was used as a reference was used. As shown in the results of Table 3, in an organic electric field device containing a polymer according to the first gist of the present invention in a hole transport layer, efficiency is improved when a light emitting layer satisfying the second gist of the present invention is provided. I found out that I would do it.

Table 6 summarizes the characteristics of the obtained organic electroluminescent devices of Example 10, Reference Example 1, and Comparative Example 3. The relative current efficiency was taken as a relative value when the current efficiency (cd / A) when light was emitted at ^{a brightness of 1000 cd / m 2 was measured and Comparative Example 3 was set to 100.} As the relative voltage, the voltage (V) when light was emitted at a current density of 10 mA / cm ² was measured, and the difference (V) when the voltage of Comparative Example 3 was used as a reference was used. As shown in the results of Table 6, it can be seen that the luminous efficiency of the organic electroluminescent device containing the polymer contained in the hole transport layer, which is the first gist of the present invention, is improved, and Comparative Example 3, Example 10 and From the comparison of Reference Example 1, it was found that the luminous efficiency of the organic electroluminescent device satisfying the third gist of the present invention is improved.

<Example 12>
[Synthesis of Polymer 8]
Polymer 8 was synthesized according to the following reaction formula.

Compound 19 (1.5 g, 2.8 mmol), 2-amino-9,9-dihexylfluorene (1.245 g, 3.6 mmol), Compound 28 (0.342 g, 0.9 mmol), Compound 26 (1.11 g). , 1.1 mmol), tert-butoxysodium (2.09 g, 21.7 mmol) and toluene (24 g, 27.7 ml) were charged, the inside of the system was sufficiently nitrogen-substituted, and the mixture was heated to 60 ° C. (solution A8). ).

[4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine (Amphos) (0) in a 3.3 ml solution of tris (dibenzylideneacetone) dipalladium complex (0.052 g, 0.06 mmol) in toluene. .12 g, 0.5 mmol) was added and heated to 60 ° C. (solution B8).

Solution B8 was added to solution A8 in a nitrogen stream, and the mixture was heated under reflux for 1.0 hour. After confirming that compound 19 had disappeared, compound 20 (1.22 g, 2.4 mmol) was added. After heating and refluxing for 2 hours, bromobenzene (1.24 g, 7.9 mmol) was added, and a heating and reflux reaction was carried out for 2 hours. The reaction mixture was allowed to cool, 40 ml of toluene was added, and the mixture was added dropwise to an ethanol / water (500 ml / 90 ml) solution to obtain an end-capped crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered off. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer 8 (2.1 g). The molecular weight and the like of the obtained polymer 8 were as follows.
Weight average molecular weight (Mw) = 39800
Number average molecular weight (Mn) = 29920
Dispersity (Mw / Mn) = 1.33

[Measurement of Excited Singlet Energy Level (S1) and Excited Triplet Energy Level (T1) of Polymer]
Each polymer 1 and polymer 8 were dissolved in 2-methyltetrahydrofuran to prepare a 1% by weight solution. The fluorescence emission spectrum and phosphorescence emission spectrum of this solution sample were measured with a fluorescence spectrophotometer (Hitachi Fluorescence Spectrophotometer F-4500) under the conditions of an excitation wavelength of 350 nm and cooling with liquid nitrogen. The S1 level and the T1 level were obtained from the peak top wavelength of the emission peak on the shortest wavelength side in the obtained fluorescence emission spectrum and phosphorescence emission spectrum. The measurement results are shown in Table 2.
The result was that the polymer 1 having no carbazole had a higher T1 rank than the polymer 8 having a carbazole terminal at the end of ^{Ar 5.} It is considered that this is because the energy cap of the molecule becomes wider and the T1 level becomes higher when the carbazole is one and the conjugation length is shorter than when the two carbazoles are conjugated to each other. It is considered that when T1 is high, energy from the light emitting layer is less likely to be transferred to the hole transport layer, and an organic EL device having high luminous efficiency can be realized.

[Confirmation of electronic state by calculation]
By calculation, the electronic states of the polymer units 1 to 5 were confirmed below.
For the calculation of electronic states, software Gaussian 09, Revision B. 01, (see * below) was used. At that time, the density functional theory was adopted as the quantum chemistry calculation method, B3LYP was used as the functional, and 6-31G was used as the basis function to perform the structure optimization calculation of the ground state. .. The software MolStudio R4.0 Rev 2.0 Pprogram (NEC Corporation) was used to display HOMO and LUMO (function value 0.03 a.u.).
The results of this calculation are shown in FIGS. 2 to 4. From FIGS. 2 and 3, it can be seen that in the polymer units 1 and 2, HOMO is present in the vicinity of N in the main chain and LUMO is localized in the terminal side of the side chain. Further, from FIG. 4, HOMO exists in the vicinity of N in the main chain in both units 3 to 5, and LUMO contains Ar ⁵ of the formula (1), and the more rings there are, the more than the carbazole ring. It can be seen that it is distributed closer to the terminal side and localized.

* Gaussian 09, Revision B. 01,
M. J. Frisch, G.M. W. Tracks, H. et al. B. Schlegel, G.M. E. Scuseria, M. et al. A. Robb, J.M. R. Cheeseman, G.M. Scalmani, V.I. Barone, B. Mennucci, G.M. A. Petersson, H. et al. Nakatsuji, M. et al. Caricato, X. Li, H. P. Hratchan, A. F. Izmaylov, J. Mol. Bloino, G.M. Zheng, J.M. L. Sonnenberg, M. et al. Hada, M.M. Ehara, K.K. Toyota, R.M. Fukuda, J.M. Hasegawa, M.M. Ishida, T.I. Nakajima, Y.M. Honda, O.D. Kitao, H.M. Nakai, T.M. Vreven, J.M. A. Montgomery, Jr. , J. E. Peralta, F. et al. Ogliaro, M. et al. Bearpark, J.M. J. Heid, E.I. Brothers, K.K. N. Kudin, V.I. N. Staroverov, T.I. Keith, R.M. Kobayashi, J. Mol. Normand, K.K. Raghavacari, A.M. Rendell, J. Mol. C. Burant, S.M. S. Iyengar, J.M. Tomasi, M.M. Cossi, N. et al. Rega, J.M. M. Millam, M.D. Klene, J.M. E. Knox, J.M. B. Cross, V. Bakken, C.I. Adamo, J.M. Jaramillo, R.M. Gomperts, R.M. E. Stratmann, O.D. Yazyev, A. J. Austin, R.M. Cammi, C.I. Pomelli, J.M. W. Ochterski, R.M. L. Martin, K.K. Morokuma, V.I. G. Zakrzewski, G.M. A. Voth, P.M. Salvador, J.M. J. Dannenberg, S.A. Dapprich, A. D. Daniels, O.D. Farkas, J.M. B. Foresman, J.M. V. Ortiz, J. et al. Cioslowski, and D. J. Fox, Gaussian, Inc. , Wallingford CT, 2010.

[Polymer unit 1]

[Polymer unit 2]

[Polymer units 3, 4, 5]

<Experiment III>
<Example 13>
An organic electroluminescent device was manufactured by the following method.
A transparent conductive film of indium tin oxide (ITO) deposited on a glass substrate to a thickness of 130 nm (manufactured by Sanyo Vacuum Co., Ltd., sputter-deposited product) is 2 mm wide using ordinary photolithography technology and hydrochloric acid etching. An anode was formed by patterning the stripes of. The substrate on which the ITO pattern is formed is washed in the order of ultrasonic cleaning with an aqueous solution of a surfactant, water washing with ultrapure water, ultrasonic cleaning with ultrapure water, and water washing with ultrapure water, and then dried with compressed air. Finally, UV ozone cleaning was performed.

As a composition for forming a hole injection layer, 100 parts by weight of a hole transporting polymer having a repeating structure of the following formula (P1) and 10 parts by weight of a compound represented by the following formula (HI-1) are weighed and benzoic acid is scented. The composition was adjusted to 3.0 wt% by dissolving in ethyl acid acid.

This solution was spin-coated on the substrate in the atmosphere and dried at an atmospheric hot plate at 230 ° C. for 30 minutes to form a uniform thin film having a film thickness of 40 nm to form a hole injection layer.
Next, 100 parts by mass of the charge-transporting polymer, which is the polymer 7, was dissolved in cyclohexylbenzene to prepare a 3.0 wt% solution.
This solution is spin-coated in a nitrogen glove box on a substrate coated with the hole injection layer and dried at 230 ° C. for 30 minutes on a hot plate in the nitrogen glove box to form a uniform thin film having a film thickness of 40 nm. It was formed and used as a hole transport layer.

Subsequently, as the material of the light emitting layer, the following structural formula (H-2) is weighed by 40 parts by mass, the following structural formula (H-5) is weighed by 60 parts by mass, and the following structural formula (D-2) is weighed by 20 parts by mass. Then, it was dissolved in cyclohexylbenzene to prepare a 7.8 wt% solution.

This solution is spin-coated on a substrate coated with the hole transport layer in a nitrogen glove box and dried on a hot plate in the nitrogen glove box at 130 ° C. for 20 minutes to form a uniform thin film having a film thickness of 80 nm. It was formed and used as a light emitting layer.
The substrate on which the film was formed up to the light emitting layer was installed in a vacuum vapor deposition apparatus, and the inside of the apparatus was exhausted until it became ^{2 × 10 -4 Pa or less.}

Next, the following structural formula (HB-1) and 8-hydroxyquinolinolatrithium are co-deposited on the light emitting layer at a film thickness ratio of 2: 3 by a vacuum vapor deposition method at a rate of 1 Å / sec to form a film. A hole blocking layer having a thickness of 30 nm was formed.

Subsequently, a striped shadow mask having a width of 2 mm was brought into close contact with the substrate so as to be orthogonal to the ITO stripe of the anode as a mask for cathode vapor deposition, and installed in another vacuum vapor deposition apparatus. Then, as a cathode, aluminum was heated by a molybdenum boat to form an aluminum layer having a film thickness of 80 nm at a vapor deposition rate of 1 to 8.6 Å / sec to form a cathode. As described above, an organic electroluminescent device having a light emitting area portion having a size of 2 mm × 2 mm was obtained.
This device contains a material having the formula (Cz-P) as a partial structure in the hole transport layer and the light emitting layer.

<Comparative Example 4>
The device was manufactured in the same manner as in Example 13 except that the hole transport layer compound was changed from polymer 7 to HT-2.

[Evaluation of element]
Table * shows the results of evaluation of the voltage and drive life of the organic electroluminescent device obtained in Example 13 and Comparative Example 4. For the voltage, the voltage when energized at 10 mA / cm2 was measured, and the difference between the voltage of the element of Example 13 and the voltage of the element of Comparative Example 4 was obtained with reference to the voltage of the element of Comparative Example 4, and the relative voltage [V] was obtained. And said. Further, the element was driven at 40 mA / cm2, the 15% luminance attenuation lifetime (LT85) was measured, and the ratio when 1 was set as the reference with respect to the 15% attenuation lifetime of Comparative Example 4 was determined as the relative lifetime. They are shown in Table 7. As shown in the results of Table 7, in an organic electroluminescent device using a material containing a material having the formula (CzP) as a partial structure in both the hole transport layer (HTL) and the light emitting layer (EML) light emitting layer. It can be seen that the voltage is low and the life is long.

<Example 14>
The device was manufactured in the same manner as in Example 13 except that the light emitting layer composition was (H-8) :( H-5) :( D-2) = 40: 60: 20. The structural formula of (H-3) is shown below.

<Comparative Example 5>
The device was manufactured in the same manner as in Example 13 except that the light emitting layer composition was (H-8) :( H-9) :( D-2) = 40: 60: 20.

<Comparative Example 6>
The hole transport layer is HT-2, and the light emitting layer composition is (H-8) :( H-9) :( D-2) = 40: 6.
The device was manufactured in the same manner as in Example 13 except that it was set to 0:20.

[Evaluation of element]
The relative voltage and relative life of the obtained organic electroluminescent devices of Example 14, Comparative Example 5, and Comparative Example 6 were determined in the same manner as in Example 13 and Comparative Example 4. At this time, Comparative Example 6 was used as a reference. They are shown in Table 8. As shown in the results of Table 8, an organic electroluminescent device using a material containing a material having the formula (CzP) as a partial structure in both the hole transport layer and the light emitting layer has a low voltage and a long life. You can see that.

Although the present invention has been described above according to specific embodiments, each embodiment is presented as an example and does not limit the scope of the present invention. Each embodiment described herein can be variously modified without departing from the spirit of the invention, and is combined with the features described by the other embodiments within a feasible range. be able to.

1 Substrate 2 Anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Hole blocking layer 7 Electron transport layer 8 Electron injection layer 9 Cathode 10 Organic electroluminescent device

Claims (22)

A polymer containing a repeating unit represented by the following formula (1).

(In equation (1),
G represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a C atom, an N atom, a B atom or a P atom.
Ar ^{2 to} Ar ⁴ each independently have a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. Represents a divalent group in which a plurality of aromatic heterocyclic groups, which may have an aromatic hydrocarbon group or a substituent which may have a substituent, are directly linked or via a linking group.
Ar ⁵ is an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aromatic hydrocarbon group and a substituent which may have a substituent. A monovalent group in which a plurality of groups selected from aromatic heterocyclic groups which may have a group are directly linked or linked via a linking group is represented.
Ar ⁶ represents a hydrogen atom or a substituent. "-*" In Ar ¹ represents the bonding position with G in the formula (1). ) The polymer according to claim 1, wherein G is an N atom. The polymer according to claim 1 or 2, wherein Ar ⁵ is represented by any of the following a-1 to e-4.

(In a-1 to e-4, "-*" ^{represents the bonding position with Ar 4,} and when there are a plurality of "-*", any one of them represents the bonding position with ^{Ar 4.)} The polymer according to claim 1 or 2, wherein the formula (1) is a repeating unit represented by any of the following formulas (2) -1 to (2) -3.

(In equation (2) -1 to equation (2) -3,
Ar ¹ is the same as Ar ¹ in the formula (1),
X represents −C (R ⁵ ) (R ⁶ ) −, −N (R ⁷ ) − or −C (R ¹¹ ) (R ¹² ) −C (R ¹³ ) (R ¹⁴ ) −.
R ^{1 to} R ⁴ each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aralkyl group which may have a substituent.
R ^{5 to} R ⁷ and R ^{11 to} R ¹⁴ may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Represents an aromatic hydrocarbon group, or aromatic hydrocarbon group which may have a substituent,
a and b are independently integers of 0 to 4, respectively.
c1 and c2 are independently integers of 1 to 3, respectively.
d1 and d2 are independently integers of 0 to 4, respectively.
When ^{there are a plurality of R 1} , R ² , R ³ , and R ⁴ in the repeating unit, R ¹ , R ² , R ³ , and R ⁴ may be the same or different. ) The polymer according to any one of claims 1 to 4, further comprising a repeating unit represented by any of the following (3) -1 to (3) -3.

(In equations (3) -1 to (3) -3,
Ar ⁷ has an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent independently in each repeating unit. It represents a divalent group in which a plurality of aromatic heterocyclic groups which may have a good aromatic hydrocarbon group or a substituent are directly or via a linking group are linked.
X, R ¹ , R ² , R ³ , R ⁴ , a, b, c1, c2, d1, and d2 are the same as those in the above formulas (2) -1 to (2) -3, respectively. ) The polymer according to any one of claims 1 to 5, wherein the polymer has a crosslinkable group as a substituent. The polymer according to any one of claims 1 to 6, wherein the polymer has a weight average molecular weight (Mw) of 10,000 or more and a dispersity (Mw / Mn) of 3.5 or less. .. A composition for an organic electroluminescent device containing the polymer according to any one of claims 1 to 7. A method for manufacturing an organic electroluminescent device having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate.
Manufacture of an organic electroluminescent device including a film forming step of forming at least one of the layers constituting the organic layer by a wet film forming method using the composition for an organic electroluminescent device according to claim 8. Method. The claim that the organic layer has a hole injection layer and a hole transport layer, and at least one of the hole injection layer and the hole transport layer is a layer formed in the film forming step. 9. The method for manufacturing an organic electroluminescent device according to 9. The organic layer further has a light emitting layer and
The method for manufacturing an organic electroluminescent device according to claim 9, wherein the hole injection layer, the hole transport layer, and the light emitting layer are layers formed in the film forming step. The substrate has an anode, a cathode, and an organic layer between the anode and the cathode, and the organic layer is crosslinked with the polymer according to any one of claims 1 to 7 or the polymer. An organic electroluminescent device having a layer containing a polymer. The layer containing the polymer or the polymer crosslinked with the polymer is a hole transport layer, the organic layer further has a light emitting layer, and the light emitting layer is in contact with the hole transport layer. The organic electroluminescent element according to claim 12, wherein at least one of the materials contained in the light emitting layer contains a compound having a partial structure represented by the following formula (CzP).

The material contained in the light emitting layer containing the compound having a partial structure represented by the formula (CzP) is a host material having at least either hole transporting property or electron transporting property, or a light emitting material. 13. The organic electroluminescent element according to 13. The skeleton of the host material includes an aromatic structure, an aromatic amine structure, a triarylamine structure, a dibenzofuran structure, a naphthalene structure, a phenanthrene structure, a phthalocyanine structure, a porphyrin structure, a thiophene structure, a benzylphenyl structure, a fluorene structure, a quinacridone structure, and a triphenylene. Structure, carbazole structure, pyrene structure, anthracene structure, phenanthroline structure, quinoline structure, pyridine structure, pyrimidine structure, triazine structure, oxadiazole structure or imidazole structure, carbazole structure, dibenzofuran structure, triarylamine structure, naphthalene structure, phenanthrene structure The organic electric field light emitting element according to claim 14, which has any of the pyrene structures. The compound having a partial structure represented by the formula (CzP) contained in the light emitting layer is a low molecular weight compound represented by any of the following formulas (14) to (16), and the low molecular weight. The organic electroluminescent element according to any one of claims 13 to 15, wherein the compound has a molecular weight of 5,000 or less.

(In equations (14) to (16),
A is a partial structure represented by the above formula (CzP) and may have a substituent.
B represents a single bond or any partial structure.
When there are a plurality of A's, they may be the same or different from each other.
When there are a plurality of B's, they may be the same or different from each other.
na, nb and nc independently represent integers of 1 or more and 5 or less. ) The organic electroluminescent device according to claim 16, wherein the low molecular weight compound represented by the formula (14) is a low molecular weight compound represented by the following formula (17).

(In the above formula (17)
Q represents either a nitrogen atom or a trivalent substituent represented by any of the following structural formulas (18-1) to (18-3).
Xb ¹ , Yb ¹ , and Zb ¹ each independently have a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms, which may have a substituent, or a carbon which may have a substituent. It represents a divalent heteroaromatic ring group of the number 3 to 30 ^{, and each of Xb 1} , Yb ¹ , and Zb ¹ may be the same or different when a plurality of them are present.
A is a partial structure represented by the above formula (CzP), may have a substituent, and a plurality of A may be the same or different from each other.
p12, q12, and r12 each independently represent an integer of 0 or more and 6 or less.
q13 and r13 independently represent 0 or 1, respectively.
^{Yb 2} when q13 is 0 ^{and Zb 2} when r13 is 0 are independently hydrogen atoms and monovalent hydrocarbon aromatic ring groups having 6 to 30 carbon atoms which may have a substituent. Alternatively, it represents a monovalent heteroaromatic ring group having 3 to 30 carbon atoms which may have a substituent.
When q13 is 1, Yb2 is a direct bond and is a direct bond.
When r13 is 1, Zb2 is a direct bond, and in the formulas (18-1) to (18-3), three * in one structural formula ^{are either Xb 1} , Yb ¹ , or Zb ¹ , respectively. Represents the bond position with the group. )

The organic electroluminescent device according to claim 16, wherein the low molecular weight compound represented by the formula (16) is a low molecular weight compound represented by the following formula (19).

(In the above formula (19),
Each of Xc ¹ and Yc ¹ independently has a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent, or 3 to 30 carbon atoms which may have a substituent. Represents a divalent heteroaromatic ring group of
Each of Xc ² and Yc ² independently has a hydrogen atom, a hydrocarbon aromatic ring group having a monovalent number of 6 to 30 carbon atoms which may have a substituent, or a carbon number which may have a substituent. Represents a monovalent heteroaromatic ring group of 3 to 30
If there are a plurality of Xc ¹ and Yc ¹ , they may be the same or different.
A is a partial structure represented by the above formula (CzP) and may have a substituent.
s11 and t11 each independently represent an integer of 0 or more and 6 or less.
nc represents an integer of 1 or more and 5 or less. ) The organic electroluminescent device according to claim 17, wherein the low molecular weight compound represented by the formula (17) is a compound represented by any of the following formulas (17-1) to (17-6).

(In the above general formulas (17-1) to (17-6),
p12'represents an integer of 1 or more and 5 or less.
q12'and r12'independently represent integers of 0 or more and 5 or less.
p14 is 12,
q14 is 12 when q13 is 1, and does not exist when q13 is 0.
r14 is 12 when r13 is 1, does not exist when r13 is 0, and does not exist.
q15 and r15 are 4 or 5 independently, respectively.
R ³¹ and R ³² are independent hydrogen atoms or substituents, respectively.
Xb ¹ , Yb ¹ , Zb ¹ , q13, and r13 are the same as those in the above equation (17), respectively. ) The organic electroluminescent device according to claim 18, wherein the low molecular weight compound represented by the formula (19) is a compound represented by the following formula (19-1).

(In the above general formula (19-1),
R ³¹ is a hydrogen atom or a substituent and is
u11 represents 11 and represents
Xc ¹ , Yc ¹ , Xc ¹ , Yc ¹ , t11, and s11 are the same as those in the above formula (19), respectively. ) An organic EL display device comprising the organic electroluminescent device according to any one of claims 12 to 20. An organic EL lighting comprising the organic electroluminescent device according to any one of claims 12 to 20.

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