KR20210127956A - Polymers, organic electroluminescent devices, organic EL display devices and organic EL lighting - Google Patents

Abstract

그 식 중, G 는 치환기를 가지고 있어도 되는 방향족 탄화수소기, 치환기를 가지고 있어도 되는 방향족 복소 고리기, 또는 C 원자, N 원자, B 원자 혹은 P 원자를 나타내고, Ar² ∼ Ar⁴ 는, 각각 독립적으로, 치환기를 가지고 있어도 되는 2 가의 방향족 탄화수소기, 치환기를 가지고 있어도 되는 방향족 복소 고리기, 또는 치환기를 가지고 있어도 되는 방향족 탄화수소기 혹은 치환기를 가지고 있어도 되는 방향족 복소 고리기가 직접 혹은 연결기를 개재하여 복수 개 연결된 2 가의 기를 나타내고, Ar⁵ 는 치환기를 가지고 있어도 되는 방향족 탄화수소기, 치환기를 가지고 있어도 되는 방향족 복소 고리기, 또는 치환기를 가지고 있어도 되는 방향족 탄화수소기 및 치환기를 가지고 있어도 되는 방향족 복소 고리기에서 선택되는 기가 직접 혹은 연결기를 개재하여 복수 개 연결된 1 가의 기를 나타내고, Ar⁶ 은 수소 원자 또는 치환기를 나타낸다. Ar¹ 중의 "-*" 가 식 (1) 중 G 와의 결합 위치이다.An object of the present invention is to provide a polymer having high hole injection and transport ability and high durability, and a composition for an organic electroluminescent device containing the polymer, and provides an organic electroluminescent device with high luminance and a long driving life It makes it a subject, and also makes it a subject to provide the organic electroluminescent element with a low driving voltage and a long lifetime.
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, and Ar ² to Ar ⁴ are each independently , a divalent 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 or an aromatic heterocyclic group which may have a substituent is linked directly or through a linking group represents a divalent group, and 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 which may have a substituent and an aromatic heterocyclic group which may have a substituent. A plurality of monovalent groups linked directly or through a linking group are represented, and Ar ⁶ represents a hydrogen atom or a substituent. "-*" in Ar ¹ is a bonding position with G in formula (1).

Description

Polymers, organic electroluminescent devices, organic EL display devices and organic EL lighting

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 using organic electroluminescent elements, such as organic electroluminescent lighting and organic electroluminescent display, are put to practical use. Since the organic electroluminescent element has a low applied voltage, low power consumption, and can emit light in three primary colors, application to small and medium-sized displays typified by mobile phones and smart phones as well as large display monitors is starting.

An organic electroluminescent device is manufactured by laminating|stacking a plurality of layers, such as a light emitting layer, a charge injection layer, and a charge transport layer. Currently, many of the organic electroluminescent devices are manufactured by vapor-depositing organic materials under vacuum, but in the vacuum vapor deposition method, the vapor deposition process becomes complicated and productivity is inferior. In the organic electroluminescent device manufactured by the vacuum deposition method, it is very difficult to enlarge the panel of lighting or display.

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-sized display or lighting. Since the wet film forming method has the advantage of being able to easily form a stable layer compared to the vacuum vapor deposition method, mass production of displays and lighting devices and application to large devices are expected.

An advantage of the wet film forming method over the vacuum vapor deposition method is that more material species can be used for one layer. In the vacuum deposition method, it becomes difficult to control the deposition rate uniformly as the material species increases, whereas in the wet film formation method, as long as each material is dissolved in the organic solvent even when the material species increases, an ink with a constant composition ratio can be created.

However, since the wet film formation method is difficult to laminate, the driving stability is inferior compared with the device by the vacuum deposition method, and it is the present situation that, with the exception of some, it has not reached a practical level.

Then, in order to perform lamination|stacking by the wet film-forming method, the charge-transporting polymer which has a crosslinkable group is desired, and the development is made|formed. For example, in Patent Documents 1 to 3, an organic electroluminescent device containing a polymer having a specific repeating unit and laminated by a wet film forming method is disclosed.

Patent Documents 4 and 5 disclose a hole injection and transport 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 a polymer.

In Patent Document 6, it is described that in a polymer having a triarylamine repeating unit, it is preferable to contain a fluorene ring in the main chain, and twist is generated by including a phenylene group having a substituent in the main chain of the polymer. to increase the triplet energy of the polymer.

Patent Document 7 discloses a compound in which a phenylene group having a substituent is linked between the 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 oligomer, and that the polymer layer does not dissolve when the light emitting layer is applied thereon.

Moreover, the polymer which has a carbazole structure in the side chain structure of the polymer which has an arylamine structure is disclosed by patent documents 9-12. As for patent documents 9-11, the thing which has only one carbazole of a side chain structure, as for patent documents 9 and 12, carbazole of a side chain structure is couple|bonded with the nitrogen atom of the amine of a principal chain directly, patent document 12 A structure having two carbazoles in the side chain structure is disclosed.

International Publication No. 2009/123269 Japanese Patent Laid-Open No. 2013-045986 International Publication No. 2013/191088 Japanese Laid-Open Patent Publication No. 2016-084370 Japanese Patent Laid-Open No. 2017-002287 Japanese Patent Publication No. 2007-520858 Japanese Patent Publication No. 2013-531658 Japanese Patent Laid-Open No. 2010-034496 International Publication No. 2011/099531 International Publication No. 2016/031639 International Publication No. 2009/110360 International Publication No. 2008/126393

However, in the prior art, it cannot be said that it is sufficient in the point of the performance of an organic electroluminescent element with respect to illumination and a display use, and further reduction of a drive voltage and improvement of a drive life were calculated|required.

These elements described in Patent Documents 1 to 3 have a problem that the luminance is low and the driving life is short. Therefore, the improvement of the charge injection/transport ability and durability of a charge-transporting material is calculated|required.

The polymers described in Patent Documents 4 and 5 have low excitation singlet energy level (S ₁ ) and triplet excitation energy level (T ₁ ) because they have diffusion of a π-conjugated system in the main chain, and the luminescent material and the luminescent exciton There is a problem in that luminous efficiency is lowered due to extinction caused by energy transfer. Therefore, a charge-transporting material having a high _{S 1} level and a _{high T 1 level is required.}

In Patent Document 6, F8-TFB (fluorene + triphenylamine type) is described in Examples as an arylamine polymer containing a fluorene ring in the main chain, but F8-TFB is between the nitrogen atom of fluorene and amine. Since the phenylene of the phenylene is not twisted because it does not have a substituent, there is a problem that the electron durability is inferior because the LUMO is diffused to the vicinity of the nitrogen atom of the amine.

Since the compound disclosed by patent document 7 does not contain a fluorene ring or a carbazole structure in a principal chain, there exists a problem that 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 polymer disclosed in Patent Documents 9 to 12 is not a copolymer containing an aromatic ring twisted in the main chain, fluorene or carbazole, and an aromatic ring without twist, the durability of the device is insufficient as will be described later. did.

The present invention is to provide a polymer having high hole injection and transport ability and high durability, and a composition for an organic electroluminescent device containing the polymer, and a low driving voltage, high luminance, that is, high luminous efficiency, and a long driving life. A first object is to provide an elongated organic electroluminescent device.

Another object of the present invention is to provide an organic electroluminescent device having a low driving voltage and a long lifespan.

MEANS TO SOLVE THE PROBLEM This inventor earnestly studied, and came to complete this invention. That is, the 1st summary of this invention can solve the said 1st subject by using the polymer which has a specific structure containing a carbazole structure in a side chain. A second aspect 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 has a hole transport layer and a light emitting layer adjacent to the hole transport layer, The hole transport layer contains a polymer having a specific structure including the carbazole structure in the side chain, and further, the material contained in the hole transport layer and the material contained in the light emitting layer both have a specific structure having a carbazole ring as a partial structure. By containing a material, the performance of an organic electroluminescent element improves, and the said 1st subject can be solved. A third aspect 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 has a hole transport layer and a light emitting layer adjacent to the hole transport layer, A material in which the hole transporting layer contains another polymer having a specific structure including a carbazole structure in the side chain, and the material contained in the hole transporting layer and the material contained in the light emitting layer both have a specific structure having a carbazole ring as a partial structure By containing, the performance of an organic electroluminescent element is improved, and the said 2nd subject can be solved.

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).

[Formula 1]

(in formula (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 are each independently a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic ring which may have a substituent represents a divalent group in which a plurality of groups are linked directly or through a linking group,

Ar ⁵ is a group selected from the aromatic hydrocarbon group which may have a substituent, the aromatic heterocyclic group which may have a substituent, or the aromatic hydrocarbon group which may have a substituent and the aromatic heterocyclic group which may have a substituent directly or through a linking group to represent a plurality of linked monovalent groups,

Ar ⁶ represents a hydrogen atom or a substituent. "-*" in Ar ¹ represents a bonding position with G in formula (1).)

[2] The polymer according to [1], wherein G is an N atom.

[3] The ^{polymer according to [1] or [2], wherein Ar 5} is any of the following a-1 to e-4.

[Formula 2]

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

[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.

[Formula 3]

(in Formula (2)-1 to Formula (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, or an aralkyl group which may have a substituent,

R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aralkyl group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent ,

a and b are each independently an integer of 0 to 4,

c1 and c2 are each independently an integer of 1 to 3;

d1 and d2 are each independently an integer of 0 to 4;

When there are ^two or more ^{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.)

[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.

[Formula 4]

(in formulas (3)-1 to (3)-3,

Ar ⁷ is independently 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 or an aromatic heterocyclic ring which may have a substituent in each repeating unit represents a divalent group in which a plurality of groups are linked directly or through a linking group,

X, R ¹ , R ² , R ³ , R ⁴ , a, b, c1, c2, d1, and d2 are the same as each of the formulas (2)-1 to (2)-3 above.)

[6] The polymer according to any one of [1] to [5], wherein the polymer has a crosslinkable group as a substituent.

[7] The polymer according to any one of [1] to [6], wherein the polymer has a weight average molecular weight (Mw) of 10,000 or more and a degree of dispersion (Mw/Mn) of 3.5 or less.

[8] A composition for an organic electroluminescent device comprising 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, the method comprising:

A method for manufacturing an organic electroluminescent element, comprising 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 element according to [8].

[10] The organic electroluminescent device manufacturing method according to [9], wherein 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.

[11] The organic layer further 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] On a substrate, an anode, a cathode, and an organic layer between the anode and the cathode, and the organic layer contains the polymer according to any one of [1] to [7] or a polymer in which the polymer is crosslinked. An organic electroluminescent device having a layer.

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

[Formula 5]

[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 either hole transport property or electron transport property, or a light emitting material as described in [13]. Organic electroluminescent device.

[15] The skeleton of the host material is 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 structure, 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, The organic electroluminescent device according to [14], which has any of a carbazole structure, a dibenzofuran structure, a triarylamine structure, a naphthalene structure, a phenanthrene structure, and a pyrene structure.

[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 the molecular weight of the low molecular weight compound is 5,000 or less , The organic electroluminescent device according to any one of [13] to [15].

[Formula 6]

(in formulas (14) to (16),

A is a partial structure represented by the said formula (CzP), and may have a substituent.

B represents a single bond or an arbitrary partial structure.

When two or more A's exist, they may be same or mutually different.

When two or more B's exist, they may be same or mutually different.

na, nb, and nc each independently represent an integer of 1 or more and 5 or less.)

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

[Formula 7]

(in the above formula (17),

Q represents a nitrogen atom or any of the trivalent substituents represented by any of the following structural formulas (18-1) to (18-3),

Xb ¹ , Yb ¹ , and Zb ¹ each independently represents a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent or a divalent heteroaromatic ring group having 3 to 30 carbon atoms which may have a substituent, Xb ¹ , Yb ¹ , and Each of Zb ¹ may be the same or different when two or more exist,

A is a partial structure represented by the above formula (CzP), may have a substituent, and A plurality of A may be the same as 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 each independently represent 0 or 1,

^{Yb 2} when q13 is 0 and Yb 2 when r13 is 0 Zb ² each independently represents a hydrogen atom, a monovalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent, or a monovalent heteroaromatic ring group having 3 to 30 carbon atoms which may have a substituent;

When q13 is 1, Yb ² is a direct bond,

When r13 is 1 Zb ² is a direct bond,

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

[Formula 8]

[18] The organic electroluminescent device according to [16], wherein the low-molecular compound represented by the formula (16) is a low-molecular compound represented by the following formula (19).

[Formula 9]

(in the above formula (19),

Xc ¹ and Yc ¹ each independently represent a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent, or a divalent heteroaromatic ring group having 3 to 30 carbon atoms which may have a substituent;

Xc ² and Yc ² each independently represent a hydrogen atom, an optionally substituted monovalent C6-C30 hydrocarbon aromatic ring group, or optionally a C3-C30 monovalent heteroaromatic cyclic group;

Each of Xc ¹ and Yc ¹ may be the same or different when there is a plurality of them,

A is a partial structure represented by the 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.)

[19] The organic electroluminescent device according to [17], wherein the low-molecular compound represented by the formula (17) is a compound represented by any of the following formulas (17-1) to (17-6).

[Formula 10]

[Formula 11]

(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' each independently represent an integer of 0 or more and 5 or less,

p14 is 12,

q14 is 12 when q13 is 1 and is absent when q13 is 0,

r14 is 12 when r13 is 1, does not exist when r13 is 0,

q15 and r15 are each independently 4 or 5;

R ³¹ and R ³² are each independently a hydrogen atom or a substituent,

Xb ¹ , Yb ¹ , Zb ¹ , q13 and r13 are each the same as in the above formula (17).)

[20] The organic electroluminescent device according to [18], wherein the low-molecular compound represented by the formula (19) is a compound represented by the following formula (19-1).

[Formula 12]

(In the above general formula (19-1),

R ³¹ is a hydrogen atom or a substituent,

u11 represents 11,

Xc ¹ , Yc ¹ , Xc ¹ , Yc ¹ , t11 , and s11 are each the same as in the above formula (19).)

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

[22] Organic EL lighting comprising the organic electroluminescent device according to any one of [12] to [20].

ADVANTAGE OF THE INVENTION According to this invention, a high hole injection-transport ability and high durability can provide the polymer and the composition for organic electroluminescent elements containing the polymer. In addition, an organic electroluminescent device having a low driving voltage, high luminous efficiency, and a long driving life can be provided.

The reason why the polymer which is one Embodiment of this invention exhibits the said effect is considered as follows.

The polymer contained in the hole transport layer transports 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 as the counter electrode seeped into the hole transport layer. Since many hole-transporting materials have low electron durability, this electron becomes a cause of decomposing|disassembling a polymer. In particular, in a polymer in which the main chain transports holes, typified by 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 a side chain and a principal chain are close as one of the factors which inhibit the improvement of the electronic durability of a polymer. In this invention, the solution of the said problem was attempted by setting it as the structure in which the principal chain which transports a hole does not easily receive an electron. ^{In a structure having two or more aromatic rings or aromatic heterocycles (Ar 4} , Ar ⁵ ) at the 9-position of carbazole as shown in the formula (1), the electron withdrawing property of the conjugated group extended from the 9-position of carbazole Since this is high, electrons are distributed on the terminal side of the side chain. In the polymer which concerns on the following embodiment, it is easy to receive an electron from a side chain rather than a main chain, and the carbazole structure of a side chain by the carbazole structure of a side chain being separated from the main chain of the amine vicinity which is inferior in electron durability moderately. Since electron durability is high, it is thought that the electronic durability as a polymer is improved. In addition, this effect as between the main chain and the carbazole of the side chain having an aromatic ring or aromatic heterocyclic rings (Ar ³⁾ is considered to be large.

Moreover, by distributing electrons to the terminal side of a side chain, the ratio which the hole transported via a main chain hops to the side chain side can be lowered|hung, and it is thought that the positive hole injection and transport ability is high.

It is preferable that a fluorene ring or a carbazole ring is contained in the main chain of the polymer of this embodiment, and in this case, it is preferable that a phenylene group couple|bonds at the 2, 7 position of these fluorene ring or carbazole ring. When the phenylene group is bonded to the 2,7 position of the fluorene ring or the carbazole ring, the fluorene ring or the carbazole ring is electrically more stable. In particular, it is considered that the electronic durability is improved and the device driving life is prolonged. At this time, when the phenylene ring has a substituent, the surface of the phenylene group having the substituent is more twisted with respect to the surface of the adjacent fluorene ring or carbazole ring because of steric hindrance by the substituent. In this case, since it has a main chain structure in which diffusion of the π-conjugated system is inhibited by steric hindrance of the substituent, there is a property that the _{excitation singlet energy level (S 1} ) and the excitation triplet energy level (T _{1 ) are high,} Since quenching due to energy transfer from light-emitting excitons is suppressed, the luminous efficiency is excellent.

Moreover, when the phenylene group of the main chain of the polymer of this embodiment has a substituent, the surface of the phenylene group which has a substituent is adjacent to a phenylene group, a bivalent fluorene group, or a divalent carboxyl group due to steric hindrance of a substituent. While it becomes a more twisted arrangement with respect to the plane of the bazole group, crystallization is difficult to occur due to steric hindrance by a substituent, and the singlet excitation energy level (S ₁ ) and the triplet excitation energy level (T ₁ ) are high. it is preferable to have

In addition, since it has a main chain structure in which diffusion of the π-conjugated system is inhibited by containing a structure alternately bonding with phenylene and oxygen atoms in the main chain of the polymer of the present embodiment, the excitation singlet energy level (S ₁ ) and the excitation Since there is a property that the triplet energy level (T ₁ ) is high, quenching due to energy transfer from light-emitting excitons is suppressed, the luminous efficiency is excellent.

In an organic electroluminescent element, if the energy level difference between each organic layer is not appropriate, carrier injection to a light emitting layer will become difficult, and a drive voltage will rise. Alternatively, it is considered that carrier leakage from the light emitting layer to the adjacent layer tends to occur and the device efficiency is lowered.

On the other hand, a charge transport material having an energy level higher than that of excitons of the light emitting material in the light emitting layer as in the present embodiment has a high effect of confinement of excitons of the light emitting material and is preferable.

Moreover, the layer obtained by wet film-forming using the composition for organic electroluminescent elements containing the polymer of this embodiment does not generate|occur|produce a crack etc. and is flat. As a result, the organic electroluminescent element which is one of embodiment of this invention which has the layer has high luminance and has a long drive life.

Moreover, since the polymer of this embodiment is excellent in electrochemical stability, the element containing the layer formed using the polymer is a flat panel display (for example, for OA computers or wall-mounted television), an in-vehicle display element, Applications are conceivable for mobile phone displays, light sources utilizing the characteristics of surface illuminators (for example, light sources for copiers, backlight light sources for liquid crystal displays and instruments), display panels, and signs, and their technical value is great. will be.

Moreover, since the organic electroluminescent element in 2nd and 3rd summary contains the material which has a specific structure which has carbazole as a partial structure in both a hole transport layer and a light emitting layer, the electric charge at the interface of a hole transport layer and a light emitting layer. It is easy to send and receive data, and it is possible to drive at a lower voltage than before. In addition, since electric charges are easily exchanged at the two-layer interface and electric charges are difficult to accumulate, quenching is suppressed, and an element with higher efficiency and longer drive life than before is possible.

Moreover, the organic electroluminescent element which concerns on embodiment of this invention can be produced by the wet film-forming method.

Moreover, since the organic electroluminescent element which concerns on embodiment of this invention is excellent in electrochemical stability, the element containing the layer formed using said polymer is a flat panel display (For example, for OA computers, or wall-mounted) Television), in-vehicle display devices, light sources that take advantage of the characteristics of cell phone displays and surface illuminants (for example, light sources for copiers, backlight light sources for liquid crystal displays and instruments), display panels, signs, etc., and their technical value is a big

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the cross section which shows the structural example of the organic electroluminescent element which concerns on this embodiment.
Fig. 2 is a diagram showing an electronic state of an electron polymerization unit 1 in an Example (a halftone image).
Fig. 3 is a diagram showing an electronic state of an electron polymerization unit 2 in an Example (a halftone image).
Fig. 4 is a diagram showing electronic states of electron polymerization units 3 to 5 in Examples (middle tone image).

Hereinafter, an organic electroluminescent element according to an embodiment of the present invention, an organic EL display device having the organic electroluminescent element, and an organic EL lighting embodiment will be described in detail, but the following description is an implementation of the present invention It is an example (representative example) of an aspect, and this invention is not specific to these content, unless it deviates from the summary.

In addition, in this specification, the numerical range shown using "-" means a range including the numerical value described before and after "-" as a lower limit and an upper limit, and "A-B" means that it is A or more and B or less. it means.

In addition, in this specification, "independently" used when describing two or more objects together is used in the meaning that these two or more objects may be same or different.

<Embodiment related to the first summary>

<Polymer>

The polymer of embodiment which concerns on 1st summary is a polymer containing the structure shown by following formula (1). In this specification, this polymer is also called polymer 1.

[Formula 13]

In formula (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 are each independently a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic ring which may have a substituent represents a divalent group in which a plurality of groups are linked directly or through a linking group,

Ar ⁵ represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a monovalent group in which a plurality of aromatic hydrocarbon groups or aromatic heterocyclic groups which may have a substituent are linked directly or through a linking group;

Ar ⁶ represents a hydrogen atom or a substituent.

In addition, ^{"-*" in Ar 1} is a site (binding site) bonding to G in formula (1).

(G)

In the repeating unit represented by the formula (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. From the viewpoint of excellent charge transport properties, LUMO distributed at the 9th position of the carbazole ring and HOMO distributed in the main chain are localized, G is a benzene ring which may have a substituent, a triazine ring which may have a substituent, a substituent The fluorene ring which may have, the spirofluorene ring which may have a substituent, and the carbazole ring which may have a substituent are preferable, and the structure shown by following Scheme 1 is more preferable. In addition, the following structure may have a substituent. In addition, in the figure, "-*" represents a bonding position with ^{Ar 3 .}

[Formula 14]

It is preferable to use any of the substituent group Z mentioned later, a C7-40 aralkyl group, or a C4-C37 heterocyclic aralkyl group as a substituent which you may have, or a combination thereof. Among them, in terms of electron durability (simply also referred to as "durability"), it is the same or different each time it appears, and is an alkyl group having 1 to 24 carbon atoms, an aralkyl group having 7 to 40 carbon atoms, or a heterocyclic ring having 3 to 37 carbon atoms. It is preferable that they are an aralkyl group, a C10-C24 arylamino group, a C6-C36 aromatic hydrocarbon group, or a C3-C36 aromatic heterocyclic group,

It is more preferably an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aralkyl group having 3 to 27 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, or an aromatic heterocyclic group having 3 to 24 carbon atoms. ,

It is more preferable that it is a C6-C24 aryl group.

From the viewpoint of charge transport properties, it is the same or different each time it appears, and it is preferably an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic heterocyclic group having 3 to 24 carbon atoms, and is preferably a phenyl group, a naphthyl group, a fluorenyl group, or a carba group. More preferably, they are a zolyl group, an indolocarbazolyl group, an indenocarbazolyl group, or an indenofluorenyl group.

Moreover, it is preferable that G is an N atom (nitrogen atom) at the point excellent in charge-transporting property.

(Ar ² , Ar ³ , Ar ⁴ )

In the repeating unit represented by the formula (1), Ar ² to Ar ⁴ each independently represent a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or a substituent The aromatic hydrocarbon group which may have or the aromatic heterocyclic group which may have a substituent represents the divalent group connected in plurality directly or via a coupling 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, a chrysene ring and a divalent group of a 6-membered monocyclic ring or a 2- to 5-condensed ring, such as a ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, or a divalent group in which a plurality of these are linked.

When two or more said bivalent groups are connected, 2-10 connected divalent groups are mentioned, It is preferable that it is 2-5 connected divalent group.

The aromatic heterocyclic group preferably has 3 or more and 60 or less carbon atoms, specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and an oxadia ring. sol ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, Benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenane A monovalent group of 5 to 6 membered ring or a divalent group of a 2 to 4 condensed ring, such as a triidine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, or 2 these are connected in plurality You can pick up the flag of the family.

When two or more said bivalent groups are connected, 2-10 connected divalent groups are mentioned, It is preferable that it is 2-5 connected divalent group.

As a divalent group in which a plurality of aromatic hydrocarbon groups which may have a substituent or aromatic heterocyclic group which may have a substituent are connected directly or via a linking group, the same group may be a plurality of connected contributions, or a plurality of different groups may be connected.

When two or more said bivalent groups are connected, 2-10 connected divalent groups are mentioned, It is preferable that it is 2-5 connected divalent group.

Ar ² is one or more groups selected from the divalent aromatic hydrocarbon group which may have a substituent and the divalent aromatic heterocyclic group which may have a substituent from the point of excellent charge transport property and excellent durability, either directly or via a linking group It is preferable that it is a divalent group bonded together, and an oxygen atom or a carbonyl group is preferable as the linking group. From the viewpoint of improving hole transport properties, the group directly bonded to the nitrogen atom is preferably an aromatic hydrocarbon group which may have a substituent, more preferably a phenylene group which may have a substituent or a divalent fluorene group which may have a substituent, The phenylene group which may have a substituent is especially preferable. A fluorene ring or a carbazole ring is preferably bonded to the phenylene ring directly bonded to the nitrogen atom, and between the phenylene ring directly bonded to the nitrogen atom and the fluorene ring or the carbazole ring, 1 or A structure in which a plurality of phenylene groups are connected is also preferable. Moreover, the structure in which the oxygen atom or the carbonyl group is connected between the phenylene rings is also preferable.

The substituent Ar ² may have is the same as the substituent which may be included when G is an aromatic hydrocarbon group or an aromatic heterocyclic group.

Ar ³ is preferably a group in which 1 to 6 divalent aromatic hydrocarbon groups which may have a substituent are linked from the viewpoint of localization of LUMO distributed in the 9th position of the carbazole ring and HOMO distributed in the main chain, even if it has a substituent A group in which 2 to 4 divalent aromatic hydrocarbon groups used is more preferably a group in which 2 to 4 phenylene rings which may have a substituent are linked, more preferably a group in which 1 to 4 phenylene rings which may have a substituent are linked, and a ratio in which two phenylene rings which may have a substituent are linked Phenylene is particularly preferred.

The substituent Ar ³ may have is the same as the ^{above substituent for Ar 2 .}

Ar ⁴ is preferably a group in which one or more divalent aromatic hydrocarbon groups, which may be the same or different, are linked from the viewpoint of excellent charge transportability and excellent durability, and the divalent aromatic hydrocarbon group may have a substituent. As described above, ^{from the viewpoint of distribution of LUMO in the structure represented by -Ar 4} -Ar ⁵ , it is preferable to have a large number of connections, but from the viewpoints of charge transport properties and film stability, it is preferable that the number of connections is small. When connecting, 2 or more and 10 or less are preferable, 6 or less are more preferable, and 3 or less is especially preferable from a viewpoint of stability of a film|membrane. As a preferable aromatic hydrocarbon structure, they are a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring, More preferably, they are a benzene ring and a fluorene ring. As the group linked to a plurality of groups, a group in which 1 to 4 phenylene rings which may have a substituent are linked, or a group in which a phenylene ring which may have a substituent and a fluorene ring which may have a substituent are linked is preferable. From the viewpoint of diffusion of LUMO, biphenylene in which two phenylene rings which may have a substituent are linked is particularly preferable.

As the substituent which may have an Ar ^4, it is possible to use either one, or a combination of substituent groups Z, which will be described later. From a viewpoint of inhibiting diffusion of LUMO, it is preferable that it is other than an N-carbazolyl group, an indolocarbazolyl group, and an indenocarbazolyl group, As a more preferable substituent, they are a phenyl group, a naphthyl group, and a fluorenyl group. . Moreover, it is also preferable that it does not have a substituent.

(Ar ⁵ )

Ar ⁵ is a group selected from 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 and an aromatic heterocyclic group which may have a substituent, directly or a linking group It is a monovalent group connected in plurality through. When two or more connected, divalent group connected 2-10 is mentioned, It is preferable that it is a divalent group connected 2-5. An aromatic hydrocarbon, aromatic heterocyclic ring, either aromatic hydrocarbon in the Ar ² Ar ~ ⁴ structure, it is possible to use one Cain structure as an aromatic heterocyclic ring structure. It is preferable to have a structure shown by any one of following scheme 2 at the 9th-position of the carbazole ring specified by ^Ar<1> of Formula (1). Furthermore, from the viewpoint of distributing the LUMO of molecules, a-1 to a-4, b-1 to b-9, c-1 to c-5, d-1 to d-16, and e1 to e4 are selected. structure is preferred. Moreover, from a viewpoint of promoting diffusion of LUMO of a molecule|numerator by having an electron withdrawing group, it is selected from a-1 to a-4, b-1 to b-9, d-1 to d-13, and e1-e4. structure is preferred. Further, a structure selected from a-1 to a-4, d-1 to d-13, and e1 to e4 is preferable from the viewpoint of the effect of confinement of excitons formed in the light emitting layer having a high triplet level. Moreover, it is also preferable that it is a phenyl group. Moreover, you may have a substituent in these structures. In addition, "-*" in the drawing ^{indicates a bonding position with Ar 4} , and when there are a plurality of “-*”, any one indicates a bonding position with ^{Ar 4 .}

[Formula 15]

As ^{a substituent which Ar 5} may have, any of the substituent group Z mentioned later or a combination thereof can be used. From the viewpoints of durability and charge transport properties, it is preferably selected from the same substituents as the substituents that ^{Ar 4 may have.}

(Ar ⁶ )

Ar ⁶ represents a hydrogen atom or a substituent. When Ar ⁶ is a substituent, there is no particular limitation, but it is preferably an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. As a preferable structure, it is the same as the aromatic hydrocarbon structure and aromatic heterocyclic structure ^{mentioned in the said Ar 2} - Ar ^{4, and it is a monovalent|monohydric structure.}

When Ar ⁶ is a substituent, it is preferably bonded to the 3-position of carbazole from the viewpoint of improving durability. Ar ⁶ is preferably a hydrogen atom from the viewpoint of easiness of synthesis and charge transport properties. Ar ⁶ is preferably an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and more preferably an aromatic hydrocarbon group which may have a substituent, from the viewpoint of improving durability and charge transport properties.

In the case where Ar ⁶ is an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, the substituent is the same as the substituent listed in the substituent group Z described below or the crosslinkable group described below, and preferred substituents are also the same, The substituents which these substituents may further have are also the same. Moreover, from a viewpoint of insolubilization, it is preferable as a substituent that at least 1 mentioned later crosslinkable group is included.

[Preferred repeating unit structure]

Among them, the formula (1) is more preferably a repeating unit represented by any of the following formulas (2)-1 to (2)-3.

[Formula 16]

In formula (2)-1 to formula (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, or an aralkyl group which may have a substituent,

R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aralkyl group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent ,

a and b are each independently an integer of 0 to 4,

c1 and c2 are each independently an integer of 1 to 3;

d1 and d2 are each independently an integer of 0 to 4;

When there are ^two or more ^{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 -C(R ⁵ )(R ⁶ )-, -N(R ⁷ )-, or -C(R ¹¹ )(R ¹² )-C(R ¹³ )(R ¹⁴ )-. From the viewpoint of durability, they are preferably -C(R ⁵ )(R ⁶ )-, -N(R ⁷ )-.

(R ¹ and R ² )

^{It is preferable that R<1>} and R<^2> in the repeating unit represented by said Formula (2)-1 - Formula (2)-3 are each independently a linear, branched or cyclic alkyl group which may have a substituent. Although carbon number of an alkyl group is not specifically limited, In order to maintain the solubility of a polymer, 1 or more and 6 or less are preferable, 3 or less are more preferable, It is still more preferable that they are 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. It is preferred that all R ¹ and R ² are the same group.

(R ³ and R ⁴ )

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

(R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ )

R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ are each independently an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aralkyl group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent desirable.

The alkyl group is not particularly limited, but a long one is preferable in order to tend to improve the solubility of the polymer, and a short one is preferable in order to improve the stability of the film and to improve the charge transport property, and has 1 or more carbon atoms, 24 The following are preferable, 12 or less are more preferable, 8 or less are still more preferable, 6 or less are especially preferable, 2 or more are more preferable, 3 or more are still more preferable, 4 or more are especially preferable. Moreover, each structure of a linear, branched or cyclic form may be sufficient.

Specifically, 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, n-octyl group, cyclohexyl group Actual machine, dodecyl group, etc. are mentioned.

Although the said alkoxy group is not specifically limited, Since there exists a tendency which can improve the solubility of a polymer, C1 or more and 24 or less are preferable, 12 or less are more preferable, 8 or less are still more preferable, 6 or less are especially preferable. and 2 or more are more preferable, 3 or more are still more preferable, and 4 or more are especially preferable.

Specifically, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, tert-butoxy group, hexyloxy group, etc. are mentioned.

Although the said aralkyl group is not specifically limited, Since there exists a tendency which can improve the solubility of a polymer, C5 or more and 60 or less are preferable, 40 or less are more preferable, 7 or more are more preferable, 10 or more are further Preferably, 12 or more are 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, 8-phenyl-1-n -octyl group, 4-phenylcyclohexyl group, etc. are mentioned.

Although it does not specifically limit as said aromatic hydrocarbon group, Since there exists a tendency which can improve the solubility of a polymer, C6 or more and 60 or less are preferable, 30 or less are more preferable, 24 or less are still more preferable, 14 or less is particularly preferred.

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, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, flu and monovalent groups of 6-membered rings, such as an orene ring, or monovalent groups of 2 to 5 condensed rings, or groups having 2 to 8 linked ring structures selected from these, preferably monocyclic or 2 to 4 or less linked groups .

From the viewpoint of improving charge transport properties 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, R ⁷ is more preferably an aromatic hydrocarbon group, and the preferred number of carbon atoms is As described above.

From the viewpoint of improving solubility and excellent charge transport properties, R ⁵ and R ⁶ are preferably an alkyl group having 3 or more and 8 or less carbon atoms or an aralkyl group having 9 or more and 40 or less carbon atoms.

The ^{alkyl group of R 1} to R ^{4 ,} the alkyl group 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. May have substituents, the preferred groups as R ⁵ ~ R ⁷ and R ¹¹ ~ R ¹⁴ an alkyl group, an aralkyl group and aromatic hydrocarbon group may be a crosslinking group to all groups, or later.

The ^{alkyl group of R 1} to R ^{4 ,} the alkyl group of R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ , the alkoxy group, the aralkyl group and the aromatic hydrocarbon group most preferably have no substituent from the viewpoint of lowering the voltage.

In addition, ^{the substituents R 5} to R ⁷ and R ¹¹ to R ¹⁴ may have are, from the viewpoint of improving the insolubility in a solvent when another layer is applied and laminated after forming the polymer of the present embodiment into a film. , It is preferable that it is a crosslinkable group mentioned later. ^{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 from the viewpoint of difficulty in interfering with the charge transport property, and at least one of ^{R 5} and R ^{6 is further} It is more preferable to have a crosslinkable group mentioned later as a substituent.

(a, b, c1, c2, d1 and d2)

In the repeating unit represented by the formulas (2)-1 to (2)-3, a and b each independently represent an integer of 0 to 4; Moreover, it is preferable that a+b is 1 or more. And, it is preferable that a and b are respectively 2 or less, and it is still more preferable that both a and b are 1.

In the repeating unit represented by the formulas (2)-1 to (2)-3, c1 and c2 are each independently an integer of 1 to 3, and d1 and d2 are each independently an integer of 0 to 4 . c1, c2, d1, and d2 are each preferably 2 or less, more preferably c1, c2, d1 and d2 are the same, more preferably c1, c2, d1, and d2 are all 1 or 2, It is particularly preferred that c1, c2, d1, and d2 are all 1.

In the repeating units represented by formulas (2)-1 to (2)-3, c1, c2, d1 and d2 are all 1, or c1, c2, d1, and d2 are all 2, and both a and b are When this is 2 or 1, it ^{is most preferable that R 1} and R ² are bonded at a position symmetrical to each other.

Here, the case where R ¹ and R ² are bonded at a position symmetrical to each other will be described by the following formula, taking the case where X = C in the above formula (2)-1 as an example. That is, it says that the bonding position of ^R<1> and R<^2> is symmetric with respect to the fluorene ring of a main chain in a following formula. At this time, 180 degree rotation about the main chain as an axis is regarded as the same structure. For example, in Formula (1a), R ^a and R ^b are symmetric, R ^a' and R ^b' are symmetric, and Formula (1a) and Formula (1b) are considered to have the same structure.

[Formula 17]

It is preferable to contain the repeating unit represented by Formula (2)-1 or Formula (2)-2 from a viewpoint of the durability or voltage reduction of the element at the time of using for an organic electroluminescent element.

[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, etc. a linear, branched, or cyclic alkyl group having usually 1 or more, preferably 4 or more, and usually 24 or less, preferably 12 or less carbon atoms;

For example, carbon number, such as a vinyl group, is 2 or more normally, 24 or less normally, Preferably it is 12 or less alkenyl group;

For example, carbon number, such as an ethynyl group, is 2 or more normally, 24 or less normally, Preferably it is 12 or less alkynyl groups;

For example, carbon number, such as a methoxy group and an ethoxy group, is 1 or more normally, 24 or less normally, Preferably it is 12 or less alkoxy groups;

For example, C4 or more, such as a phenoxy group, a naphthoxy group, a pyridyloxy group, C4 or more, Preferably it is 5 or more, Usually 36 or less, Preferably it is an aryloxy group or heteroaryloxy group;

For example, carbon number, such as a methoxycarbonyl group and an ethoxycarbonyl group, is 2 or more normally, It is 24 or less normally, Preferably it is 12 or less Alkoxycarbonyl group;

For example, carbon number, such as a dimethylamino group and a diethylamino group, is 2 or more normally, It is 24 or less normally, Preferably it is 12 or less dialkylamino group;

For example, carbon number, such as a diphenylamino group, a ditolylamino group, N-carbazolyl group, is 10 or more normally, Preferably it is 12 or more, Usually 36 or less, Preferably it is 24 or less diarylamino groups;

For example, carbon number, such as a phenylmethylamino group, is 7 or more normally, 36 or less normally, Preferably it is 24 or less arylalkylamino group;

For example, carbon number, such as an acetyl group and a benzoyl group, is 2 or more normally, It is 24 or less normally, Preferably it is 12 or less acyl group;

For example, Halogen atoms, such as a fluorine atom and a chlorine atom;

For example, carbon number, such as a trifluoromethyl group, is 1 or more normally, 12 or less normally, Preferably it is 6 or less haloalkyl group;

For example, carbon number, such as a methylthio group and an ethylthio group, is 1 or more normally, It is 24 or less normally, Preferably it is 12 or less alkylthio groups;

For example, C4 or more, such as a phenylthio group, a naphthylthio group, and a pyridylthio group, Preferably it is 5 or more, Usually 36 or less, Preferably it is 24 or less arylthio group;

For example, carbon number, such as a trimethylsilyl group and a triphenylsilyl group, is 2 or more normally, Preferably it is 3 or more, It is 36 or less normally, Preferably it is 24 silyl groups;

For example, carbon number, such as a trimethylsiloxy group and a triphenylsiloxy group, is 2 or more normally, Preferably it is 3 or more, Usually 36 or less, Preferably it is 24 or less siloxy groups;

cyano group;

For example, carbon number, such as a phenyl group and a naphthyl group, is 6 or more normally, 36 or less normally, Preferably it is 24 or less aromatic hydrocarbon groups;

For example, aromatic heterocyclic groups, such as a thienyl group and a pyridyl group, whose carbon number is usually 3 or more, Preferably it is 4 or more, and is 36 or less normally, Preferably it is 24 or less.

Among the substituent group Z described above, the alkyl group, alkoxy group, aromatic hydrocarbon group and aromatic heterocyclic group are preferable. It is more preferable not to have a substituent from a viewpoint of charge-transporting property.

Moreover, each substituent of the said substituent group Z may have a substituent further. As these substituents, the thing similar to the said substituent (substituent group Z), or the crosslinkable group mentioned later is mentioned. Preferably, it does not have an additional substituent, or it is a C6 or less alkyl group, a C6 or less alkoxy group, a phenyl group, or a crosslinkable group mentioned later. It is more preferable not to have an additional substituent from a viewpoint of charge-transporting property.

[end stage]

In this embodiment, a terminal group refers to the structure of the terminal part of a polymer formed with the end cap agent used at the time of completion|finish of polymerization of a polymer. The terminal group of the polymer of this embodiment is a hydrocarbon group normally. As a hydrocarbon group, from a viewpoint of charge-transporting property, C1-C60 is preferable, 1 or more and 40 or less are more preferable, 1 or more and 30 or less are still more preferable.

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, etc. a linear, branched, or cyclic alkyl group having usually 1 or more, preferably 4 or more, and usually 24 or less, preferably 12 or less carbon atoms;

For example, carbon number, such as a vinyl group, is 2 or more normally, 24 or less normally, Preferably it is 12 or less alkenyl group;

For example, carbon number, such as an ethynyl group, is 2 or more normally, 24 or less normally, Preferably it is 12 or less alkynyl groups;

For example, C6 or more, such as a phenyl group and a naphthyl group, is 36 or less normally 36 or less, Preferably it is an aromatic hydrocarbon ring group 24 or less;

can be heard

These hydrocarbon groups may further have a substituent, and, as for the substituent which may further have, an alkyl group or an aromatic hydrocarbon group is preferable, and when there are two or more substituents which you may have these further, they may couple|bond with each other and may form a ring.

Preferably, it is an alkyl group or an aromatic hydrocarbon group from a viewpoint of charge transport property and durability, More preferably, it is an aromatic hydrocarbon group.

[Availability Period]

It is preferable that the polymer of this embodiment has a soluble group for soluble expression with respect to a solvent. The soluble group in the present embodiment is a group having 3 to 24 carbon atoms, preferably a linear or branched alkyl group or alkylene group having 12 or less carbon atoms. Among these, an alkyl group, an alkoxy group, or an aralkyl group is preferable, for example, n-propyl group, 2-propyl group, n-butyl group, 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 R 1} to R ⁷ and R ¹¹ to R ¹⁴ have these structures, those groups are considered to be soluble groups. In addition, when the substituents in this embodiment satisfy|fill the conditions of the said soluble group, these substituents are considered as a soluble group.

(Number of Availability Periods)

It is preferable that there are many soluble groups which the polymer of this embodiment has from a point which becomes easy to obtain the polymer solution which can be used for the wet film-forming method. On the other hand, when another layer is formed by the wet film-forming method on the layer formed into a film, from the point with few film thickness reduction|decrease by a layer melt|dissolving in a solvent, it is preferable that there are few.

The number of soluble groups 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 in the polymer of the present embodiment is expressed in moles per 1 g of polymer, it is usually 4.0 mmol or less, preferably 3.0 mmol or less, more preferably 2.0 mmol or less, per 1 g of polymer, and Usually 0.1 mmol or more, Preferably it is 0.5 mmol or more.

When the number of soluble groups is within the above range, the polymer is easily dissolved in the solvent, and a composition containing a polymer suitable for the wet film forming method can be easily obtained. Moreover, since the soluble group density is moderate, since the poor solubility with respect to the organic solvent after heating solvent drying is sufficient, the multilayer laminated structure by the wet film-forming method becomes possible to form.

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, excluding the terminal groups from the polymer, and the structural formula.

In the case of Polymer 1 synthesized in Example 1 to be described below, in Polymer 1, the molecular weight of the repeating unit excluding the terminal group is an average of 767, and the soluble hexyl group has an average of 2 per repeating unit. it's a dog If this is calculated by simple proportionality, the number of soluble groups per 1 g of molecular weight is calculated to be 2.09 mmol.

[Formula 18]

[Crosslink]

The polymer of this embodiment may have a crosslinkable group as a substituent. The crosslinkable group in the polymer of this embodiment may exist in the repeating unit represented by Formula (1), and may exist in the repeating unit different from the repeating unit represented by Formula (1). In particular, it is preferable to have a crosslinkable group in ^{Ar 1 which is a side chain, since crosslinking reaction advances easily.}

By having a crosslinkable group, a big difference in solubility with respect to an organic solvent can be produced before and behind the reaction (poorly soluble reaction) which occurs by irradiation of a heat|fever and/or an active energy ray.

A crosslinkable group refers to a group which reacts with the group which comprises the other molecule|numerator located in the vicinity of the crosslinkable group by irradiation of a heat|fever and/or an active energy ray, and produces|generates a new chemical bond. In this case, the reactive group may have the same contribution as a crosslinkable group, or a different contribution may be sufficient as it.

The crosslinkable group is preferably a group containing a cyclobutene ring condensed to an aromatic ring or an alkenyl group bonded to an aromatic ring, and more preferably a group selected from the following crosslinkable group group T. It is preferable that the crosslinkable group is further substituted by the substituent which each said structure has.

(Crosslinked sexual organ group T)

The crosslinkable group group T is a structure shown below.

[Formula 19]

In the crosslinkable group 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 represents the integer of 1-4, q represents the integer of 1-5, r represents the integer of 1-7.

When p is 2 or more, a plurality of R ²⁴ may be the same or different, and adjacent R ²⁴ may be bonded to each other to form a ring.

When q is 2 or more, a plurality of R ²⁵ may be the same or different, and adjacent R ²⁵ may be bonded to each other to form a ring.

When r is 2 or more, some R ²⁶ may be 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 for 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, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, etc. are mentioned. More preferably, it is a methyl group or an ethyl group. When ^{the carbon number of R 21} to R ²⁶ is 6 or less, the crosslinking reaction is not sterically inhibited, and insolubilization of the film tends to occur.

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

Further, ^{examples of the aromatic hydrocarbon group which may have a substituent for Ar 21} and Ar ²² include, for example, a 6-membered monocyclic ring or 2- to 5-condensed ring having one free valence, such as a benzene ring and a naphthalene ring. have. Particularly preferred is a benzene ring having one free valence.

Ar ²² may be a contribution obtained by bonding two or more aromatic hydrocarbon groups which may have a substituent. As such a group, a biphenylene group, a terphenylene group, etc. are mentioned, The 4,4'- biphenylene group is preferable.

The ^{substituent Ar 21} , Ar ²² may have is the same as the substituent group Z described above.

As the crosslinkable group, a group that undergoes cyclization addition reaction such as an arylvinylcarbonyl group such as a cinnamoyl group, a benzocyclobutene ring having a monovalent free valence, and a 1,2-dihydrocyclobuta[a]naphthalene ring having a monovalent free valence , which is preferable in terms of further improving the electrochemical stability of the device.

Among the crosslinkable groups, since the structure after crosslinking is particularly stable, a cyclobutene ring condensed on an aromatic ring having a monovalent free valence, and a 1,2-dihydrocyclobuta[a]naphthalene ring having a monovalent free valence The containing group is preferable, and among them, a benzocyclobutene ring or a 1,2-dihydrocyclobuta[a]naphthalene ring having a monovalent free valence is more preferable, and has a monovalent free valency because of a low crosslinking reaction temperature A 1,2-dihydrocyclobuta[a]naphthalene ring is particularly preferred.

(Number of crosslinkable groups)

The crosslinkable group which the polymer of this embodiment has is fully insolubilized by bridge|crosslinking, and many things are preferable at the point which becomes easy to form another layer on it by the wet film-forming method. On the other hand, it is preferable that there are few crosslinkable groups at the point which a crack is hard to produce in the formed layer, an unreacted crosslinkable group is hard to remain, and an organic electroluminescent element becomes easy to become long life.

The crosslinkable group present in one polymer chain in the polymer of this embodiment becomes like this. Preferably it is 1 or more, More preferably, it is 2 or more, More preferably, it is 200 or less, More preferably, it is 100 or less.

In addition, the number of the crosslinkable groups which the polymer of this embodiment has can be represented by the number per 1000 molecular weight of a polymer.

When the number of crosslinkable groups of the polymer of the present embodiment is expressed as the number per 1000 molecular weight of the polymer, it is usually 3.0 or less, preferably 2.0 or less, more preferably 1.0 or less, and usually 0.01 per molecular weight of 1000. or more, preferably 0.05 or more.

When the number of crosslinkable groups is within the above range, cracks or the like are less likely to occur, and a flat film is easily obtained. Moreover, since the crosslinking density is moderate, there are few unreacted crosslinkable groups remaining in the layer after a crosslinking reaction, and it is hard to affect the lifetime of the element obtained.

Moreover, since the poor solubility with respect to the organic solvent after a crosslinking reaction is sufficient, it is easy to form the multilayer laminated structure in 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 and structural formula of the charged monomer at the time of synthesis, excluding the terminal groups from the polymer.

For example, in the case of Polymer 3 synthesized in Examples to be described later, in Polymer 3, the molecular weight of the repeating unit excluding the terminal group is 816 on average, and the number of crosslinkable groups is 0.138 per repeating unit. When this is calculated by simple proportionality, the number of crosslinkable groups per 1000 molecular weight is calculated to be 0.15 pieces.

[Formula 20]

[Content of repeat unit]

In the polymer of the present embodiment, the content of the repeating unit represented by the formula (1) is not particularly limited, but it is usually contained in the polymer at 50 mol% or more, preferably at 60 mol% or more, and at 70 mol% or more. It is more preferable, and it is especially preferable to contain 80 mol% or more. In the polymer of this embodiment, although the repeating unit may be comprised only with the repeating unit represented by Formula (1), for the purpose of balancing various performances when it is set as an organic electroluminescent element, it repeats different from Formula (1) You may have a unit, and in that case, content of the repeating unit represented by Formula (1) in a polymer is 95 mol% or more normally, Preferably it is 99 mol% or more.

[Other preferred repeating units which may be contained]

It is also preferable that the polymer of this embodiment further contains the repeating unit represented by any one of following (3)-1 - Formula (3)-3.

[Formula 21]

In formulas (3)-1 to (3)-3,

Ar ⁷ is independently 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 or an aromatic heterocyclic ring which may have a substituent in each repeating unit represents a divalent group in which a plurality of groups are linked directly or through a linking group,

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 each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aralkyl group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent ,

a and b are each independently an integer of 0 to 4,

c1 and c2 are each independently an integer of 1 to 3;

d1 and d2 are each independently an integer of 0 to 4;

When there are ^two or more ^{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 independently an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic ring which may have a substituent in each repeating unit. represents the 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, a chrysene ring and monovalent groups in which 6-membered monocyclic rings such as a ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, or a 2 to 5 condensed ring, or a plurality of these are connected.

When two or more said bivalent groups are connected, 2-10 connected divalent groups are mentioned, It is preferable that it is a 2-5 connected divalent group.

The aromatic heterocyclic group preferably has 3 or more and 60 or less carbon atoms, specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and an oxadia ring. sol ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, Benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenane and monovalent groups in which 5 to 6 membered monocyclic rings, 2 to 4 condensed rings, or a plurality of these are linked, such as triidine ring, benzoimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. have.

When two or more said bivalent groups are connected, 2-10 connected divalent groups are mentioned, It is preferable that it is a 2-5 connected divalent group.

Ar ⁷ is preferably an aromatic hydrocarbon group which may have a substituent from the viewpoint of excellent charge transport properties and excellent durability, and among them, a monovalent group of a benzene ring or fluorene ring which may have a substituent, that is, has a substituent The phenyl group or fluorenyl group which may have a substituent is more preferable, the fluorenyl group which may have a substituent is still more preferable, and the 2-fluorenyl group which may have a substituent is especially preferable.

There is no restriction|limiting in particular as a substituent which the aromatic hydrocarbon group of Ar<^7> or aromatic heterocyclic group may have, as long as the characteristic of the polymer of this embodiment is not reduced remarkably. Preferably, the group selected from the said substituent group Z or the said crosslinkable group is mentioned, An alkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group, or the said crosslinkable group is preferable, and an alkyl group is more preferable.

Ar ⁷ is preferably a fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms, particularly preferably a 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms, from the viewpoint of solubility in the application solvent. Further, a 9-alkyl-2-fluorenyl group in which an 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 an alkyl group is 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, solubility in a solvent and durability of the fluorene ring tend to improve. And when both the 9-position and the 9'-position are the fluorenyl groups substituted with the alkyl group, there exists a tendency for the solubility with respect to a solvent and the durability of a fluorene ring to improve further.

In addition, Ar ⁷ is preferred because it improves the water-insoluble to a solvent when it is, after forming the film, the laminated coating comprising the above crosslinking group.

From the viewpoint of insolubilization, the polymer preferably contains a repeating unit represented by formulas (3)-1 to (3)-3 containing at least one of the aforementioned crosslinkable groups as an additional substituent, and the crosslinking thereof It is preferable that the sexual group is further substituted with the substituent which the aromatic hydrocarbon group or aromatic heterocyclic group represented by Ar<^{7> may have.}

It is preferable to contain the repeating unit represented by Formula (3)-1 or Formula (3)-2 from a viewpoint of the durability or voltage reduction of the element at the time of using for an organic electroluminescent element.

[Molecular weight of polymer]

The weight average molecular weight (Mw) of the polymer of this embodiment is 3,000,000 or less normally, Preferably it is 1,000,000 or less, More preferably, it is 500,000 or less, More preferably, it is 200,000 or less, Especially preferably, it is 100,000 or less. Moreover, it is 10,000 or more normally, Preferably it is 20,000 or more, More preferably, it is 30,000 or more.

When the weight average molecular weight of a polymer is below the said upper limit, solubility with respect to a solvent is acquired and it exists in the tendency excellent in film-forming property. Moreover, when the weight average molecular weight of a polymer is more than the said lower limit, the fall of the glass transition temperature of a polymer, melting|fusing point, and vaporization temperature is suppressed, and heat resistance may improve. In addition, the insolubility with respect to the organic solvent of the coating film after a crosslinking reaction may be sufficient.

Moreover, the number average molecular weight (Mn) in the polymer of this embodiment is 2,500,000 or less normally, Preferably it is 750,000 or less, More preferably, it is 400,000 or less, Especially preferably, it is 100,000 or less. Moreover, it is 2,000 or more normally, Preferably it is 4,000 or more, More preferably, it is 8,000 or more, More preferably, it is 20,000 or more.

Moreover, the degree of dispersion (Mw/Mn) in the polymer of this embodiment becomes like this. Preferably it is 3.5 or less, More preferably, it is 2.5 or less, Especially preferably, it is 2.0 or less. In addition, since a dispersion degree is so good that a value is small, the lower limit is ideally 1. If the degree of dispersion of the polymer is equal to or less than the upper limit, purification is easy, and solubility in a solvent and charge transport ability are good.

Usually, the weight average molecular weight and number average molecular weight of a polymer are determined by SEC (size exclusion chromatography) measurement. In the SEC measurement, the elution time of the high molecular weight component is shorter, and the elution time is longer as the low molecular weight component. By converting to , a weight average molecular weight and a number average molecular weight are computed.

[Other repeat units]

The polymer of this embodiment may contain the repeating unit represented by Formula (4) or Formula (5) further from the point of charge-transporting property and durability. The repeating unit represented by the following formula (4) is a part of the repeating units represented by the formulas (1), (2)-1 to (2)-3, and (3)-1 to (3)-3. The structure of the repeating unit may match, but differ from them.

[Formula 22]

In formula (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 is a divalent aromatic hydrocarbon group which may have a substituent, a divalent 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 The plurality of groups used is a divalent group connected directly or through a linking group.

In formula (5),

Ar ¹⁰ is a divalent aromatic hydrocarbon group which may have a substituent, a divalent 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 A plurality of groups represents a divalent group in which a plurality of groups are linked directly or via a linking group.

(Ar ⁸ , Ar ⁹ and Ar ¹⁰ )

As the aromatic hydrocarbon group and aromatic heterocyclic group for ^{Ar 8} , Ar ⁹ and Ar ^{10 , Ar 8} is a group selected from the same group as the aromatic hydrocarbon group and aromatic heterocyclic group that ^{Ar 6} of formula (1) can take, , Ar ⁹ and Ar ¹⁰ represent a divalent group as a group selected from the same group as the aromatic hydrocarbon group and aromatic heterocyclic group which the formula (1) Ar ^{2 can take.} When two or more of these divalent groups are connected, 2-10 are similarly preferable and 2-5 are more preferable. The substituent which you may have is preferably the same group as the said substituent group Z or the said crosslinkable group.

[Preferred Polymer]

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

[Formula 23]

In each polymer of formula (6),

Ar ^T represents Ar ¹ or Ar ⁷ above, a plurality of Ar ^T in each polymer may be the same or different, and at least one ^{of Ar T} in each polymer represents ^{Ar 1 above,}

X, R ¹ , R ² , R ³ , and R ⁴ are the same as in the above formulas (2)-1 to (2)-3.

n and m represent the number of repetitions.

The polymer of another embodiment of the 1st summary of this invention is a polymer containing the structure shown by following formula (12) or following formula (13).

[Formula 24]

In formula (12),

G, Ar ² , Ar ⁴ , and Ar ⁶ are each the same ^{as G, Ar 2} , and Ar ⁴ in Formula (1),

Ar ⁵⁵ is any 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 a single structure.

In addition, ^{"-*" in Ar 12} is a site (binding site) bonding to G in formula (12).

[Formula 25]

Equation (12), G, Ar ^2, Ar ^4, substituent groups which may desirable range, has the Ar ⁶ are each is the same as G, Ar ^2, Ar ^4, Ar ⁶ in the above-mentioned formula (1).

In Formula (12), ^{the preferable range of Ar 55} is the same as the preferable range of Ar ⁵ in Formula (1) mentioned above, and the substituent which you may have is the same as ^{Ar 5 in Formula (1) mentioned above.}

[Formula 26]

In formula (13),

G, Ar ² , Ar ⁴ , and Ar ⁶ are the same as G, Ar ² , and Ar ⁴ in Formula (1) described above, respectively;

Ar ³³ and Ar ³⁴ are each independently a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent A cyclic group represents a divalent group in which a plurality of cyclic groups are linked directly or through a linking group,

Ar ⁵⁵⁵ is a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a plurality of aromatic hydrocarbon groups or aromatic heterocyclic groups which may have a substituent directly or through a linking group, 1 represents the ag.

In addition, ^{"-*" in Ar 13} is a site (binding site) bonding to G in formula (13).

In formula (13), ^{preferred ranges of G, Ar 2} , Ar ⁴ , and Ar ⁶ , and substituents which may be included are respectively G, Ar ² , Ar ⁴ , and Ar ⁶ in formula (1) described above, respectively. same.

In Formula (13), ^{the preferable ranges of Ar 33} , and Ar ³⁴ and the substituents you may have are the ^{same as Ar 2} and Ar ⁴ in Formula (1) described above, and also the preferable ranges in the case of connecting a plurality of them. same.

The preferable range of Ar ⁵⁵⁵ is the same as the preferable range ^{of Ar 5} in the formula (1) described above. The substituent you may have is the same as ^{Ar 5 in Formula (1).}

Preferred repeating unit structures of formulas (12) and (13), terminal groups, soluble groups, crosslinkable groups, content of repeating units, other preferred repeating units that may be contained, molecular weight of the polymer, and other repeating units that may be included etc. are the same as that of the polymer of Formula (1) mentioned above.

In Formula (12), since Ar ⁵⁵ can distribute|distribute the LUMO of a molecule|numerator to the terminal side of a side chain, hole injection|transport ability is high and durability can be made high. Moreover, in Formula (13), since HOMO and LUMO can be isolate|separated by taking the distance between a main chain and carbazole by ^{Ar 33} and Ar ^{34, hole injection transport ability and durability can be improved.} Equation (1), Ar ^3, Ar ⁵ and since it has a distribution of the LUMO of the molecule at the terminal side of the side chain, is also preferred than it is possible to separate the main chain of the HOMO and LUMO of the side chain.

[Specific Example]

Although the specific example of the polymer of this embodiment is shown below, it is not limited to these. In addition, a number in a formula represents the molar ratio of a repeating unit.

Any of a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer, etc. may be sufficient as these polymers, and the arrangement order of a monomer is not limited.

[Formula 27]

[Method for producing polymer]

The manufacturing method in particular of the polymer of this embodiment is not restrict|limited. For example, it can be produced by a polymerization method by Suzuki reaction, polymerization method by Grignard reaction, polymerization method by Yamamoto reaction, polymerization method by Ullmann reaction, polymerization method by Buchwald-Hartwig reaction, and the like.

In the case of the polymerization method by the Ullmann reaction and the polymerization method by the Buchwald-Hartwig reaction, for example, an aryl dihalide represented by the formula (1a) (Y represents a halogen atom such as I, Br, Cl, F) and The polymer of this embodiment is synthesize|combined by making primary aminoaryl represented by Formula (1b) react and making it react with 2a again.

[Formula 28]

In the above formulas, Ar ¹ , R ¹ to R ² , X, a, and b have the same meanings as in the formulas (2)-1 to (2)-3, respectively. c and d have the same meaning as c1 or c2 and d1 or d2 in the formulas (2)-1 to (2)-3, respectively. n and m represent the number of repetitions.

In the polymerization method described above, the reaction for forming an N-aryl bond is usually carried out in the presence of a base such as potassium carbonate, sodium tert-butoxy, or triethylamine. Moreover, it can also carry out, for example in presence of transition metal catalysts, such as copper and a palladium complex.

<Embodiment related to the second summary>

<Same part structure>

An organic electroluminescent device as an embodiment of the second aspect of the present invention is an organic electroluminescent device having an anode, a cathode, and an organic layer between the anode and the cathode, wherein the organic layer is adjacent to the hole transport layer and the hole transport layer wherein the hole transporting layer contains a polymer 1 represented by the formula (1) or a polymer in which the polymer 1 is crosslinked, the polymer 1 or a polymer in which the polymer 1 is crosslinked, and at least one of a material contained in the light emitting layer It is preferable that it is an organic electroluminescent element containing the material (compound which has a partial structure represented by the following formula (CzP)) which has a partial structure represented by following formula (CzP) which all have a carbazole ring. In addition, with respect to the description of "material" in this specification, you may substitute "compound" for the description which can be replaced with "compound".

[Formula 29]

More preferably, both the material contained in the hole transport layer and the material contained in the light emitting layer contain a material having a partial structure represented by formula (CzP), and the material contained in the hole transport layer or the material contained in the light emitting layer one of which contains a material having two or more partial structures represented by formula (CzP), and more preferably, a material contained in the light emitting layer has two or more partial structures represented by formula (CzP) (compound) and, particularly preferably, a material (compound) in which both the material contained in the hole transport layer and the material contained in the light emitting layer have two or more partial structures represented by the formula (CzP). With such a combination, driving at a lower voltage, high-efficiency light emission, and longer life are expected. Further, it is also preferable that at least one of the hole transport layer or the light emitting layer contains two or more materials having a partial structure represented by formula (CzP), and in particular, a material having a partial structure represented by formula (CzP) in the light emitting layer is 2 It is preferable to contain more than one kind. Also in such a combination, it is expected to drive at a lower voltage, to emit light with high efficiency, and to increase the lifespan.

Although there is no restriction|limiting in particular as to the material contained in the hole transport layer which has a partial structure represented by Formula (CzP), Preferably it is a high molecular compound. The high molecular compound is preferably a high molecular compound having an arylamine structure. The arylamine polymer compound is more preferably a polymer having a repeating unit represented by the following formula (20).

Although there is no restriction|limiting in particular as for the material contained in the light emitting layer which has a partial structure represented by Formula (CzP), It is preferable that it is a low molecular compound.

When the material having the partial structure represented by the formula (CzP) is a polymer compound, the number of formula (CzP) contained in the polymer compound is preferably not less than the number of formula (CzP) contained in the repeating unit of the polymer compound. When two formulas (CzP) exist in the repeating unit, the number of formulas (CzP) contained in the polymer compound is twice that of the repeating units of the polymer compound. When the high molecular compound has a plurality of repeating units, at least one repeating unit may have the formula (CzP). Formula (CzP) may have a substituent.

In addition, the bonding method of the material contained in a hole transport layer or the material contained in a light emitting layer, and Formula (CzP) is not specifically limited. For example, the carbazole moiety and the material contained in the hole transport layer or the material contained in the light emitting layer may be bound, or the benzene moiety and the material contained in the hole transport layer or the material contained in the light emitting layer may be bound.

<Low molecular weight compound>

Next, the case where the material having a partial structure represented by the formula (CzP) contained in the device of the present embodiment is a low molecular compound will be described. Formula (CzP) can be used for the light emitting material used for a light emitting layer, or the low molecular compound used as a host material, In the case of a host material, it is the following, for example.

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

[Formula 30]

In the formula (CzP-2), *1, *2, and *3 are bonding positions with the skeleton of the host material, and at least any of *1, *2, and *3 may be bonded. It may couple|bond directly with the frame|skeleton of a host material, and may couple|bond via another structure. Formula (CzP-2) may have a substituent. The other structures that may be interposed are not particularly limited, but preferably 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 and a substituent. An aromatic hydrocarbon group which may have a substituent which can be used as B in Formulas (14) - Formula (16) which are specifically mentioned below in which the structure in which two or more groups selected from aromatic heterocyclic group were connected in multiple numbers is mentioned. , an aromatic heterocyclic group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent, and a structure in which two or more groups selected from the aromatic heterocyclic group which may have a substituent are linked, and may have a substituent; The preferred range is also the same.

As the substituent, a group selected from the aforementioned 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 host material used for the light emitting layer is the formula (CzP), and/or by having the formula (CzP-2), it is possible to improve the hole transportability at the interface in particular.

As a skeleton of a host material, it is preferable to select from what has 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, a benzylphenyl structure, Fluorene structure, quinacridone structure, triphenylene structure, carbazole structure, pyrene structure, anthracene structure, phenanthroline structure, quinoline structure, pyridine structure, pyrimidine structure, triazine structure, oxadiazole structure or imidazole What has a structure etc. are mentioned.

As the electron transport material, from the viewpoint of being a material having excellent electron transport properties and having a relatively stable structure, a compound having a pyridine structure, a pyrimidine structure, or a triazine structure is more preferable, and a compound having a pyrimidine structure or a triazine structure It is more preferable that

The hole-transporting material is a compound having a structure excellent in hole-transporting property, and as the skeleton having excellent charge-transporting property, one having a carbazole structure, a dibenzofuran structure, a triarylamine structure, a naphthalene structure, a phenanthrene structure or a pyrene structure Among these, 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 three or more rings, and more preferably a compound having two or more condensed rings of three or more rings, or a compound having at least one condensed ring of five or more rings. By using these compounds, the rigidity of molecules increases, and the effect of suppressing the degree of molecular motion in response to heat is easily obtained. Moreover, it is preferable from the point of charge-transporting property and durability of a material that the condensed ring of 3 or more rings and the condensed ring of 5 or more rings have an aromatic hydrocarbon ring or an aromatic heterocyclic ring.

Specific examples of the three or more condensed ring structures include anthracene structure, phenanthrene structure, pyrene structure, chrysene structure, naphthacene structure, triphenylene structure, fluorene structure, benzofluorene structure, and indenofluorene structure. , an indolofluorene structure, a carbazole structure, an indenocarbazole structure, an indolocarbazole structure, a dibenzofuran structure, a dibenzothiophene structure, and the like. In view of charge transport properties and solubility, 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 are formed. At least one selected from the group is preferable, and a carbazole structure or an indolocarbazole structure is more preferable from the viewpoint of durability against electric charge.

From the viewpoint of durability against electric charge of the organic electroluminescent device, 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, and may have a branch.

The host material of the light emitting layer is preferably a polymer material from the viewpoint of excellent flexibility. The light emitting layer formed using the material excellent in flexibility is preferable as a light emitting layer of the organic electroluminescent element formed on the 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 and 500,000 or less, more preferably 10,000 or more and 100,000 or less.

[Preferred low molecular weight compound]

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

[Formula 31]

In the above formulas (14) to (16),

A is a partial structure represented by the said formula (CzP), and may have a substituent.

B represents a single bond or an arbitrary partial structure.

When two or more A's exist, they may be same or mutually different.

When two or more B's exist, they may be same or mutually different.

na, nb and nc each independently represent an integer of 1 or more and 5 or less,

The molecular weight of the compound represented by said Formula (14)-(16) is 5,000 or less.

(A)

It is preferable that the substituent in A which you may have is selected from the said substituent group Z, and a preferable group and the substituent which you may have are also the same.

(B)

B in the formulas (14) to (16) is not particularly limited, but preferably a functional group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, Or the structure in which two or more groups selected from the aromatic hydrocarbon group which may have a substituent and the aromatic heterocyclic group which may have a substituent connected in plurality is shown. As these substituents which you may have, any of the substituent group Z mentioned above, or these combinations can be used.

Examples of the functional group include a structure having hole transport properties, a structure having electron transport properties, a structure inhibiting charge transport, a structure imparting solubility in organic solvents, a structure inhibiting crystallization and improving amorphous properties, or a structure having luminescence properties. is preferable

As the monovalent group in which two or more groups selected from an aromatic hydrocarbon group, an aromatic heterocyclic group, an aromatic hydrocarbon group, and an aromatic heterocyclic group are connected in plurality, the same structure as that ^{of Ar 2 in the above formula (1) is preferable.} Similarly, when connecting two or more, it is preferable to connect 2-10, and it is more preferable to connect 2-5.

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 N of the carbazole ring in the partial structure A It is more preferable that it is the benzene ring couple|bonded with.

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 which has a partial structure represented by Formula (CzP) contained in a light emitting layer, Preferably it is the said Formula (14) or the said Formula (16).

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 preferably a compound represented by the following formula (19).

[Formula 32]

In the above formula (17),

Q represents 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 represents a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent or a divalent heteroaromatic ring group having 3 to 30 carbon atoms which may have a substituent, Xb ¹ , Yb ¹ , and Each of Zb ¹ may be the same or different when two or more exist,

A is a partial structure represented by the above formula (CzP), may have a substituent, and A plurality of A may be the same as 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 each independently represent 0 or 1,

^{Yb 2} when q13 is 0 and Yb 2 when r13 is 0 Zb ² each independently represents a hydrogen atom, a monovalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent, or a monovalent heteroaromatic ring group having 3 to 30 carbon atoms which may have a substituent;

When q13 is 1, Yb ² is a direct bond,

When r13 is 1 Zb ² is a direct bond.

[Formula 33]

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

[Formula 34]

In the above formula (19),

Xc ¹ and Yc ¹ each independently represent a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent, or a divalent heteroaromatic ring group having 3 to 30 carbon atoms which may have a substituent;

Xc ² and Yc ² each independently represent a hydrogen atom, an optionally substituted monovalent C6-C30 hydrocarbon aromatic ring group, or optionally a C3-C30 monovalent heteroaromatic cyclic group;

Each of Xc ¹ and Yc ¹ may be the same or different when there are two or more,

A is a partial structure represented by the 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 said Formulas (17) and said Formula (19), as a C6-C30 hydrocarbon aromatic ring, a 6-membered monocyclic ring or a 2-5 condensed ring is preferable. Specifically, 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, a fluoranthene ring, etc. can be heard More preferably, it is a monocyclic ring or a 2-3 condensed ring, Specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring are mentioned. Among 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 formulas (17) and (19), the heteroaromatic ring having 3 to 30 carbon atoms is preferably a monocyclic 5- or 6-membered ring or a 2- to 5-condensed ring thereof. Specifically, a furan ring, a benzofuran ring, a dibenzofuran ring, a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, Carbazole ring, indolocarbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, Benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, peri and a midine ring, a quinazoline ring, and a quinazolinone ring.

Among them, a thiophene ring, a pyrrole ring, an imidazole ring, a pyridine ring, a pyrimidine ring, a triazine ring, a quinoline ring, a quinazoline ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, an indole ring a locarbazole ring, a phenanthroline ring, or an indolocarbazole ring,

More preferably, 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,

Even more preferred are a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, or an indolocarbazole ring.

^{Moreover, Yb 2} in the case of q13 = 0 in the formula (17), and Yb 2 in the case of r13 = 0 Zb ^{2 , Xc 2} , and Yc ² in the formula (19) are a benzene ring, a naphthalene ring or a phenanthrene ring as particularly preferable aromatic hydrocarbon rings, and a dibenzofuran ring as a particularly preferable aromatic heterocyclic ring , a dibenzothiophene ring, or an indolocarbazole ring.

As a substituent which the said formula (CzP) represented by said A may have, Preferably it is a C6-C30 aromatic hydrocarbon group which may have a substituent, or a C3-C30 aromatic heterocyclic group which may have a substituent. It is more preferable that it is an aromatic hydrocarbon group which may have a substituent from a viewpoint of durability improvement and charge-transporting property. Moreover, it is preferable from a viewpoint of durability improvement that the substituent couple|bonded with the 3-position or 6-position of carbazole in partial structure A.

The Xb ¹ , Yb ¹ , Zb ¹ , Yb ² , The ^{substituent which Zb 2} , Xc ¹ , Xc ² , Yc ¹ , and Yc ² may have, the substituent which the aforementioned aromatic hydrocarbon ring having 6 to 30 carbon atoms may have, and the heteroaromatic ring having 3 to 30 carbon atoms may have The substituent and the substituent which the substituent which A may have have further are the same as the substituent or the said crosslinkable group given in the said substituent group Z in the polymer represented by Formula (1) mentioned above, A preferable substituent and addition The substituents you may have are also the same.

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

[Formula 35]

[Formula 36]

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' each independently represent an integer of 0 or more and 5 or less,

p14 is 12,

q14 is 12 when q13 is 1 and is absent when q13 is 0,

r14 is 12 when r13 is 1, does not exist when r13 is 0,

q15 and r15 are each independently 4 or 5;

R ³¹ and R ³² are each independently a hydrogen atom or a substituent,

Xb ¹ , Yb ¹ , Zb ¹ , q13 and r13 are each the same as in the formula (17).

As R ^{31 which} is a substituent, it is the same as a hydrogen atom or the substituent which said A may have, It is the same as a preferable substituent, and the substituent which you may have is also the same.

^{As R 32 which} is a substituent, it is the same as a hydrogen atom, or the substituent or the said crosslinkable group mentioned in the said substituent group Z in the polymer represented by the said Formula (1), A preferable substituent and the substituent which you may have are also the same.

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

[Formula 37]

In the general formula (19-1),

R ³¹ is a hydrogen atom or a substituent,

u11 represents 11,

Xc ¹ , Yc ¹ , Xc ¹ , Yc ¹ , t11 , and s11 are respectively the same as in the above formula (19).

^{R 31} in the case of a substituent is the same as the substituent or the crosslinkable group given in the substituent group Z in the polymer represented by the formula (1) described above, and a preferable substituent and a substituent which may be further included are also the same.

In addition, the host material (compound) of the light emitting layer is preferably a low molecular weight from the viewpoints of easiness of synthesis and purification, easiness of design of electron transport performance and hole transport performance, and easiness of viscosity adjustment when dissolved in a solvent. When the host material contained in the light emitting layer is a low molecular material, the molecular weight is preferably 5,000 or less, more preferably 4,000 or less, particularly preferably 3,000 or less, most preferably 2,000 or less, usually 300 or more, preferably Preferably it is 350 or more, More preferably, it is 400 or more.

As a host material which has the above-mentioned formula (CzP-2), the following compounds are mentioned, for example.

[Formula 38]

Other examples of the low molecular weight compound include a luminescent material, and a luminescent material having a formula (CzP) can be used. As the luminescent material, phosphorescent luminescent materials mentioned later can be used, and those having the formula (CzP) in these structures can be used.

<Embodiment related to the 3rd summary>

An embodiment of the third aspect 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 adjacent to the hole transport layer It is an organic electroluminescent element which has a light emitting layer, and contains the material which has a partial structure represented by the following formula (CzP) in which both the material contained in a hole transport layer and the material contained in a light emitting layer have a carbazole ring.

[Formula 39]

More preferably, both the material contained in the hole transport layer and the material contained in the light emitting layer contain a material having a partial structure represented by formula (CzP), and the material contained in the hole transport layer or the material contained in the light emitting layer any one contains a material having two or more partial structures represented by the formula (CzP), and particularly preferably, both the material contained in the hole transport layer and the material contained in the light emitting layer are a moiety represented by the formula (CzP) It contains the material which has two or more structures. With such a combination, driving at a lower voltage and increasing the lifespan is expected.

Although there is no restriction|limiting in particular as for the material contained in the hole transport layer which has a partial structure represented by Formula (CzP), Preferably it is a high molecular compound. As a high molecular compound, Preferably it is a high molecular compound which has 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). Let the polymer which has a repeating unit shown by following formula (20) be the polymer 2 for convenience, and let the polymer which has Formula (30) mentioned later in a side chain be the polymer 3.

Although there is no restriction|limiting in particular as for the material contained in the light emitting layer which has a partial structure represented by Formula (CzP), Preferably it is a low molecular compound.

When the material having a partial structure represented by the formula (CzP) is a polymer compound, the number of formula (CzP) contained in the polymer compound is preferably not less than the number of formula (CzP) contained in the repeating unit of the polymer compound. When two formulas (CzP) exist in the repeating unit, the number of formulas (CzP) contained in the polymer compound is 2 repeating units of the polymer compound. When the polymer compound has a plurality of repeating units, at least one repeating unit may have the formula (CzP). Formula (CzP) may have a substituent.

Moreover, the bonding method of the material contained in a hole transport layer or the material contained in a light emitting layer, and Formula (CzP) is not specifically limited. For example, the carbazole moiety and the material contained in the hole transport layer or the material contained in the light emitting layer may be bound, or the benzene moiety and the material contained in the hole transport layer or the material contained in the light emitting layer may be bound.

<Polymer 2>

[Formula 40]

In formula (20),

Ar ¹ ′ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and ^{at least one of Ar 1} ′ is represented by the following formula (21),

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 represent an optionally substituted alkyl group,

R ³ ' to R ⁵ ' and R ¹¹ ' to R ¹⁴ ' each independently represent an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent,

a and b are each independently an integer of 0 to 4, a+b is 1 or more,

c is an integer of 1 to 3,

d is an integer of 0 to 4,

When there ^{are two or more R 1} ′ and R 2 ′ in the repeating unit, R ¹ ′ and R ² ′ may be the same or different.

[Formula 41]

In formula (21),

Ar ¹¹ ′ and Ar ¹² ′ each independently represent a divalent aromatic hydrocarbon group or aromatic heterocyclic group which may have a substituent,

Ar ¹³ ′ to Ar ¹⁵ ′ each independently represent a hydrogen atom or a substituent.

* indicates a binding position.

At least one of Ar ¹¹ ' to Ar ¹⁵ ' may be a formula (CzP) other than formula (21), and may have the following formula (CzP-1).

[Formula 42]

In the formula (CzP-1), *1, *2, and *3 represent bonding positions with the backbone of the polymer, and at least any of *1, *2, and *3 may be bonded. It may couple|bond directly with skeleton of a polymer, and may couple|bond via another structure. Formula (CzP-1) may have a substituent.

As a substituent, the ^{thing similar to Ar 13} ' to Ar ¹⁵ ' described above can be used, for example.

(R ¹ ' and R ² ')

^{R 1} ′ and R ² ′ in the repeating unit represented by the formula (20) each independently represent an optionally substituted alkyl group. Although carbon number of an alkyl group is not specifically limited, In order to maintain the solubility of a polymer, 1 or more and 6 or less are preferable, 3 or less are more preferable, It is still more preferable that they are a methyl group or an ethyl group. Moreover, each structure of linear, branched or cyclic form may be sufficient as this alkyl 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 electric charge can be uniformly distributed around the nitrogen atom, and further synthesis is easy. In this respect, ^{it is preferred that all R 1} and R ² are the same group.

(R ³ ' to R ⁵ ' and R ¹¹ ' to R ¹⁴ ')

R ³ ′ to R ⁵ ′ and R ¹¹ ′ to R ¹⁴ each independently represent an optionally substituted alkyl group, an optionally substituted aralkyl group, or an optionally substituted aromatic hydrocarbon group.

Although the said alkyl group is not specifically limited, Since there exists a tendency which can improve the solubility of a polymer, C1 or more and 24 or less are preferable, and 6 or less are more preferable. Moreover, each structure of a linear, branched or cyclic form may be sufficient.

Specifically, 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, n-octyl group, cyclohexyl group Actual machine, dodecyl group, etc. are mentioned.

Although the said aralkyl group is not specifically limited, Since it exists in the tendency which can improve the solubility of a polymer, C5 or more and 60 or less are preferable, and 40 or less are more 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, 8-phenyl-1-n -octyl group, 4-phenylcyclohexyl group, etc. are mentioned.

Although it does not specifically limit as said aromatic hydrocarbon cyclic group, Since it exists in the tendency which can improve the solubility of a polymer, C6 or more and 60 or less are preferable, and 30 or less are more preferable.

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, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, flu and monovalent groups of a 6-membered monocyclic ring or a 2- to 5-condensed ring such as an orene ring, or groups in which a plurality of these are linked.

From the viewpoint of improving charge transportability and durability, R ³ ′ to R ⁵ ′ are preferably a methyl group or an aromatic hydrocarbon group, R ³ ′ and R ⁴ ′ are more preferably a methyl group, and R ⁵ ′ is more preferably a phenyl group. .

From the viewpoint of improving solubility and excellent charge transport properties, R ³ ′ and R ⁴ ′ are preferably an alkyl group having 3 to 6 carbon atoms or an aralkyl group having 9 to 40 carbon atoms.

The ^{alkyl group of R 1} ′ and R ² ′, the alkyl group of R ³ ′ to R ⁵ ′ and R ¹¹ ′ to R ¹⁴ ′, the aralkyl group and the aromatic hydrocarbon group may have a substituent. May have substituents, as a preferred group of the R ³ '~ R ^5' and R ¹¹ '~ R ^14' group, an aralkyl group and aromatic hydrocarbon group may be a crosslinking group to all groups, or later.

The ^{alkyl group of R 1} ' and R ² ', the alkyl group of R ³ ' to R ⁵ ' and R ¹¹ ' to R ¹⁴ ', the aralkyl group and the aromatic hydrocarbon group are most preferably not having a substituent from the viewpoint of lowering the voltage. .

In addition, from the ^{viewpoint of insolubilization, the alkyl group, aralkyl group and aromatic hydrocarbon group of R 3} ' to R ⁵ ' and R ¹¹ ' to R ¹⁴ ' include at least one crosslinkable group to be described later as a substituent, the formula ( It is preferable to contain the repeating unit represented by 20).

(a', b', c' and d')

In the repeating unit represented by the formula (20), a' and b' are each independently an integer of 0 to 4, and a'+b' is 1 or more. Further, each of a' and b' is preferably 2 or less, and more preferably both a' and b' are 1.

In the repeating unit represented by the formula (20), c' is an integer of 1-3, and d' is an integer of 0-4. c' and d' are preferably 2 or less, respectively, c' and d' are more preferably the same, more preferably c' and d' are 1, or both c' and d' are 2 desirable.

In the repeating unit represented by the formula (20), when both c' and d' are 1, or both c' and d' are 2, and when both a' and b' are 2 or 1, R ¹ ' and R ² ' are most preferably bonded at positions symmetrical to each other.

Here, "and the R ¹ 'and R ^2' coupled in symmetrical positions with each other" means, with respect to the fluorene ring or a carbazole ring in the formula (20), and the binding position of R ¹ 'and R ^2' symmetrical say that it is For example, in the following formula (20a) included in formula (20), it can be said that ^{R 1a} ' and R ^2a ' are symmetric positions, and R ^1b ' and R ^{2b ' are symmetric positions.} In addition, at this time, 180 degree rotation about the main chain as an axis is regarded as the same structure. For example, the following formulas (20a) and (20b) can be regarded as the same structure.

[Formula 43]

(Ar ¹ ')

In the repeating unit represented by the formula (20), Ar ¹ ′ represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a group represented by the following formula (21).

The aromatic hydrocarbon cyclic 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, a cre and monovalent groups of a 6-membered monocyclic ring or a 2- to 5-condensed ring, such as a sen ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, or groups in which a plurality of these are linked.

The aromatic heterocyclic group preferably has 3 or more 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 oxadia ring. sol ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, Benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenane A monovalent group of a 5- or 6-membered ring, a monovalent group of a 2- to 4-condensed ring, such as a triidine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring, or a group in which a plurality of them are connected can be heard

Ar ¹ ′ is preferably an aromatic hydrocarbon ring group which may have a substituent from the viewpoint of excellent charge transport properties and excellent durability, and among them, a monovalent group of a benzene ring or fluorene ring which may have a substituent, that is, a substituent The phenyl group or fluorenyl group which may have is more preferable, the fluorenyl group which may have a substituent is still more preferable, and the 2-fluorenyl group which may have a substituent is especially preferable.

There is no restriction|limiting in particular as a substituent which the aromatic hydrocarbon cyclic group or aromatic heterocyclic group of Ar ^{1' may have, as long as it does not reduce the characteristic of this polymer remarkably.} Preferably, a group selected from the following substituent group Z' or a crosslinkable group mentioned later is mentioned, An alkyl group, an alkoxy group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, or a crosslinkable group mentioned later is preferable, and an alkyl group is more preferable. .

Ar ¹ ′ is preferably a fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms, particularly preferably a 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms, from the viewpoint of solubility in the application solvent. Further, a 9-alkyl-2-fluorenyl group in which an 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 an alkyl group is 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, solubility in a solvent and durability of the fluorene ring tend to improve. Moreover, when both the 9-position and the 9'-position are the fluorenyl groups substituted by the alkyl group, there exists a tendency for the solubility to a solvent and the durability of a fluorene ring to improve further.

^{(Ar 1} ' in 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).

[Formula 44]

In formula (21),

Ar ¹¹ ′ and Ar ¹² ′ each independently represent a divalent aromatic hydrocarbon group or aromatic heterocyclic group which may have a substituent,

Ar ¹³ ′ to 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. 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, etc. a linear, branched, or cyclic alkyl group having usually 1 or more, preferably 4 or more, and usually 24 or less, preferably 12 or less carbon atoms;

For example, carbon number, such as a vinyl group, is 2 or more normally, 24 or less normally, Preferably it is 12 or less alkenyl group;

For example, carbon number, such as an ethynyl group, is 2 or more normally, 24 or less normally, Preferably it is 12 or less alkynyl groups;

For example, carbon number, such as a methoxy group and an ethoxy group, is 1 or more normally, 24 or less normally, Preferably it is 12 or less alkoxy groups;

For example, C4 or more, such as a phenoxy group, a naphthoxy group, a pyridyloxy group, Preferably it is 5 or more, Usually 36 or less, Preferably it is 24 aryloxy groups;

For example, carbon number, such as a methoxycarbonyl group and an ethoxycarbonyl group, is 2 or more normally, It is 24 or less normally, Preferably it is 12 or less Alkoxycarbonyl group;

For example, carbon number, such as a dimethylamino group and a diethylamino group, is 2 or more normally, It is 24 or less normally, Preferably it is 12 or less dialkylamino group;

For example, carbon number, such as a diphenylamino group, a ditolylamino group, N-carbazolyl group, is 10 or more normally, Preferably it is 12 or more, Usually 36 or less, Preferably it is 24 or less diarylamino groups;

For example, carbon number, such as a phenylmethylamino group, is 7 normally, 36 or less normally, Preferably it is 24 or less arylalkylamino group;

For example, carbon number, such as an acetyl group and a benzoyl group, is 2 normally, 24 or less normally, Preferably it is 12 acyl group;

For example, Halogen atoms, such as a fluorine atom and a chlorine atom;

For example, carbon number, such as a trifluoromethyl group, is 1 or more normally, 12 or less normally, Preferably it is 6 or less haloalkyl group;

For example, carbon number, such as a methylthio group and an ethylthio group, is 1 or more normally, It is 24 or less normally, Preferably it is 12 or less alkylthio groups;

For example, C4 or more, such as a phenylthio group, a naphthylthio group, and a pyridylthio group, Preferably it is 5 or more, Usually 36 or less, Preferably it is 24 or less arylthio group;

For example, carbon number, such as a trimethylsilyl group and a triphenylsilyl group, is 2 or more normally, Preferably it is 3 or more, Usually 36 or less, Preferably it is 24 or less silyl group;

For example, carbon number, such as a trimethylsiloxy group and a triphenylsiloxy group, is 2 or more normally, Preferably it is 3 or more, Usually 36 or less, Preferably it is 24 or less siloxy groups;

cyano group;

For example, C6 or more, such as a phenyl group and a naphthyl group, is 36 or less normally 36 or less, Preferably it is an aromatic hydrocarbon ring group 24 or less;

For example, aromatic heterocyclic groups, such as a thienyl group and a pyridyl group, whose carbon number is usually 3 or more, Preferably it is 4 or more, and is 36 or less normally, Preferably it is 24 or less.

Among the above-mentioned substituent group Z', Preferably, they are the said alkyl group, an alkoxy group, an aromatic hydrocarbon ring group, and an aromatic heterocyclic group. It is more preferable not to have a substituent from a viewpoint of charge-transporting property.

Moreover, each substituent of the said substituent group Z' may have a substituent further. As these substituents, the thing similar to the said substituent (substituent group Z'), or the crosslinkable group mentioned later is mentioned. Preferably, it does not have an additional substituent, or it is a C6 or less alkyl group, a C6 or less alkoxy group, a phenyl group, or a crosslinkable group mentioned later. It is more preferable not to have an additional substituent from a viewpoint of charge-transporting property.

From the viewpoint of insolubilization, it is preferable to contain, as an additional substituent, a repeating unit represented by the formula (20) containing at least one crosslinkable group described later, wherein the crosslinkable group is an aromatic hydrocarbon ring group represented by ^{Ar 1 ′.} Or it is preferable to further substituted with the substituent which the aromatic heterocyclic group may have.

(Ar ¹³ ' to Ar ¹⁵ ')

Ar ¹³ ′ to Ar ¹⁵ ′ each independently represent a hydrogen atom or a substituent. When Ar ¹³ ′ to Ar ¹⁵ ′ are a substituent, there is no particular limitation, but it is preferably an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Preferred structures are the same as the groups ^{mentioned for Ar 1 ′.}

When Ar ¹³ ′ to Ar ¹⁵ ′ are a substituent, it is preferably bonded to the 3-position or 6-position of each carbazole from the viewpoint of improving durability.

Ar ¹³ ′ to Ar ¹⁵ ′ are preferably hydrogen atoms from the viewpoint of easiness of synthesis and charge transport properties.

Ar ¹³ ′ to Ar ¹⁵ ′ are preferably an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and more preferably an aromatic hydrocarbon group which may have a substituent, from the viewpoint of improving durability and transporting charges. desirable.

When Ar ¹³ ′ to Ar ¹⁵ ′ are an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, the substituent is the same as the substituent in the above substituent group Z′ or the crosslinkable group described later, preferably The substituents are also the same, and the substituents which these substituents may further have are also the same.

Moreover, from a viewpoint of insolubilization, it is preferable as a substituent to contain the group represented by Formula (21) containing at least 1 below-mentioned crosslinkable group.

On the other hand, it is preferable not to include a crosslinking group as a substituent from the viewpoint that there is no adverse effect on the light emitting layer by the uncrosslinked residue after film formation.

(Ar ¹² ')

Ar ¹² ′ is a divalent group optionally connected to a divalent aromatic hydrocarbon group which may have a substituent or a divalent aromatic hydrocarbon group which may have a substituent and a divalent aromatic heterocyclic group which may have a substituent, Formula (21) A structure bonded to N of at least one of the two carbazole rings constituting the carbazole ring is a phenylene 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, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, flu and a divalent group of a 6-membered monocyclic ring or a 2- to 5-condensed ring such as an orene ring, or a group in which a plurality of these are linked. When these are connected in plurality, it is preferably a group in which the two or more connected divalent aromatic hydrocarbon groups are conjugated.

The aromatic heterocyclic group preferably has 3 or more and 60 or less carbon atoms, specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and an oxadia ring. sol ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, Benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenane A monocyclic or 2- to 4-condensed ring of a 5- or 6-membered ring, such as a triidine ring, a benzoimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, or an azulene ring, or a group in which a plurality of them are connected and the like.

Examples of the substituent which the aromatic hydrocarbon group or aromatic heterocyclic group may have include an alkyl group, an aralkyl group and an aromatic hydrocarbon group in the ^{above R 3} ' to R ⁵ ' and R ¹¹ ' to R ^{14 ', and the preferred ranges are the same.} do. When ^{distortion of the structure of Ar 12} ' occurs due to the steric effect of the substituent, it is preferable that there is no substituent. When ^{the distortion of the structure of Ar 12} ' does not occur due to the steric effect of the substituent, it is preferable to have a substituent. .

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 them are connected, more preferably a divalent group of a benzene ring or a group in which a plurality of them are connected, particularly preferably , a 1,4 phenylene group in which the benzene ring is bilaterally linked at the 1,4 position, a 2,7 fluorenylene group in which the benzene ring is bilaterally linked at the 2,7 position of the fluorene ring, or a group thereof in which a plurality of them are linked, most preferably, It is a group containing 1,4 phenylene group-2,7 fluorenylene group-1,4 phenylene group-. In these preferred structures, it is preferable that the phenylene group does not have a substituent other than the linking position ^{so that distortion of Ar 12} ′ due to the steric effect of the substituent does not occur. Moreover, it is preferable from a viewpoint of solubility and durability improvement of a fluorene structure that the fluorenylene group has a substituent at the 9,9' position.

When Ar ¹² ′ has the structure as described above, it becomes a structure in which an aromatic hydrocarbon group between nitrogen atoms of two carbazole structures is conjugated, and LUMO is easily distributed on this conjugated aromatic hydrocarbon group. Therefore, since LUMO is hard to diffuse around the nitrogen atom of the main chain which is weak to electrons or excitons, it is thought that durability improves.

Moreover, when an aromatic heterocyclic group is included, since electron withdrawing property is improved and LUMO is easy to distribute, LUMO hardly diffuses around the nitrogen atom of the main chain which is weak to electrons or excitons, It is thought that durability improves.

(Ar ¹¹ ')

Ar ¹¹ ′ is a divalent group connected to the nitrogen atom of the amine of the main chain in the formula (20). Although Ar ¹¹ ' is not particularly limited, a divalent aromatic hydrocarbon group which may have a substituent or a divalent aromatic heterocyclic group which may have a substituent is preferable.

The aromatic hydrocarbon group for Ar ¹¹ ′ 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, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, flu and a divalent group of a 6-membered monocyclic ring or a 2- to 5-condensed ring such as an orene ring, or a group in which a plurality of these are linked.

The aromatic heterocyclic group for Ar ¹¹ ′ preferably has 3 or more and 60 or less carbon atoms. Specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, pyr Rolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzoimidazole ring, perimidine ring, quinazoline ring, and a divalent group of a monocyclic or 2- to 4-condensed ring of a 5- or 6-membered ring, such as a quinazolinone ring and an azulene ring, or a group in which a plurality of these are linked.

The substituents that these aromatic hydrocarbon groups or aromatic heterocyclic groups may have include the same groups as the alkyl group, aralkyl group, and aromatic hydrocarbon group in ^{R 3} ' to R ⁵ ' and R ¹¹ ' to R ^{14 ', and a preferred range is also} same.

When two or more of these divalent aromatic hydrocarbon groups or divalent aromatic heterocyclic groups are connected, it is preferably a group bonded so that a plurality of connected divalent aromatic hydrocarbon groups are not conjugated. Specifically, it is preferable to include a 1,3 phenylene group or a group having a substituent and forming a torsion structure due to the steric effect of the substituent. By including such a linking group, ^{LUMO distributed on Ar 12} ' is difficult to diffuse into the main chain, and LUMO is difficult to distribute around nitrogen atoms in the main chain that are weak to electrons or excitons, and it is considered that durability is improved.

In addition, it may be in the polymer having the repeating unit represented by the formula 20 of the present ^{embodiment, Ar 1 ', R 1'} , R 2 in the case where a plurality ', X', respectively, may be the same or different. Preferably, the polymer contains a plurality of repeating units in which the repeating units represented by the formula (20) have the same structure. In this case, since the HOMO and LUMO of the repeating unit become the same by containing a plurality of repeating units of the same structure, charges are not concentrated and trapped in a specific shallow level, and excellent charge transport properties and improved durability It is thought to be

[preferred repeat unit]

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

[Formula 45]

In the formula (20-I), R ¹ ′ and R ² ′ are the same, and R ¹ ′ and R ² ′ are bonded to each other at a position symmetrical to each other.

[end stage]

In this embodiment, a terminal group refers to the structure of the terminal part of a polymer formed with the end cap agent used at the time of completion|finish of polymerization of a polymer. It is preferable that the terminal group of the polymer which has a repeating unit represented by Formula (20) is a hydrocarbon group. As a hydrocarbon group, from a viewpoint of charge-transporting property, C1-C60 is preferable, 1 or more and 40 or less are more preferable, 1 or more and 30 or less are still more preferable.

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, etc. a linear, branched, or cyclic alkyl group having usually 1 or more, preferably 4 or more, and usually 24 or less, preferably 12 or less carbon atoms;

For example, carbon number, such as a vinyl group, is 2 or more normally, 24 or less normally, Preferably it is 12 or less alkenyl group;

For example, carbon number, such as an ethynyl group, is 2 or more normally, 24 or less normally, Preferably it is 12 or less alkynyl groups;

For example, C6 or more, such as a phenyl group and a naphthyl group, is 36 or less normally 36 or less, Preferably it is an aromatic hydrocarbon ring group 24 or less;

can be heard

These hydrocarbon groups may further have a substituent, and the substituent which may further have an alkyl group or an aromatic hydrocarbon ring group is preferable, and when there exists a plurality of substituents which may further have these, they may couple|bond with each other and may form a ring.

Preferably, it is an alkyl group or an aromatic hydrocarbon cyclic group from a viewpoint of charge transport property and durability, More preferably, it is an aromatic hydrocarbon cyclic group.

[Other repeat units]

The polymer having a repeating unit represented by the formula (20) may further contain a repeating unit different from the repeating unit represented by the formula (20).

As another repeating unit, a repeating unit represented by the following formula (22) is preferable from the viewpoints of charge transportability and durability. Here, the repeating unit represented by the following formula (22) may coincide with some structural moieties in the repeating units of the formula (20), but here, to the last, structures other than the repeating unit represented by the formula (20) means to be

[Formula 46]

In formula (22),

Ar ³ ′ represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,

Ar ⁴ ′ represents a divalent aromatic hydrocarbon group optionally having a substituent, a divalent aromatic heterocyclic group, or a divalent group in which a plurality of aromatic hydrocarbon groups and aromatic heterocyclic groups are linked directly or through a linking group.

(Ar ³ ' and Ar ⁴ ')

Aromatic hydrocarbon group and aromatic hydrocarbon ring group in Ar ³ 'and Ar ^4' are, Ar ³ 'is Ar ¹ of formula (20)', Ar ¹ in the formula (20), the same group, Ar ⁴ and It represents a divalent group as the same group as . Moreover, the substituent which you may have is preferably the same group as the said substituent group Z' or the crosslinkable group mentioned later, and also the substituent which you may have is the same as that of the said substituent group Z'.

From the viewpoint of excellent hole injection from the anode side in addition to charge transport properties and durability, Ar ⁴ ′ in the formula (22) is more preferably a group represented by the following formula (23).

[Formula 47]

In formula (23),

k' and n' each independently represent an integer of 0 to 3, k'+n' is 1 or more,

m' represents the integer of 0 or 1.

X' is the same as that of formula (20), and *1 and *2 represent a bonding position with an adjacent structure.

(k', n' and m')

In Formula (23), from the viewpoint of excellent electron durability, 2 is preferable and, as for k'+n', 3 is more preferable.

Moreover, it is preferable that k' is 1 or more, and it is preferable to couple|bond with N in said Formula (22) in *1. Moreover, it is more preferable that both of k' and n' are 1, or that both of k' and n' are 2 or more.

It is more preferable that m' is 1 at the point which is excellent in the solubility with respect to the solvent of a polymer.

In the formula (22), the linking group in the case where a plurality of aromatic hydrocarbon groups and aromatic heterocyclic groups are linked through a linking group, specifically, for example, a -O- group, -C (=O )- group and a divalent group formed by connecting 1 to 30, preferably 1 to 5, more preferably 1 to 3 groups in any order selected from _{a -CH 2} - group optionally substituted with a hydrogen atom. A connector etc. are mentioned.

Among them, from the viewpoint of excellent hole injection into the light emitting layer, Ar ⁴ ′ in the formula (22) is preferably an aromatic hydrocarbon group or an aromatic heterocyclic group in which a plurality of Ar 4 ′ is connected via a linking group represented by the following formula (24).

[Formula 48]

In formula (24),

p' represents an integer of 1 to 10,

R ⁸ ′ and R ⁹ ′ each independently represent a hydrogen atom or an optionally substituted alkyl group, an aromatic hydrocarbon group, or an aromatic heterocyclic group.

When two or more R ⁸ ′ and R ⁹ ′ exist, they may be the same or different.

(R ⁸ ' and R ⁹ ')

The alkyl group for R ⁸ ′ and R ^{9 ′ is the same group as the alkyl group mentioned for R 1} ′, and the aromatic hydrocarbon group and aromatic heterocyclic group are the same groups as the aromatic hydrocarbon group and aromatic heterocyclic group for Ar ¹ ′. am. Moreover, the substituent which these groups may have is preferably the same group as the said substituent group Z' or the crosslinkable group mentioned later, and also the substituent which may further have the same as the said substituent group Z'.

As another repeating unit which the polymer which has a repeating unit represented by Formula (20) contains, it is preferable that it is a repeating unit represented by following formula (25). In the repeating unit represented by Formula (25), the singlet excitation energy level and the triplet excitation energy level tend to increase due to twisting of the aromatic ring. Further, due to the steric hindrance of the twist of the aromatic ring, the solubility of the polymer in the solvent is excellent, and the coating film formed by the wet film forming method and subjected to heat treatment tends to be excellent in the insolubility in the solvent.

[Formula 49]

In formula (25),

Ar ² ′ represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,

R ¹⁷ ′ to R ¹⁹ ′ each independently represent an optionally substituted alkyl group, alkoxy group, aralkyl group, aromatic hydrocarbon group or aromatic heterocyclic group,

f', g', and h' each independently represent an integer of 0 to 4, f'+g'+h' is 1 or more,

e' represents the integer of 0-3.

(Ar ² ' and R ¹⁷ ' to R ¹⁹ ')

The aromatic hydrocarbon group and aromatic heterocyclic group in Ar ² ′ and R ¹⁷ ′ to R ¹⁹ ′ are each independently the same groups as those described for ^{Ar 1 ′ above.} Moreover, as for the substituent which these groups may have, the group similar to the said substituent group Z' or the crosslinkable group mentioned later is preferable.

The alkyl group and aralkyl group in R ¹⁷ '~ R ^19', the R ⁷ is preferably the same group as "the same groups are preferred as all in, and also substituents which may optionally have in addition the R ⁷ '.

The alkoxy group for R ¹⁷ ′ to R ¹⁹ ′ is preferably the alkoxy group listed in the substituent group Z′, and the substituent which may further be included is also the same as the substituent group Z′.

(h' to j')

f', g', and h' each independently represent the integer of 0-4, and f'+g'+h' is 1 or more.

f'+h' is preferably 1 or more,

f'+h' is 1 or more, and f', g' and h' are more preferably 2 or less,

f'+h' is 1 or more, and f' and h' are more preferably 1 or less,

It is most preferable that both f' and h' are 1.

When both f' and h' are 1, R ¹⁷ ' and R ¹⁹ ' are preferably bonded to each other at a symmetrical position.

In addition, R ¹⁷ ' and R ¹⁹ ' are preferably the same,

It is more preferable that g' is 2.

When g' is 2, it ^{is most preferable that two R 18} ' are bonded to each other at the para position,

When g' is 2, it ^{is most preferred that the two R 18} 's are the same.

Here, R ¹⁷ ' and R ¹⁹ ' bonding to a position symmetrical to each other refers to the following bonding position. However, on the notation, 180 degree rotation about the main chain is regarded as the same structure.

[Formula 50]

Moreover, it is preferable that the repeating unit represented by said formula (22) is a repeating unit represented by following formula (26).

[Formula 51]

In the case of the repeating unit represented by the formula (26), it is preferable that g' = 0 or 2. When g' = 2, the binding sites are the 2nd and 5th positions. When g' = 0, when ^{there is no steric hindrance by R 18} ', and when g' = 2 and the bonding positions are 2 and 5, the steric hindrance is that of the benzene ring to which ^{two R 18 ' are bonded.} It is a diagonal position, and ^{it is possible for R 17} ' and R ¹⁹ ' to bind at a position symmetrical to each other.

Moreover, it is more preferable that the repeating unit represented by said formula (26) is a repeating unit represented by following formula (27).

[Formula 52]

In the case of the repeating unit represented by the formula (27), it is preferable that g' = 0 or 2. When g' = 2, the binding sites are the 2nd and 5th positions. When g' = 0, when ^{there is no steric hindrance by R 18} ', and when g' = 2 and the bonding positions are 2 and 5, the steric hindrance is that of the benzene ring to which ^{two R 18 ' are bonded.} It is a diagonal position, and ^{it is possible for R 7} ′ and R ⁹ ′ to bind at positions symmetric to each other.

[Content of repeat 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 10 mol% or more in the polymer, preferably 30 mol% or more, It is more preferable to contain 40 mol% or more, and it is especially preferable to contain 50 mol% or more. In the polymer having a repeating unit represented by the formula (20), the repeating unit may be composed of only the repeating unit represented by the formula (20). You may have a repeating unit different from 20), and in that case, content of the repeating unit represented by Formula (20) in a polymer is 99 mol% or less normally, Preferably it is 95 mol% or less.

When the repeating unit represented by the formula (25) is contained, the ratio of the repeating unit represented by the formula (20) to the repeating unit represented by the formula (25) is (number of moles of the repeating unit represented by the formula (25))/(formula (number of moles of the repeating unit represented by (20)) is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, still more preferably 0.9 or more, and particularly preferably 1.0. Moreover, 2.0 or less are preferable, 1.5 or less are more preferable, and 1.2 or less are still more preferable.

[Preferred combination of repeating units]

Although the combination of the repeating units of the polymer is not particularly limited, a repeating unit represented ^{by the following formula (28) containing a repeating unit represented by the formula (20) and a repeating unit in which Ar 4} in the formula (22) is the formula (23) It is preferable from a viewpoint of a charge-transporting property improvement and durability improvement to have.

[Formula 53]

In formula (28),

Ar ¹ ', Ar ³ ', X', R ¹ ', R ² ', a', b', c', d', k', m' and n' are the formulas (20), (22) and in Formula (23), respectively.

A preferable structure, a range, etc. are also the same as that in Formula (20), Formula (22), and Formula (23).

More preferably, c' = d' = k' = n' and m' = 1.

In the formula (28), a fluorene ring close to phenylene having a substituent, a carbazole ring, or a biphenyl skeleton connected with an ethylene group is A, a fluorene ring close to phenylene having no substituent, a carbazole ring, or When the biphenyl skeleton connected with an ethylene group is set to B, since A which has a bond which is not conjugated with an amine is not conjugated with an amine, LUMO is difficult to distribute|distribute, and there exists a tendency for durability to improve. In addition, since B conjugated with an amine has a wider conjugation, the hole transport property tends to be improved and more 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 ')-. At this time, R ³ ', R ⁴ ', R ⁵ ', R ¹¹ ', R ¹² ', R ¹³ ' and R ¹⁴ ' of A and B may be the same or different.

X' of A and X' of B are -C(R ³ ')(R ⁴ ')-, or X' of A and X' of B are -NR ⁵ '-, or X' of A and B of When X' is -C(R ¹¹ ')(R ¹² ')-C(R ¹³ ')(R ¹⁴ ')-, the basic backbone of the repeats contained in the polymer is the same, so a level that becomes a trap of charges It is thought that it is difficult to form, is excellent in charge transport property, and is excellent in durability.

More preferably, A and B are the same, still more preferably X' of A and B is -C(R ³ ')(R ⁴ ')-, Especially preferably, X' of A and B are X' is -C(R ³ ')(R ⁴ ')-, and it becomes the same.

<Polymer 3>

The polymer 3 which can be used for a positive hole transport layer in this embodiment has a structure shown in a side chain by following formula (30).

[Formula 54]

In formula (30),

Ar ³¹ ' represents a divalent group connected to the main chain,

Ar ¹² ′ represents a divalent aromatic hydrocarbon group which may have a substituent or a divalent aromatic heterocyclic group which may have a substituent,

Ar ¹³ ′ to Ar ¹⁵ ′ each independently represent a hydrogen atom or a substituent.

* indicates a binding position.

Ar ³¹ ′ represents a divalent group connected to the main chain. Although it does not specifically limit, Preferably it is the ^{same as that of Ar 11} ' in Formula (21), and a preferable range, the substituent which you may have, etc. are also the same. Ar ¹² '~ Ar ^15' is the same as Ar ¹² '~ Ar ^15' of the equation (21), and the like are the same preferred range, may have substituents.

[Formula 55]

In formula (21),

Ar ¹¹ ′ and Ar ¹² ′ each independently represent a divalent aromatic hydrocarbon group or aromatic heterocyclic group which may have a substituent,

Ar ¹³ ′ to Ar ¹⁵ ′ each independently represent a hydrogen atom or a substituent.

It is preferable that the polymer which has a structure represented by Formula (21) in the said side chain has a structure represented by following formula (31).

[Formula 56]

In formula (31),

Ar ¹³ ' to Ar ¹⁵ ' and Ar ³¹ ' are the same as in Formula (21),

Ar ¹⁶ ′ represents a structure constituting the main chain of the polymer.

Polymers having a structure shown in the side chain with the formula (21), the structure represented by the above formula (22), Ar ³ 'is (20) a polymer containing a repeating unit represented by the polymer, or the formula (25) As the polymer containing the repeating unit ^{represented by , it is also preferable that Ar 3} ′ is a polymer having a structure represented by formula (20).

[Availability Period]

It is preferable that the polymer of this embodiment which has a partial structure represented by Formula (CzP) has a soluble group for soluble expression with respect to a solvent. The soluble group in the present embodiment is a group having 3 to 24 carbon atoms, preferably a linear or branched alkyl group or alkylene group having 12 or less carbon atoms. Among these, an alkyl group, an alkoxy group, or an aralkyl group is preferable, for example, n-propyl group, 2-propyl group, n-butyl group, 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 Availability Periods)

It is preferable that there are many soluble groups which the polymer of this embodiment which has a partial structure represented by Formula (CzP) has from a point which becomes easy to obtain the polymer solution which can be used for a wet film-forming method. On the other hand, when another layer is formed by the wet film-forming method on the layer formed into a film, from the point with few film thickness reduction|decrease by a layer melt|dissolving in a solvent, it is preferable that there are few.

The number of soluble groups in the polymer of the present embodiment having a partial structure represented by the formula (CzP) can be expressed by the number of moles per 1 g of the polymer.

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

When the number of soluble groups is within the above range, the polymer is easily dissolved in the solvent, and a composition containing the polymer suitable for the wet film forming method can be easily obtained. Moreover, since the soluble group density is moderate, since the poor solubility with respect to the organic solvent after heating solvent drying is sufficient, it becomes possible to form the multilayer laminated structure in a wet film-forming method.

Here, the number of soluble groups per 1 g of the polymer can be calculated from the molar ratio and structural formula of the charged monomer at the time of synthesis, excluding the terminal groups thereof from the polymer.

For example, in the case of Polymer 1 synthesized in Example 1 to be described later, in Polymer 1, the molecular weight of the repeating unit excluding the terminal group is 650 on average, and the average number of soluble groups is 1 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 1.54 mmol.

[Formula 57]

[Crosslink]

The polymer of this embodiment which has a partial structure represented by Formula (CzP) may have a crosslinkable group. The crosslinkable group which the polymer of this embodiment which has the partial structure represented by Formula (CzP) may have may exist in the repeating unit represented by Formula (20), and a repeating unit different from the repeating unit represented by Formula (20). may exist in In particular, it is preferable to have a crosslinkable group in ^{Ar 1' which is a side chain, since crosslinking reaction advances easily.}

By having a crosslinkable group, a big difference in solubility with respect to an organic solvent can be produced before and behind the reaction (poorly soluble reaction) which occurs by irradiation of a heat|fever and/or an active energy ray.

A crosslinkable group refers to a group which reacts with the group which comprises the other molecule|numerator located in the vicinity of the crosslinkable group by irradiation of a heat|fever and/or an active energy ray, and produces|generates a new chemical bond. In this case, the reactive group may have the same contribution as a crosslinkable group, or a different contribution may be sufficient as it.

The crosslinkable group is preferably a group containing a cyclobutene ring condensed to an aromatic ring or an alkenyl group bonded to an aromatic ring, and more preferably a group selected from the following crosslinkable group group T'.

It is preferable that the crosslinkable group is further substituted by the substituent which each said structure has.

(Crosslinked genital group T')

Crosslinkable group group T' is a structure shown below.

[Formula 58]

In the crosslinkable group group T', R ²¹ ′ 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 the integer of 1-4, q' represents the integer of 1-5, r' represents the integer of 1-7.

When p' is 2 or more, a plurality of R ²⁴ ′ may be the same or different, and adjacent R ²⁴ ′ may be bonded to each other to form a ring.

When q' is 2 or more, a plurality of R ²⁵ ′ may be the same or different, and adjacent R ²⁵ ′ may be bonded to each other to form a ring.

When r' is 2 or more, some R ²⁶ ' may be 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 for 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, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, etc. are mentioned. More preferably, it is a methyl group or an ethyl group. When ^{the carbon number of R 21} ′ to R ²⁶ ′ is 6 or less, the crosslinking reaction is not sterically inhibited, and insolubilization of the film tends to occur.

Examples of the alkoxy group for R ²⁵ ′ and R ²⁶ ′ include a linear or branched alkoxy group having 6 or less carbon atoms. For example, a methoxy group, an ethoxy group, an n-propoxy group, a 2-propoxy group, n-butoxy group, and the like. More preferably, it is a methoxy group or an ethoxy group. When ^{the carbon number of R 25} ′ and R ²⁶ ′ is 6 or less, the crosslinking reaction is not sterically inhibited, and insolubilization of the film tends to occur.

Moreover, as ^{an aromatic hydrocarbon cyclic group which may have a substituent for R 21} ' and R ²² ', for example, a 6-membered monocyclic ring or a 2- to 5-condensed ring having one free valence, such as a benzene ring and a naphthalene ring. can be heard Particularly preferred is a benzene ring having one free valence.

Ar ²² ′ may be a contribution obtained by bonding two or more aromatic hydrocarbon ring groups which may have a substituent. As such a group, a biphenylene group, a terphenylene group, etc. are mentioned, The 4,4'- biphenylene group is preferable.

The ^{substituents Ar 21} ′ and Ar ²² ′ may have are the same as those of the aforementioned substituent group Z′.

As the crosslinkable group, a group that undergoes cyclization addition reaction such as an arylvinylcarbonyl group such as a cinnamoyl group, a benzocyclobutene ring having a monovalent free valence, and a 1,2-dihydrocyclobuta[a]naphthalene ring having a monovalent free valence , which is preferable from the viewpoint of further improving the electrochemical stability of the device.

Among the crosslinkable groups, since the structure after crosslinking is particularly stable, a cyclobutene ring condensed on an aromatic ring having a monovalent free valence, and a 1,2-dihydrocyclobuta[a]naphthalene ring having a monovalent free valence The containing group is preferable, and among them, a benzocyclobutene ring or a 1,2-dihydrocyclobuta[a]naphthalene ring having a monovalent free valence is more preferable, and has a monovalent free valency because of a low crosslinking reaction temperature A 1,2-dihydrocyclobuta[a]naphthalene ring is particularly preferred.

(Number of crosslinkable groups)

The crosslinkable group which the polymer of this embodiment which has a partial structure represented by Formula (CzP) has fully insolubilized by crosslinking, and from the point which becomes easy to form another layer by the wet film-forming method on it, many things are preferable. On the other hand, it is preferable that there are few crosslinkable groups from the point which a crack is hard to generate|occur|produce in the formed layer, unreacted crosslinkable group is hard to remain, and an organic electroluminescent element tends to become long life.

In the polymer of the present embodiment having a partial structure represented by the formula (CzP), the crosslinkable groups present in one polymer chain are preferably 1 or more, more preferably 2 or more, and preferably 200 Hereinafter, more preferably, it is 100 or less.

Moreover, the number of the crosslinkable groups which the polymer which has a partial structure represented by Formula (CzP) has can be represented by the number per 1000 molecular weight of a 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 as the number per 1000 molecular weight of the polymer, it is usually 3.0 or less, preferably 2.0 or less, and more Preferably it is 1.0 or less, and is 0.01 or more normally, Preferably it is 0.05 or more.

When the number of crosslinkable groups is within the above range, cracks or the like are less likely to occur, and a flat film is easily obtained. Moreover, since the crosslinking density is moderate, there are few unreacted crosslinkable groups remaining in the layer after a crosslinking reaction, and it is hard to affect the lifetime of the element obtained.

Moreover, since the poor solubility with respect to the organic solvent after a crosslinking reaction is sufficient, it is easy to form the multilayer laminated structure in a wet film-forming method.

Here, the number of crosslinkable groups per 1000 molecular weight of the polymer can be calculated from the molar ratio and structural formula of the charged monomer at the time of synthesis, excluding the terminal groups from the polymer.

For example, in the case of Polymer 3 synthesized in Examples to be described later, in Polymer 3, the molecular weight of the repeating unit excluding the terminal group is 868 on average, and the number of crosslinkable groups is 0.114 per repeating unit. When this is calculated by simple proportionality, the number of crosslinkable groups per 1000 molecular weight is calculated to be 0.132 pieces.

[Formula 59]

[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 or less, particularly preferably 100,000 or less. Moreover, it is 2,500 or more normally, Preferably it is 5,000 or more, More preferably, it is 10,000 or more, More preferably, it is 20,000 or more, Especially preferably, it is 30,000 or more.

When the weight average molecular weight of a polymer is below the said upper limit, solubility with respect to a solvent is acquired and it exists in the tendency excellent in film-forming property. Moreover, when the weight average molecular weight of a polymer is more than the said lower limit, the fall of the glass transition temperature of a polymer, melting|fusing point, and vaporization temperature is suppressed, and heat resistance may improve. In addition, the insolubility with respect to the organic solvent of the coating film after a crosslinking reaction may be sufficient.

Moreover, the number average molecular weight (Mn) in the polymer which has a partial structure represented by Formula (CzP) is 2,500,000 or less normally, Preferably it is 750,000 or less, More preferably, it is 400,000 or less, Especially preferably, it is 100,000 or less. Moreover, it is 2,000 or more normally, Preferably it is 4,000 or more, More preferably, it is 8,000 or more, More preferably, it is 20,000 or more.

And the degree of dispersion (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, particularly preferably 2.0 or less. In addition, since a dispersion degree is so good that a value is small, the lower limit is ideally 1. If the degree of dispersion of the polymer is equal to or less than the upper limit, purification is easy, and solubility in a solvent and charge transport 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 elution time of a high molecular weight component is shorter, and the elution time is longer as a low molecular weight component. By converting to , a weight average molecular weight is computed.

[Specific Example]

Although the specific example of the polymer which has a partial structure represented by a formula (CzP) is shown below, the polymer which has a partial structure represented by a formula (CzP) is not limited to these. In addition, a number in a formula represents the molar ratio of a repeating unit.

These polymers may be any of random copolymers, alternating copolymers, block copolymers, graft copolymers, and the like, and are not limited to the sequence of the monomers.

[Formula 60]

[Formula 61]

[Method for producing polymer]

The manufacturing method in particular of the polymer which has a partial structure represented by Formula (CzP) is not restrict|limited, It is arbitrary as long as the polymer which has a partial structure represented by Formula (CzP) is obtained. For example, it can be produced by a polymerization method by Suzuki reaction, polymerization method by Grignard reaction, polymerization method by Yamamoto reaction, polymerization method by Ullmann reaction, polymerization method by Buchwald-Hartwig reaction, and the like.

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

[Formula 62]

In the above formula, Y represents a halogen atom, and Ar ¹ ′, R ¹ ′ to R ⁴ ′ and X have the same meanings as in the above formula (20).

In the polymerization method described above, the reaction for forming an N-aryl bond is usually carried out in the presence of a base such as potassium carbonate, sodium tert-butoxy, or triethylamine. Moreover, it can also carry out, for example in presence of transition metal catalysts, such as copper and a palladium complex.

<Low molecular weight compound>

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

<Composition for organic electroluminescent device>

The hole transporting layer and the light emitting layer adjacent to the hole transporting layer of the organic electroluminescent device, which are embodiments of the second and third aspects of the present invention, use a composition in which a material having the formula (CzP) as a partial structure is dissolved in a solvent. can be filmed

The composition for an organic electroluminescent device for forming the hole transport layer preferably contains any of the above-mentioned polymers 1 to 3, and the composition for an organic electroluminescent device for forming the light emitting layer contains the above-mentioned low molecular weight compound. It is preferable to contain

[Content of a material having the formula (CzP) as a partial structure]

Content of the material which has Formula (CzP) as a partial structure in the said composition is 0.01-70 mass % normally, Preferably it is 0.1-60 mass %, More preferably, it is 0.5-50 mass %.

If it is in the said range, since it is hard to produce a defect in the formed organic layer, and it is hard to produce a film thickness nonuniformity, it is preferable.

[menstruum]

The composition usually contains a solvent. It is preferable that this solvent melt|dissolves the material which has Formula (CzP) as a partial structure. Specifically, a solvent which dissolves the material having the formula (CzP) as a partial structure is usually 0.05 mass% or more, preferably 0.5 mass% or more, and more preferably 1 mass% or more at room temperature.

Specific examples of the solvent include aromatic solvents such as toluene, xylene, mesitylene and cyclohexylbenzene; halogen-containing solvents such as 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene; Aliphatic ethers 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, ether solvents such as aromatic ethers such as 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, and 2,4-dimethylanisole; aliphatic ester solvents such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate; ester solvents such as aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, isopropyl benzoate, propyl benzoate, and n-butyl benzoate; Organic solvents, such as organic solvents, and the organic solvent used for the composition for hole injection layer formation, and the composition for hole transport layer formation mentioned later are mentioned.

In addition, one type may be used for a solvent, and may use two or more types together by arbitrary combinations and arbitrary ratios.

Among them, as the solvent contained in the composition for an organic electroluminescent device, the surface tension at 20°C is usually less than 40 dyn/cm, preferably 36 dyn/cm or less, more preferably 33 dyn/cm or less. Solvents are preferred.

The composition used for the wet film forming method is required to have a lower surface tension so as to form a more uniform coating film with higher leveling properties. Therefore, it is preferable to use a solvent having a low surface tension as described above, because it is possible to form a uniform layer containing a material having the formula (CzP) as a partial structure.

Specific examples of the low surface tension solvent include the aforementioned aromatic solvents such as toluene, xylene, mesitylene and cyclohexylbenzene, ester solvents such as ethyl benzoate, ether solvents such as anisole, trifluoromethoxy anisole, pentafluoromethoxybenzene, 3-(trifluoromethyl)anisole, ethyl (pentafluorobenzoate), etc. are mentioned.

On the other hand, as a solvent contained in the said composition, the vapor pressure in 25 degreeC is 10 mmHg or less normally, Preferably it is 5 mmHg or less, It is preferable that it is 0.1 mmHg or more normally. By using such a solvent, the composition for organic electroluminescent elements suitable for the property of the material which is suitable for the process of manufacturing an organic electroluminescent element by the wet film-forming method, and has Formula (CzP) as a partial structure can be prepared. .

Specific examples of such a solvent include the aforementioned aromatic solvents such as toluene, xylene, and mesitylene, ether solvents, and ester solvents.

By the way, moisture may cause performance degradation of an organic electroluminescent element, and especially may accelerate|stimulate the luminance fall at the time of continuous driving. Then, in order to reduce the water|moisture content remaining during wet film-forming as much as possible, among the said solvent, it is preferable that the solubility of water in 25 degreeC is 1 mass % or less, and the solvent which is 0.1 mass % or less is more preferable.

Content of the solvent contained in the composition for organic electroluminescent elements is 10 mass % or more normally, Preferably it is 30 mass % or more, More preferably, it is 50 mass % or more, Especially preferably, it is 80 mass % or more. When content of a solvent is more than the said lower limit, the flatness and uniformity of the layer to be formed can be made favorable.

[electron accepting compound]

It is preferable that the composition for organic electroluminescent elements contains an electron-accepting compound further at the point of reducing resistance. In particular, when using the composition for organic electroluminescent elements in order to form a hole injection layer, it is preferable to contain an electron-accepting compound.

As an electron-accepting compound, it has oxidizing power and the compound which has the 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 of 5 eV or more is more preferable.

Examples of the electron-accepting compound include triaryl boron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, and salts of arylamines and Lewis acids. 1 type or 2 or more types of compounds etc. used are mentioned.

Specifically, onium salts substituted with organic groups such as 4-isopropyl-4'-methyldiphenyliodoniumtetrakis(pentafluorophenyl)borate and triphenylsulfoniumtetrafluoroborate (International Publication No. 2005/ 089024) (International Publication No. 2017/164268) ; high valence inorganic compounds, such as iron (III) chloride (Unexamined-Japanese-Patent No. 11-251067) and ammonium peroxodisulfate; Cyano compounds, such as tetracyanoethylene; Aromatic boron compounds, such as tris (pentafluorophenyl) borane (Unexamined-Japanese-Patent No. 2003-31365); A fullerene derivative, an iodine, etc. are mentioned.

The composition for organic electroluminescent elements may contain individually 1 type of the above electron-accepting compounds, and may contain 2 or more types by arbitrary combinations and a 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 mass% or more, preferably 0.001 mass% or more, and usually 20 mass% or less, Preferably it is 10 mass % or less. Moreover, the ratio of the electron-accepting compound with respect to the polymer in the composition for organic electroluminescent elements is 0.5 mass % or more normally, Preferably it is 1 mass % or more, More preferably, it is 3 mass % or more, Usually 80 mass % or less, Preferably Preferably it is 60 mass % or less, More preferably, it is 40 mass % or less.

If the content of the electron-accepting compound in the composition for an organic electroluminescent device is at least the above lower limit, the electron acceptor accepts electrons from the polymer and the formed organic layer lowers the resistance. Moreover, since it is hard to produce a film-thickness nonuniformity, it is preferable.

[Cation radical compound]

The composition for organic electroluminescent elements may contain the cation radical compound further.

As a cation radical compound, the ionic compound which consists of a cation radical which is the chemical species which removed 1 electron from the hole transport 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.

Moreover, as a cation radical, it is preferable that it is the chemical species which removed 1 electron from the hole-transporting compound mentioned later. A chemical species in which one electron has been removed from a compound preferable as the hole-transporting compound is preferable from the viewpoints of amorphousness, visible light transmittance, heat resistance, solubility, and the like.

Here, the cation radical compound can be produced|generated by mixing the hole transporting compound mentioned later and the electron-accepting compound mentioned 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 a cation-ion compound composed of a cation radical and a counter anion of the hole-transporting compound is generated.

When the composition for organic electroluminescent elements contains a cation radical compound, content of the cation radical compound of the composition for organic electroluminescent elements is 0.0005 mass % or more normally, Preferably it is 0.001 mass % or more, Usually 40 mass % Below, Preferably it is 20 mass % or less. Since the formed organic layer lowers resistance as content of a cation radical compound is more than a lower limit, it is preferable, and if it is below an upper limit, since it is difficult to produce a defect in the formed organic layer and a film thickness nonuniformity does not arise easily, it is preferable.

In addition, in the composition for organic electroluminescent elements, you may contain the component contained in the composition for hole injection layer formation or the composition for hole transport layer formation mentioned later other than the said component by content mentioned later.

<Organic electroluminescent element>

The organic electroluminescent element in this invention is an organic electroluminescent element which has an anode, a cathode, and an organic layer between the anode and the cathode on a board|substrate. In the organic electroluminescent element in the embodiment of the first aspect of the present invention, the organic layer has a layer containing the above-mentioned polymer 1 or a polymer in which the polymer 1 is crosslinked. In the organic electroluminescent device in the embodiment of the second aspect 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 the above-described polymer 1 or polymer 1 crosslinked. The polymer used is contained, and the light emitting layer contains a material having a partial structure represented by the above formula (CzP). The organic electroluminescent device in the embodiment of the third aspect of the present invention has a hole transport layer and a light emitting layer adjacent to the hole transport layer, and at least one of the hole transport layer and the material contained in the light emitting layer is a carbazole ring. It contains the material (compound) which has the partial structure represented by the above-mentioned formula (CzP) which has. In the embodiment of the third aspect, the material having a partial structure represented by formula (CzP) contained in the hole transport layer is a polymer in which the polymer 2 or the polymer 2 is crosslinked, or the polymer 3 or the polymer 3 is crosslinked. It is preferred that the polymer is used.

Each condition and aspect in the organic electroluminescent element which concerns on said each embodiment can be combined arbitrarily. The specific description of the manufacturing method and characteristic applicable to these organic electroluminescent elements is shown below.

Although the manufacturing method in particular of this organic electroluminescent element in embodiment of this invention is not restrict|limited, At least 1 layer among the layers which comprises an organic layer is wet-film-forming using the composition for organic electroluminescent elements mentioned above using the above-mentioned composition. It is preferable to manufacture by a method including the film-forming step of forming. When an organic layer consists of a several layer, a well-known method can be used for the method of laminating|stacking the several layer, etc.

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

The wet film forming method in this embodiment is a film forming method, ie, a coating method, for example, a spin coat method, a dip coat method, a die coat method, a bar coat method, a blade coat method, a roll coat method, or a spray coat method. A method of forming a film by using a wet method such as a method, capillary coating method, inkjet method, nozzle printing method, screen printing method, gravure printing method, flexographic printing method, etc., and drying this coating film to form a film say Among these film-forming methods, the spin coating method, the spray coating method, the inkjet method, the nozzle printing method, etc. are preferable.

As an example of the structure of an organic electroluminescent element, the schematic diagram (cross section) of the structural example of the organic electroluminescent element 10 is shown 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, 8 is an electron injection layer, 9 is a cathode, respectively. indicates.

Hereinafter, an example of embodiment, such as the layer structure of an organic electroluminescent element and its general formation method, is demonstrated with reference to FIG.

[Board]

The board|substrate 1 becomes a support body of an organic electroluminescent element, Usually, a plate of quartz or glass, a metal plate, metal foil, a plastic film, a sheet|seat, etc. are used. Among these, a glass plate and a plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate or polysulfone are preferable. The substrate is preferably made of a material having high gas barrier properties since deterioration of the organic electroluminescent element by external air hardly occurs. For this reason, especially when using a material with low gas barrier properties, such as a synthetic resin substrate, it is preferable to form a dense silicon oxide film or the like on at least one surface of the substrate to increase the gas barrier properties.

[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, or platinum; metal oxides such as oxides of indium and/or tin; metal halides such as copper iodide; It is comprised by carbon black and conductive polymers, such as poly(3-methylthiophene), polypyrrole, and polyaniline.

Formation of the anode 2 is normally performed by dry methods, such as a sputtering method and a vacuum vapor deposition method, in many cases. In the case of forming the anode using fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide particles, conductive polymer fine powder, etc., disperse in a suitable binder resin solution and apply on the substrate. can also be formed. Further, in the case of a conductive polymer, a thin film may be formed directly on a substrate by electrolytic polymerization, or an anode may be formed by coating a conductive polymer on the substrate (Appl. Phys. Lett., Vol. 60, page 2711, 1992). year).

Although the anode 2 is normally a single-layer structure, it is good also considering it as a laminated structure suitably. When the anode 2 has a laminated structure, different conductive materials may be laminated on the anode of the first layer.

What is necessary is just to determine the thickness of the anode 2 according to transparency, material etc. which are required. When especially high transparency is required, the thickness used as 60 % or more of the transmittance|permeability of visible light is preferable, and the thickness used as 80 % or more is more preferable. The thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and is usually 1000 nm or less, preferably 500 nm or less. On the other hand, when transparency is unnecessary, the thickness of the anode 2 may be any thickness depending on the required strength or the like, and in this case, the anode 2 may have the same thickness as the substrate.

In the case of forming another layer on the surface of the anode 2, treatment with ultraviolet/ozone, oxygen plasma, argon plasma, etc. is performed before film formation to remove impurities on the anode 2 and adjust the ionization potential. Thus, it is preferable to improve the hole injection property.

[Hole Injection Layer]

The layer responsible for the 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. In addition, when there are two or more layers responsible for the function of transporting holes from the anode 2 side to the light emitting layer 5 side, the layer closer to the anode side may be called a hole injection layer 3 in some cases. . The hole injection layer 3 is preferably formed from the viewpoint of enhancing the function of transporting holes from the anode 2 to the light emitting layer 5 side. When forming the positive hole injection layer 3, the positive hole injection layer 3 is formed on the anode 2 normally.

The 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.

A vacuum vapor deposition method may be sufficient as the formation method of a positive hole injection layer, and the wet film-forming method may be sufficient as it. It is preferable to form by the wet film-forming method from the point which is excellent in film-forming property.

The hole injection layer 3 preferably contains a hole transporting compound, and more preferably contains a hole transporting compound and an electron-accepting compound. Furthermore, it is preferable to contain a cation radical compound in a positive hole injection layer, and it is especially preferable to contain a cation radical compound and a hole transport compound.

Hereinafter, a general method for forming the hole injection layer will be described. In an organic electroluminescent device, the hole injection layer is preferably formed by a wet film forming method using a composition for an organic electroluminescent device.

[Hole-transporting compound]

The composition for hole injection layer formation contains the hole-transporting compound used as the positive hole injection layer 3 normally. Moreover, in the case of a wet film-forming method, it also contains a solvent further normally. It is preferable that the composition for hole injection layer formation has high hole transport property and can transport the injected hole efficiently. For this reason, it is preferable that the hole mobility is large and the impurity used as a trap is difficult to generate|occur|produce at the time of manufacture, use, etc. Moreover, it is preferable that it is excellent in stability, the ionization potential is small, and transparency with respect to visible light is high. In particular, when the hole injection layer is in contact with the light emitting layer, it is preferable not to quench the light emission from the light emitting layer or to form an exciplex with the light emitting layer so as not to lower the luminous efficiency.

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 the charge injection barrier from the anode to the hole injection layer. Examples of the hole transporting compound include an aromatic amine compound, a phthalocyanine compound, a porphyrin compound, an oligothiophene compound, a polythiophene compound, a benzylphenyl compound, a compound in which a tertiary amine is linked with a fluorene group, hydra A zone-based compound, a silazane-based compound, and a quinacridone-based compound may be mentioned.

Among the above-mentioned exemplary compounds, an aromatic amine compound is preferable and an aromatic tertiary amine compound is especially preferable at the point of amorphousness and visible light transmittance. Here, the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and includes a compound having a group derived from an aromatic tertiary amine.

Although the type of the aromatic tertiary amine compound is not particularly limited, a high molecular weight compound having a weight average molecular weight of 1000 or more and 1000000 or less (a polymer compound in which repeating units are continued) is used in that it is easy to obtain uniform light emission due to the surface smoothing effect. It is preferable to do

The hole injection layer 3 preferably contains the electron-accepting compound and the cation radical compound described above because the conductivity of the hole injection layer can be improved by oxidation of the hole transport compound.

Cationic radical compounds derived from high molecular weight compounds such as PEDOT/PSS (Adv. Mater., 2000, vol. 12, p. 481) or emeraldine hydrochloride (J. Phys. Chem., 1990, vol. 94, p. 7716) are , also produced by oxidative polymerization (dehydrogenation polymerization).

The oxidative polymerization referred to herein is to chemically or electrochemically oxidize a monomer in an acidic solution using peroxodisulfate or the like. In the case of this oxidative polymerization (dehydrogenation polymerization), while a monomer is polymerized by oxidation, the cation radical which uses the anion derived from an acidic solution as a counter anion, one electron was removed from the repeating unit of a polymer is produced|generated.

[Formation of hole injection layer by wet film forming method]

When the hole injection layer 3 is formed by the wet film forming method, the material for forming the hole injection layer is usually mixed with a soluble solvent (solvent for the hole injection layer) to prepare a film forming composition (the composition for forming the hole injection layer). It is prepared, this composition for hole injection layer formation is apply|coated on the layer (usually an anode) corresponding to the lower layer of a hole injection layer, it forms into a film, and it forms by drying.

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 preferably low in terms of uniformity of the film thickness, and on the other hand, in the hole injection layer It is preferable that it is high from the point which a defect is hard to generate|occur|produce. Specifically, it is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, particularly preferably 0.5 mass% or more, and, on the other hand, preferably 70 mass% or less, still more preferably 60 mass% or less, , 50% by mass or less is particularly preferred.

As a solvent, an ether type solvent, an ester type solvent, an aromatic hydrocarbon type solvent, an amide type solvent etc. are mentioned, for example.

Examples of the ether-based solvent include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA) and 1,2-dimethoxybenzene, 1,3- and aromatic ethers such as dimethoxybenzene, anisole, phenetol, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, and 2,4-dimethylanisole. can

Examples of the ester 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, and cyclohexylbenzene. , methyl naphthalene, and the like.

Examples of the amide solvent include N,N-dimethylformamide and N,N-dimethylacetamide.

In addition to these, dimethyl sulfoxide and the like can also be used.

Formation of the hole injection layer 3 by the wet film-forming method is usually after preparing the composition for hole injection layer formation, this is the layer corresponding to the lower layer of the hole injection layer 3 (usually the anode 2). It is carried out by coating and film-forming on the top and drying.

The hole injection layer 3 usually dries a coating film by heating, reduced pressure drying, etc. after film-forming.

[Formation of hole injection layer by vacuum deposition method]

In the case of forming the hole injection layer 3 by vacuum deposition, one or more of the constituent materials of the hole injection layer 3 (the above-described hole transporting compound, electron accepting compound, etc.) Put it in the installed crucible (if two or more types of materials are used, usually put each in each crucible), ^{exhaust the inside of the vacuum container to about 10 -4} Pa with a vacuum pump, and then heat the crucible (2 or more types of materials). When materials are used, each crucible is usually heated) and evaporated while controlling the evaporation amount of the material in the crucible (when two or more types of materials are used, they are usually evaporated while controlling the evaporation amount independently of each other), the crucible A hole injection layer is formed on the anode on the substrate placed opposite to the . In the case of using two or more types of materials, a mixture thereof may be put in a crucible, 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 usually 0.1 × 10 ^-6 Torr (0.13 × 10 ^-4 Pa) or more, 9.0 × 10 ^-6 Torr (12.0 × 10 ^-4) Pa) or less. The deposition rate is not limited as long as the effect of the present invention is not significantly impaired, and is usually 0.1 angstrom/sec or more and 5.0 angstrom/sec or less. Although the film-forming temperature at the time of vapor deposition is not limited unless the effect of this invention is impaired remarkably, Preferably, it implements at 10 degreeC or more and 50 degrees C or less.

In addition, the positive hole injection layer 3 may be bridge|crosslinked similarly to the positive hole transport layer 4 mentioned later.

[Hole transport layer]

The hole transport layer 4 is a layer that has 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). In the case of forming the hole transport layer 4 , the hole transport layer 4 is usually formed between the anode 2 and the light emitting layer 5 . Moreover, when there exists the positive hole injection layer 3 mentioned above, it is formed between the positive hole injection layer 3 and the light emitting layer 5. As shown in FIG.

The 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.

A vacuum vapor deposition method may be sufficient as the formation method of the positive hole transport layer 4, and the wet film-forming method may be sufficient as it. It is preferable to form by the wet film-forming method from the point which is excellent in film-forming property.

Although the general method of forming a hole transport layer is demonstrated below, in an organic electroluminescent element, it is preferable that a hole transport layer is formed by the wet film-forming method using the composition for organic electroluminescent elements.

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 positive hole transport layer 4 contains a positive hole transport compound normally. 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. In addition, 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, and condensed two or more Aromatics having a starburst structure, such as aromatic diamine in which an aromatic ring is substituted with a nitrogen atom (Japanese Patent Laid-Open No. 5-234681), 4,4',4''-tris(1-naphthylphenylamino)triphenylamine, etc. Amine compounds (J. Lumin., vol. 72-74, pp. 985, 1997), aromatic amine compounds consisting of a tetramer of triphenylamine (Chem. Commun., pp. 2175, 1996), 2,2',7, Spiro compounds such as 7'-tetrakis-(diphenylamino)-9,9'-spirobifluorene (Synth. Metals, vol. 91, p. 209, 1997), 4,4'-N,N'- Carbazole derivatives, such as dicarbazole biphenyl, etc. are mentioned as a preferable thing. Further, for example, polyvinylcarbazole, polyvinyltriphenylamine (Japanese Patent Application Laid-Open No. 7-53953), polyarylene ether sulfone containing tetraphenylbenzidine (Polym. Adv. Tech., Vol. 7, 33) Page, 1996) and the like.

[Formation of hole transport layer by wet film formation method]

In the case of forming the hole transport layer by the wet film forming method, usually, in the same manner as in the case of forming the above-described hole injection layer by the wet film forming method, the composition for forming the hole transport layer is used instead of the composition for forming the hole injection layer. make it

When forming a positive hole transport layer by the wet film-forming method, normally, the composition for positive hole transport layer formation contains a solvent further. 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 the hole injection layer described above can be used.

The concentration of the hole-transporting compound in the composition for forming a hole-transporting layer can be in the same range as the concentration of the hole-transporting compound in the composition for forming a hole-injecting layer.

Formation of a hole transport layer by the wet film-forming method can be performed similarly to the hole injection layer film-forming method mentioned above.

[Formation of hole transport layer by vacuum deposition method]

In the case of forming the hole transport layer by the vacuum deposition method, in general, in the same manner as in the case of forming the hole injection layer by the vacuum deposition method, a composition for forming the hole transport layer is used instead of the composition for forming the hole injection layer. can Film formation conditions such as the degree of vacuum at the time of deposition, deposition rate and temperature, etc., can be formed under the same conditions as those during vacuum deposition of the hole injection layer.

[Light emitting layer]

When an electric field is applied between a pair of electrodes, the light emitting layer 5 is excited by recombination of the holes injected from the anode 2 and the electrons injected from the cathode 9, and is a layer which bears the function of emitting light. 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 on the anode When there is a transport layer, 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, but a thicker one is preferable in that the film is less prone to defects, and on the other hand, a thinner one is easier to achieve a lower driving voltage. desirable. For this reason, it is preferable that it is 3 nm or more, It is more preferable that it is 5 nm or more, On the other hand, it is usually preferable that it is 200 nm or less, and it is still more preferable that it is 100 nm or less.

The light emitting layer 5 preferably contains a host material having at least any of hole transport properties or electron transport properties, such as a light emitting material to be described later or a compound having a partial structure represented by the formula (CzP) described above, and in particular, at least , It is preferable to contain a material (light emitting material) having a property of emitting light, and preferably, a material having a charge transporting 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 embodiment according to the second and third aspects of the present invention, the light emitting layer contains a material having a partial structure represented by formula (CzP). The light emitting layer may contain materials 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 light-emitting material>

The phosphorescent light emitting material refers to a material that emits light from a triplet excited state. For example, a metal complex compound having Ir, Pt, Eu or the like is a representative example thereof, and it is preferable to include a metal complex as a structure of the material.

Among metal complexes, a phosphorescent organometallic complex that emits light via a triplet state is a long-period periodic table (hereinafter, when referred to as a "periodic table" unless otherwise specified, it shall refer to a long-period periodic table). and Werner-type complexes or organometallic complex compounds containing a metal selected from Groups 7 to 11 as a central metal. As such a phosphorescent material, the compound represented by the following formula (201) or the compound represented by the formula (205) is preferable, and a compound represented by the formula (201) is more preferable.

[Formula 63]

Ring A1 represents the aromatic hydrocarbon ring structure which may have a substituent, or the aromatic heterocyclic structure which may have a substituent.

Ring A2 represents the aromatic heterocyclic structure which may have a substituent.

R ²⁰¹ and R ²⁰² each independently represent a structure 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 two or more R ²⁰¹ and R ²⁰² each exist, 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 represents 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.

Each other and the substituent bonded to the substituent, and ring A2 binding to each other substituents bonded to the A ring ^201, between the substituent, or a ring bonded to the ring A1 A2, may be combined with each other to form a ring.

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 an atomic group constituting a bidentate ligand together with ^{B 201} and B ^{202 .} When two or more B ²⁰¹ -L ²⁰⁰ -B ²⁰² exist, they may be the same or different.

i1 and i2 each independently represent an integer of 0 or more and 12 or less.

i3 is an integer of 0 or more whose upper limit is the number substitutable by ^{Ar 202 .}

j is an integer of 0 or more whose upper limit is the number that can be substituted with ^{Ar 201 .}

each of k1 and k2 is independently an integer of 0 or more with the upper limit of the number substitutable for the ring A1 and the ring A2.

v is an integer of 1-3.

For each group in the formulas (201) and (202), unless otherwise specified, a group selected from the following substituent group Z2 is preferable as a substituent which may be included.

<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, still more preferably an alkyl group having 1 to 8 carbon atoms, 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, still more 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 an aryloxy group having 6 to 12 carbon atoms. an aryloxy group.

- Heteroaryloxy group, Preferably a C3-C20 heteroaryloxy group, More preferably, a C3-C12 heteroaryloxy group.

- Alkylamino group, Preferably it is a C1-C20 alkylamino group, More preferably, it is a C1-C12 alkylamino group.

· An arylamino group, preferably an arylamino group having 6 to 36 carbon atoms, 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, still more 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, still more preferably an alkenyl group having 2 to 8 carbon atoms, particularly preferably an alkenyl group having 2 to 6 carbon atoms .

- Alkynyl group, Preferably it is a C2-C20 alkynyl group, More preferably, it is a C2-C12 alkynyl group.

An aryl group, preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, still more preferably an aryl group having 6 to 18 carbon atoms, particularly preferably an aryl group having 6 to 14 carbon atoms .

- A heteroaryl group, preferably a C3-C30 heteroaryl group, more preferably a C3-C24 heteroaryl group, still more preferably a C3-C18 heteroaryl group, particularly preferably a C3-C30 heteroaryl group. The heteroaryl group of 14.

· An alkylsilyl group, preferably an alkylsilyl group having 1 to 20 carbon atoms in the alkyl group, more preferably an alkylsilyl group having 1 to 12 carbon atoms in the alkyl group.

· An arylsilyl group, preferably an arylsilyl group having 6 to 20 carbon atoms in the aryl group, and more preferably an arylsilyl group having 6 to 14 carbon atoms in the aryl group.

- An 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 substituted with fluorine atoms, or one or more hydrogen atoms may be substituted with deuterium atoms.

Unless otherwise specified, aryl is an aromatic hydrocarbon and heteroaryl is an aromatic heterocyclic ring.

- A hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, or -SF5.

(preferred group in the substituent group Z2)

Among these substituent groups Z2, preferably, an alkyl group, an alkoxy group, an aryloxy group, an arylamino group, an aralkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkylsilyl group, an arylsilyl group, and at least one hydrogen of these groups A group in which an atom is substituted with a fluorine atom, a fluorine atom, a cyano group, or -SF5, more preferably an alkyl group, an arylamino group, an aralkyl group, an alkenyl group, an aryl group, a heteroaryl group, and at least one hydrogen of these groups A group in which atoms are substituted with a fluorine atom, a fluorine atom, a cyano group, or -SF5, more preferably an alkyl group, an alkoxy group, an aryloxy group, an arylamino group, an aralkyl group, an alkenyl group, an aryl group, a heteroaryl group, An alkylsilyl group or an arylsilyl group, particularly preferably an alkyl group, an arylamino group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group, and most preferably an alkyl group, an arylamino group, an aralkyl group, an aryl group, or a heteroaryl group. am.

In these substituent group Z2, you may have a substituent further selected from the substituent group Z2 as a substituent. A preferable group, a more preferable group, a still more preferable group, a particularly preferable group, and the most preferable group of the substituents you may have are the same as the preferable groups in the substituent group Z2.

Ring A1 represents the aromatic hydrocarbon ring structure which may have a substituent, or the 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 are preferable. do.

The aromatic heterocyclic ring is preferably a C3-C30 aromatic heterocyclic ring containing any of a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, more preferably a furan ring, a benzofuran ring, or a thiophene. ring, a 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 the aromatic heterocyclic structure which may have a substituent.

The aromatic heterocyclic ring is preferably an aromatic heterocyclic ring having 3 to 30 carbon atoms containing any of a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, specifically, a pyridine ring, a pyrimidine ring, and a pyrazine ring. , triazine ring, imidazole ring, oxazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzoimidazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, naphthyridine a ring and a phenanthridine ring are mentioned, 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 quinoxaline ring , a quinazoline ring, more preferably a pyridine ring, an imidazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a quinazoline ring, most preferably a pyridine ring, an imidazole ring , a benzothiazole ring, a quinoline ring, a quinoxaline ring, and a quinazoline ring.

Preferred combinations of ring A1 and ring A2 include (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).

Although the substituents which the ring A1 and the ring A2 may have can be selected arbitrarily, Preferably they are 1 type or multiple types of substituents selected from the said 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 represents 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.

When any of Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ is an aromatic hydrocarbon ring structure which may have a substituent, the aromatic hydrocarbon ring structure is preferably an aromatic hydrocarbon ring having 6 to 30 carbon atoms, specifically, a benzene ring; A naphthalene ring, an anthracene ring, a triphenylyl ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring are preferable, More preferably, a benzene ring, a naphthalene ring, a fluorene ring are preferable, Most preferably, a benzene ring am.

When any of Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ is a fluorene ring which may have a substituent, it is preferable that the 9-position and 9' position of the fluorene ring have a substituent or are bonded to an adjacent structure.

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 an ortho or meta position, and at least one benzene ring is It is more preferable to couple|bond with the structure adjacent to the meta position.

When any of Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ is an aromatic heterocyclic structure which may have a substituent, the aromatic heterocyclic structure preferably contains any of a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom , an aromatic heterocyclic ring 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, a benzothiazole ring, or a benzoxazole ring , a benzimidazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a quinazoline ring, a naphthyridine ring, a phenanthridine ring, a carbazole ring, a dibenzofuran ring, and a dibenzothiophene ring; More preferably, they are a pyridine ring, a pyrimidine ring, a triazine ring, a carbazole ring, a dibenzofuran ring, and a dibenzothiophene ring.

When any of Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ is a carbazole ring which may have a substituent, it is preferable that the N position of the carbazole ring has a substituent or is bonded to an adjacent structure.

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, more preferably 1 or more carbon atoms. It is 12 or less, More preferably, carbon number is 1 or more and 8 or less.

i1 represents the integer of 0-12, Preferably it is 1-12, More preferably, it is 1-8, More preferably, it is 1-6. By being in this range, a solubility improvement and a charge-transporting property improvement are anticipated.

i3 preferably represents the integer of 0-5, More preferably, it is 0-2, More preferably, it is 0 or 1.

j preferably represents an integer of 0 to 2, more preferably 0 or 1.

k1 and k2 preferably represent the integer of 0-3, More preferably, it is 1-3, More preferably, it is 1 or 2, Especially preferably, it is 1.

The ^{substituents Ar 201} , Ar ²⁰² , and Ar ²⁰³ may have can be arbitrarily selected, but are preferably one or more substituents selected from the above substituent group Z2, and a preferred group is the same as the above substituent group Z2, but more preferably is a hydrogen atom, an alkyl group or an aryl group, particularly preferably a hydrogen atom or an alkyl group, and most preferably unsubstituted (hydrogen atom).

Among the structures represented by the formula (202), materials having the following structures are preferable. A structure having a group in which a benzene ring is linked, that is, Ar ²⁰¹ is a benzene ring structure, i1 is 1 to 6, and at least one benzene ring is bonded to an adjacent structure at an ortho position or a meta position. It is expected that solubility improves and charge transport property improves by this structure.

A structure having an aromatic hydrocarbon group or an aromatic heterocyclic group in which an alkyl group or an aralkyl group is bonded to the ring A1 or ring A2. That is, Ar ²⁰¹ is an aromatic hydrocarbon structure or aromatic heterocyclic structure, i1 is 1 to 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. Preferably, Ar ²⁰¹ is the above aromatic hydrocarbon structure, more preferably a structure in which 1 to 5 benzene rings are connected, and more preferably one benzene ring. It is expected that solubility improves and charge transport property improves by this structure.

A structure in which a dendron is bonded to a ring A1 or a ring A2. For example, when Ar ²⁰¹ , Ar ²⁰² is a benzene ring structure, Ar ²⁰³ is a biphenyl or terphenyl structure, i1, i2 is 1 to 6, i3 is 2, j is 2. This structure improves solubility, Further, it is expected that the charge transport property 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 an atomic group constituting a bidentate ligand together with ^{B 201} and B ^{202 .} When two or more B ²⁰¹ -L ²⁰⁰ -B ²⁰² exist, they may be the same or different.

Among the structures represented by B ²⁰¹ -L ²⁰⁰ -B ²⁰² , it is preferably a structure represented by the following formula (203) or (204).

[Formula 64]

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

[Formula 65]

In Formula (204), ring B3 represents the aromatic heterocyclic structure containing the nitrogen atom which may have a substituent. Ring B3 is preferably a pyridine ring. As a substituent which this may have, the group chosen from the substituent group Z2 mentioned above is preferable.

Although limitation in particular is not carried out as a phosphorescent light emitting material represented by Formula (201), Specifically, the following structure is mentioned.

[Formula 66]

[Formula 67]

[Formula 68]

As the phosphorescent material, a compound represented by the formula (205) other than the formula (201) can also be used.

[Formula 69]

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, R ⁹⁴ and R ⁹⁵ are absent.

In formula (205), M ² represents a metal. Specific examples include the metals described above as metals selected from Groups 7 to 11 of the periodic table. Among them, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum or gold is particularly preferred, and divalent metals such as platinum and palladium are particularly preferred.

In the formula (205), R ⁹² and R ⁹³ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, a cyano group, an amino group, an acyl group, an alkoxycarbonyl group, a carboxyl group, 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.

In addition, when T is a carbon atom, R ⁹⁴ and R ⁹⁵ each independently represent the substituent represented by the same example as ^{R 92} and R ^{93 .} Further, when T is a nitrogen atom, R ⁹⁴ or R ⁹⁵ directly bonded to T does not exist. In addition, R ⁹² ~ R ⁹⁵ are, or may have a substituent further. As a substituent, it can be set as said substituent. Further, ^{any two or more groups of R 92} to R ^{95 may} be linked 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. Moreover, the molecular weight of a phosphorescent light emitting material is 800 or more normally, Preferably it is 1000 or more, More preferably, it is 1200 or more. It is thought that a light emitting layer with high luminous efficiency can be obtained by being uniformly mixed with a charge transport material without aggregation of phosphorescent light emitting materials by this molecular weight range.

The molecular weight of the phosphorescent material has a high Tg, melting point, decomposition temperature, etc., excellent heat resistance of the phosphorescent material and the formed light-emitting layer, and deterioration of film quality and thermal decomposition of the material due to gas generation, recrystallization, and molecular migration. A large one is preferable from the viewpoint that an increase in impurity concentration, etc., is unlikely to occur. On the other hand, the molecular weight of the phosphorescent material is preferably small from the viewpoint of easy purification of the organic compound.

In an organic electroluminescent device in which a polymer is used as a charge-transporting material for forming at least one of a hole injection layer and a hole transport layer, when the light emitting layer is a phosphorescent material, the following materials are preferable as the host material.

<Host Material (Compound)>

As a host material (compound) of a light emitting layer, what has the above-mentioned formula (CzP) and a formula (CzP-2) can be used. Moreover, when a light emitting material and another host material have a formula (CzP), you can also use suitably the host material which does not have a formula (CzP) and a formula (CzP-2). In this case, the skeleton, molecular weight, substituents, and the like are as described above.

In an organic electroluminescent device using a polymer as a charge-transporting material for forming at least one of a hole injection layer and a hole transport layer, when the light emitting layer is a fluorescent material, it is preferably the following blue fluorescent material.

Although it does not specifically limit as a light emitting material for blue fluorescent light emitting layers, The compound represented by following formula (211) is preferable.

[Formula 70]

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 optionally substituted alkyl group, an aromatic hydrocarbon group, or a group to which they are bonded.

n41 is 1-4.

Ar ²⁴¹ preferably represents an aromatic hydrocarbon condensed ring structure having 10 to 30 carbon atoms, and specific structures include naphthalene, acenaphthene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, tetracene, chrysene, perylene. and the like.

More preferably, it is a C12-C20 aromatic hydrocarbon condensed ring structure, and specific structures include acenaphthene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, tetracene, chrysene, and perylene. More preferably, it is a C16-C18 aromatic hydrocarbon condensed ring structure, and fluoranthene, pyrene, and chrysene are mentioned as a specific structure.

n41 is 1-4, Preferably it is 1-3, More preferably, it is 1-2, Most preferably, it is 2.

The ^{substituent Ar 241} , Ar ²⁴² , and Ar ²⁴³ may have is preferably a group selected from the above substituent group Z2, more preferably a hydrocarbon group included in the substituent group Z2, and still more preferably a substituent group Z2. It is a hydrocarbon group in the group.

In an organic electroluminescent device in which a polymer is used as a charge-transporting material for forming at least one of a hole injection layer and a hole transport layer, when the light emitting layer is a phosphorescent material, the following materials are preferable as the host material.

Although it does not specifically limit as a host material for blue fluorescent light emitting layers, The compound represented by following formula (212) is preferable.

[Formula 71]

[In the above formula (212),

R ²⁴¹ , R ²⁴² are each independently a structure represented by Formula (213),

R ²⁴³ represents a substituent, and ^{when there are a plurality of R 243 , they} may be the same or different,

n43 is 0 to 8.]

[Formula 72]

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,

Ar ²⁴⁴ , Ar ²⁴⁵ may be the same or different when there are a plurality of each,

n44 is 1-5, n45 is 0-5.

Ar ²⁴⁴ is preferably an aromatic hydrocarbon structure which may have a substituent and is a monocyclic or condensed ring having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon structure having 6 to 12 carbon atoms or a condensed ring which may have a substituent. hydrocarbon structure.

Ar ²⁴⁵ is preferably an aromatic hydrocarbon structure which may have a substituent and is a monocyclic or condensed ring having 6 to 30 carbon atoms, or an aromatic heterocyclic structure which is a condensed ring having 6 to 30 carbon atoms which may have a substituent, and more Preferably, it is an aromatic hydrocarbon structure which is a C6-C12 monocyclic or condensed ring which may have a substituent, or an aromatic heterocyclic structure which is a C12-C12 condensed ring which may have a substituent.

n44 is preferably 1 to 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 which are substituents may have are preferably a group selected from the above substituent group Z, more preferably a hydrocarbon group included in the substituent group Z, and still more preferably a substituent group. It is a hydrocarbon group in a group preferable as Z.

The molecular weight of the light emitting material for a 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, most preferably 2,000 or less, and usually 300 or more, preferably 350 or less. or more, more preferably 400 or more.

[Formation of light emitting layer by wet film forming method]

A vacuum deposition method or a wet film formation method may be sufficient as the formation method of a light emitting layer, However, From the point which is excellent in film-forming property, the wet film-forming method is preferable, and the spin coating method and the inkjet method are more preferable. In particular, when the composition for an organic electroluminescent device is used to form a hole injection layer or a hole transport layer serving as a lower layer of the light emitting layer, lamination by a wet film forming method is easy, so it is preferable to employ a wet film forming method. In the case of forming the light emitting layer by the wet film forming method, normally, in the same manner as in the case of forming the above-described hole injection layer by the wet film forming method, instead of the composition for forming the hole injection layer, the material used as the light emitting layer is a soluble solvent. (Solvent for light emitting layer) It forms using the composition for light emitting layer formation prepared by mixing.

Examples of the solvent include, in addition to the ether solvents, ester solvents, aromatic hydrocarbon solvents, and amide solvents mentioned for the formation of the hole injection layer, alkane solvents, halogenated aromatic hydrocarbon solvents, aliphatic alcohol solvents, and alicyclic solvents. A group alcohol solvent, an aliphatic ketone solvent, an alicyclic ketone solvent, etc. are mentioned. Although the specific example of a solvent is given below, unless the effect of this invention is impaired, it is not limited to these.

For example, Aliphatic ether solvents, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol 1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetol, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2, Aromatic ether solvents, such as 4-dimethylanisole and diphenyl ether; aromatic ester solvents such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate; Toluene, xylene, mesitylene, cyclohexylbenzene, tetralin, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, methylnaphthalene, etc. of aromatic hydrocarbon solvents; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; alkane solvents such as n-decane, cyclohexane, ethylcyclohexane, decalin, and bicyclohexane; 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; aliphatic ketone solvents such as methyl ethyl ketone and dibutyl ketone; and alicyclic ketone solvents such as cyclohexanone, cyclooctanone, and fenchon. Among these, an alkane solvent and an aromatic hydrocarbon solvent are especially preferable.

[Hole blocking layer]

Between the light emitting layer 5 and the electron injection layer 8 mentioned later, you may provide the hole blocking layer 6 . The hole blocking layer 6 is a layer laminated on the light emitting layer 5 so as to be in contact with the interface of the light emitting layer 5 on the cathode 9 side.

This hole blocking layer 6 serves to block the holes moving from the anode 2 from reaching the cathode 9 , and efficiently transports electrons injected from the cathode 9 in the direction of the light emitting layer 5 . has a role to Physical properties required for the material constituting the hole blocking layer 6 include high electron mobility and low hole mobility, large energy gap (difference between HOMO and LUMO), and triplet excitation level (T1) higher can be heard.

Examples of the material of the hole blocking layer satisfying these conditions include bis(2-methyl-8-quinolinolato)(phenollatto)aluminum, and bis(2-methyl-8-quinolinolato). Mixed ligand complexes such as (triphenylsilanolato)aluminum, bis(2-methyl-8-quinolato)aluminum-μ-oxo-bis-(2-methyl-8-quinolato)aluminum binuclear metal complex Metal complexes such as, styryl compounds such as distyrylbiphenyl derivatives (Japanese Patent Application Laid-Open No. 11-242996), 3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl) triazole derivatives such as -1,2,4-triazole (Japanese Patent Application Laid-Open No. 7-41759) and phenanthroline derivatives such as vasocuproin (Japanese Patent Application Laid-Open No. Hei 10-79297) can Further, a compound having at least one pyridine ring substituted at the 2,4,6-position described in International Publication No. 2005/022962 is also preferable as a material for the hole blocking layer.

There is no restriction|limiting in the formation method of the positive hole blocking layer 6 . Therefore, it can form by a wet film-forming method, a vapor deposition method, or another method.

The 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 is usually 100 nm or less, preferably 50 nm. is below.

[electron transport layer]

The electron transport layer 7 is formed 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 from a compound that can efficiently transport electrons injected from the cathode 9 in the direction of the light emitting layer 5 between the electrodes to which the electric field is applied. As the electron transporting compound used for the electron transporting layer 7, the electron injection efficiency from the cathode 9 or the electron injection layer 8 is high, and it has high electron mobility and can efficiently transport the injected electrons. It needs to be a compound that can.

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 Application Laid-Open No. 59-194393), and 10-hydroxybenzo[h]. ]quinoline metal complex, oxadiazole derivative, distyrylbiphenyl derivative, silol derivative, 3-hydroxyflavone metal complex, 5-hydroxyflavone metal complex, benzoxazole metal complex, benzothiazole metal complex, trisbenzimi Dazolylbenzene (specification of U.S. Patent No. 5645948), quinoxaline compound (Japanese Patent Laid-Open No. 6-207169), phenanthroline derivatives (Japanese Patent Application Laid-Open No. Hei-5-331459), 2-t-butyl-9 , 10-N,N'-dicyanoanthraquinonediimine, n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type zinc selenide, etc. are mentioned.

The thickness of the electron transport layer 7 is usually 1 nm or more, preferably 5 nm or more, and is usually 300 nm or less, preferably 100 nm or less.

The electron transport layer 7 is formed by laminating|stacking on the hole blocking layer 6 by a wet film-forming method or a vacuum vapor deposition method similarly to the above. Usually, the vacuum vapor deposition method is used.

[electron injection layer]

The electron injection layer 8 plays a role of efficiently injecting electrons injected from the cathode 9 into the electron transport layer 7 or the light emitting layer 5 .

In order to perform electron injection efficiently, as for the material which forms the electron injection layer 8, a metal with a low work function is preferable. Examples include alkali metals such as sodium and cesium, and alkaline earth metals such as barium and calcium. The film thickness is usually preferably 0.1 nm or more and 5 nm or less.

In addition, an alkali metal such as sodium, potassium, cesium, lithium or rubidium is doped into an organic electron transporting material typified by a metal complex such as a nitrogen-containing heterocyclic compound such as vasophenanthroline or an aluminum complex of 8-hydroxyquinoline. (Described in Japanese Patent Application Laid-Open No. 10-270171, Japanese Patent Application Laid-Open No. 2002-100478, Japanese Patent Application Laid-Open No. 2002-100482, etc.) is also preferable because electron injection and transport properties are improved and it becomes possible to achieve both excellent film quality. do.

The 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|stacking on the light emitting layer 5 or the hole blocking layer 6 or the electron carrying layer 7 thereon by a wet film-forming method or a vacuum vapor deposition method.

The details in the case of the wet film forming method are the same as in the case of the light emitting layer described above.

[cathode]

The cathode 9 plays a role of injecting electrons into a layer (such as an electron injection layer or a light emitting layer) on the light emitting layer 5 side.

As the material of the cathode 9, it is possible to use the material used for the anode 2, but in order to efficiently inject electrons, it is preferable to use a metal having a low work function, for example, For example, metals, such as tin, magnesium, indium, calcium, aluminum, silver, or their alloys, etc. are used. As a specific example, alloy electrodes of low work function, such as a magnesium-silver alloy, a magnesium-indium alloy, and an aluminum-lithium alloy, etc. are mentioned, for example.

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. As a metal to be laminated|stacked, metals, such as aluminum, silver, copper, nickel, chromium, gold|metal|money, platinum, are mentioned, for example.

The film thickness of the negative electrode is usually the same as that of the positive electrode.

[Other floors]

The organic electroluminescent element may further have another layer, unless the effect of this invention is impaired remarkably. That is, you may have the other arbitrary layers mentioned above between an anode and a cathode.

[Other device configurations]

The organic electroluminescent device may have a structure opposite to that described above, that is, the cathode, the electron injection layer, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode may be laminated in the order of the anode. have.

When an organic electroluminescent element is applied to an organic electroluminescent device, you may use as a single organic electroluminescent element, and you may use it as a structure arrange|positioned in the array shape of a plurality of organic electroluminescent elements, and an anode and a cathode are XY You may use it as a structure arrange|positioned in matrix form.

<Organic EL display device>

An organic EL display device (organic EL device display device) according to another embodiment of the present invention includes the above-described organic EL display device. There is no restriction|limiting in particular about the form or structure of an organic electroluminescent display, An organic electroluminescent element can be used and can be assembled according to a conventional method.

For example, an organic EL display device can be formed by a method as described in "Organic EL Display" (Oumsa, published on August 20, 2004, by Shizuo Tokito, Chihaya Adachi, and Hideyuki Murata). .

<Organic EL lighting>

The organic EL lighting (organic electroluminescent element lighting) which is another embodiment of this invention was equipped with the organic electroluminescent element mentioned above. There is no restriction|limiting in particular about the form or structure of organic electroluminescent lighting, It can assemble according to a conventional method using an organic electroluminescent element.

Example

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 implemented without departing from the gist thereof.

<Experiment I>

<Synthesis of intermediates>

[Synthesis of compound 3]

[Formula 73]

Under a 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 poured into the flask, and the inside of the system was sufficiently purged 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 with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 85/15) to obtain compound 3 (4.4 g, yield 55.8%).

[Synthesis of compound 4]

[Formula 74]

In a 200 ml flask under a nitrogen stream, 50 ml of dimethylsulfoxide, compound 3 (4.4 g, 13.6 mmol), bis(pinacolato)diboron (4.2 g, 16.34 mmol), potassium acetate (4.0 g, 40.83 mmol) was added, and it stirred at 60 degreeC for 30 minute(s). 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, 85 The reaction was carried out at ℃ for 4 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 prepared with activated clay. Further, the crude product was purified by column chromatography (eluent: hexane/ethyl acetate = 90/10) to obtain compound 4 (5.0 g, yield 98%).

[Synthesis of compound 6]

[Formula 75]

Under a 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 poured into the flask, and the inside of the system was sufficiently purged 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 85/15) to obtain compound 6 (6.3 g, yield 81.0%).

[Synthesis of compound 7]

[Formula 76]

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 poured into the flask, and the inside of the system was sufficiently purged 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 3/1) to obtain compound 7 (20.3 g, yield 41%).

[Synthesis of compound 8]

[Formula 77]

In a nitrogen stream, in a 500 ml flask, 260 ml of 1,4-dioxane, compound 7 (20.3 g, 72.99 mmol), bis(pinacolato)diboron (22.2 g, 89.6 mmol), potassium acetate ( 35.9 g, 365.8 mmol) was put, and it stirred at 60 degreeC for 30 minute(s). 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, 85 The reaction was carried out at ℃ for 3.5 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 prepared with activated clay. Further, the crude product was purified by column chromatography (eluent: hexane/methylene chloride = 1/1) to obtain compound 8 (19.1 g, yield 84%).

[Synthesis of compound 9]

[Formula 78]

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 poured into the flask, and the inside of the system was sufficiently purged 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 1/1) to obtain compound 9 (3.5 g, yield 80.2%).

[Synthesis of compound 10]

[Formula 79]

In a 500 ml flask 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% hydrated product), 0.4 g) and stirred at 50°C for 10 minutes. Thereafter, hydrazine monohydrate (1.8 g) was added dropwise and reacted at this temperature for 3 hours.

The reaction solution was filtered under reduced pressure through celite for water moisture, the filtrate was concentrated, washed with methanol, and purified to obtain compound 10 (3.0 g, yield 91%).

[Synthesis of compound 12]

[Formula 80]

Under a 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) was poured into the flask, and the inside of the system was sufficiently purged 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 85/15) to obtain compound 12 (4.1 g, yield 90.3%).

[Synthesis of compound 13]

[Formula 81]

In a 200 ml flask under a nitrogen stream, 35 ml of dimethylsulfoxide, compound 12 (4.1 g, 8.38 mmol), bis(pinacolato)diboron (3.2 g, 12.6 mmol), potassium acetate (2.5 g, 25.1 mmol) was added, and it stirred at 60 degreeC for 30 minute(s). 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, 85 The reaction was carried out at ℃ for 3 hours.

The reaction solution was filtered under reduced pressure, and the filtrate was extracted with toluene, dried over anhydrous magnesium sulfate, and prepared with activated clay. Further, the crude product was purified by column chromatography (eluent: hexane/ethyl acetate = 90/10) to obtain compound 13 (4.5 g, yield 97%).

[Synthesis of compound 14]

[Formula 82]

Under a 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 m) mol), toluene (30 ml), ethanol (10 ml), and water (10.5 ml) were charged into the flask, and the inside of the system was sufficiently purged 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 75/25) to obtain compound 14 (2.2 g, yield 35.9%).

[Synthesis of compound 15]

[Formula 83]

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 poured into the flask, and the inside of the system was sufficiently purged with nitrogen and 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 50/50) to obtain compound 15 (1.75 g, yield 68.5%).

[Synthesis of compound 16]

[Formula 84]

In a nitrogen stream, 20 ml of tetrahydrofuran, 10 ml of ethanol, compound 15 (1.75 g, 2.06 mmol), and palladium/carbon (10%, about 55% water supply, 0.18 g) were placed in a 100 ml flask. , and stirred at 52 °C for 10 min. Thereafter, hydrazine monohydrate (0.7 g) was added dropwise and reacted at this temperature for 8 hours.

The reaction solution was filtered under reduced pressure through celite for water moisture, and the filtrate was concentrated and purified by recrystallization with ethanol to obtain compound 16 (0.9 g, yield 53.3%).

[Synthesis of compound 17]

[Formula 85]

In a nitrogen stream, in a 300 ml flask, 4-bromophenol (11.6 g, 67.21 mmol), 4,4'-difluorobenzophenone (6.67 g, 30.55 mmol), and 100 ml of N,N'- Dimethylformamide and potassium carbonate (16.9 g, 122.29 mmol) were put, and it stirred at 140 degreeC for 3 hours. Then, the reaction liquid at 40 degreeC was put into 500 mL pure water, stirred for 10 minutes, and filtered under reduced pressure, and the filtrate was washed with ethanol and methanol in this order, filtered, dried, and compound 17 (12.6) g, yield 78.6%) was obtained.

[Synthesis of compound 19]

[Formula 86]

In a 1 liter flask, 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, aqueous potassium phosphate (2 M, That is, after vacuum degassing, the solution in which 191 ml of 2 mol/liter concentration) was put was replaced with nitrogen. It was heated under a stream of nitrogen 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 solution, extracted with toluene, _{and treated with MgSO 4} and activated clay. After heating the toluene solution to reflux, the insoluble material was filtered and recrystallized to obtain Compound 19 as a colorless solid (amount 14.2 g, yield 60.2%).

[Synthesis of compound 20]

[Formula 87]

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

[Synthesis of compound 22]

[Formula 88]

Under a nitrogen stream, compound 21 (17.8 g, 33.0 mmol), 4-(9H-carbazol-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 poured into the flask, and the inside of the system was sufficiently purged 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 80/20) to obtain compound 22 (18.4 g, yield 85.2%).

[Synthesis of compound 23]

[Formula 89]

In a 300 ml flask under a nitrogen stream, 100 ml of dimethyl sulfoxide, compound 22 (18.2 g, 27.8 mmol), bis(pinacolato)diboron (10.6 g, 41.7 mmol), potassium acetate (8.2 g, 83.4 mmol) was added, and it stirred at 60 degreeC for 30 minute(s). 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, 85 The reaction was carried out at ℃ for 4.5 hours.

The reaction solution was filtered under reduced pressure, and the filtrate was extracted with toluene, dried over anhydrous magnesium sulfate, and prepared with activated clay. Further, the crude product was purified by column chromatography (eluent: hexane/ethyl acetate = 90/10) to obtain compound 23 (17.7 g, yield 90.7%).

[Synthesis of compound 24]

[Formula 90]

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 poured into the flask, and the inside of the system was sufficiently purged 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 75/25) to obtain compound 24 (4.8 g, yield 76.0%).

[Synthesis of compound 26]

[Formula 91]

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 poured into the flask, and the inside of the system was sufficiently purged with nitrogen and 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 60/40) to obtain compound 26' (3.9 g, yield 74.9%).

[Formula 92]

In a 300 ml flask 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% water supply, 0.29 g) were added and stirred at 52°C for 10 minutes. Thereafter, hydrazine monohydrate (1.3 g) was added dropwise and reacted at this temperature for 5 hours.

The reaction liquid was filtered under reduced pressure through celite for water moisture, and the filtrate was concentrated and purified by recrystallization with ethanol to obtain compound 26 (3.3 g, yield 87.2%).

[Synthesis of compound 27]

[Formula 93]

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 (2 M aqueous solution, 103) g, 205 mmol), toluene (200 ml), and ethanol (100 ml) were charged into the flask, and the inside of the system was sufficiently purged 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 950/50) to obtain compound 27 (23.1 g, yield 81%).

[Synthesis of compound 28]

[Formula 94]

Compound 27 (23.1 g, 66.1 mmol), commercially available 3-aminophenylboronic acid (9.8 g, 63.0 mmol), potassium phosphate (2 M aqueous solution, 79 g, 158 mmol), and toluene (160 mL), Ethanol (80 ml) was poured into the flask, and the inside of the system was sufficiently purged 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/ethyl acetate = 8/2) to obtain compound 28 (22.2 g, yield 92.9%).

[Synthesis of compound 30]

[Formula 95]

Compound 29 was used instead of compound 26, and compound 30 was synthesized in the same manner as that of compound 27.

[Synthesis of compound 31]

[Formula 96]

Compound 30 was used instead of Compound 27, and Compound 31 was synthesized in the same manner as that of Compound 28.

[Synthesis of compound 32]

[Formula 97]

Under a nitrogen stream, 2-(9,9-dimethyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (commercially available from Tokyo Chemical Industry) ( 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 poured into the flask, and the inside of the system was sufficiently purged 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 75/25) to obtain compound 32 (2.2 g, yield 35.9%).

[Synthesis of compound 33]

[Formula 98]

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 poured into the flask, and the inside of the system was sufficiently purged with nitrogen and 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 50/50) to obtain compound 33 (1.75 g, yield 68.5%).

[Synthesis of compound 34]

[Formula 99]

In a nitrogen stream, 20 ml of tetrahydrofuran, 10 ml of ethanol, compound 33 (1.75 g, 2.06 mmol), and palladium/carbon (10%, about 55% water supply, 0.18 g) were placed in a 100 ml flask. , and stirred at 52 °C for 10 min. Thereafter, hydrazine monohydrate (0.7 g) was added dropwise and reacted at this temperature for 8 hours.

The reaction solution was filtered under reduced pressure through celite for water moisture, and the filtrate was concentrated and purified by recrystallization with ethanol to obtain compound 34 (0.9 g, yield 53.3%).

[Synthesis of compound 35]

[Formula 100]

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 poured into the flask, and the inside of the system was sufficiently purged 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 prepared with activated clay. The crude product was purified by column chromatography (eluent: hexane/methylene chloride = 1/1) to obtain compound 35 (3.5 g, yield 80.2%).

[Synthesis of compound 36]

[Formula 101]

In a nitrogen stream, 350 ml of tetrahydrofuran, 20 ml of ethanol, compound 35 (3.5 g, 5.13 mmol), and palladium/carbon (10%, about 55% hydrated product, 0.4 g) were placed in a 500 ml flask under a nitrogen stream. , and stirred at 50 °C for 10 minutes. Thereafter, hydrazine monohydrate (1.8 g) was added dropwise and reacted at this temperature for 3 hours.

The reaction solution was filtered under reduced pressure through celite for water moisture, the filtrate was concentrated, washed with methanol, and purified to obtain compound 36 (3.0 g, yield 91%).

<Example 1>

[Synthesis of Polymer 1]

Polymer 1 was synthesized according to the following scheme.

[Formula 102]

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, and the inside of the system was sufficiently purged with nitrogen and heated to 60°C (solution A1).

[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos) (0.14) in an 11 ml solution of tris(dibenzylideneacetone) dipalladium complex (0.062 g, 0.07 mmol) in toluene g, 0.5 mmol) and warmed to 60°C (solution B1).

The solution B1 was added to the solution A1 in a nitrogen stream, and it heated and refluxed for 1.0 hour. It was confirmed that compound 19 had disappeared, and 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, followed by heating and refluxing for 2 hours. The reaction solution was left to cool, toluene 73 ml was added, and it was dripped at the ethanol/water (500 ml/90 ml) solution, and the crude polymer which carried out the end cap was obtained.

This end-capped crude polymer was dissolved in toluene, re-precipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The filtered polymer 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) = 40000

Number average molecular weight (Mn) = 29850

Dispersion (Mw/Mn) = 1.34

<Example 2>

[Synthesis of Polymer 2]

According to the following scheme, Polymer 2 was synthesized.

[Formula 103]

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, and the inside of the system was sufficiently purged with nitrogen and heated to 60°C (solution A2).

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

The solution B2 was added to the solution A2 in a nitrogen stream, and it heated and refluxed for 1.0 hour. It was confirmed that compound 19 had disappeared, and 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, followed by heating and refluxing for 2 hours. The reaction solution was left to cool, toluene 73 ml was added, and it was dripped at the ethanol/water (500 ml/90 ml) solution, and the crude polymer which carried out the end cap was obtained.

This end-capped crude polymer was dissolved in toluene, re-precipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The filtered polymer was purified by column chromatography to obtain a 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

Dispersion (Mw/Mn) = 1.44

<Example 3>

[Synthesis of Polymer 3]

According to the following scheme, polymer 3 was synthesized.

[Formula 104]

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, and the inside of the system was sufficiently purged with nitrogen and heated to 60°C (solution A3).

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

The solution B3 was added to the solution A3 in a nitrogen stream, and it heated and refluxed for 1.0 hour. It was confirmed that compound 19 had disappeared, and compound 17 (0.91 g, 1.74 mmol) was added. After heating and refluxing for 2 hours, bromobenzene (0.83 g, 5.3 mmol) was added, followed by heating and refluxing for 2 hours. The reaction solution was allowed to cool, and it was added dropwise to an ethanol/water (200 ml/20 ml) solution to obtain a crude polymer with an end cap.

This end-capped crude polymer was dissolved in toluene, re-precipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The filtered polymer 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

Dispersion (Mw/Mn) = 1.32

<Example 4>

[Synthesis of Polymer 4]

Polymer 4 was synthesized according to the following scheme.

[Formula 105]

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, and the inside of the system was sufficiently purged with nitrogen and heated to 60°C (solution A4).

[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos) (0.16) to a 11.9 ml solution of tris(dibenzylideneacetone)dipalladium complex (0.069 g, 0.075 mmol) in toluene g, 0.6 mmol) and warmed to 60°C (solution B4).

The solution B4 was added to the solution A4 in a nitrogen stream, and it heated and refluxed for 1.0 hour. It was confirmed that compound 19 had disappeared, and 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, followed by heating and refluxing for 2 hours. The reaction solution was allowed to cool, and it was added dropwise to an ethanol/water (315 ml/50 ml) solution to obtain an end-capped crude polymer.

This end-capped crude polymer was dissolved in toluene, re-precipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The filtered polymer 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

Dispersion (Mw/Mn) = 1.36

<Example 5>

[Synthesis of Polymer 5]

Polymer 5 was synthesized according to the following scheme.

[Formula 106]

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 purged with nitrogen, and the mixture was heated to 60°C (solution A5).

[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos) (0.136) in a 10 ml solution of tris(dibenzylideneacetone)dipalladium complex (0.059 g, 0.06 mmol) in toluene g, 0.51 mmol) and warmed to 60°C (solution B5).

The solution B5 was added to the solution A5 in a nitrogen stream, and it heated and refluxed for 1.0 hour. After confirming that the compound 19 had disappeared, compound 20 (0.81 g, 1.61 mmol) was added, and after heating and refluxing 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, followed by heating and refluxing for 2 hours. After leaving the reaction liquid to cool, 58 ml of toluene was added, and it was dripped at the ethanol/water (270 ml/43 ml) solution, and the crude polymer which carried out the end cap was obtained.

This end-capped crude polymer was dissolved in toluene, re-precipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The filtered polymer 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

Dispersion (Mw/Mn) = 1.34

[Insolubilization Experiment]

Using the polymer prepared in Examples, an insolubilization test was conducted for cyclohexylbenzene and butyl benzoate. Polymers 1, 2 and 5 were dissolved in anisole to prepare a coating composition. A film of 110 nm to 130 nm was produced by spin coating on a slide glass substrate using the coating composition. Further, the film was heat-treated at 230°C for 30 minutes. Then, the thickness of each film was measured at room temperature.

Then, each membrane was rinsed with cyclohexylbenzene or butyl benzoate. After rinsing process, 130 microliters of solvents were dripped on the coating film, and it left still for 90 seconds, the board|substrate was spun and performed. The rinse-processed film|membrane was heat-processed for every slide glass substrate, and the film thickness of the residual film on a slide glass substrate was measured. Table 1 shows the ratio (insolubilization rate) of the film thickness before and after the rinse treatment.

As shown in Table 1, it was shown that the organic film of the polymers 1, 2, and 5 after heat processing did not melt|dissolve in cyclohexylbenzene or butyl benzoate, and wet film formation was possible.

<Experiment II>

<Example 6>

[Synthesis of Polymer 6]

According to the following scheme, polymer 6 was synthesized.

[Formula 107]

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 purged with nitrogen, and the mixture was heated to 60°C (solution A6).

[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos) (0.11) in 7 ml solution of tris(dibenzylideneacetone)dipalladium complex (0.045 g, 0.05 mmol) in toluene g, 0.42 mmol) and warmed to 60°C (solution B6).

The solution B6 was added to the solution A6 in a nitrogen stream, and it heated and refluxed for 1.0 hour. It was confirmed that compound 19 had disappeared, and 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, followed by heating and refluxing for 2 hours. The reaction liquid was left to cool, 57 ml of toluene was added, and it was dripped at the ethanol/water (240 ml/50 ml) solution, and the crude polymer which carried out the end cap was obtained.

This end-capped crude polymer was dissolved in toluene, re-precipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The filtered polymer 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

Dispersion (Mw/Mn) = 1.37

<Example 7>

[Synthesis of Polymer 7]

According to the following scheme, polymer 7 was synthesized.

[Formula 108]

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), sodium tert-butoxy (2.09 g, 21.7 mmol) and toluene (24 g, 27.7 ml) were charged, the system was sufficiently purged with nitrogen, and the mixture was heated to 60°C. (solution A3).

[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos) (0.12) in 3.3 ml solution of tris(dibenzylideneacetone)dipalladium complex (0.052 g, 0.06 mmol) in toluene g, 0.5 mmol) and warmed to 60°C (solution B3).

The solution B3 was added to the solution A3 in a nitrogen stream, and it heated and refluxed for 1.0 hour. It was confirmed that compound 19 had disappeared, and 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, followed by heating and refluxing for 2 hours. The reaction liquid was left to cool, 40 ml of toluene was added, and it was dripped at the ethanol/water (500 ml/90 ml) solution, and the crude polymer which carried out the end cap was obtained.

This end-capped crude polymer was dissolved in toluene, re-precipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The filtered polymer 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) = 40000

Number average molecular weight (Mn) = 29600

Dispersion (Mw/Mn) = 1.35

[Device Example]

Hereinafter, the results of manufacturing devices using polymers 1, 5, 6, and 7 and polymer HT-1 and evaluating their performance are shown. The present invention is not limited to the following examples, and the present invention can be arbitrarily modified and implemented without departing from the gist of the present invention.

<Example 8>

The organic electroluminescent element was produced by the following method.

An indium tin oxide (ITO) transparent conductive film deposited to a thickness of 50 nm on a glass substrate (manufactured by Sanyo Vacuum Co., Ltd., sputtered film formation product) is patterned into 2 mm wide stripes using a conventional photolithography technique and hydrochloric acid etching. Thus, an anode was formed. The substrate on which the ITO pattern was formed in this way was cleaned in the order of ultrasonic cleaning with a surfactant aqueous solution, water washing with ultrapure water, ultrasonic cleaning with ultrapure water, and water washing with ultrapure water, followed by drying with compressed air, and finally UV ozone washing. was carried out.

As a composition for forming a hole injection layer, a composition in which 3.0% by weight of a hole-transporting high molecular compound having a repeating structure of the following formula (P1) and 0.6% by weight of an oxidizing agent (HI-1) were dissolved in ethyl benzoate was prepared.

[Formula 109]

This solution was spin-coated on the substrate in the air, and dried on a hot plate in the air at 240°C for 30 minutes to form a uniform thin film with a film thickness of 40 nm, which was used as a hole injection layer.

Next, 100 mass parts of charge-transporting high molecular compounds which have the following polymer 5 were melt|dissolved in cyclohexylbenzene, and the 1.5 wt% solution was prepared.

[Formula 110]

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

Then, as a material of a light emitting layer, 95 mass parts of following structural formula (H-1) and 5 mass parts of (D-1) were weighed, it was made to melt|dissolve in cyclohexylbenzene, and the 4.0 wt% solution was prepared.

[Formula 111]

This solution was spin-coated in a nitrogen glove box on the substrate on which the hole transport layer was coated and formed, and dried at 120° C. for 20 minutes on a hot plate in a nitrogen glove box to form a uniform thin film with a film thickness of 40 nm, and a light emitting layer was done with

The substrate on which the light emitting layer was formed was installed in a vacuum vapor deposition apparatus, and the inside of the apparatus was evacuated until it became ^{2 x 10 -4 Pa or less.}

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

[Formula 112]

Then, as a mask for cathode deposition, a stripe-shaped shadow mask with a width of 2 mm was adhered to the substrate so as to be orthogonal to the ITO stripe of the anode, and placed in another vacuum deposition apparatus. And aluminum was heated as a cathode by a molybdenum boat, the 80-nm-thick aluminum layer was formed at the vapor deposition rate of 1-8.6 angstrom/sec, and the cathode was formed. As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm x 2 mm was obtained.

<Example 9>

A device was fabricated in the same manner as in Example 1 except that the hole transport layer was polymer 1.

[Formula 113]

<Comparative Example 1>

A device was fabricated in the same manner as in Example 1 except that the hole transport layer was set to (HT-1).

[Formula 114]

[Evaluation of device]

Table 1 summarizes the characteristics of the organic electroluminescent devices of Examples 1-2 and Comparative Example 1 obtained. The relative luminous efficiency is obtained by measuring the current luminous efficiency (cd/A) when light is emitted at a luminance of 1000 cd/m2, and dividing the current luminous efficiency of the Example by the current luminous efficiency of the comparative example to obtain a relative value, and the comparative example is 100. was made relative to the time. A value exceeding 100 indicates that the current luminous efficiency is high. The relative voltage is the 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 has been reduced. It was found that the organic electric field device having a hole transport layer containing the polymer according to the summary 1 of the present invention has improved efficiency and lowered the voltage than the organic field device of the comparative example.

<Example 10>

The same as in Example 1, except that the hole transport layer was polymer 5 and the light emitting layer composition was a thin film with a film thickness of 75 nm with (H-2): (H-3): (D-2) = 60: 40: 15 to make the device. (H-2), (H-3) and (D-2) are shown below.

[Formula 115]

<Comparative Example 2>

A device was fabricated in the same manner as in Example 3 except that the hole transport layer was set to (HT-1).

[Evaluation of device]

Table 2 summarizes the characteristics of the obtained organic electroluminescent devices of Example 10 and Comparative Example 2. Relative current efficiency and relative voltage have the same meanings as in Table 1. As shown in the results of Table 2, it was found that the organic electric field device having the composition of the hole transport layer and the light emitting layer of the present invention, which is the second gist, has improved efficiency and lowered the voltage than the organic field device of the comparative example.

<Example 11>

The hole injection layer was a thin film of (P1): (HI-1) = 100: 20 with a film thickness of 60 nm, the hole transport layer was a thin film of polymer 5 with a film thickness of 25 nm, and the light emitting layer composition was (H-4): (H-5): (D-2) =60:40:15 A device was fabricated 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.

[Formula 116]

<Comparative example 3>

The same as in Example 4, except that the hole transport layer was polymer 6 and the light emitting layer composition was a thin film with a film thickness of 70 nm with (H-6): (H-7): (D-2) = 60: 40: 15 to make the device. (H-6) and (H-7) are shown below.

[Formula 117]

<Reference Example 1>

A device was fabricated in the same manner as in Example 4, except that the hole transport layer was polymer 6 and the light emitting layer composition was the same as in Example 4.

<Reference Example 2>

A device was fabricated in the same manner as in Example 4, except that the hole transport layer was polymer 5 and the light emitting layer composition was the same as in Comparative Example 3.

[Evaluation of device]

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

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

Table 5 summarizes the characteristics of the obtained organic electroluminescent devices of Example 10 and Reference Example 2. The relative current efficiency was measured as the current efficiency (cd/A) when light was emitted at a luminance of 1000 cd/m 2 , and was taken as a relative value when Reference Example 2 was set to 100. The relative voltage was measured as the voltage (V) when light was emitted at a current density of 10 mA/cm 2 , and was taken as the difference (V) when the voltage of Reference Example 2 was used as a reference. As shown in the results of Table 3, in the organic electric field device containing the polymer, which is the first aspect of the present invention, in the hole transport layer, it can be seen that the efficiency is improved when the light emitting layer satisfying the second aspect of the present invention is provided. there was.

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

<Example 12>

[Synthesis of Polymer 8]

According to the following scheme, polymer 8 was synthesized.

[Formula 118]

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 system was sufficiently purged with nitrogen, and the mixture was heated to 60°C (solution A8).

[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos) (0.12) in 3.3 ml solution of tris(dibenzylideneacetone)dipalladium complex (0.052 g, 0.06 mmol) in toluene g, 0.5 mmol) and warmed to 60°C (solution B8).

The solution B8 was added to the solution A8 in a nitrogen stream, and it heated and refluxed for 1.0 hour. It was confirmed that compound 19 had disappeared, and 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, followed by heating and refluxing for 2 hours. The reaction liquid was left to cool, 40 ml of toluene was added, and it was dripped at the ethanol/water (500 ml/90 ml) solution, and the crude polymer which carried out the end cap was obtained.

This end-capped crude polymer was dissolved in toluene, re-precipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The filtered polymer 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

Dispersion (Mw/Mn) = 1.33

[Measurement of Singlet Excitation Energy Level (S1) and Triplet Excitation Energy Level (T1) of Polymer]

Each of Polymer 1 and Polymer 8 was dissolved in 2-methyltetrahydrofuran to prepare a concentration of 1% by weight solution. The fluorescence emission spectrum and the phosphorescence emission spectrum were measured for this solution sample with a fluorescence spectrophotometer (Hitachi fluorescence spectrophotometer F-4500) under excitation wavelength 350nm and cooling conditions 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. Table 2 shows the measurement results.

Polymer 1, which is not carbazole, has a higher T1 ranking than Polymer 8 whose Ar ^{5 terminal is carbazole.} This is considered that when there is only one carbazole, the energy cap of the molecule is widened and the T1 level becomes high by shortening the conjugate length compared with the case where two carbazoles are conjugated. When T1 is high, it is difficult for energy from a light emitting layer to move to a hole transport layer, and it is thought that the organic electroluminescent element with high luminous efficiency can be implement|achieved.

[Confirmation of electronic state by calculation]

By calculation, the electronic states of the following polymer units 1-5 were confirmed.

For the calculation of the electronic state, software Gaussian 09, Revision B.01, (refer to * below) was used. At that time, as the quantum chemical calculation method, the density functional method was adopted, B3LYP was used for the functional function, and 6-31G was used as the basis function to perform the structural optimization calculation of the ground state. Software MolStudio R4.0 Rev2.0 Pprogram (NEC Corporaion) was used for display of HOMO and LUMO (function value 0.03 a.u.).

The results of this calculation are shown in FIGS. 2 to 4 . 2 and 3, in the polymer units 1 and 2, it turns out that HOMO exists in N vicinity of a main chain, and LUMO is localized at the terminal side of a side chain. In addition, from FIG. 4, in HOMO, all of units 3 - 5 exist in the vicinity of N of a main chain, and in LUMO, Ar ⁵ of formula (1) exists, and, as there are many rings, it is more terminal than a carbazole ring. It can be seen that it is distributed on the side and is localized.

※ Gaussian 09, Revision B.01,

MJ Frisch, GW Trucks, HB Schlegel, GE Scuseria, MA Robb, JR Cheeseman, G. Scalmani, V. Barone, B. Mennucci, GA Petersson, H. Nakatsuji, M. Caricato, X. Li, HP Hratchian, AF Izmaylov , J. Bloino, G. Zheng, JL Sonenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, JA Montgomery, Jr. , JE Peralta, F. Ogliaro, M. Bearpark, JJ Heyd, E. Brothers, KN Kudin, VN Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, JC Burant, SS Iyengar , J. Tomasi, M. Cossi, N. Rega, JM Millam, M. Klene, JE Knox, JB Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, RE Stratmann, O. Yazyev, AJ Austin, R. Cammi, C. Pomelli, JW Ochterski, RL Martin, K. Morokuma, VG Zakrzewski, GA Voth, P. Salvador, JJ dannenberg, S. Dapprich, AD daniels, O. Farkas, JB Foresman, JV Ortiz, J. Cioslowski, and DJ Fox, Gaussian, Inc. , Wallingford CT, 2010.

[Polymer Unit 1]

[Formula 119]

[Polymer Unit 2]

[Formula 120]

[Polymer Units 3, 4, 5]

[Formula 121]

<Experiment III>

<Example 13>

The organic electroluminescent element was produced by the following method.

An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate to a thickness of 130 nm (manufactured by Sanyo Vacuum Co., Ltd., sputtered film formation product) is patterned into 2 mm wide stripes using a conventional photolithography technique and hydrochloric acid etching. Thus, an anode was formed. The substrate on which the ITO pattern was formed in this way was cleaned in the order of ultrasonic cleaning with a surfactant aqueous solution, water washing with ultrapure water, ultrasonic cleaning with ultrapure water, and water washing with ultrapure water, followed by drying with compressed air, and finally UV ozone washing. was carried out.

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) were weighed, dissolved in ethyl benzoate, and 3.0 wt% of the composition was prepared.

[Formula 122]

This solution was spin-coated on the substrate in the air, and dried on a hot plate at 230°C in the air for 30 minutes to form a uniform thin film with a film thickness of 40 nm, which was used as a hole injection layer.

Next, 100 mass parts of charge-transporting polymers which are polymer 7 were melt|dissolved in cyclohexylbenzene, and the 3.0 wt% solution was prepared.

This solution was spin-coated in a nitrogen glove box on the substrate on which the hole injection layer was applied and formed into a film, and dried at 230° C. for 30 minutes on a hot plate in a nitrogen glove box to form a uniform thin film with a film thickness of 40 nm; It was set as a positive hole transport layer.

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

[Formula 123]

This solution was spin-coated in a nitrogen glove box on the substrate on which the hole transport layer was applied and then dried on a hot plate in a nitrogen glove box at 130° C. for 20 minutes to form a uniform thin film with a film thickness of 80 nm, and a light emitting layer was done with

The substrate on which the light emitting layer was formed was installed in a vacuum vapor deposition apparatus, and the inside of the apparatus was evacuated until it became ^{2 x 10 -4 Pa or less.}

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

[Formula 124]

Then, as a mask for cathode deposition, a stripe-shaped shadow mask with a width of 2 mm was adhered to the substrate so as to be orthogonal to the ITO stripe of the anode, and placed in another vacuum deposition apparatus. And aluminum was heated as a cathode by a molybdenum boat, the 80-nm-thick aluminum layer was formed at the vapor deposition rate of 1-8.6 angstrom/sec, and the cathode was formed. As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm x 2 mm was obtained.

This element contains, in a hole transport layer and a light emitting layer, the material which has Formula (CzP) as a partial structure.

<Comparative Example 4>

A device was fabricated in the same manner as in Example 13, except that the hole transport layer compound was changed from polymer 7 to HT-2.

[Formula 125]

[Evaluation of device]

The results of evaluation of the voltage and driving life of the organic electroluminescent devices obtained in Example 13 and Comparative Example 4 are shown in Table *. The voltage was measured when the voltage was applied at 10 mA/cm 2 , and the difference between the voltage of the device of Example 13 and the voltage of the device of Comparative Example 4 was calculated based on the voltage of the device of Comparative Example 4, and the relative voltage [V ] was set as d,. In addition, the device was driven at 40 mA/cm 2 , the 15% luminance decay lifetime (LT85) was measured, and the ratio when the 15% decay life of Comparative Example 4 was set to 1 was calculated 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, the voltage is low and the lifetime is low. You can see this is long.

<Example 14>

A device was fabricated 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.

[Formula 126]

<Comparative example 5>

A device was fabricated 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.

[Formula 127]

<Comparative Example 6>

A device was manufactured in the same manner as in Example 13, except that the hole transport layer was HT-2 and the light emitting layer composition was (H-8): (H-9): (D-2) = 40: 60: 20.

[Evaluation of device]

The organic electroluminescent elements of Example 14, Comparative Example 5, and Comparative Example 6 obtained were carried out similarly to Example 13 and Comparative Example 4, and the relative voltage and the relative lifetime were calculated|required. At this time, Comparative Example 6 was used as a reference. They are shown in Table 8. As shown in the results in Table 8, in the organic electroluminescent device using a material containing a material having the formula (CzP) as a partial structure for both the hole transport layer and the light emitting layer, the voltage is low and the lifetime is long. .

As mentioned above, although this invention was demonstrated based on specific embodiment, each embodiment is presented as an example and does not limit the scope of the present invention. Each embodiment described in this specification can be variously modified within the range which does not deviate from the meaning of invention, Moreover, it can combine with the characteristic demonstrated by other embodiment within the range which can be implemented.

1: substrate
2: positive electrode
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 formula (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 are each independently a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic ring which may have a substituent represents a divalent group in which a plurality of groups are linked directly or through a linking group,
Ar ⁵ is a group selected from the aromatic hydrocarbon group which may have a substituent, the aromatic heterocyclic group which may have a substituent, or the aromatic hydrocarbon group which may have a substituent and the aromatic heterocyclic group which may have a substituent directly or through a linking group to represent a plurality of linked monovalent groups,
Ar ⁶ represents a hydrogen atom or a substituent. "-*" in Ar ¹ represents a bonding position with G in formula (1).) The method of claim 1,
wherein G is an N atom. 3. The method according to claim 1 or 2,
Ar ⁵ is a polymer represented by any of the following a-1 to e-4.

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

(in Formula (2)-1 to Formula (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, or an aralkyl group which may have a substituent,
R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aralkyl group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent ,
a and b are each independently an integer of 0 to 4,
c1 and c2 are each independently an integer of 1 to 3;
d1 and d2 are each independently an integer of 0 to 4;
When there are ^two or more ^{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.) 5. The method according to any one of claims 1 to 4,
A polymer further comprising a repeating unit represented by any of the following (3)-1 to (3)-3.

(in formulas (3)-1 to (3)-3,
Ar ⁷ is independently 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 or an aromatic heterocyclic ring which may have a substituent in each repeating unit represents a divalent group in which a plurality of groups are linked directly or through a linking group,
X, R ¹ , R ² , R ³ , R ⁴ , a, b, c1, c2, d1, and d2 are the same as each of the formulas (2)-1 to (2)-3 above.) 6. The method according to any one of claims 1 to 5,
The polymer in which the said polymer has a crosslinkable group as a substituent. 7. The method according to any one of claims 1 to 6,
The polymer having a weight average molecular weight (Mw) of 10,000 or more and a degree of dispersion (Mw/Mn) of 3.5 or less. The composition for organic electroluminescent elements containing the polymer in any one of Claims 1-7. 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, the method comprising:
A method for manufacturing an organic electroluminescent element, comprising 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 element according to claim 8. 10. The method of claim 9,
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, the method of manufacturing an organic electroluminescent device. 11. The method of claim 9 or 10,
The organic layer further has a light emitting layer,
The method for manufacturing an organic electroluminescent device, wherein the hole injection layer, the hole transport layer, and the light emitting layer are layers formed in the film forming step. On a substrate, an anode, a cathode, and an organic layer between the anode and the cathode, wherein the organic layer contains the polymer according to any one of claims 1 to 7 or a layer in which the polymer is crosslinked. having, an organic electroluminescent device. 13. The method of claim 12,
The polymer or the layer containing the polymer crosslinked is a hole transport layer, the organic layer further has a light emitting layer, the light emitting layer is in contact with the hole transport layer, and at least one of the materials contained in the light emitting layer is represented by the following formula ( An organic electroluminescent device containing a compound having a partial structure represented by CzP).

14. The method of claim 13,
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 transport property or electron transport property, or a light emitting material. 15. The method of claim 14,
The skeleton of the host material is 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 quina structure Cridone 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 , an organic electroluminescent device having any of a dibenzofuran structure, a triarylamine structure, a naphthalene structure, a phenanthrene structure, and a pyrene structure. 16. The method according to any one of claims 13 to 15,
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 molecular weight of the low molecular weight compound is 5,000 or less, an organic electric field light emitting element.

(in formulas (14) to (16),
A is a partial structure represented by the said formula (CzP), and may have a substituent.
B represents a single bond or an arbitrary partial structure.
When two or more A's exist, they may be same or mutually different.
When two or more B's exist, they may be same or mutually different.
na, nb, and nc each independently represent an integer of 1 or more and 5 or less.) 17. The method of claim 16,
The organic electroluminescent element whose low molecular weight compound represented by said Formula (14) is a low molecular compound represented by following formula (17).

(in the above formula (17),
Q represents a nitrogen atom or any of the trivalent substituents represented by any of the following structural formulas (18-1) to (18-3),
Xb ¹ , Yb ¹ , and Zb ¹ each independently represents a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent or a divalent heteroaromatic ring group having 3 to 30 carbon atoms which may have a substituent, Xb ¹ , Yb ¹ , and Each of Zb ¹ may be the same or different when two or more exist,
A is a partial structure represented by the above formula (CzP), may have a substituent, and A plurality of A may be the same as 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 each independently represent 0 or 1,
^{Yb 2} when q13 is 0 and Yb 2 when r13 is 0 Zb ² each independently represents a hydrogen atom, a monovalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent, or a monovalent heteroaromatic ring group having 3 to 30 carbon atoms which may have a substituent;
When q13 is 1, Yb ² is a direct bond,
When r13 is 1 Zb ² is a direct bond,
In formulas (18-1) to (18-3), three * in one structural formula are each Xb ¹ , Yb ¹ , or It represents a bonding position with any group of ^{Zb 1 .)}

17. The method of claim 16,
The organic electroluminescent element whose low molecular weight compound represented by said Formula (16) is a low molecular weight compound represented by following formula (19).

(in the above formula (19),
Xc ¹ and Yc ¹ each independently represent a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms which may have a substituent, or a divalent heteroaromatic ring group having 3 to 30 carbon atoms which may have a substituent;
Xc ² and Yc ² each independently represent a hydrogen atom, an optionally substituted monovalent C6-C30 hydrocarbon aromatic ring group, or optionally a C3-C30 monovalent heteroaromatic cyclic group;
Each of Xc ¹ and Yc ¹ may be the same or different when there is a plurality of them,
A is a partial structure represented by the 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.) 18. The method of claim 17,
The organic electroluminescent element whose low molecular weight compound represented by the said Formula (17) is a compound represented by any one of following formula (17-1) - (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' each independently represent an integer of 0 or more and 5 or less,
p14 is 12,
q14 is 12 when q13 is 1 and is absent when q13 is 0,
r14 is 12 when r13 is 1, does not exist when r13 is 0,
q15 and r15 are each independently 4 or 5;
R ³¹ and R ³² are each independently a hydrogen atom or a substituent,
Xb ¹ , Yb ¹ , Zb ¹ , q13 and r13 are each the same as in the above formula (17).) 19. The method of claim 18,
The organic electroluminescent element whose low molecular weight compound represented by said Formula (19) is a compound represented by following formula (19-1).

(In the above general formula (19-1),
R ³¹ is a hydrogen atom or a substituent,
u11 represents 11,
Xc ¹ , Yc ¹ , Xc ¹ , Yc ¹ , t11 , and s11 are each the same as in the above formula (19).) The organic electroluminescent display provided with the organic electroluminescent element in any one of Claims 12-20. Organic EL lighting provided with the organic electroluminescent element in any one of Claims 12-20.

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