TWI832973B - Polymers, organic electroluminescent devices, organic EL display devices and organic EL lighting devices - Google Patents

Abstract

The object of the present invention is to provide a polymer with high hole injection and transport capability and high durability and a composition for an organic electroluminescent element containing the polymer; to provide an organic electroluminescent element with high brightness and long driving life; and to provide a low-voltage organic electroluminescent element. Organic electroluminescent elements with high driving voltage and long life. The present invention is a polymer containing repeating units represented by the following formula (1). In this formula, G represents an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or a C atom, an N atom, a B atom or a P atom; Ar ² ~ Ar ⁴ independently represent 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 may be linked directly or via A divalent group with multiple linked groups; Ar ⁵ represents an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or an aromatic hydrocarbon group that may also have a substituent, and The group of the aromatic heterocyclic group which may have a substituent is a monovalent group connected directly or via a plurality of connecting groups; Ar ⁶ represents a hydrogen atom or a substituent; "-*" in Ar ¹ is represented in formula (1) The bonding position with G.

Description

Polymers, organic electroluminescent components, organic EL display devices and Organic EL lighting device

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

Various electronic devices using organic EL elements, such as organic EL lighting and organic EL displays, have been put into practical use. Organic electroluminescent elements consume less power due to low applied voltage and can emit light in three primary colors. Therefore, they have begun to be used not only in large display screens, but also in small and medium-sized displays such as mobile phones and smart phones.

Organic electroluminescent elements are manufactured by laminating a plurality of layers such as a light-emitting layer, a charge injection layer, and a charge transport layer. Currently, organic electroluminescent devices are mostly manufactured by evaporating organic materials under vacuum. However, the vacuum evaporation method has a complicated evaporation process and poor productivity. It is extremely difficult to increase the size of lighting or display panels using organic electroluminescent devices manufactured by vacuum evaporation.

In recent years, a wet film-forming method (coating method) has been studied as a process for efficiently manufacturing organic electroluminescent elements that can be used in large-scale displays or lighting. Compared with the vacuum evaporation method, the wet film formation method has the advantage of easily forming a stable layer, and is expected to be applied to mass production of displays or lighting devices, or to large-scale displays.

Compared with the vacuum evaporation method, the wet film forming method has advantages such as being able to use multiple material species in one layer. In the vacuum evaporation method, if the number of material species increases, it is difficult to control the evaporation speed to be constant. In contrast, in the wet film-forming method, even if the number of material species increases, as long as each material can be dissolved in an organic solvent, a constant composition ratio can be achieved. ink.

However, due to the difficulty of lamination, the wet film formation method has poor driving stability compared to components obtained by the vacuum evaporation method, and the current situation is still at a level that is not practical except for some parts.

Therefore, for lamination by a wet film-forming method, a charge-transporting polymer having a cross-linkable group is desired, and its development has begun. For example, Patent Documents 1 to 3 disclose organic electroluminescent devices that contain polymers with specific repeating units and are laminated by a wet film-forming method.

Patent Documents 4 and 5 disclose a hole injection transport material having a structure in which a fluorine ring or carbazole ring and an unsubstituted phenyl ring are bonded to the main chain of a polymer.

Patent Document 6 describes that in a polymer having triarylamine repeating units, it is preferable that the main chain contains a fluorine ring, and furthermore, the polymer main chain contains a substituted phenylene group to generate a twist, thereby polymerizing The energy of the triplet state of matter increases.

Patent Document 7 discloses a compound in which a phenylene group having a substituent is connected between the nitrogen atoms of the main chain amine of an arylamine polymer or oligomer.

Patent Document 8 discloses a mixed layer containing an arylamine polymer or oligomer having a polymerizable substituent as a hole transport layer. Furthermore, it is described that the thermal stability of the layer can be improved by polymerizing the polymer or oligomer, and the polymerized layer will not dissolve when the light-emitting layer is coated thereon.

Furthermore, Patent Documents 9 to 12 disclose polymers having a carbazole structure as a side chain structure of a polymer having an arylamine structure. Patent Documents 9 to 11 disclose that there is only one carbazole in the side chain structure; Patent Documents 9 and 12 disclose that the carbazole in the side chain structure is directly bonded to the nitrogen atom of the amine in the main chain; Patent Document 12 discloses that the carbazole in the side chain structure is directly bonded to the nitrogen atom of the amine in the main chain. The chain structure of carbazole is 2.

[Prior technical literature] [Patent Document]

[Patent Document 1] International Publication No. 2009/123269

[Patent Document 2] Japanese Patent Application Publication No. 2013-045986

[Patent Document 3] International Publication No. 2013/191088

[Patent Document 4] Japanese Patent Application Publication No. 2016-084370

[Patent Document 5] Japanese Patent Application Publication No. 2017-002287

[Patent Document 6] Japanese Patent Publication No. 2007-520858

[Patent Document 7] Japanese Patent Publication No. 2013-531658

[Patent Document 8] Japanese Patent Application Publication No. 2010-034496

[Patent Document 9] International Publication No. 2011/099531

[Patent Document 10] International Publication No. 2016/031639

[Patent Document 11] International Publication No. 2009/110360

[Patent Document 12] International Publication No. 2008/126393

However, in the conventional technology, the performance of organic electroluminescent elements is not sufficient for lighting or display applications, and it is required to further reduce the driving voltage and improve the driving life.

The devices described in Patent Documents 1 to 3 have problems such as low brightness and short driving life. Therefore, there is a demand for improvement in charge injection and transport capability or durability of charge transport materials.

Since the polymerization systems described in Patent Documents 4 and 5 have an expansion of the π conjugated system in the main chain, the excited singlet energy level (S ₁ ) and the excited triplet energy level (T ₁ ) are low, which are caused by the luminescent material and luminescence. Extinction caused by the energy movement of excitons leads to the problem of reduced luminous efficiency. Therefore, charge transport materials with higher S1 energy level and higher T1 energy level are required.

Patent Document 6 describes F8-TFB (fluorine + triphenylamine series) as an arylamine polymer containing a fluorine ring in the main chain in the Examples. The phenyl group has no substituent and is not twisted, and the LUMO expands to the vicinity of the nitrogen atom of the amine, so there is a problem of deterioration of electronic durability.

Since the compound disclosed in Patent Document 7 does not contain a fluorine ring or a carbazole structure in the main chain, there is a problem of deterioration in electronic durability.

Patent Document 8 discloses an arylamine polymer or oligomer having a benzoyl or carbazolyl group in the main chain, but the durability of the device is insufficient.

In addition, since the polymers disclosed in Patent Documents 9 to 12 are not copolymers containing twisted aromatic rings and fluorine or carbazole and untwisted aromatic rings in the main chain, the durability of their devices is insufficient as will be described later.

The first object of the present invention is to provide a polymer with high hole injection and transport capability and high durability and a composition for an organic electroluminescent element containing the same, as well as to provide a polymer with low driving voltage and high luminance, that is, high luminous efficiency. Driving organic electroluminescent devices with long lifespan.

Furthermore, a second object of the present invention is to provide an organic electroluminescent element with low driving voltage and long life.

The inventor of this case completed the present invention after painstaking research. That is, the first gist of the present invention is to solve the above-mentioned first problem by using a polymer having a specific structure having a carbazole-containing structure in the side chain. The second gist of the present invention is that in an organic electroluminescent element having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate, the organic layer has a hole transport layer and is adjacent to the hole transport layer The light-emitting layer, the hole transport layer contains the above-mentioned polymer with a specific structure containing a carbazole ring in the side chain, and further the materials contained in the hole transport layer and the materials contained in the light-emitting layer both contain a specific structure with a carbazole ring as Partially structured materials can improve the performance of organic electroluminescent devices and solve the first problem mentioned above. The third gist of the present invention is that in an organic electroluminescent element having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate, the organic layer has a hole transport layer and is adjacent to the hole transport layer The light-emitting layer, the hole transport layer contains other polymers with a specific structure containing carbazole structures in the side chains, the materials contained in the hole transport layer and the materials contained in the light-emitting layer both contain the specific structure with carbazole rings as part The structural material can improve the performance of the organic electroluminescent element and solve the second problem mentioned above.

That is, the gist of the present invention is as follows [1] to [22].

[1] A polymer containing repeating units represented by the following formula (1);

(In formula (1), G represents an aromatic hydrocarbon group that may have a substituent; an aromatic heterocyclic group that may also have a substituent; or a C atom, an N atom, a B atom or a P atom; Ar ² ~ Ar ⁴ respectively Independently means a divalent aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or an aromatic hydrocarbon group that may have a substituent or an aromatic heterocyclic group that may have a substituent directly Or a plurality of divalent groups connected via a linking group; Ar ⁵ represents an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or an aromatic group that may have a substituent. The base of a hydrocarbon group and an aromatic heterocyclic group that may have a substituent is a monovalent group connected directly or via a plurality of connecting groups; Ar ⁶ represents a hydrogen atom or a substituent; "-*" in Ar ¹ is represented by the formula ( 1) The bonding position between center and G.)

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

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

[Chemicalization 2]

(In a-1~e-4, "-*" represents the bonding position with Ar ^4. When there are plural "-*"s, any one of them represents the bonding position with Ar ^4. )

[4] The polymer of [1] or [2], wherein the above formula (1) is a repeating unit represented by any one of the following formulas (2)-1 to (2)-3; [Chemical 3]

(In formula (2)-1 to formula (2)-3, Ar ¹ is the same as Ar ¹ in the above 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 ~ R ⁴ independently represent an alkyl group that may have a substituent, or an alkoxy group that may have a substituent. , or an aralkyl group that may also have a substituent; R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ each independently represent an alkyl group that may also have a substituent, an alkoxy group that may also have a substituent, or an alkoxy group that may also have a substituent. an aralkyl group, or an aromatic hydrocarbon group that may also have a substituent; a and b are each independently an integer from 0 to 4; c1 and c2 are each independently an integer from 1 to 3; d1 and d2 are each independently an integer from 0 to 4 Integers; when R ¹ , R ² , R ³ , and R ⁴ are plural 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 containing a repeating unit represented by any one of the following (3)-1 to (3)-3;

(In formulas (3)-1~(3)-3, Ar ⁷ represents independently in each repeating unit an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or A divalent group in which an aromatic hydrocarbon group that may have a substituent or an aromatic heterocyclic group that may have a substituent is connected directly or via a plurality of connecting groups; X, R ¹ , R ² , R ³ , R ⁴ , a, b, c1, c2, d1, and d2 are the same as the above formulas (2)-1~(2)-3 respectively.)

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

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

[8] A composition for organic electroluminescent elements, containing the polymer of any one of [1] to [7].

[9] A method of manufacturing an organic electroluminescent element, which is a method of manufacturing an organic electroluminescent element having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate, which includes: using [8] The composition for an organic electroluminescent element includes a film forming step of forming at least one layer among the layers constituting the organic layer by a wet film forming method.

[10] The method for manufacturing an organic electroluminescent element 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 formed by the above-mentioned The layer formed by the film forming step.

[11] The method for manufacturing an organic electroluminescent element according to [9] or [10], wherein the organic layer further has a light-emitting layer; the hole injection layer, the hole transport layer and the light-emitting layer are formed by the film forming step the layer formed.

[12] An organic electroluminescent element having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate, the organic layer having: a polymer containing any one of [1] to [7] Or a layer of polymer in which the polymer is cross-linked.

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

[14] The organic electroluminescent element according to [13], wherein the material contained in the above-mentioned light-emitting layer containing a compound having a partial structure represented by the above formula (CzP) has at least one of hole transporting properties or electron transporting properties. Either host material or luminescent material.

構造、

二唑構造或咪唑構造，或者具有咔唑構造、二苯并呋喃構造、三芳基胺構造、萘構造、菲構造、芘構造之任一者 [15] The organic electroluminescent device according to [14], wherein the skeleton of the host material has an aromatic structure, an aromatic amine structure, a triarylamine structure, a dibenzofuran structure, a naphthalene structure, a phenanthrene structure, or a phthalocyanine structure. Structure, porphyrin structure, thiophene structure, benzylphenyl structure, fluorine structure, quinacridone structure, triphenyl structure, carbazole structure, pyrene structure, anthracene structure, phenanthroline structure, quinoline structure, pyridine structure, pyrimidine structure, three

structure,

Diazole structure or imidazole structure, or any one having carbazole structure, dibenzofuran structure, triarylamine structure, naphthalene structure, phenanthrene structure, or pyrene structure

[16] The organic electroluminescent device according to any one of [13] to [15], wherein the compound having the partial structure represented by the above formula (CzP) contained in the above-mentioned light-emitting layer is the following formula (14)~ The low molecular compound represented by any one of (16), and the molecular weight of the low molecular compound is 5,000 or less.

[Chemical 6]

(In formulas (14) to (16), A is a partial structure shown in the above formula (CzP), and may also have a substituent; B represents a single bond or any partial structure; when A exists in plural, it may be the same or Different; when B exists in plural form, it can be the same or different; na, nb and nc respectively independently represent integers above 1 and below 5.)

[17] The organic electroluminescent device of [16], wherein the low molecular compound represented by the above formula (14) is a low molecular compound represented by the following formula (17); [Chemical 7]

(In the above formula (17), Q represents a nitrogen atom or any one of the trivalent substituents represented by any one 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 that may have a substituent, or a divalent heteroaromatic ring group having 3 to 30 carbon atoms that may have a substituent; in Xb ¹ , Yb When ¹ and Zb ¹ exist in plural, they may be the same or different; A is a partial structure shown in the above formula (CzP), and may also have a substituent, and A when present in plural may be the same or different; p12 , q12 and r12 independently represent integers above 0 and below 6; q13 and r13 independently represent 0 or 1; Yb ² when q13 is 0 and Zb ² when r13 is 0 independently represent hydrogen atoms, and may also have substitutions The base has a monovalent hydrocarbon aromatic ring group with 6 to 30 carbon atoms, or a monovalent heteroaromatic ring group with 3 to 30 carbon atoms that may have a substituent; when q13 is 1, Yb ² is a direct bond; r13 is 1 At this time, Zb ² is a direct bond; in formulas (18-1) ~ (18-3), the three * in a structural formula respectively represent the bond with any base of Xb ¹ , Yb ¹ or Zb ¹ Location.)

[18] The organic electroluminescent device of [16], wherein the low molecular compound represented by the above formula (16) is a low molecular compound represented by the 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 that may have a substituent, or a divalent hydrocarbon aromatic ring group having 3 to 30 carbon atoms that may have a substituent. Heteroaromatic ^ring group ^; Heteroaromatic ring group; when Xc ¹ and Yc ¹ exist in plural, they may be the same or different; A is a partial structure shown in the above formula (CzP), and may also have a substituent; s11 and t11 independently represent 0 or more and An integer below 6; nc represents an integer above 1 and below 5.)

[19] The organic electroluminescent device of [17], wherein the low molecular compound represented by the above formula (17) is a compound represented by any one of the following formulas (17-1) to (17-6); [Chemical 10]

[Chemical 11]

(In the above general formulas (17-1) ~ (17-6), p12' represents an integer from 1 to 5; q12' and r12' independently represent an integer from 0 to 5; p14 is 12; q14 is When q13 is 1, it is 12, and there is no case where q13 is 0; r14 is 12 when r13 is 1, and there is no case where r13 is 0; q15 and r15 are independently 4 or 5 respectively; R ³¹ and R ³² are respectively are independently hydrogen atoms or substituents; Xb ¹ , Yb ¹ , Zb ¹ , q13, and r13 are respectively the same as the above formula (17).)

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

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

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

[22] An organic EL lighting, which is an organic electroluminescent element having any one of [12]~[20].

According to the present invention, it is possible to provide a polymer with high hole injection and transport capability and high durability, and a composition for an organic electroluminescent element containing the polymer. In addition, an organic electroluminescent element with low driving voltage, high luminous efficiency and long driving life can be provided.

The reason why the polymer according to one embodiment of the present invention exhibits the above-mentioned effects is presumed to be as follows.

The polymer contained in the hole transport layer transports the holes injected from the anode to the light-emitting layer. On the other hand, trace amounts of electrons from the cathode side belonging to the counter electrode and not recombined with holes in the light-emitting layer leak out to the hole transport layer. Most hole-transporting materials have low electron durability, so electrons cause polymer decomposition. In particular, polymers in which electron holes are transported by the main chain, such as polymers having an arylamine in the main chain, have low electron durability and there is still room for improvement.

One of the factors that hinders the improvement of the electronic durability of polymers is that the side chains are close to the main chain. In the present invention, an attempt is made to solve the above problem by making the main chain that transports holes into a structure that is less likely to receive electrons. As shown in the above formula (1), in the structure of carbazole with two or more aromatic rings or aromatic heterocycles (Ar ⁴ , Ar ⁵ ) at the 9-position, due to the electron pulling of the conjugated group extended from the 9-position of the carbazole The electrons are relatively high, so the electrons are distributed at the terminal side of the side chain. In the polymers of the following embodiments, since the carbazole structure of the side chain is appropriately far away from the main chain near the amine, which has poor electron durability, it is easier for the side chain to receive electrons than for the main chain. The carbazole structure of the side chain The electronic durability of the structure is high, so it is thought that the electronic durability of the polymer can be improved. It is believed that this effect will be further amplified by having an aromatic ring or aromatic heterocyclic ring (Ar ³ ) between the main chain and the carbazole in the side chain.

In addition, since electrons are distributed on the end side of the side chain, the proportion of holes transported via the main chain that jumps to the side chain side can be reduced, which is thought to increase the hole injection transport capability.

The main chain of the polymer of this embodiment preferably contains a fluorine ring or a carbazole ring. In this case, it is preferable that a phenylene group is bonded to positions 2 and 7 of the fluorine ring or carbazole ring. By bonding the phenylene groups at positions 2 and 7 of the fluorine ring or carbazole ring, the fluorine ring or carbazole ring is electrically stable. In particular, it is believed that the electronic durability is improved and the driving life of the components is lengthened. At this time, when the phenylene ring has a substituent, due to the steric hindrance caused by the substituent, the surface of the phenylene group having the substituent becomes a more twisted arrangement relative to the surface of the adjacent fluorine ring or carbazole ring. At this time, due to the steric hindrance of the substituent, it has a main chain structure that hinders the expansion of the π conjugated system, so it exhibits high excited singlet energy levels (S ₁ ) and excited triplet energy levels (T ₁ ). , the extinction caused by the energy transfer of luminescent excitons is suppressed, so the luminous efficiency is superior.

Furthermore, in the case where the phenylene group in the main chain of the polymer of this embodiment has a substituent, due to the steric hindrance of the substituent, the surface of the phenylene group having the substituent is relative to the adjacent fluorenyl group, divalent fluorenyl group, or Or the surface of the divalent carbazolyl group becomes a more twisted configuration. At the same time, due to the steric hindrance caused by the substituent, it is not easy to crystallize, and exhibits an excited singlet energy level (S ₁ ) and an excited triplet energy level (T ₁ ) Higher properties, so better.

In addition, since the main chain of the polymer of this embodiment contains a structure in which phenylene groups and oxygen atoms are alternately bonded, it has a main chain structure that hinders the expansion of the π conjugated system, and therefore exhibits an excited singlet energy level (S ₁ ) and the property of high excited triplet energy level (T ₁ ), the extinction caused by the energy transfer of luminescent excitons is suppressed, so the luminous efficiency is superior.

In an organic electroluminescent element, if the energy level difference between the organic layers is inappropriate, it will be difficult to inject carriers into the light-emitting layer, and the driving voltage will increase. Furthermore, it is considered that carriers easily leak from the light-emitting layer to the adjacent layer, and the device efficiency is reduced.

On the other hand, as in this embodiment, a charge transport material having a higher energy level than the exciton energy level of the light-emitting material located in the light-emitting layer is more effective in sealing the excitons of the light-emitting material, and is therefore preferable.

In addition, the layer obtained by wet film formation using the composition for organic electroluminescence elements containing the polymer of this embodiment is flat without causing luminescence cracks or the like. As a result, the organic electroluminescent element according to one embodiment of the present invention having this layer has high brightness and long driving life.

In addition, since the polymer of this embodiment has excellent electrochemical stability, it is considered that components including layers formed using this polymer can be applied to flat-panel displays (such as for OA computers or wall-mounted TVs), vehicle-mounted display components, and mobile devices. Telephone displays, light sources that function as surface illuminators (such as light sources for photocopiers, backlights for liquid crystal displays or instruments), display panels, and sign lights have great technical value.

Furthermore, the organic electroluminescent device according to the second and third aspects includes a material having a specific structure having carbazole as a partial structure in both the hole transport layer and the light-emitting layer. The interface of the light-emitting layer is easy to accept charges and can be driven by a lower voltage than conventional ones. Furthermore, since charges are easily accepted at the interface between the two layers and charges are not easily accumulated, extinction is suppressed, and the device can be more efficient and have a longer driving life than conventional devices.

Furthermore, the organic electroluminescent element related to the embodiment of the present invention can be produced by a wet film forming method.

In addition, since the organic electroluminescent element according to the embodiment of the present invention has excellent electrochemical stability, it contains an element using a layer formed of the above-mentioned polymer, and is considered to be applicable to flat-panel displays (such as for OA computers or wall-mounted TVs). , vehicle display components, mobile phone displays, light sources that function as surface illuminators (such as light sources for photocopiers, backlights for LCD monitors or instruments), display panels, and sign lights have great technical value.

1:Substrate

2:Anode

3: Hole injection layer

4: Hole transport layer

5: Luminous layer

6: Hole blocking layer

7:Electron transport layer

8:Electron injection layer

9:Cathode

10: Organic electroluminescent components

FIG. 1 is a schematic cross-sectional view showing a structural example of an organic electroluminescent element according to this embodiment.

FIG. 2 is a diagram (halftone image) showing the electron state of the electron polymerization unit 1 of the embodiment.

FIG. 3 is a diagram (halftone image) showing the electron state of the electron aggregation unit 2 of the embodiment.

FIG. 4 is a diagram (halftone image) showing the electron states of the electron polymerization units 3 to 5 of the embodiment.

The following describes in detail the organic electroluminescent element according to the embodiment of the present invention, the organic EL display device and the organic EL lighting having the organic electroluminescent element. However, the following description is only an example (representative) of the embodiment of the present invention. Example), the present invention is not limited to these contents as long as the gist thereof is not exceeded.

In addition, in this specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit, and "A~B" means A or more and B or less.

In addition, in this specification, "independent" used when combining two or more objects for description is used in the sense that these two or more objects may be the same or different.

<Implementation form of the first point>

The polymer according to the first embodiment includes a structure represented by the following formula (1). In this specification, this polymer is also called polymer a.

In formula (1), G represents an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or a C atom, an N atom, a B atom or a P atom; Ar ² ~ Ar ⁴ are independently means a divalent aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or an aromatic hydrocarbon group that may have a substituent or an aromatic heterocyclic group that may have a substituent directly or A divalent group connected through a plurality of linking groups; Ar ⁵ represents an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or an aromatic hydrocarbon group that may have a substituent, or An aromatic heterocyclic group which may have a substituent is a monovalent group connected directly or via a plurality of connecting groups; Ar ⁶ represents a hydrogen atom or a substituent; In addition, "-*" in Ar ¹ represents the formula (1) and The part where G's are bonded (bonding position).

(G)

環、亦可具有取代基之茀環、亦可具有取代基之螺茀環、亦可具有取代基之咔唑環，更佳為下述圖表1所示之構造。尚且，下述構造亦可具有取代基。又，圖中，「-＊」表示與Ar³間之鍵結位置。 In the repeating unit represented by the above 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 superior charge transport properties and the localization of LUMO distributed at position 9 of the carbazole ring and HOMO distributed in the main chain, G is preferably a benzene ring which may have a substituent, or a benzene ring which may have a substituent. The third substituent

The ring may be a fluorine ring that may have a substituent, a spirofluorine ring that may have a substituent, or a carbazole ring that may have a substituent, and is more preferably a structure shown in Figure 1 below. In addition, the following structures may have substituents. In addition, in the figure, "-*" indicates the bonding position with Ar ³ .

As the optional substituent, it is preferable to use any one of the substituent group Z described below, an aralkyl group having 7 to 40 carbon atoms, or an aralkyl group having a heterocyclic ring having 4 to 37 carbon atoms, or a combination thereof. combination. Among these, from the perspective of electronic durability (also referred to as "durability"), each time When appearing, they are the same or different, and are preferably alkyl groups with 1 to 24 carbon atoms, aralkyl groups with 7 to 40 carbon atoms, aralkyl groups with heterocyclic rings of 3 to 37 carbon atoms, and aromatic groups with 10 to 24 carbon atoms. Amino group, aromatic hydrocarbon group with 6 to 36 carbon atoms, or aromatic heterocyclic group with 3 to 36 carbon atoms; more preferably, alkyl group with 1 to 12 carbon atoms, aralkyl group with 7 to 30 carbon atoms, or aromatic heterocyclic group with 3 to 36 carbon atoms. An aralkyl group with a heterocyclic ring of 3 to 27 carbon atoms, an aromatic hydrocarbon group with a carbon number of 6 to 24 carbon atoms, or an aromatic heterocyclic group with a carbon number of 3 to 24 carbon atoms; more preferably, it is an aryl group with a carbon number of 6 to 24 carbon atoms.

From the perspective of charge transport properties, each occurrence may be the same or different, preferably an aromatic hydrocarbon group with 6 to 24 carbon atoms, or an aromatic heterocyclic group with 3 to 24 carbon atoms, and more preferably benzene. base, naphthyl, benzoyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, or indenobenzene.

Furthermore, from the viewpoint of superior charge transport properties, G is preferably an N atom (nitrogen atom).

(Ar ² , Ar ³ , Ar ⁴ )

In the repeating unit represented by the above formula (1), Ar ² to Ar ⁴ independently represent a divalent aromatic hydrocarbon group that may have a substituent, a divalent aromatic heterocyclic group that may have a substituent, or a divalent aromatic heterocyclic group that may also have a substituent. The aromatic hydrocarbon group of the substituent or the aromatic heterocyclic group which has the substituent may be a divalent group connected directly or via a linking group in plural.

環、聯伸三苯環、苊環、1,2-苯并苊環、茀環等6元環之單環或2~5縮合環之2價基，或此等經複數連結的二價基。 As the aromatic hydrocarbon group, the number of carbon atoms is preferably 6 or more and 60 or less. Specific examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,

Rings, biextended triphenyl rings, acenaphthylene rings, 1,2-benzoacenaphthylene rings, fluorine rings and other 6-membered single rings or divalent radicals of 2 to 5 condensed rings, or these bivalent radicals connected in plural.

When the above-mentioned divalent groups are connected in plural numbers, examples include 2 to 10 connected divalent groups, and preferably 2 to 5 connected divalent groups.

二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異

唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡

環、噠

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉環、喹

啉環、菲啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等5~6元環之單環或2~4縮合環之二價基，或此等複數個連結的二價基。 The aromatic heterocyclic group preferably has a carbon number of 3 or more and 60 or less, and specific examples include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, and an imidazole ring.

Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furanofuran ring, thieno Furan ring, benziiso

Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring

ring, da

ring, pyrimidine ring, tri

ring, quinoline ring, isoquinoline ring,

pholine ring, quinine

Monocyclic rings of 5 to 6 members such as phenanthridine ring, benzimidazole ring, phenanthridine ring, quinazoline ring, quinazolinone ring, azulene ring, or divalent groups of 2 to 4 condensed rings, or These plurality of linked bivalent bases.

When the above-mentioned divalent group is connected by a plurality of divalent groups, for example, there can be 2 to 10 connected divalent groups, and preferably 2 to 5 connected divalent groups.

The divalent group in which a plurality of aromatic hydrocarbon groups which may have a substituent or an aromatic heterocyclic group which may have a substituent are connected directly or via a linking group may be a group in which a plurality of the same groups are connected, or the divalent group may be It is a base connected by multiple bases with different bases.

When the above-mentioned divalent group is a plurality of linked groups, for example, 2 to 10 linked divalent groups may be used, and preferably 2 to 5 linked divalent groups are used.

From the viewpoint of superior charge transport properties and superior durability, Ar ² is preferably one or a plurality of aromatic hydrocarbon groups selected from an aromatic hydrocarbon group that may have a substituent and an aromatic heterocyclic group that may have a substituent. A divalent group bonded directly or via a linking group. The linking group is preferably an oxygen atom or a carbonyl group. Since the electron hole transporting property is improved, the group directly bonded to the nitrogen atom is preferably an aromatic hydrocarbon group which may also have a substituent, and more preferably a phenylene group which may also have a substituent, or a bisphenol group which may also have a substituent. The fluorinated group is particularly preferably a phenylene group which may have a substituent. The phenylethylene ring directly bonded to the nitrogen atom is preferably bonded to a fluorine ring or carbazole ring; between the phenylethylene ring directly bonded to the nitrogen atom and the fluorine ring or carbazole ring, 1 The structure of one or more phenylene groups is also preferred. In addition, a structure in which phenylene rings are connected via an oxygen atom or a carbonyl group is also preferred.

The substituent Ar ² has is the same as the substituent it may have when G is an aromatic hydrocarbon group or an aromatic heterocyclic group.

From the viewpoint of localizing LUMO distributed at position 9 of the carbazole ring and HOMO distributed in the main chain, Ar ³ is preferably 1 to 6 positions of a divalent aromatic hydrocarbon group that may have a substituent. The bonded groups are more preferably 2 to 4 bonded divalent aromatic hydrocarbon groups which may have a substituent; among these, 1 to 4 phenylene rings which may have a substituent are more preferably The linked group is particularly preferably two linked biphenylene groups of a phenylene ring which may have a substituent.

The substituents that Ar ³ may have are the same as the substituents of Ar ² mentioned above.

From the viewpoint of superior charge transport properties and superior durability, Ar ⁴ is preferably one or a plurality of connected groups of the same or different divalent aromatic hydrocarbon groups. It may also have a substituent. As mentioned above, from the viewpoint of distributing LUMO in the structure represented by -Ar ⁴ -Ar ⁵ , a larger number of connections is preferable. However, from the viewpoint of charge transport properties and film stability, a smaller number of connections is more preferable. good. When connecting, the number is preferably 2 or more and 10 or less, more preferably 6 or less, and particularly preferably 3 or less from the viewpoint of film stability. Preferable aromatic hydrocarbon structures include benzene ring, naphthalene ring, anthracene ring, and fluorine ring, and more preferably benzene ring and fluorine ring. As the plurality of linked groups, it is preferable to use a phenylene ring which may have a substituent and 1 to 4 linked groups, or a phenylene ring which may have a substituent and a fluorine ring which may have a substituent. The base of the ring connection. From the viewpoint of LUMO expansion, a biphenylene group having two linked phenylene rings which may have a substituent is particularly preferred.

As a substituent that Ar ⁴ may have, any one of the substituent groups Z described below, or a combination thereof can be used. From the viewpoint of inhibiting the expansion of LUMO, those other than N-carbazolyl, indolocarbazolyl, and indenocarbazolyl are preferred; and more preferred substituents are phenyl, naphthyl, and fluorenyl. In addition, those without substituents are also preferred.

(Ar ⁵ )

Ar ⁵ represents an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or an aromatic hydrocarbon group that may have a substituent, and an aromatic heterocyclic group that may have a substituent. A univalent base connected by a plurality of bases directly or via connecting bases. In the case of a plurality of links, there may be, for example, 2 to 10 linked divalent groups, preferably 2 to 5 linked divalent groups. As the aromatic hydrocarbon and the aromatic heterocyclic ring, the aromatic hydrocarbon structure and the aromatic heterocyclic structure exemplified by the above-mentioned Ar ² to Ar ⁴ and having a monovalent structure can be used. Preferably, it is a 9-ring carbazole ring clearly described as Ar ¹ in the formula (1), and has a structure shown in any one of the following diagrams 2. Furthermore, from the perspective of LUMO distribution of the molecule, it is preferably selected from a-1~a-4, b-1~b-9, c-1~c-5, d-1~d-16 and e1 ~e4. Furthermore, from the viewpoint of promoting the LUMO expansion of the molecule by having an electron-withdrawing group, it is preferably selected from a-1 to a-4, b-1 to b-9, d-1 to d-13, and e1~ The structure of e4. Furthermore, from the viewpoint of the high triplet energy level and the effect of confining the formed excitons in the light-emitting layer, it is preferred to be selected from a-1 to a-4, d-1 to d-13 and e1 to e4. Construct. Furthermore, phenyl group is also preferred. Furthermore, these structures may have a substituent. In addition, "-*" in the figure represents the bonding position with Ar ⁴ ; when there are plural "-*"s, any one of them represents the bonding position with Ar ⁴ .

As a substituent that Ar ⁵ may have, any one of the substituent groups Z described below, or a combination thereof can be used. From the viewpoint of durability and charge transport properties, the substituents are preferably selected from the same substituents as those that Ar ⁴ may have.

(Ar ⁶ )

Ar ⁶ represents a hydrogen atom or a substituent. When Ar ⁶ is a substituent, it is not particularly limited, but is preferably an aromatic hydrocarbon group that may have a substituent or an aromatic heterocyclic group that may have a substituent. A preferred structure is the same monovalent structure as the aromatic hydrocarbon structure and the aromatic heterocyclic structure listed above for Ar ² to Ar ⁴ .

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

When Ar ⁶ is an aromatic hydrocarbon group that may have a substituent or an aromatic heterocyclic group that may have a substituent, the substituent is the same as the substituent listed for the substituent group Z described below or the crosslinking group described below. , and preferred substituents; these substituents may further have the same substituents. Moreover, from the viewpoint of insolubilization, it is preferable that the substituent contains at least one crosslinking group described below.

[Better repeating unit structure]

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

[Chemical 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 that may have a substituent, an alkoxy group that may have a substituent, or An aralkyl group that may also have a substituent; R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ independently represent an alkyl group that may also have a substituent, an alkoxy group that may also have a substituent, and an aryl group that may also have a substituent. Alkyl group, or aromatic hydrocarbon group that may also have a substituent; a and b are each independently an integer from 0 to 4; c1 and c2 are each independently an integer from 1 to 3; d1 and d2 are each independently an integer from 0 to 4; When R ¹ , R ² , R ³ and R ⁴ are plural in the repeating unit, R ¹ , R ² , R ³ and R ⁴ may be the same or different.

(X)

X represents any one of -C(R ⁵ )(R ⁶ )-, -N(R ⁷ ), or -C(R ¹¹ )(R ¹² )-C(R ¹³ )(R ¹⁴ )-. From the viewpoint of durability, -C(R ⁵ )(R ⁶ )- and -N(R ⁷ ) are preferred.

(R ¹ and R ² )

R ¹ and R ² in the repeating units represented by the above formulas (2)-1 to (2)-3 each independently represent 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. However, in order to maintain the solubility of the polymer, the number of carbon atoms is preferably 1 or more and 6 or less, more preferably 3 or less; more preferably it is a methyl group or an ethyl group.

When R ¹ and R ² are plural in the repeating unit, R ¹ and R ² can be the same or different. In order to make the charge evenly distributed around the nitrogen atom and thereby facilitate the synthesis, it is preferable that all R ¹ and R ² are the same basis.

(R ³ and R ⁴ )

R ³ and R ⁴ in the repeating units represented by the above formulas (2)-1 to (2)-3 each independently represent a linear, branched or cyclic alkyl group which may have a substituent. The carbon number of the alkyl group is not particularly limited, but in order to maintain the solubility of the polymer, the carbon number is preferably 1 or more, more preferably 4 or more; the carbon number is preferably 12 or less, more preferably 8 or less; particularly preferably hexyl group .

(R ⁵ ~R ⁷ and R ¹¹ ~R ¹⁴ )

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

The above-mentioned alkyl group is not particularly limited. In order to show a tendency to improve the solubility of the polymer, a longer one is preferred; in order to improve film stability and charge transport properties, A shorter one is preferred; the number of carbon atoms is preferably 1 or more and 24 or less, more preferably 12 or less, further preferably 8 or less, and particularly preferably 6 or less; more preferably 2 or more, further preferably 3 or more, and particularly preferably 4 or more. In addition, each structure may be linear, branched or cyclic.

Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-hexyl, n-octyl, cyclohexyl, and dodecyl. wait.

The above-mentioned alkoxy group is not particularly limited. In order to show a tendency to improve the solubility of the polymer, the carbon number is preferably 1 or more and 24 or less, more preferably 12 or less, further preferably 8 or less, particularly preferably 6 or less; and, more preferably Best is 2 or more, more preferably 3 or more, particularly best 4 or more.

Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hexyloxy, and the like.

The above-mentioned aryloxy group is not particularly limited. In order to show a tendency to improve the solubility of the polymer, the number of carbon atoms is preferably 5 or more and 60 or less, more preferably 40 or less; more preferably 7 or more, further preferably 10 or more, and particularly preferably 12 and above.

Specific examples include 1,1-dimethyl-1-phenylmethyl, 1,1-di(n-butyl)-1-phenylmethyl, and 1,1-di(n-hexyl)-1-phenyl methyl, 1,1-di(n-octyl)-1-phenylmethyl, phenylmethyl, phenylethyl, 3-phenyl-1-propyl, 4-phenyl-1-n- Butyl, 1-methyl-1-phenylethyl, 5-phenyl-1-n-propyl, 6-phenyl-1-n-hexyl, 6-naphthyl-1-n-hexyl, 7-phenyl -1-n-heptyl, 8-phenyl-1-n-octyl, 4-phenylcyclohexyl, etc.

The aromatic hydrocarbon group is not particularly limited. In order to tend to improve the solubility of the polymer, the number of carbon atoms is preferably 6 or more and 60 or less, more preferably 30 or less, more preferably 24 or less, and particularly preferably 14 or less.

環、聯伸三苯環、苊萘環、1,2-苯并苊環、茀環等之6元環的單環或2~5縮合環之一價基，或使選自此等之環構造2~8個連結的基；較佳為單環或2至4個經連結的基。 Specific examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,

Ring, biextended triphenyl ring, acenaphthylene ring, 1,2-benzoacenaphthylene ring, fluorine ring, etc., a single ring of 6-membered rings or a valent group of 2~5 condensed rings, or a ring structure selected from these 2 to 8 linked groups; preferably a single ring or 2 to 4 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, and R ⁷ is more preferably an aromatic hydrocarbon group. The number of carbons is as above.

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

The alkyl groups of R ¹ to R ⁴ , the alkyl groups of R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ , alkoxy groups, aralkyl groups and aromatic hydrocarbon groups may also have substituents. Examples of substituents that may be included include those listed as preferred groups for the alkyl group, alkoxy group, aralkyl group and aromatic hydrocarbon group of the above-mentioned R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ , or those mentioned below. Cross-linking group.

The above-mentioned alkyl groups of R ¹ to R ⁴ , alkyl groups of R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ , alkoxy groups, aralkyl groups and aromatic hydrocarbon groups are most preferred from the viewpoint of lowering the voltage. No substituents.

In addition, the substituents that R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ may have are added by lifting when other layers are further coated to form a film and laminated after the polymer film of this embodiment is formed. From the viewpoint of insolubility in the solvent, a cross-linkable group described below is preferred. Among them, from the viewpoint of not easily hindering charge transport properties, it is preferable that any one of R ⁵ , R ⁶ and R ¹¹ to R ¹⁴ has a cross-linkable group as a substituent as described below, and more preferably one of R ⁵ and R ⁶ At least one of them has a crosslinkable group described below as a further substituent.

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

Among the repeating units shown in the above formulas (2)-1 to (2)-3, a and b are independently integers from 0 to 4. Moreover, a+b is preferably 1 or more. Furthermore, it is preferable that a and b are each 2 or less, and it is more preferable that both a and b are 1.

Among the repeating units shown in the above formulas (2)-1 to (2)-3, c1 and c2 are independently integers from 1 to 3, and d1 and d2 are independently integers from 0 to 4. It is preferable that c1, c2, d1 and d2 are each 2 or less, more preferably c1, c2, d1 and d2 are equal, still more preferably c1, c2, d1 and d2 are all 1 or 2, particularly preferably c1, c2, d1 and d2 are both 1.

In the repeating units shown in the above formula (2)-1 to formula (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 2 or 1, R ¹ and R ² are best bonded at symmetrical positions to each other.

Here, R ¹ and R ² are bonded at symmetrical positions to each other. Taking the case of X=C in the above formula (2)-1 as an example, the following formula is used to explain. That is, the bonding positions of R ¹ and R ² are symmetrical with respect to the fluorine ring of the main chain in the following formula. At this time, the 180-degree rotation with the main chain as the axis becomes the same structure. For example, in Formula (1a), R ^a and R ^b are symmetrical, R ^a' and R ^b' are symmetrical, and Formula (1a) and Formula (1b) have the same structure.

[Chemical 17]

From the viewpoint of durability or low voltage of the element when used in an organic electroluminescent element, it is preferable to include repeating units represented by Formula (2)-1 or Formula (2)-2.

[Substituent group Z]

Examples of the substituent group Z include the following structures.

For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-hexyl, cyclohexyl, dodecyl, etc. The number of carbon atoms is usually 1 or more. , preferably 4 or more and usually 24 or less, preferably 12 or less linear, branched or cyclic alkyl groups; for example, vinyl and other carbon numbers are usually 2 or more, and usually 24 or less, preferably 12 or less. Alkenyl; for example, an alkynyl group with a carbon number of usually 2 or more and usually 24 or less, preferably 12 or less, such as an ethynyl group; such as a methoxy group, an ethoxy group, etc., with a carbon number of usually 1 or more, and usually 24 or less, Alkoxy groups preferably less than 12; for example, phenoxy, naphthyloxy, pyridyloxy and other carbon numbers are usually 4 or more, preferably 5 or more, and usually 36 or less, preferably 24 or less aryloxy or hetero groups. aryloxy; For example, methoxycarbonyl, ethoxycarbonyl and other alkoxycarbonyl groups usually have 2 or more carbon atoms, and usually 24 or less, preferably 12 or less; for example, dimethylamino group, diethylamino group, etc. have usually 2 or more carbon atoms. , and the dialkylamino group is usually 24 or less, preferably 12 or less; for example, the carbon number of diphenylamino group, xylylamine group, N-carbazolyl group, etc. is usually 10 or more, preferably 12 or more, and A diarylamine group with a carbon number of usually 36 or less, preferably 24 or less; for example, a phenylmethylamino group or other arylalkylamine group with a carbon number of usually 7 or more, and usually 36 or less, preferably 24 or less; for example Acetyl group, benzyl group and other carbon numbers are usually 2 or more, and usually 24 or less, preferably 12 or less; such as fluorine atoms, chlorine atoms and other halogen atoms; such as trifluoromethyl and other carbon numbers are usually A haloalkyl group with a carbon number of 1 or more and usually 12 or less, preferably 6 or less; for example, a methylthio group, an ethylthio group, or other alkylthio group with a carbon number of usually 1 or more, and usually 24 or less, preferably 12 or less; for example Arylthio groups with a carbon number of usually 4 or more, preferably 5 or more, and usually 36 or less, preferably 24 or less, such as phenylthio group, naphthylthio group, pyridylthio group, etc.; for example, trimethylsilyl group, triphenylsilyl group Silicon groups with a carbon number of usually 2 or more, preferably 3 or more, and usually 36 or less, preferably 24 or less; for example, trimethylsiloxane group, triphenylsiloxane group, etc., usually have a carbon number of 2 More than 3, preferably 3 or more, and usually 36 or less, preferably 24 or less siloxane group; cyano group; For example, aromatic hydrocarbon groups with a carbon number of usually 6 or more, usually 36 or less, preferably 24 or less, such as phenyl, naphthyl, etc.; such as thienyl, pyridyl, etc., with a carbon number of usually 3 or more, preferably 4 or more, and usually It is an aromatic heterocyclic group of 36 or less, preferably 24 or less.

Among the above-mentioned substituent groups Z, preferred are the above-mentioned alkyl groups, alkoxy groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups. From the viewpoint of charge transport properties, it is more preferable that it has no substituent.

In addition, each substituent of the above-mentioned substituent group Z may further have a substituent. Examples of these substituents include the same substituents as the above-described substituents (substituent group Z) or crosslinking groups described below. Preferably, it has no substituent, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, a phenyl group or a cross-linkable group mentioned below. From the viewpoint of charge transport properties, it is more preferred not to have further substituents.

[Terminal group]

In this embodiment, the terminal group refers to the terminal structure of the polymer formed by the end-capping agent used when the polymerization of the polymer is completed. The terminal group of the polymer of this embodiment is usually a hydrocarbon group. From the viewpoint of charge transport properties, the hydrocarbon group preferably has a carbon number of 1 or more and 60 or less, more preferably 1 or more and 40 or less, and still more preferably 1 or more and 30 or less.

Preferable examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-hexyl, cyclohexyl, dodecyl, etc. A straight-chain, branched or cyclic alkyl group with a carbon number of usually 1 or more, preferably 4 or more, and usually 24 or less, preferably 12 or less; for example, a vinyl group with a carbon number of usually 2 or more, and usually 24 Alkenyl group below, preferably below 12; For example, an alkynyl group with a carbon number of usually 2 or more and usually 24 or less, preferably 12 or less, such as an ethynyl group; an alkynyl group with a carbon number of usually 6 or more, and usually 36 or less, preferably 24 or less, such as a phenyl, naphthyl group, etc. Aromatic hydrocarbon ring group.

These hydrocarbon groups may further have a substituent, and the substituent that may further have is preferably an alkyl group or an aromatic hydrocarbon group. When there are a plurality of substituents that may further have them, they may be bonded to each other to form a ring.

From the viewpoint of charge transport properties and durability, an alkyl group or an aromatic hydrocarbon group is preferred, and an aromatic hydrocarbon group is more preferred.

[Soluble base]

In order to express solubility in a solvent, the polymer of this embodiment preferably has a soluble group. The soluble group in this embodiment is a group having a linear or branched alkyl or alkenyl group having a carbon number of 3 to 24, preferably 12 or less. Among these, an alkyl group, an alkoxy group, or an aralkyl group is preferred, such as n-propyl, 2-propyl, n-butyl, isobutyl, and the like. More preferably, it is n-hexyl group or n-octyl group. The soluble group may have a substituent. When one or more of the above-mentioned R ¹ to R ⁷ and R ¹¹ to R ¹⁴ have such structures, these groups are regarded as soluble groups. In addition, when the substituents of this embodiment satisfy the above-mentioned conditions for soluble groups, these substituents are regarded as soluble groups.

(number of soluble groups)

From the viewpoint of easily obtaining a polymer solution that can be used by a wet film-forming method, the polymer of this embodiment preferably has a larger number of soluble groups. On the other hand, from the viewpoint of reducing the amount of reduction in film thickness caused by dissolution of the layer in the solvent when forming other layers on the formed layer by a wet film forming method, the smaller amount is preferred.

The number of soluble groups contained in the polymer of this embodiment can be expressed by the mole number per 1 g of the polymer.

When the number of soluble groups contained in the polymer of this embodiment is represented by the number of moles per 1 g of the polymer, it is usually 4.0 mmol or less, preferably 3.0 mmol or less, per 1 g of the polymer. More preferably, it is 2.0 mmol or less, and usually it is 0.1 mmol or more, preferably 0.5 mmol or more.

When the number of soluble groups is within the above range, the polymer can be easily dissolved in the solvent, and a composition containing a polymer suitable for wet film formation can be easily obtained. In addition, since the density of the soluble base is appropriate, the refractory solvent to the organic solvent is sufficient after drying by heating the solvent, and a multi-layer laminated structure can be formed by a wet film forming method.

Here, the number of soluble groups per 1 g of the polymer is calculated by removing the terminal groups from the polymer and calculating the molar ratio and structural formula of the filling monomers at the time of synthesis.

As an illustration of the polymer 1 synthesized in Example 1 to be described below, in the polymer 1, the average molecular weight of the repeating units excluding the terminal groups is 767, and the hexyl group belonging to the soluble group is An average of 2 per repeat unit. If this is calculated based on a simple ratio, the number of soluble groups per 1g of molecular weight can be calculated to be 2.09 millimoles.

[Crosslinking group]

The polymer of this embodiment may have a crosslinking group as a substituent. The crosslinkable group in the polymer of this embodiment may be present in the repeating unit represented by formula (1), or may be present in other repeating units different from the repeating unit represented by formula (1). It is particularly preferable when Ar ¹ belonging to the side chain has a cross-linking group because the cross-linking reaction proceeds easily.

By having a crosslinking group, a large difference can be made in the solubility of the organic solvent before and after the reaction (refractory reaction) caused by irradiation with heat and/or active energy rays.

The so-called "cross-linking group" refers to a group that reacts with groups constituting other molecules located near the cross-linking group by irradiation with heat and/or active energy rays to form novel chemical bonds. In this case, the group that reacts may be the same as or different from the crosslinking group.

As the crosslinkable group, a group containing a cyclobutene ring condensed to an aromatic ring and an alkenyl group bonded to an aromatic ring is preferred, and a group selected from the following crosslinkable group T is more preferred. The crosslinkable group is preferably further substituted on the substituent contained in each of the above structures.

(Crosslinking group T)

The cross-linkable group T has the structure shown below.

In the above crosslinkable group T, R ²¹ to R ²³ each independently represent a hydrogen atom or an alkyl group.

R ²⁴ ~ R ²⁶ independently represent an alkyl group or an alkoxy group. p is an integer from 1 to 4, q is an integer from 1 to 5, and r is an integer from 1 to 7.

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

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

When r is 2 or more, the plural R ²⁶ may be the same or different.

Ar ²¹ and Ar ²² represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent.

Examples of the alkyl group of R ²¹ to R ²⁶ include linear or branched chain alkyl groups having 6 or less carbon atoms. For example, methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, etc. More preferably, it is methyl or ethyl. When the number of carbon atoms in R ²¹ to R ²⁶ is 6 or less, the cross-linking reaction will not be sterically hindered and the film will tend to become insolubilized.

Examples of the alkoxy group of R ²⁴ to R ²⁶ include a linear or branched chain alkoxy group having 6 or less carbon atoms. For example, methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, etc. More preferably, it is methoxy or ethoxy. When the carbon number of R ²⁴ to R ²⁶ is 6 or less, the cross-linking reaction will not be sterically hindered and the film will tend to become insolubilized.

Examples of the optionally substituted aromatic hydrocarbon group of Ar ²¹ and Ar ²² include a 6-membered monocyclic ring or a 2- to 5-membered fused ring such as a benzene ring or naphthalene ring having one free atom valence. Particularly preferred is a benzene ring having one free atom valence.

Ar ²² may be a group in which two or more aromatic hydrocarbon groups, which may have a substituent, are bonded. Examples of such a group include a biphenylene group, a biphenylene triphenyl group, and the like, and a 4,4'-biphenylene group is preferred.

The substituents that Ar ²¹ and Ar ²² may have are the same as the substituent group Z mentioned above.

As the cross-linking group, from the viewpoint of further improving the electrochemical stability of the device, preferred are arylvinyl carbonyl groups such as cinnamonyl group, benzocyclobutene rings having one free atomic valence, and A radical for cycloaddition reaction such as 1,2-dihydrocyclotetra[a]naphthalene ring with free atomic valence.

Furthermore, among the crosslinkable groups, in terms of particularly stable structure after crosslinking, it is preferable to include a cyclobutene ring having a monovalent free atom that has been condensed into an aromatic ring, and a monovalent free atom. A group of 1,2-dihydrocyclotetrakis[a]naphthalene ring with valence; among them, 1,2-dihydrocyclotetrakis[a]naphthalene with a benzocyclobutene ring or a monovalent free atom is more preferred. ring; in view of the lower cross-linking reaction temperature, a 1,2-dihydrocyclic tetra[a]naphthalene ring with a monovalent free atom is particularly preferred.

(Number of cross-linking groups)

The polymer of this embodiment has a larger number of crosslinkable groups from the viewpoint of being sufficiently insolubilized by crosslinking and making it easy to form other layers thereon by a wet film-forming method. On the other hand, from the viewpoint that cracks are less likely to occur in the formed layer, unreacted crosslinking groups are less likely to remain, and the life of the organic electroluminescent element is likely to be long, it is preferable to have fewer crosslinking groups.

In the polymer of this embodiment, the number of crosslinkable groups present in one polymer chain is preferably 1 or more, more preferably 2 or more, and more preferably 200 or less, more preferably 100 or less.

In addition, the number of crosslinkable groups contained in the polymer of this embodiment can be expressed as the number per molecular weight of 1,000 of the polymer.

When the number of crosslinkable groups in the polymer of the present embodiment is expressed as the number per 1,000 molecular weight of the polymer, it is usually 3.0 or less, preferably 2.0 or less, and more preferably 2.0 or less per 1,000 molecular weight. 1.0 or less, usually 0.01 or more, preferably 0.05 or more.

When the number of crosslinkable groups is within the above range, cracks are less likely to occur, and a flat film is easily obtained. In addition, due to the appropriate cross-linking density, there are fewer unreacted cross-linking groups remaining in the layer after the cross-linking reaction, which will not easily affect the life of the resulting device.

Furthermore, since the cross-linking reaction has sufficient insolubility in organic solvents, it is easy to form a multi-layer laminated structure by a wet film forming method.

Here, the number of crosslinkable groups per molecular weight of 1,000 in the polymer is calculated by removing the terminal groups from the polymer, the molar ratio of the filling monomers at the time of synthesis, and the structural formula.

For example, in the case of Polymer 3 synthesized in the Examples described below, in Polymer 3, the molecular weight of the repeating units excluding the terminal groups is an average of 816, and the crosslinking group per repeating unit is 0.138. Piece. If this is calculated based on a simple ratio, the number of cross-linkable groups per 1,000 molecular weight can be calculated to be 0.15.

[Content of repeating units]

In the polymer of this embodiment, the content of the repeating unit represented by formula (1) is not particularly limited. It is usually contained in the polymer at least 50 mol%, preferably at least 60 mol%, and more preferably at least 60 mol%. More than 70 mol%, especially preferably more than 80 mol%. In the polymer of this embodiment, the repeating unit may be composed only of repeating units represented by formula (1). However, for the purpose of balancing various properties when used as an organic electroluminescent element, it may also have other components different from formula (1). Repeating unit; at this time, the content of the repeating unit represented by formula (1) in the polymer is usually 95 mol% or more, preferably 99 mol% or more.

[Other preferred repeating units may also be included]

The polymer of this embodiment preferably further contains a repeating unit represented by any one of the following formulas (3)-1 to (3)-3.

In formulas (3)-1~(3)-3, Ar ⁷ represents independently in each repeating unit an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or An aromatic hydrocarbon group that may have a substituent or an aromatic heterocyclic group that may have a substituent is a divalent group connected directly or via a plurality of connecting groups; 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 that may have a substituent, or may have a substituent. an alkoxy group, or an aralkyl group that may also have a substituent; R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ respectively independently represent an alkyl group that may also have a substituent, or an alkoxy group that may have a substituent, or An aralkyl group that may have a substituent, or an aromatic hydrocarbon group that may have a substituent; a and b are each independently an integer from 0 to 4; c1 and c2 are each independently an integer from 1 to 3; d1 and d2 are each independently an integer. An integer from 0 to 4; when R ¹ , R ² , R ³ and R ⁴ are plural 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 above formulas (3)-1 to (3)-3, Ar ⁷ in each repeating unit independently represents an aromatic hydrocarbon group that may also have a substituent or an aromatic heterocycle that may also have a substituent. base.

環、聯伸三苯環、苊環、1,2-苯并苊環、茀環等6元環之單環或2~5縮合環或此等經複數連結的一價基。 As the aromatic hydrocarbon group, the number of carbon atoms is preferably 6 or more and 60 or less. Specific examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,

Ring, biextended triphenyl ring, acenaphthylene ring, 1,2-benzoacenaphthylene ring, fluorine ring and other 6-membered single rings or 2~5 condensed rings or these monovalent groups linked in plural.

When the above-mentioned divalent groups are connected in plural numbers, examples include 2 to 10 connected divalent groups, and preferably 2 to 5 connected divalent groups.

二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異

唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡

環、噠

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉環、喹

啉環、菲啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等5~6元環之單環或2~4縮合環或此等複數個連結的一價基。 The aromatic heterocyclic group preferably has a carbon number of 3 or more and 60 or less, and specific examples include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, and an imidazole ring.

Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furanofuran ring, thieno Furan ring, benziiso

Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring

ring, da

ring, pyrimidine ring, tri

ring, quinoline ring, isoquinoline ring,

pholine ring, quinine

Single rings of 5 to 6 membered rings such as phenanthridine ring, benzimidazole ring, coridine ring, quinazoline ring, quinazolinone ring, azulene ring, or 2 to 4 condensed rings, or a plurality of these links of a single price basis.

When the above-mentioned divalent group is connected by a plurality of divalent groups, for example, there can be 2 to 10 connected divalent groups, and preferably 2 to 5 connected divalent groups.

From the viewpoint of superior charge transport properties and durability, Ar ⁷ is preferably an aromatic hydrocarbon group that may have a substituent, and more preferably a monovalent group of a benzene ring or a fluorine ring that may also have a substituent, that is, A phenyl group or a fluorine group which may have a substituent is more preferred, and a 2-benzoyl group which may have a substituent is particularly preferred.

The substituents that the aromatic hydrocarbon group and the aromatic heterocyclic group of Ar ⁷ may have are not particularly limited as long as they do not significantly reduce the characteristics of the polymer of this embodiment. Preferable examples include a group selected from the above-mentioned substituent group Z or the above-mentioned crosslinkable group, preferably an alkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group or the above-mentioned crosslinkable group, more preferably alkyl.

From the viewpoint of solubility in the coating solvent, Ar ⁷ is preferably a fluoryl group substituted with an alkyl group having 1 to 24 carbon atoms, and particularly preferably a 2-fluoryl group substituted with an alkyl group having 4 to 12 carbon atoms. . More preferred is 9-alkyl-2-benzoyl substituted with an alkyl group at the 9-position of 2-benzoyl, and particularly preferred is 9,9-dialkyl-2-benzoyl substituted with 2 alkyl groups. When at least one of the 9-position and 9'-position is a fluorine group substituted by an alkyl group, the solubility in the solvent and the durability of the fluorine ring tend to be improved. Furthermore, when both the 9-position and the 9'-position are substituted with alkyl groups, the solubility in the solvent and the durability of the fluorine ring tend to be further improved.

In addition, when Ar ⁷ contains the above-mentioned cross-linkable group, it is preferable because the insolubility in the solvent after film formation and during multi-layer coating is improved.

From the viewpoint of insolubilization, the polymer preferably contains at least one of the above-mentioned crosslinking groups as a further substituent, and contains repeating units represented by formula (3)-1 to formula (3)-3; the crosslinking The sexual group is preferably further substituted by a substituent that the aromatic hydrocarbon group or the aromatic heterocyclic group represented by Ar ⁷ may have.

When used in an organic electroluminescent element, from the viewpoint of element durability or low voltage, it is preferable to contain a repeating unit represented by Formula (3)-1 or Formula (3)-2.

[Molecular weight of polymer]

The weight average molecular weight (Mw) of the polymer in this embodiment is usually 3,000,000 or less, preferably 1,000,000 or less, more preferably 500,000 or less, particularly preferably 200,000 or less, and even more preferably 100,000 or less. Moreover, it is usually 10,000 or more, preferably 20,000 or more, more preferably 30,000 or more.

By setting the weight average molecular weight of the polymer to be equal to or less than the above-mentioned upper limit, solubility in the solvent can be obtained and film-forming properties tend to be excellent. Furthermore, when the weight average molecular weight of the polymer is equal to or higher than the above-mentioned lower limit, the decrease in the glass transition temperature, melting point, and vaporization temperature of the polymer may be suppressed, and the heat resistance may be improved. In addition, there are cases where the coating film after the cross-linking reaction is sufficiently insoluble in the organic solvent.

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

Furthermore, the dispersion degree (Mw/Mn) of the polymer in this embodiment is preferably 3.5 or less, more preferably 2.5 or less, particularly preferably 2.0 or less. In addition, since the smaller the dispersion value, the better, so the lower limit value is ideally 1. When the dispersion degree of the polymer is below the above-mentioned upper limit, purification is easy and the solubility in the solvent and the charge transport ability are good.

Generally, the weight average molecular weight and number average molecular weight of a polymer are determined by SEC (size exclusion chromatography) measurement. During SEC measurement, high molecular weight components have a short dissolution time, while low molecular weight components have a long dissolution time. Use a calibration curve calculated from the dissolution time of polystyrene (standard sample) with a known molecular weight, by dividing the dissolution time of the sample. Time is converted into molecular weight, and the weight average molecular weight and number average molecular weight can be calculated.

[Other repeating units]

From the viewpoint of charge transport properties and durability, the polymer of this embodiment may further contain repeating units represented by formula (4) or formula (5). The repeating units shown in the following formula (4) can be repeated with those shown in the above formula (1), formula (2)-1~formula (2)-3 and formula (3)-1~formula (3)-3 The structure of one part of a unit that is partially the same but still belongs to the structure of other repeating units that are different from it.

[Chemistry 22]

In the 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 represents a divalent aromatic hydrocarbon group which may have a substituent and may also have a substituent. A divalent aromatic heterocyclic group of a base, or a plurality of plural groups selected from the aromatic hydrocarbon group that may have a substituent and the aromatic heterocyclic group that may have a substituent, directly or via a linking group. Bivalent base.

In formula (5), Ar ¹⁰ represents a divalent aromatic hydrocarbon group that may have a substituent, a divalent aromatic heterocyclic group that may have a substituent, or a group selected from the aromatic hydrocarbon group that may have a substituent, and The aromatic heterocyclic group which may have a substituent is a plurality of divalent groups connected directly or via a linking group.

(Ar ⁸ , Ar ⁹ , Ar ¹⁰ )

As the aromatic hydrocarbon group and aromatic heterocyclic group in Ar ⁸ , Ar ⁹ and Ar ¹⁰ , Ar ⁸ is selected from the same aromatic hydrocarbon group and aromatic heterocyclic group that can be used for Ar ⁶ of formula (1). group; Ar ⁹ and Ar ¹⁰ represent groups selected from the same aromatic hydrocarbon groups and aromatic heterocyclic groups that can be used as Ar ² in formula (1) and are divalent groups. In the case where the bivalent bases are a plurality of links, the number is also preferably 2 to 10, and more preferably 2 to 5. The substituent which may be present is preferably the same group as the above-mentioned substituent group Z or the above-mentioned crosslinkable group.

[Better polymer]

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

In each polymer of formula (6), Ar ^T represents the above-mentioned Ar ¹ or the above-mentioned Ar ⁷ , the plural Ar ^T in each polymer may be the same or different, and at least one of the Ar ^T in each polymer represents the above-mentioned Ar ^{1 ; _ _ _}

n and m represent the number of repetitions.

A polymer according to another embodiment of the first aspect of the present invention is a polymer having a structure represented by the following formula (12) or the following formula (13).

G, Ar ² , Ar ⁴ and Ar ⁶ in the formula (12) are the same as G, Ar ² and Ar ⁴ in the formula (1) respectively; Ar ⁵⁵ represents a-1~ shown in the following figure 2. Any structure of a-4, b-1~b-9, c-1~c-5, d-1~d-16 and e1~e4.

Incidentally, "-*" in Ar ¹² represents the site (bonding position) where G is bonded in the formula (12).

In the formula (12), the preferred ranges of G, Ar ² , Ar ⁴ and Ar ⁶ and the substituents they may have are the same as those of G, Ar ² , Ar ⁴ and Ar ⁶ in the above formula (1) respectively.

In the formula (12), the preferred range of Ar ⁵⁵ and the substituents it may have are the same as those of Ar ⁵ in the above formula (1).

In formula (13), G, Ar ² , Ar ⁴ and Ar ⁶ are the same as G, Ar ² and Ar ⁴ in the above formula (1) respectively; Ar ³³ and Ar ³⁴ respectively represent independently and may have two substituents. A valent aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, or a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups connected directly or via a linking group Divalent radical; Ar ⁵⁵⁵ represents a hydrogen atom, an aromatic hydrocarbon group that may also have a substituent, an aromatic heterocyclic group that may also have a substituent, or an aromatic hydrocarbon group that may also have a substituent, or an aromatic hydrocarbon group that may also have a substituent. The aromatic heterocyclic group is a monovalent group connected in plural directly or via a linking group.

Incidentally, "-*" in Ar ¹³ represents the site where G is bonded (bonding position) in the formula (13).

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

In the formula (13), the preferred ranges of Ar ³³ and Ar ³⁴ and the substituents they may have are the same as those of Ar ² and Ar ⁴ in the above formula (1); the preferred ranges when a plurality of them are connected are also the same. .

The preferred range of Ar ⁵⁵⁵ is the same as Ar ⁵ in the above formula (1). The substituent that may be present is the same as Ar ⁵ in formula (1).

The preferred repeating unit structure of formula (12) and formula (13), its terminal group, soluble group, cross-linking group, content of repeating units, other preferred repeating units that may also be included, the molecular weight of the polymer, and The other repeating units it has are the same as the polymer of the above formula (1).

In formula (12), since Ar ⁵⁵ can distribute the LUMO of the molecule at the terminal side of the side chain, the hole injection and transport capability is high and the durability can be improved. In addition, formula (13) uses Ar ³³ and Ar ³⁴ to maintain a distance between the main chain and carbazole, and can separate HOMO and LUMO, so the hole injection transport capability and durability can be improved. Since Ar ³ and Ar ⁵ are present in formula (1), the LUMO of the molecule is distributed at the terminal side of the side chain, and the HOMO of the main chain and the LUMO of the side chain can be separated, so it is more preferable.

[Specific example]

Specific examples of the polymer in this embodiment are shown below, but they are not limited thereto. Moreover, the numbers in the chemical formula represent the molar ratio of repeating units.

These polymers can be any of random copolymers, alternating copolymers, block copolymers, or graft copolymers, and the arrangement order of the monomers is not limited.

[Production method of polymer]

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

In the polymerization method using the Ullmann reaction and the polymerization method using the Buchwald-Hartwig reaction, for example, the dihalogenated aryl group represented by the formula (1a) (Y represents a halogen atom such as I, Br, Cl, F, etc.) and The polymer of this embodiment can be synthesized by reacting the primary aminoaryl group represented by formula (1b) and further reacting with 2a.

In the above formula, Ar ¹ , R ¹ ~R ² , X, a and b are synonymous with the above formulas (2)-1 ~ (2)-3 respectively. c and d are respectively synonymous with c1 or c2, and d1 or d2 in the above formulas (2)-1~(2)-3. n and m represent the number of repetitions.

Furthermore, in the above-mentioned polymerization method, the reaction to form an N-aryl bond is usually carried out in the presence of a base such as potassium carbonate, sodium tert-butoxide, or triethylamine. Alternatively, it may be carried out in the presence of a transition metal catalyst such as copper or palladium complex.

<Implementation form of the second point>

<Same partial structure>

The organic electroluminescent device according to the second aspect of the present invention preferably has an anode, a cathode, and an organic layer between the anode and the cathode, and the organic layer has a hole transport layer and a hole transport layer. The layer is adjacent to the light-emitting layer; the hole transport layer contains the polymer a represented by the above formula (1) or a cross-linked polymer of the polymer a; the polymer a or the cross-linked polymer of the polymer a At least one of the material contained in the body and the light-emitting layer contains a material having a partial structure represented by the following formula (CzP) each having a carbazole ring (a compound having a partial structure represented by the following formula (CzP)). In addition, the description of "material" in this specification may be replaced by the description of "compound" or "compound".

More preferably, the material contained in the above-mentioned hole transport layer and the material contained in the above-mentioned light-emitting layer both contain a material having a partial structure represented by the formula (CzP), and any one of the material contained in the above-mentioned hole transport layer or the material contained in the above-mentioned light-emitting layer It is more preferable that the material contained in the above-mentioned light-emitting layer contains a material (compound) having at least two partial structures represented by formula (CzP); particularly preferably, it is the above-mentioned material. The material contained in the hole transport layer and the material contained in the above-mentioned light-emitting layer both contain materials (compounds) having two or more partial structures represented by formula (CzP). If this type of group If combined, it will be driven at a lower voltage, and high-efficiency light emission and long life can be expected. In addition, it is also preferable that at least one of the above-mentioned hole transport layer or the above-mentioned light-emitting layer contains two or more kinds of materials having a partial structure represented by the formula (CzP). It is particularly preferable that the light-emitting layer contains two or more kinds of materials having a partial structure represented by the formula (CzP). ) of the construction of the parts shown. In this combination, it is driven by a lower voltage, and high-efficiency light emission and long life can be expected.

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

The material contained in the light-emitting layer having a partial structure represented by formula (CzP) is not particularly limited, and is preferably a low molecular compound.

When the material having a partial structure represented by formula (CzP) is a polymer compound, the number of formula (CzP) contained in the polymer compound is preferably the number of formula (CzP) contained in the repeating unit of the polymer compound. above. When there are two formulas (CzP) in the repeating unit, the number of formulas (CzP) contained in the polymer compound becomes twice the repeating units of the polymer compound. When the polymer compound has a plurality of repeating units, it is sufficient if at least one of the repeating units has the formula (CzP). Formula (CzP) may have a substituent.

Furthermore, the bonding method between the material contained in the hole transport layer or the material contained in the light-emitting layer and the formula (CzP) is not particularly limited. For example, the carbazole part may be bonded with the material contained in the hole transport layer or the material contained in the light-emitting layer, or the benzene part may be bonded with the material contained in the hole transport layer or the material contained in the light-emitting layer.

<Low molecular compounds>

Next, a case will be described in which the material having a partial structure represented by formula (CzP) contained in the element of this embodiment is a low molecular compound. The low molecular compound used as a light-emitting material or a host material in the light-emitting layer can use the formula (CzP). In the case of the host material, for example, the following can be used.

It has the following formula (CzP-2) as the host material of the formula (CzP).

In the above formula (CzP-2), *1, *2, and *3 are the bonding positions with the skeleton of the host material. It is sufficient if at least one of *1, *2, and *3 is bonded. It can be bonded directly to the skeleton of the host material or through other structures. Formula (CzP-2) may have a substituent. There are no particular limitations on the other structures that may be used, and preferred examples include an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or an aromatic group that may have a substituent. A structure in which two or more groups of an aromatic hydrocarbon group and an aromatic heterocyclic group that may have a substituent are connected in plural; specifically, those that can be used as B in formulas (14) to (16) described below can be used. An aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or two or more selected from the group consisting of an aromatic hydrocarbon group which may have a substituent and an aromatic heterocyclic group which may have a substituent The substituents and preferable ranges that the base may have are also the same for structures connected by plurality of bases.

As the substituent, a group selected from the above substituent group Z can be used.

The charge transfer between the hole transport layer and the light-emitting layer adjacent to the hole transport layer mainly occurs between the material forming the hole transport layer and the host material in the light-emitting layer. Therefore, by using the host material in the light-emitting layer The material has the formula (CzP) and/or the formula (CzP-2), which can especially improve the hole transportability of the interface.

The skeleton of the host material is preferably selected from the group consisting of electron transport properties, hole transport properties, and both electron transport properties and hole transport properties.

構造、

二唑構造，或咪唑構造等者 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, and a thiophene structure. Benzyl phenyl structure, fluorine structure, quinacridone structure, diphenyl structure, carbazole structure, pyrene structure, anthracene structure, phenanthroline structure, quinoline structure, pyridine structure, pyrimidine structure, tris

structure,

Diazole structure, or imidazole structure, etc.

構造的化合物，進而更佳為具有嘧啶構造、三

構造的化合物。 As an electron transporting material, from the viewpoint of being excellent in electron transporting properties and having a relatively stable structure, a material having a pyridine structure, a pyrimidine structure, or a three-dimensional structure is more preferred.

structure, and more preferably a compound having a pyrimidine structure, a tri-

Constructed compounds.

The hole transporting material is a compound having a structure that is excellent in hole transporting properties. As the skeleton having excellent hole transporting properties, a carbazole structure, a dibenzofuran structure, a triarylamine structure, a naphthalene structure, and a phenanthrene structure can be used. Or those with pyrene structure; among them, those with carbazole structure, dibenzofuran structure or triarylamine structure are particularly preferred.

The host material of the light-emitting layer is preferably a compound having a condensed ring structure of three or more rings, more preferably a compound having two or more condensed ring structures of three or more rings, or a compound having at least one condensed ring structure of five or more rings. By using these compounds, the rigidity of the molecule is increased, making it easier to obtain The effect of inhibiting the degree of molecular movement in response to heat. Furthermore, from the viewpoint of hole transport properties and material durability, it is preferable that the condensed ring with three or more rings and the condensed ring with five or more rings have an aromatic hydrocarbon ring or an aromatic heterocyclic ring.

構造、稠四苯構造、聯伸三苯構造、茀構造、苯并茀構造、茚并茀構造、吲哚并茀構造、咔唑構造、茚并咔唑構造、吲哚并咔唑構造、二苯并呋喃構造、二苯并噻吩構造等。由電荷輸送性及溶解性的觀點而言，較佳為選自由菲構造、茀構造、茚并茀構造、咔唑構造、茚并咔唑構造、吲哚并咔唑構造、二苯并呋喃構造及二苯并噻吩構造所構成之群之至少一者；由對電荷之耐久性的觀點而言，更佳為咔唑構造或吲哚并咔唑構造。 Specific examples of the condensed ring structure with three or more rings include anthracene structure, phenanthrene structure, pyrene structure,

Structure, fused tetraphenyl structure, diphenyl triphenyl structure, fluorine structure, benzoquinone structure, indenoquinone structure, indoloquinide structure, carbazole structure, indenocarbazole structure, indolocarbazole structure, diphenyl Furan structure, dibenzothiophene structure, etc. From the viewpoint of charge transport and solubility, it is preferable to be selected from a phenanthrene structure, a fluorine structure, an indenofluoride structure, a carbazole structure, an indenocarbazole structure, an indolocarbazole structure, and a dibenzofuran structure. and at least one of the group consisting of a dibenzothiophene structure; from the viewpoint of charge durability, a carbazole structure or an indolocarbazole structure is more preferred.

骨架的材料。 From the viewpoint of the durability of the charge of the organic electroluminescent element, it is preferred that at least one of the host materials of the light-emitting layer has a pyrimidine skeleton or a three-dimensional structure.

Skeleton material.

As a structure used between the skeleton of the host material and the formula (CzP-2), for example, an aryl group can be used. Examples of the aryl group include a phenylene group, a biphenylene group, and a biphenylene group, and may have branches.

From the viewpoint of superior flexibility, the main material of the light-emitting layer is preferably a polymer material. The light-emitting layer formed of a material with excellent flexibility is preferably used as the light-emitting layer of an organic electroluminescent element formed on a flexible substrate. When the host material contained in the light-emitting layer is a polymer material, the molecular weight is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 500,000, and even more preferably from 10,000 to 100,000.

[Better low molecular compounds]

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

In the above formulas (14) to (16), A is a partial structure shown in the above formula (CzP), and may also have a substituent; B represents a single bond or any partial structure; when A exists in plural, they may be the same or different; when B exists in plural form, it can be the same or different; na, nb and nc respectively independently represent integers from 1 to 5.

The molecular weight of the compounds represented by the above formulas (14) to (16) is 5,000 or less.

(A)

The substituents that A may have are preferably selected from the above substituent group Z, and the preferred substituents and optional substituents are also the same.

(B)

B in the above formulas (14) to (16) is not particularly limited, but preferably represents a functional group that may have a substituent, an aromatic hydrocarbon group that may have a substituent, or an aromatic hetero group that may have a substituent. A ring group or a structure in which two or more groups selected from an aromatic hydrocarbon group which may have a substituent and an aromatic heterocyclic group which may have a substituent are connected in plural. As these optional substituents, any one of the above substituent groups Z or a combination thereof can be used.

The functional group is preferably a structure that has hole transport properties, a structure that has electron transport properties, a structure that suppresses charge transport, a structure that imparts solubility in organic solvents, a structure that inhibits crystallization and improves amorphousness, or Luminous structure.

As an aromatic hydrocarbon group, an aromatic heterocyclic group, or a monovalent group in which two or more groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group are connected in plural, Ar ² in the above formula (1) is preferred. Same construction. The same applies to the case of plural links, preferably 2 to 10 links, more preferably 2 to 5 links.

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 more preferably at least one B is a carbazole bonded to part of the structure A. The N of the ring is the benzene ring.

The low molecular compound having a partial structure represented by formula (CzP) is preferably a charge transport material in the light-emitting layer.

The low molecular compound having a partial structure represented by formula (CzP) contained in the light-emitting layer is preferably the above formula (14) or the above formula (16).

Furthermore, the compound represented by the above 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 below-mentioned formula (19).

In the above formula (17), Q represents a nitrogen atom or any of the trivalent substituents represented by the following structural formulas (18-1), (18-2) and (18-3); Xb ¹ , Yb ¹ and Zb ¹ each independently represent a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms that may have a substituent, or a divalent heteroaromatic ring group having 3 to 30 carbon atoms that may have a substituent; in Xb ¹ , When Yb ¹ and Zb ¹ exist in plural, they may be the same or different; A is a partial structure shown in the above formula (CzP), and may also have a substituent, and the plural A's may be the same or different; p12, q12 and r12 independently represent integers above 0 and below 6; q12 and r13 independently represent 0 or 1; Yb ² when q13 is 0 and Zb ² when r13 is 0 independently represent hydrogen atoms, which can also have The substituent is a monovalent hydrocarbon aromatic ring group with 6 to 30 carbon atoms, or a monovalent heteroaromatic ring group with 3 to 30 carbon atoms that may have a substituent; when q13 is 1, Yb ² is a direct bond; r13 is Zb ² at 1 time is a direct bond.

In formulas (18-1) to (18-3), * in a structural formula respectively represents the bonding position with any base of Xb ¹ , Yb ¹ or Zb ¹ .

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 that may have a substituent, or a divalent heterocyclic group having 3 to 30 carbon atoms that may have a substituent. Aromatic ^ring group ^; Aromatic ring group; when Xc ¹ and Yc ¹ exist in plural, they can be the same or different; A is a partial structure shown in the above formula (CzP), and may also have a substituent; s11 and t11 independently represent 0 or more and 6 or less an integer; nc represents an integer above 1 and below 5.

環、聯伸三苯環、1,2-苯并苊環等。更佳為單環或2~3縮合環，具體可舉例如苯環、萘環、蒽環、菲環、茀環。其中較佳為苯環、萘環、菲環、茀環，更佳為苯環或茀環。 In the above formula (17) and the above formula (19), the hydrocarbon aromatic ring having 6 to 30 carbon atoms is preferably a 6-membered monocyclic ring or a 2- to 5-membered condensed ring. Specific examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorine ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,

ring, biextended triphenyl ring, 1,2-benzoacenaphthylene ring, etc. More preferably, it is a single ring or 2 to 3 condensed rings. Specific examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and fluorine ring. Among them, benzene ring, naphthalene ring, phenanthrene ring and fluorine ring are preferred, and benzene ring or fluorine ring is more preferred.

二唑環、吲哚環、咔唑環、吲哚并咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異

唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡

環、噠

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉環、喹

啉環、呸啶環、喹唑啉環、喹唑啉酮環等。 In the above formula (17) and the above formula (19), the heteroaromatic ring having 3 to 30 carbon atoms is preferably a 5- or 6-membered monocyclic ring, or a 2 to 5-membered condensed ring thereof. Specific examples include furan ring, benzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring,

Diazole ring, indole ring, carbazole ring, indolocarbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, Furanofuran ring, thienofuran ring, benzoiso

Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring

ring, da

ring, pyrimidine ring, tri

ring, quinoline ring, isoquinoline ring,

pholine ring, quinine

Phenoline ring, phenidine ring, quinazoline ring, quinazolinone ring, etc.

環、喹啉環、喹唑啉環、咔唑環、二苯并呋喃環、二苯并噻吩環、吲哚并咔唑環、啡啉環、或吲哚并咔啉環；更佳為吡啶環、嘧啶環、三

環、喹啉環、喹唑啉環、咔唑環、二苯并呋喃環、二苯并噻吩環、或吲哚并咔唑環；進而更佳為咔唑環、二苯并呋喃環、二苯并噻吩環、或吲哚并咔唑環。 Among them, preferred ones are thiophene ring, pyrrole ring, imidazole ring, pyridine ring, pyrimidine ring, tris

ring, quinoline ring, quinazoline ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring, indolocarbazole ring, phenanthroline ring, or indolocarboline ring; more preferably, pyridine ring, pyrimidine ring, tri

ring, quinoline ring, quinazoline ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring, or indolocarbazole ring; more preferably, it is carbazole ring, dibenzofuran ring, dibenzofuran ring, dibenzothiophene ring, or indolocarbazole ring. benzothiophene ring, or indolocarbazole ring.

In addition, in the above formula (17), Yb ² when q13 is 0, Zb ² when r13 is 0, and Xc ² and Yc ² in the above formula (19) are particularly suitable aromatic hydrocarbon rings, such as benzene ring and naphthalene ring. Ring, or phenanthrene ring, particularly preferred aromatic heterocycles include dibenzofuran ring, dibenzothiophene ring, or indolocarbazole ring.

As the substituent that the above formula (CzP) represented by the above A may have, it is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms that may have a substituent or an aromatic group having 3 to 30 carbon atoms that may have a substituent. Family heterocyclyl. From the viewpoint of durability improvement and charge transport properties, an aromatic hydrocarbon group which may have a substituent is more preferred. Furthermore, from the viewpoint of durability improvement, it is preferable that a substituent is bonded to the 3-position or 6-position of the carbazole in the partial structure A.

The substituents that the above-mentioned Xb ¹ , Yb ¹ , Zb ¹ , Yb ² , Zb ² , Xc ¹ , Xc ² , Yc ¹ and Yc ² may have, and the above-mentioned hydrocarbon aromatic ring having 6 to 30 carbon atoms may also have The substituents, the substituents that the heteroaromatic ring having 3 to 30 carbon atoms may have, and the substituents that A may have and may further have are the same as those in the polymer represented by the above formula (1) The substituents listed in the above-mentioned substituent group Z or the above-mentioned crosslinkable groups are the same, and the preferred substituents and optional substituents are also the same.

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

[Chemical 35]

[Chemical 36]

In the above general formulas (17-1) ~ (17-6), p12' represents an integer from 1 to 5; q12' and r12' independently represent an integer from 0 to 5; p14 is 12; q14 is When q13 is 1, it is 12, and it does not exist when q13 is 0; r14 is 12 when r13 is 1, and it does not exist when r13 is 0; q15 and r15 are independently 4 or 5 respectively; R ³¹ and R ³² Each is independently a hydrogen atom or a substituent; Xb ¹ , Yb ¹ , Zb ¹ , q13 and r13 are respectively the same as the above formula (17).

R ³¹ which is a substituent is a hydrogen atom or the same substituent as the above-mentioned A which may have it. The substituent is preferably the same and it may further have the same substituent.

R ³² as a substituent is a hydrogen atom, or the same substituent or the crosslinking group listed in the above-mentioned substituent group Z in the polymer represented by the above formula (1), and is preferably a substituent and also a substituent. The substituents that may be further possessed are also the same.

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

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

As a substituent, R ³¹ is the same as the substituent listed for the above-mentioned substituent group Z in the polymer represented by the above formula (1) or the above-mentioned cross-linkable group. Preferable substituents and optional substituents may be further included. The base is also the same.

In addition, from the viewpoint of ease of synthesis and purification, ease of designing electron transport performance and hole transport performance, and ease of viscosity adjustment when dissolved in a solvent, the host material (compound) of the light-emitting layer is preferably a low molecular weight compound. . 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, and most preferably 2,000 or less; usually it is 300 or more, preferably 350 or more, and more preferably 400 or more.

Examples of the host material having the formula (CzP-2) include the following compounds.

Other examples of the low molecular compound include luminescent materials, and those having the formula (CzP) can be used as the luminescent material. As the luminescent material, a phosphorescent luminescent material described below can be used, and one having the formula (CzP) among these structures can be used.

<Implementation form of the third point>

An embodiment of the third gist of the present invention is an organic electroluminescent element having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate, and the organic layer has a hole transport layer and a hole transport layer. The adjacent light-emitting layer; the material contained in the hole transport layer and the material contained in the light-emitting layer both contain: a material containing a partial structure represented by the formula (CzP) below a carbazole ring.

More preferably, the material contained in the above-mentioned hole transport layer and the material contained in the above-mentioned light-emitting layer both contain a material having a partial structure represented by formula (CzP), and the material contained in the above-mentioned hole transport layer or the material contained in the above-mentioned light-emitting layer is one of Any one of them is a material containing two or more partial structures represented by the formula (CzP); particularly preferably, the material contained in the above-mentioned hole transport layer and the material contained in the above-mentioned light-emitting layer contain two partial structures represented by the formula (CzP) the above materials. With this combination, lower voltage driving and longer life can be expected.

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

The material contained in the light-emitting layer having the partial structure represented by formula (CzP) is not particularly limited, but is preferably a low molecular compound.

When the material having a partial structure represented by the formula (CzP) is a polymer compound, the number of the formula (CzP) contained in the polymer compound is preferably one of the formula (CzP) contained in the repeating unit of the polymer compound. number or more. When there are two formulas (CzP) in the repeating unit, the number of formulas (CzP) contained in the polymer compound becomes the repeating units of the polymer compound × 2. When the polymer compound has a plurality of repeating units, it is sufficient if at least one of the repeating units has the formula (CzP). Formula (CzP) may have a substituent.

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

<polymerb>

In formula (20), Ar ^1' represents an aromatic hydrocarbon group that may have a substituent or an aromatic heterocyclic group that may have a substituent. At least one of Ar ^1' is represented by the following formula (21); X represents -C(R ^3' )(R ^4' )-, -N(R ^5' )- or -C(R ^11' )(R ^12' )-C(R ^13' ), (R ^14' )-; R ^1' and R ^2' each independently represent an alkyl group that may have a substituent; R ^3' ~ R ^5' and R ^11' ~ R ^14' each independently represent an alkyl group that may have a substituent, and may also have a substitution The aralkyl group of the base, or the aromatic hydrocarbon group that may also have a substituent; a and b are each independently an integer from 0 to 4, a+b is 1 or more; c is an integer from 1 to 3; d is an integer from 0 to 4 Integer; when R ^1' and R ^2' are plural in the repeating unit, R ^1' and R ^2' can be the same or different.

In formula (21), Ar ^11' and Ar ^12' each independently represent a divalent aromatic hydrocarbon group or aromatic heterocyclic group that may have a substituent; Ar ^13' ~ Ar ^15' each independently represent a hydrogen atom or a substituent. .

* indicates the bonding position.

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

In the above formula (CzP-1), *1, *2, and *3 are bonding positions with the skeleton of the polymer, and they may be bonded to at least one of *1, *2, and *3. It can be bonded directly to the polymer skeleton or through other structures. Formula (CzP-1) may have a substituent.

As the substituent, for example, the same ones as those described above for Ar ^13' to Ar ^15' can be used.

(R ^1' and R ^2' )

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

When R ^1' and R ^2' are plural in the repeating unit, R ^1' and R ^2' can be the same or different, which is preferred in terms of uniform distribution of charges around the nitrogen atoms and ease of synthesis. All R ^1' and R ^2' are the same group.

(R ^3' ~R ^5' and R ^11' ~R ^14' )

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.

The alkyl group is not particularly limited. In order to tend to improve the solubility of the polymer, the number of carbon atoms is preferably 1 or more and 24 or less, and more preferably 6 or less. In addition, each structure may be linear, branched or cyclic.

Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-hexyl, n-octyl, cyclohexyl, and dodecyl. wait.

The aryloxy group is not particularly limited. In order to tend to improve the solubility of the polymer, the number of carbon atoms is preferably 5 or more and 60 or less, and more preferably 40 or less.

Specific examples include 1,1-dimethyl-1-phenylmethyl, 1,1-di(n-butyl)-1-phenylmethyl, and 1,1-di(n-hexyl)-1-phenyl methyl, 1,1-di(n-octyl)-1-phenylmethyl, phenylmethyl, phenylethyl, 3-phenyl-1-propyl, 4-phenyl-1-n- Butyl, 1-methyl-1-phenylethyl, 5-phenyl-1-n-propyl, 6-phenyl-1-n-hexyl, 6-naphthyl-1-n-hexyl, 7-phenyl -1-n-heptyl, 8-phenyl-1-n-octyl, 4-phenylcyclohexyl, etc.

The aromatic hydrocarbon ring group is not particularly limited. In order to tend to improve the solubility of the polymer, the number of carbon atoms is preferably 6 or more and 60 or less, and more preferably 30 or less.

環、聯伸三苯環、苊萘環、1,2-苯并苊環、茀環等之6元環的單環或2~5縮合環之一價基，或使此等之複數個連結的基等。 Specific examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,

Ring, biextended triphenyl ring, acenaphthylene ring, 1,2-benzoacenaphthylene ring, fluorine ring, etc., a single ring of a 6-membered ring or a valent group of a 2 to 5 condensed ring, or a plurality of these connected Key et al.

From the viewpoint of improving charge transport properties and durability, R ^3' to R ^5' are preferably methyl or aromatic hydrocarbon groups, R ^3' and R ^4' are more preferably methyl, and R ^5' is more preferably benzene. base.

From the viewpoint of improved solubility and superior charge transport properties, R ^3' and R ^4' are preferably an alkyl group having 3 or more and 6 or less carbon atoms or an aralkyl group having 9 or more carbon atoms and 40 or less carbon atoms.

The alkyl groups of R ^1' and R ^2' , the alkyl groups of R ^3' to R ^5' and R ^11' to R ^14' , aralkyl groups and aromatic hydrocarbon groups may also have substituents. Examples of substituents that may be included include those listed as preferred groups for the alkyl group, aralkyl group and aromatic hydrocarbon group of the above-mentioned R ^3' to R ^5' and R ^11' to R ^14' , or those mentioned below. Cross-linking group.

The above-mentioned alkyl groups of R ^1' to R ^2' , alkyl groups of R ^3' to R ^5' and R ^11' to R ^14' , aralkyl groups and aromatic hydrocarbon groups are the most suitable ones from the viewpoint of low voltage. Preferably it has no substituents.

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' preferably contain at least one substituent as described below. Cross-linking group and containing repeating units represented by the above formula (20).

(a’, b’, c’ and d’)

In the repeating unit shown in the above formula (20), a’ and b’ are independently integers between 0 and 4. Also, a’+b’ is 1 or more. Furthermore, it is preferable that a' and b' are respectively 2 or less, and it is more preferable that both a' and b' are 1.

In the repeating unit shown in the above formula (20), c’ is an integer from 1 to 3, and d’ is an integer from 0 to 4. It is preferable that c' and d' are respectively 2 or less, more preferably c' and d' are equal, further more preferably both c' and d' are 1 or both c' and d' are 2.

In the repeating unit shown in the above formula (20), when both c' and d' are 1 or both c' and d' are 2, and both a' and b' are 2 or 1, R ^1' and R ^2' is best bonded at positions that are symmetrical to each other.

Here, the so-called "R ^1' and R ^2' are bonded at symmetrical positions to each other" means that relative to the fluorine ring or carbazole ring in formula (20), the bonding position of R ^1' and R ^2' is Symmetry. For example, in the following formula (20a) included in the formula (20), it can be said that R ^1a' and R ^2a' are symmetrical positions, and R ^1b' and R ^2b' are symmetrical positions. In addition, at this time, the 180-degree rotation with the main chain as the axis becomes the same structure. For example, below, formula (20a) and formula (20b) can be regarded as the same structure.

(Ar ¹ )

In the repeating unit represented by the above 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).

環、聯伸三苯環、苊環、1,2-苯并苊環、茀環等6元環之單環或2~5縮合環之一價基，或此等經複數連結的基。 As the aromatic hydrocarbon group, the number of carbon atoms is preferably 6 or more and 60 or less. Specific examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,

Ring, biextended triphenyl ring, acenaphthylene ring, 1,2-benzoacenaphthylene ring, fluorine ring and other 6-membered single rings or monovalent groups of 2 to 5 condensed rings, or these groups connected in plural.

二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、 吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異

唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡

環、噠

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉環、喹

啉環、菲啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等5~6元環之單環或2~4縮合環之一價基，或此等複數個連結的基。 The aromatic heterocyclic group preferably has a carbon number of 3 or more and 60 or less, and specific examples include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, and an imidazole ring.

Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furanofuran ring, thieno Furan ring, benziiso

Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring

ring, da

ring, pyrimidine ring, tri

ring, quinoline ring, isoquinoline ring,

pholine ring, quinine

Single rings of 5 to 6 membered rings such as phenanthridine ring, benzimidazole ring, phenanthridine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. or one valent group of 2 to 4 condensed rings, or The base of these plural connections.

From the viewpoint of superior charge transport properties and durability, Ar ^1' is preferably an aromatic hydrocarbon ring group that may have a substituent; among them, a monovalent benzene ring or a fluorine ring that may also have a substituent is more preferred. group, that is, a phenyl group or a fluoryl group which may have a substituent; more preferably a fluoryl group which may have a substituent; and particularly preferably a 2-benzoyl group which may have a substituent.

The substituents that the aromatic hydrocarbon ring group and the aromatic heterocyclic group of Ar ^1' may have are not particularly limited as long as they do not significantly reduce the characteristics of the polymer. Preferable examples include a group selected from the following substituent group Z' or a crosslinkable group described later, more preferably an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group or a crosslinkable group described later. , more preferably an alkyl group.

From the viewpoint of solubility in the coating solvent, Ar ^1' is preferably a fluorine group substituted with an alkyl group having 1 to 24 carbon atoms, and particularly preferably a 2-fluoryl group substituted with an alkyl group having 4 to 12 carbon atoms. base. More preferred is 9-alkyl-2-benzoyl substituted with an alkyl group at the 9-position of 2-benzoyl, and particularly preferred is 9,9-dialkyl-2-benzoyl substituted with 2 alkyl groups. When at least one of the 9-position and the 9'-position is a fluorine group substituted with an alkyl group, the solubility in the solvent and the durability of the fluorine ring tend to be improved. Furthermore, when both the 9-position and the 9'-position are substituted with alkyl groups, the solubility in the solvent and the durability of the fluorine ring tend to be further improved.

(Ar ^1' belonging to formula (21))

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

In formula (21), Ar ^11' and Ar ^12' each independently represent a divalent aromatic hydrocarbon group or aromatic heterocyclic group that may have a substituent; Ar ^13' ~ Ar ^15' each independently represent a hydrogen atom or a substituent. .

[Substituent group Z’]

As the substituent, for example, a substituent selected from the following substituent group Z' can be used. Examples of the substituent group Z' include the following structures.

For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-hexyl, cyclohexyl, dodecyl, etc. The number of carbon atoms is usually 1 or more. , preferably 4 or more and usually 24 or less, preferably 12 or less linear, branched or cyclic alkyl groups; such as vinyl, etc. The number of carbon atoms is usually 2 or more, and usually 24 or less, preferably 12 or less. Alkenyl; for example, an alkynyl group with a carbon number of 2 or more, usually 24 or less, preferably 12 or less, such as ethynyl; For example, alkoxy groups with a carbon number of usually 1 or more, and usually 24 or less, preferably 12 or less, such as methoxy and ethoxy groups; such as phenoxy, naphthyloxy, pyridyloxy, etc., with a carbon number of usually 4 or more , preferably 5 or more, and usually 36 or less, preferably 24 or less aryloxy groups; for example, methoxycarbonyl, ethoxycarbonyl and other alkoxy groups with a carbon number of usually 2 or more, and usually 24 or less, preferably 12 or less Carbonyl group; for example, dimethylamino group, diethylamino group and other dialkylamino groups with a carbon number of usually 2 or more and usually 24 or less, preferably 12 or less; for example, diphenylamine group, xylylamine Diarylamine groups, such as N-carbazolyl groups, usually have a carbon number of 10 or more, preferably 12 or more, and usually 36 or less, preferably 24 or less; for example, a phenylmethylamine group, etc., usually have a carbon number of 7 Arylalkylamino groups above, and usually 36 or less, preferably 24 or less; for example, acetyl, benzyl, and other aryl groups with a carbon number of usually 2 or more, and usually 24 or less, preferably 12 or less ; For example, halogen atoms such as fluorine atom and chlorine atom; such as trifluoromethyl and other carbon numbers, which are usually 1 or more and usually 12 or less, preferably 6 or less; such as methylthio group, ethylthio group, etc. An alkylthio group that is usually 1 or more, and usually 24 or less, and preferably 12 or less; for example, a phenylthio group, a naphthylthio group, a pyridylthio group, etc. The number of carbon atoms is usually 4 or more, preferably 5 or more, and usually 36 or less. , preferably an arylthio group of less than 24; For example, trimethylsilyl, triphenylsilyl and other silicon groups with a carbon number of usually 2 or more, preferably 3 or more, and usually 36 or less, preferably 24 or less; such as trimethylsiloxane, triphenylsilyl A siloxane group with a carbon number of usually 2 or more, preferably 3 or more, and usually 36 or less, preferably 24 or less, such as a siloxane group; a cyano group; such as a phenyl, naphthyl group, etc., with a carbon number of usually 6 or more , and are usually 36 or less, preferably 24 or less aromatic hydrocarbon groups; for example, thienyl, pyridyl and other aromatic heterocyclic rings with a carbon number of usually 3 or more, preferably 4 or more, and usually 36 or less, preferably 24 or less. base.

Among the above-mentioned substituent group Z', preferred are the above-mentioned alkyl group, alkoxy group, aromatic hydrocarbon ring group and aromatic heterocyclic group. From the viewpoint of charge transport properties, it is more preferred not to have a substituent.

Furthermore, each substituent of the above-mentioned substituent group Z' may further have a substituent. Examples of such substituents include the same substituents as the above-mentioned substituents (substituent group Z') or crosslinking groups described below. Preferably, it has no substituent, an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, a phenyl group or a cross-linkable group mentioned below. From the viewpoint of charge transport properties, it is more preferred not to have further substituents.

From the viewpoint of insolubilization, the further substituent preferably contains a repeating unit represented by formula (20) having at least one cross-linking group described below; the cross-linking group is preferably further substituted by Ar ^1' The indicated aromatic hydrocarbon ring group or aromatic heterocyclic group may also have substituents.

(Ar ^13' ~Ar ^15' )

Ar ^13' ~Ar ^15' independently represent a hydrogen atom or a substituent. When Ar ^13' to Ar ^15' are substituents, they are not particularly limited, but are preferably aromatic hydrocarbon groups that may have a substituent or aromatic heterocyclic groups that may have a substituent. As a preferred structure, they are the same as those listed for Ar ^1' above.

When Ar ^13' to Ar ^15' are substituents, from the viewpoint of improving durability, they are preferably bonded to the 3-position or 6-position of each carbazole.

From the viewpoint of ease of synthesis and charge transportability, Ar ^13' to Ar ^15' are preferably hydrogen atoms.

From the viewpoint of durability improvement and charge transport properties, Ar ^13' to Ar ^15' are preferably aromatic hydrocarbon groups that may have a substituent or aromatic heterocyclic groups that may have a substituent, and more preferably An aromatic hydrocarbon group which may have a substituent.

When Ar ^13' to Ar ^15' are aromatic hydrocarbon groups that may have a substituent or aromatic heterocyclic groups that may have a substituent, the substituents are the same as the substituents listed for the above-mentioned substituent group Z' or The crosslinking groups described below are the same and preferred substituents are the same; the substituents that these substituents may further have are also the same.

Moreover, from the viewpoint of insolubilization, the substituent preferably contains a group represented by formula (21) having at least one crosslinkable group described below.

On the other hand, from the viewpoint of preventing uncrosslinked residues after film formation from adversely affecting the light-emitting layer, it is preferable to not include a crosslinking group as a substituent.

(Ar ^12' )

Ar ^12' represents 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 optionally linked to each other. A valency group, and the structure bonded to N of at least one of the two carbazole rings constituting the formula (21) is a phenylene group.

環、聯伸三苯環、苊環、1,2-苯并苊環、茀環等6元環之單環或2~5縮合環之2價基，或此等經複數連結的基。在此等為複數連結的情況，較佳係複數連結之二價之芳香族烴基經共軛的基。 As the aromatic hydrocarbon group, the number of carbon atoms is preferably from 6 to 60, more preferably from 10 to 50, and particularly preferably from 12 to 40. Specific examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,

Rings, biextended triphenyl rings, acenaphthylene rings, 1,2-benzoacenaphthylene rings, fluorine rings and other 6-membered single rings or divalent groups of 2 to 5 condensed rings, or these groups connected in plural. In the case of plural linkages, it is preferably a conjugated group of divalent aromatic hydrocarbon groups linked in plural units.

二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異

唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡

環、噠

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉環、喹

啉環、菲啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等5或6元環之單環或2~4縮合環之二價基，或此等複數個連結的基等。 The aromatic heterocyclic group preferably has a carbon number of 3 or more and 60 or less, and specific examples include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, and an imidazole ring.

Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furanofuran ring, thieno Furan ring, benziiso

Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring

ring, da

ring, pyrimidine ring, tri

ring, quinoline ring, isoquinoline ring,

pholine ring, quinine

Monocyclic rings of 5 or 6 members such as phenanthridine ring, benzimidazole ring, phenanthridine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. or divalent groups of 2~4 condensed rings, or The base of these plural links.

The substituents that these aromatic hydrocarbon groups or aromatic heterocyclic groups may have include, for example, the alkyl groups, aralkyl groups and aromatic groups listed above for R ^3' to R ^5' and R ^11' to R ^14'. For hydrocarbon groups, the preferred ranges are also the same. When the structural twist of Ar ^12' occurs due to the stereo effect of the substituent, it is preferable that it has no substituent; when the structural twist of Ar ^12' does not occur due to the stereo effect of the substituent, it is preferable that it has a substitution base.

Specifically, the preferred structure is a divalent group of a benzene ring, a naphthalene ring, an anthracene ring, a fluorine ring or a plurality of these connected groups; more preferably, a divalent group of a benzene ring or a plurality of these connected groups; particularly preferred. It is a 1,4-phenyl group with a divalent linkage of the benzene ring at the 1,4-position, a 2,7-phenyl group with a divalent linkage of the fluorine ring at the 2,7-position, or these groups connected in plural; The most preferred one is a group containing 1,4 phenylene-2,7 phenylene-1,4 phenylene. In these preferred structures, it is preferable that the phenylene group has no substituent other than the linking position because Ar ^12' torsion due to the steric effect of the substituent does not occur. In addition, when the fluoride group has a substituent at the 9, 9' position, it is preferable from the viewpoint of improving solubility and durability of the fluoride structure.

Since Ar ^12' has the above structure, the aromatic hydrocarbon group between the nitrogen atoms of the two carbazole structures is conjugated, and LUMO is easily distributed on the conjugated aromatic hydrocarbon group. Therefore, since LUMO is less likely to expand to the periphery of nitrogen atoms in the main chain, which are weak to electrons or excitons, it is considered that the durability will be improved.

In addition, when an aromatic heterocyclic group is included, LUMO is easily distributed due to increased electron attraction, so LUMO is less likely to expand around the nitrogen atoms of the main chain, which are weak to electrons or excitons, and it is considered that durability will be improved.

(Ar ^11' )

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

環、聯伸三苯 環、苊環、1,2-苯并苊環、茀環等6元環之單環或2~5縮合環之2價基，或此等經複數連結的基。 The aromatic hydrocarbon group of Ar ^11' preferably has a carbon number of 6 or more and 60 or less, more preferably a carbon number of 10 or more and 50 or less, and particularly preferably a carbon number of 12 or more and 40 or less. Specific examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,

Rings, biextended triphenyl rings, acenaphthylene rings, 1,2-benzoacenaphthylene rings, fluorine rings and other 6-membered single rings or divalent groups of 2 to 5 condensed rings, or these groups connected in plural.

二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異

唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡

環、噠

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉環、喹

啉環、菲啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等5或6元環之單環或2~4縮合環之二價基，或此等複數個連結的基等。 The aromatic heterocyclic group of Ar ^11' preferably has a carbon number of 3 or more and 60 or less. Specific examples include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, and imidazole. ring,

Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furanofuran ring, thieno Furan ring, benziiso

Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring

ring, da

ring, pyrimidine ring, tri

ring, quinoline ring, isoquinoline ring,

pholine ring, quinine

Monocyclic rings of 5 or 6 members such as phenanthridine ring, benzimidazole ring, phenanthridine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. or divalent groups of 2~4 condensed rings, or The base of these plural links.

The substituents that these aromatic hydrocarbon groups or aromatic heterocyclic groups may have include, for example, the alkyl groups, aralkyl groups and aromatic groups listed above for Rr ^3' to Rr ^5' and Rr ^11' to Rr ^14'. For groups with the same family hydrocarbon group, the preferred ranges are also the same.

In the case where the divalent aromatic hydrocarbon groups or divalent aromatic heterocyclic groups are connected in plural, it is preferably a group in which the plurality of bivalent aromatic hydrocarbon groups are connected in an unconjugated manner. Specifically, a 1,3 phenylene group or a group containing a substituent and having a twisted structure due to the stereoscopic effect of the substituent is preferred. By containing such a linking group, the LUMO distributed on Ar ^12' is less likely to expand to the main chain, and the LUMO is less likely to be distributed around the nitrogen atoms of the main chain, which are weak to electrons or excitons. Therefore, it is considered that the durability will be improved.

In addition, in the polymer having the repeating unit represented by the above formula (20) in this embodiment, when Ar ^1' , R ^1' , R ^2' and X are plural, they may be the same or different respectively. Preferably, the polymer contains a plurality of repeating units having the same structure as the repeating unit shown in formula (20). In this case, by containing a plurality of repeating units with the same structure, the HOMO and LUMO of the repeating units become the same, so it does not In cases where charges are concentrated at a specific shallow energy level and become a trap, it is considered that the charge transport performance is superior and the durability is also improved.

[Better repeating unit]

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

In the above formula (20-I), R ^1' and R ^2' are the same, and R ^1' and R ^2' are bonded at positions relative to each other.

[Terminal group]

In this embodiment, the terminal group refers to the terminal structure of the polymer formed by the end-capping agent used when the polymerization of the polymer is completed. The terminal group of the polymer having the repeating unit represented by formula (20) is preferably a hydrocarbon group. From the viewpoint of charge transport properties, the hydrocarbon group preferably has a carbon number of 1 or more and 60 or less, more preferably 1 or more and 40 or less, and still more preferably 1 or more and 30 or less.

Preferable examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-hexyl, cyclohexyl, dodecyl, etc. A straight-chain, branched or cyclic alkyl group with a carbon number of usually 1 or more, preferably 4 or more, and usually 24 or less, preferably 12 or less; for example, a vinyl group with a carbon number of usually 2 or more, and usually 24 Alkenyl groups with a carbon number of less than or equal to 12, preferably less than 12; for example, an alkynyl group with a carbon number of usually 2 or more, and usually 24 or less, preferably 12 or less, such as an ethynyl group; an alkynyl group with a carbon number of usually 6 or more, such as a phenyl or naphthyl group, and The aromatic hydrocarbon ring group is usually 36 or less, preferably 24 or less.

These hydrocarbon groups may further have substituents. The substituents that may further have are preferably alkyl groups or aromatic hydrocarbon ring groups. When these substituents that may further have multiple substituents may be bonded to each other to form a ring. .

From the viewpoint of charge transport properties and durability, an alkyl group or an aromatic hydrocarbon group is preferred, and an aromatic hydrocarbon ring group is more preferred.

[Other repeating units]

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

As other repeating units, from the viewpoint of charge transport properties and durability, repeating units represented by the following formula (22) are preferred. Moreover, here, the repeating unit represented by the following formula (22) may be partially consistent with the structure of a part of the repeating unit of the above formula (20), but here, it still means that it belongs to the repeating represented by the formula (20). Structures other than units.

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 or a divalent aromatic heterocyclic group which may have a substituent. Or a plurality of divalent groups are connected to the aromatic hydrocarbon group and the aromatic heterocyclic group directly or via a linking group.

(Ar ^3' and Ar ^4' )

As the aromatic hydrocarbon group and aromatic heterocyclic group in Ar ^3' and Ar ^4' , Ar ^3' represents the same group as Ar ^1' in formula (20), and Ar ^4' represents the same group as Ar 1' in formula (20). Ar ^1' is the same base and a divalent base. Moreover, the substituent which may be contained is preferably the same group as the said substituent group Z' or the crosslinking group mentioned later, and the substituent which may be further contained is also the same as the said substituent group Z'.

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

In formula (23), k’ and n’ independently represent integers from 0 to 3, k’+n’ is 1 or more; m’ represents an integer of 0 or 1.

X’ is the same as formula (20), and *1 and *2 represent the bonding positions with adjacent structures.

(k’, n’ and m’)

In the formula (23), k’+n’ is preferably 2 and more preferably 3 from the viewpoint of superior electron durability.

In addition, k' is preferably 1 or more, and *1 is preferably bonded to N in the above formula (22). Furthermore, more preferably, both k' and n' are 1, or both k' and n' are 2 or more.

In view of the excellent solubility of the polymer in the solvent, m' is more preferably 1.

In the above formula (22), specific examples of the connecting group when connecting a plurality of aromatic hydrocarbon groups and aromatic heterocyclic groups via a connecting group include -O- groups and -C(=O)- groups. And the hydrogen atom may also be substituted in the -CH ₂ - group in which 1 to 30, preferably 1 to 5, and more preferably 1 to 3 are connected in any order to form a divalent linking group, etc.

Among them, from the viewpoint of excellent hole injection into the light-emitting layer, aromatic hydrocarbon groups or aromatic aromatic groups in which Ar ^4' in the formula (22) are connected via a plurality of connecting groups represented by the following formula (24) are preferred. Heterocyclyl.

In formula (24), p' represents an integer from 1 to 10; R ^8' and R ^9' each independently represent a hydrogen atom or an alkyl group that may have a substituent, an aromatic hydrocarbon group or an aromatic heterocyclic group.

When R ^8' and R ^9' exist in plural, they may be the same or different.

(R ^8' and R ^9' )

The alkyl groups in R ^8' and R ^9' are the same as the alkyl groups listed above for R ^1' , and the aromatic hydrocarbon groups and aromatic heterocyclic groups are the same as the aromatic hydrocarbon groups and aromatic groups listed above for Ar ^1' . The same group of heterocyclic groups. Moreover, the substituent which these groups may have is preferably the same group as the said substituent group Z' or the crosslinking group mentioned later, and they may further have the same substituent as the said substituent group Z'.

As other repeating units contained in the polymer having the repeating unit represented by formula (20), the repeating unit represented by the following formula (25) is preferred. The repeating unit shown in formula (25) tends to increase the excited singlet energy level and the excited triplet energy level through the twist of the aromatic ring. In addition, due to the steric hindrance of the aromatic ring twist, the polymer has excellent solubility in the solvent, and at the same time, the coating film formed by the wet film-forming method and subjected to heat treatment tends to have excellent insolubility in the solvent.

In formula (25), Ar ^2' represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent; R ^17' ~ R ^19' respectively independently represent an alkyl group, an alkoxy group or an aromatic group which may have a substituent. Oxygen group, aromatic hydrocarbon group or aromatic heterocyclic group; f', g', h' independently represent an integer from 0 to 4, f'+g'+h' is more than 1; e' represents an integer from 0 to 3 .

(Ar ^2' and R ^17' ~R ^19' )

The aromatic hydrocarbon groups and aromatic heterocyclic groups in Ar ^2' and R ^17' to R ^19' are independently the same groups as those listed for Ar ^1' above. In addition, these groups may also have substituents. Preferably, it is the same group as the above-mentioned substituent group Z' or the crosslinkable group mentioned later.

The alkyl group and aralkyl group among R ^17' to R ^19' are preferably the same groups as those exemplified for R ^7' above, and the substituents they may further have are preferably the same groups as those for R ^7' above.

The alkoxy group in R ^17' to R ^19' is preferably an alkoxy group listed in the above-mentioned substituent group Z', and may further have a substituent that is also the same as the above-mentioned substituent group Z'.

(h’~j’)

f’, g’, and h’ independently represent integers from 0 to 4, and f’+g’+h’ is 1 or more.

f'+h' is preferably 1 or more; more preferably, f'+h' is 1 or more, and f', g' and h' are 2 or less; further more preferably, f'+h' is 1 or more and f ' and h' are 1 or less; the optimal system f' or h' is 1.

When either f' or h' is 1, R ^17' and R ^19' are preferably bonded at symmetrical positions to each other.

Moreover, R ^17' and R ^19' are preferably the same; g' is more preferably 2.

When g' is 2, the two R ^18's are optimally bonded to each other at the opposite positions; when g' is 2, the two R ^18's are optimally the same.

Here, the position where R ^17' and R ^19' are bonded relative to each other means the following bonding position. Among them, the record regards the 180-degree rotation of the main chain as the axis as the same structure.

[Chemical 50]

Moreover, the repeating unit represented by the above formula (22) is preferably the repeating unit represented by the following formula (26).

In the case of the repeating unit shown in the above formula (26), g'=0 or 2 is preferred. In the case of g'=2, the bonding positions are 2nd and 5th position. In the case of g'=0, there is no steric obstacle caused by R ^18' , and in the case of g'=2 and the bonding positions are 2 and 5, the steric obstacle becomes bonded by two R ^18' The diagonal position of the benzene ring allows R ^17' and R ^19' to be bonded at positions that are symmetrical to each other.

Furthermore, the repeating unit represented by the above formula (26) is more preferably the repeating unit represented by the following formula (27).

In the case of the repeating unit shown in the above formula (27), g'=0 or 2 is preferred. In the case of g'=2, the bonding positions are 2nd and 5th position. In the case of g'=0, there is no steric obstacle caused by R ^18' , and in the case of g'=2 and the bonding positions are 2 and 5, the steric obstacle becomes bonded by two R ^18' The diagonal position of the benzene ring allows R ^7' and R ^9' to be bonded at positions that are symmetrical to each other.

[Content of repeating units]

In the polymer having the repeating unit represented by formula (20), the content of the repeating unit represented by formula (20) is not particularly limited. It is usually contained in the polymer at least 10 mol%, preferably 30 mol%. % or more, preferably more than 40 mol%, particularly preferably more than 50 mol%. In the polymer having the repeating unit represented by formula (20), the repeating unit may be composed only of the repeating unit represented by formula (20). However, for the purpose of balancing various properties when used as an organic electroluminescent element, it may also have Other repeating units different from formula (20); at this time, the content of the repeating unit represented by formula (20) in the polymer is usually 99 mol% or less, preferably 95 mol% or less.

In the case of containing a repeating unit represented by formula (25), the ratio of the repeating unit represented by formula (20) to the repeating unit represented by formula (25), (the molar number of the repeating unit represented by formula (25) )/(the mole number of the repeating unit shown in formula (20)) is preferably 0.1 or more, more preferably 0.3 or more. The best is 0.5 or more, the best is 0.9 or more, and the best is 1.0. Moreover, it is preferably 2.0 or less, more preferably 1.5 or less, and still more preferably 1.2 or less.

[Better combination of repeating units]

The combination of repeating units of the polymer is not particularly limited. From the viewpoint of improving charge transport properties and durability, it is preferable to have a repeating unit represented by formula (20) and Ar ⁴ of formula (22): The repeating unit of formula (23) is a repeating unit represented by the following formula (28).

In formula (28), Ar ^1' , Ar ^3' , X', R ^1' , R ^2' , a', b', c', d', k', m' and n' are the same as formula (20) ), formula (22) and formula (23) are the same.

The preferred structure, range, etc. are also the same as each of Formula (20), Formula (22), and Formula (23).

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

In the formula (28), let the biphenyl skeleton connected by the fluorine ring, carbazole ring or ethylene group close to the phenylene group having a substituent be A, and let the biphenyl skeleton connected by the phenylene ring close to the unsubstituted phenylene group be When the biphenyl skeleton connected to the fluorine ring, carbazole ring or ethyl group is set to B, A, which has a bond that is not conjugated with the amine, is not conjugated with the amine, so the LUMO is not easily distributed and is durable. sexual enhancement tendency to rise. Furthermore, since the conjugation of the B system conjugated with the amine is wider, the hole transport property tends to be improved and stabilized.

Furthermore, 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.

By X' of A and X' of B is -C(R ^3' )(R ^4' )-, or X' of A and X' of B is -NR ^5' -, or X' of A and B X' is -C(R ^11' )(R ^12' )-C(R ^13' )(R ^14' )-. Since the repeated basic skeleton contained in the polymer is the same, it is not easy to form a charge trap. The energy level is considered to be superior in charge transport and durability.

More preferably, A and B are the same, further preferably, X' of A and B is -C(R ^3' )(R ^4' )-, and particularly preferably, X' of A and B are -C(R ^3' )(R ^4' )-and the same.

<polymerc>

The polymer c that can be used in the hole transport layer in this embodiment has a side chain having a structure represented by the following formula (30).

In formula (30), Ar ^31' represents a divalent group connected to the main chain; Ar ^12' represents a divalent aromatic hydrocarbon group that may have a substituent or a divalent aromatic heterocyclic group that may have a substituent. ;Ar ^13' ~Ar ^15' independently represent hydrogen atoms or substituents.

* indicates the bonding position.

Ar ^31' represents a divalent group connected to the main chain. Although not particularly limited, it is preferably the same as Ar ^11′ in the formula (21), and the preferred range, optional substituents, etc. are also the same. Ar ^12' to Ar ^15' are the same as Ar ^12' to Ar ^15' in the formula (21), and the preferred ranges, optional substituents, etc. are also the same.

In formula (21), Ar ^11' and Ar ^12' each independently represent a divalent aromatic hydrocarbon group or aromatic heterocyclic group that may have a substituent; Ar ^13' ~ Ar ^15' each independently represent a hydrogen atom or a substituent. .

The polymer having the structure represented by formula (21) in the side chain preferably has the structure represented by the following formula (31).

In the formula (31), Ar ^13' to Ar ^15' and Ar ^31' are the same as the formula (21); Ar ^16' represents the structure of the main chain constituting the polymer.

The above-mentioned polymer having a structure represented by the formula (21) in the side chain is preferably a polymer containing a repeating unit represented by the above formula (22) and Ar ^3' has a structure represented by the formula (20). , or a polymer containing a repeating unit represented by the above formula (25) and Ar ^3' having a structure represented by the formula (20).

[Soluble base]

In order to express solubility in the solvent, the polymerization system of this embodiment having a partial structure represented by formula (CzP) preferably has a soluble group. The soluble group in this embodiment is a group having a linear or branched alkyl or alkenyl group having a carbon number of 3 to 24, preferably 12 or less. Among these, an alkyl group, an alkoxy group, or an aralkyl group is preferred, such as n-propyl, 2-propyl, n-butyl, isobutyl, and the like. More preferably, it is n-hexyl group or n-octyl group. The soluble group may have a substituent.

(number of soluble groups)

From the viewpoint of easily obtaining a polymer solution that can be used by a wet film-forming method, the polymer of the present embodiment having a partial structure represented by formula (CzP) preferably has a larger number of soluble groups. On the other hand, from the viewpoint of reducing the film thickness due to the layer dissolving in the solvent when another layer is formed on the formed layer by a wet film forming method, the smaller amount is preferred.

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

When the number of soluble groups in the polymer of the present embodiment having the partial structure represented by formula (CzP) is expressed as the number of moles per 1 g of the polymer, it is usually 4.0 mmol per 1 g of the polymer. Below the ear, preferably below 3.0 mmol, more preferably below 2.0 mmol, and usually above 0.1 mmol, preferably above 0.5 mmol.

If the number of soluble groups is within the above range, the polymer can be easily dissolved in the solvent, and a composition containing the polymer suitable for the wet film-forming method can be easily obtained. In addition, since the density of the soluble base is appropriate, the refractory solvent to the organic solvent is sufficient after drying by heating the solvent, and a multi-layer laminated structure can be formed by a wet film forming method.

Here, the number of soluble groups per 1 g of the polymer is calculated by removing the terminal groups from the polymer, the molar ratio of the filled monomers at the time of synthesis, and the structural formula.

For example, in the case of Polymer 1 synthesized in Example 1 described later, the molecular weight of the repeating units excluding the terminal group in Polymer 1 is an average of 650, and the average molecular weight is 1 per repeating unit. If this is calculated based on a simple ratio, the number of soluble groups per 1g of molecular weight can be calculated to be 1.54 millimoles.

[Chemistry 57]

[Crosslinking group]

The polymer of this embodiment having a partial structure represented by formula (CzP) may have a crosslinking group. The polymer of this embodiment having a partial structure represented by formula (CzP) may have a crosslinking group that may exist in the repeating unit represented by formula (20) or may exist in the same group as formula (20) Among other repeating units that differ from the repeating unit shown. It is particularly preferable when Ar ^1' belonging to the side chain has a cross-linking group because the cross-linking reaction proceeds easily.

By having a crosslinking group, a large difference can be made in the solubility of the organic solvent before and after the reaction (refractory reaction) caused by irradiation with heat and/or active energy rays.

The so-called "cross-linking group" refers to a group that reacts with groups constituting other molecules located near the cross-linking group by irradiation with heat and/or active energy rays to form novel chemical bonds. In this case, the group that reacts may be the same as or different from the crosslinking group.

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

The crosslinkable group is preferably further substituted on the substituent contained in each of the above structures.

(Crosslinking group T’)

The cross-linkable group T' has the structure shown below.

[Chemical 58]

In the crosslinkable 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' is an integer from 1 to 4, q' is an integer from 1 to 5, and r' is an integer from 1 to 7.

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

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

When r ^' is 2 or more, the plural R ^26' may be the same or different.

Ar ^21' and Ar ^22' represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent.

Examples of the alkyl group of R ^21' to R ^26' include a linear or branched chain alkyl group having 6 or less carbon atoms. For example, methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, etc. More preferably, it is methyl or ethyl. When the number of carbon atoms in R ^21' to R ^26' is 6 or less, the cross-linking reaction will not be sterically hindered and the film will tend to become insolubilized.

Examples of the alkoxy group of R ^25' and R ^26' include a linear or branched chain alkoxy group having 6 or less carbon atoms. For example, methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, etc. More preferably, it is methoxy or ethoxy. When the carbon number of R ^25' and R ^26' is 6 or less, the cross-linking reaction will not be sterically hindered and the film will tend to become insolubilized.

Moreover, as the aromatic hydrocarbon ring group which may have a substituent for R ^21' and R ^22' , for example, a 6-membered monocyclic ring or a 2 to 5-membered ring such as a benzene ring or a naphthalene ring having a valence of 1 free atom. Condensation ring. Particularly preferred is a benzene ring having one free atom valence.

Ar ²² may be a group in which two or more aromatic hydrocarbon ring groups which may have a substituent are bonded. Examples of such a group include a biphenylene group, a biphenylene triphenyl group, and the like, and a 4,4'-biphenylene group is preferred.

The substituents that Ar ²¹ and Ar ²² may have are the same as the above-mentioned substituent group Z'.

As the cross-linking group, from the viewpoint of further improving the electrochemical stability of the device, preferred are arylvinyl carbonyl groups such as cinnamonyl group, benzocyclobutene rings having one free atomic valence, and A radical for cycloaddition reaction such as 1,2-dihydrocyclotetra[a]naphthalene ring with free atomic valence.

In addition, among the crosslinkable groups, in terms of particularly stable structure after crosslinking, it is preferable to include a cyclobutene ring having a monovalent free atom valence and condensed into an aromatic ring. A base of 1,2-dihydrocyclotetrakis[a]naphthalene ring; among them, a 1,2-dihydrocyclotetrakis[a]naphthalene ring having a benzocyclobutene ring or a monovalent free atom valence is more preferred ; In view of the lower cross-linking reaction temperature, a 1,2-dihydrocyclotetra[a]naphthalene ring with a monovalent free atom is particularly preferred.

(Number of cross-linking groups)

The cross-linkable group of the polymer of this embodiment having the partial structure represented by formula (CzP) is sufficiently insolubilized by cross-linking, and other groups can be easily formed thereon by a wet film-forming method. From a layer perspective, the one with more is better. On the other hand, from the viewpoint that cracks are less likely to occur in the formed layer, unreacted crosslinking groups are less likely to remain, and the organic electroluminescent element is likely to have a longer life, a smaller number of crosslinking groups is preferred.

In the polymer of this embodiment having a partial structure represented by formula (CzP), the number of crosslinking groups present in one polymer chain is preferably 1 or more, more preferably 2 or more, and more preferably Less than 200, preferably less than 100.

In addition, the number of crosslinkable groups possessed by a polymer having a partial structure represented by formula (CzP) can be expressed as the number per molecular weight of 1,000 of the polymer.

When the number of crosslinkable groups in the polymer of this embodiment having the partial structure represented by formula (CzP) is expressed as the number per 1,000 molecular weight of the polymer, it is usually 3.0 per 1,000 molecular weight. Less than one, preferably less than 2.0, more preferably less than 1.0, and usually more than 0.01, preferably more than 0.05.

When the number of crosslinkable groups is within the above range, cracks are less likely to occur, and a flat film is easily obtained. In addition, due to the appropriate cross-linking density, there are fewer unreacted cross-linking groups remaining in the layer after the cross-linking reaction, which will not easily affect the life of the resulting device.

Furthermore, since the cross-linking reaction has sufficient insolubility in organic solvents, it is easy to form a multi-layer laminated structure by a wet film forming method.

Here, the number of crosslinkable groups per molecular weight of 1,000 in the polymer is calculated by removing the terminal groups from the polymer, the molar ratio of the filling monomers at the time of synthesis, and the structural formula.

For example, in the case of Polymer 3 synthesized in Examples described below, in Polymer 3, the molecular weight of the repeating units excluding the terminal groups is an average of 868, and the crosslinkability is based on 0.114 per 1 repeating unit. If this is calculated based on a simple ratio, the number of cross-linkable groups per 1,000 molecular weight can be calculated to be 0.132.

[Molecular weight of polymer]

The weight average molecular weight of the polymer having a partial structure represented by 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, and particularly preferably 100,000 or less. In addition, it is usually 2,500 or more, preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more.

By setting the weight average molecular weight of the polymer to be equal to or less than the above upper limit, solubility in the solvent can be obtained and film-forming properties tend to be excellent. Furthermore, when the weight average molecular weight of the polymer is equal to or higher than the above-mentioned lower limit, the decrease in the glass transition temperature, melting point, and vaporization temperature of the polymer may be suppressed, and the heat resistance may be improved. In addition, there are cases where the coating film after the cross-linking reaction is sufficiently insoluble in the organic solvent.

Moreover, the number average molecular weight (Mn) of the polymer having the partial structure represented by formula (CzP) is usually 2,500,000 or less, preferably 750,000 or less, more preferably 400,000 or less. Specially priced below 100,000. Moreover, it is usually 2,000 or more, preferably 4,000 or more, more preferably 8,000 or more, and particularly preferably 20,000 or more.

Furthermore, the degree of dispersion (Mw/Mn) of the polymer having the partial structure represented by formula (CzP) is preferably 3.5 or less, more preferably 2.5 or less, particularly preferably 2.0 or less. In addition, since the smaller the dispersion value, the better, so the lower limit value is ideally 1. When the dispersion degree of the polymer is below the above-mentioned upper limit, purification is easy and the solubility in the solvent and the charge transport ability are good.

Generally, the weight average molecular weight of a polymer is determined by SEC (size exclusion chromatography) measurement. During SEC measurement, high molecular weight components have a short dissolution time, while low molecular weight components have a long dissolution time. Use a calibration curve calculated from the dissolution time of polystyrene (standard sample) with a known molecular weight, by dividing the dissolution time of the sample. Time is converted into molecular weight and the weight average molecular weight can be calculated.

[Specific example]

Specific examples of the polymer having the partial structure represented by the formula (CzP) are shown below, but the polymer having the partial structure represented by the formula (CzP) is not limited to these. Moreover, the numbers in the chemical formula represent the molar ratio of repeating units.

These polymers can be any of random copolymers, alternating copolymers, block copolymers, or graft copolymers, and the arrangement order of the monomers is not limited.

[Chemical 60]

[Production method of polymer]

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

In the polymerization method using Ullmann reaction and the polymerization method using Buchwald-Hartwig reaction, for example, by dihalogenating an aryl group represented by formula (1a') (X' represents a halogen atom such as I, Br, Cl, F, etc. ) reacts with the primary aminoaryl group represented by formula (1b'), a polymer having a partial structure represented by formula (CzP) can be synthesized.

In the formula, Y represents a halogen atom, and Ar ^1' , R ^1' ~R ^4' and X are synonymous with the above formula (20).

Furthermore, in the above-mentioned polymerization method, the reaction to form an N-aryl bond is usually carried out in the presence of a base such as potassium carbonate, sodium tert-butoxide, or triethylamine. Alternatively, it may be carried out in the presence of a transition metal catalyst such as copper or palladium complex.

<Low molecular compounds>

In the third gist of the present invention, when the material contained in the light-emitting layer has a specific structure of a carbazole ring and contains the above formula (CzP) as a partial structure is a low molecular material, the same situation as in the second gist of the present invention is achieved. The low molecular compounds contained above are the same. That is, a host material having the above formula (CzP-2) is preferred, and the preferred range is also the same.

<Composition for organic electroluminescent devices>

In the organic electroluminescent device according to the embodiments of the second and third aspects of the present invention, the hole transport layer and the light-emitting layer adjacent to the hole transport layer are made of a material having the formula (CzP) as a partial structure dissolved in The composition of the solvent can be used for wet film formation.

The composition for organic electroluminescent elements used to form the hole transport layer preferably contains any one of the above-mentioned polymers a to polymer c; the composition for organic electroluminescent elements used to form the light-emitting layer is preferably The system contains the above low molecular compounds.

[Content of materials having formula (CzP) as part of the structure]

The content of the material having the formula (CzP) as a partial structure in the above composition is usually 0.01 to 70 mass%, preferably 0.1 to 60 mass%, and more preferably 0.5 to 50 mass%.

If it is within the above range, it is preferable because the formed organic layer is less likely to have defects and uneven film thickness.

[solvent]

The above compositions usually contain solvents. The solvent is preferably one that dissolves materials having formula (CzP) as a partial structure. Specifically, a solvent capable of dissolving a material having formula (CzP) as a partial structure at room temperature is usually 0.05% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more.

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; ethanol; Aliphatic ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anise Ether, phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and other aromatic ethers, etc. Ether solvents; aliphatic ester solvents such as ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, etc.; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, isobenzoate Ester-based solvents such as propyl ester, propyl benzoate, n-butyl benzoate and other aromatic esters; and other organic solvents; other organic solvents used in the hole injection layer forming composition and the hole transport layer forming composition described later .

In addition, one type of solvent may be used, or two or more types may be used in any combination and at any ratio.

Among them, the solvent contained in the composition for organic electroluminescent devices of the present invention is preferably a solvent whose surface tension at 20°C is usually less than 40 dyn/cm, preferably less than 36 dyn/cm, and more preferably less than 33 dyn/cm. .

The above-mentioned composition used in the wet film-forming method requires low surface tension in order to achieve higher uniformity and form a uniform coating film. Therefore, by using the above-mentioned Surface tension solvents that form a uniform layer containing a material having formula (CzP) as a partial structure are preferred.

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

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

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

However, moisture may cause deterioration in the performance of organic electroluminescent elements, and may contribute to a decrease in brightness especially during continuous driving. Therefore, in order to reduce residual moisture in wet film formation as much as possible, among the above-mentioned solvents, the solubility of water at 25°C is preferably 1 mass% or less, more preferably 0.1 mass% or less.

The content of the solvent contained in the composition for organic electroluminescent elements is usually 10 mass% or more, preferably 30 mass% or more, more preferably 50 mass% or more, and particularly preferably 80 mass% or more. When the solvent content is equal to or higher than the above lower limit, the flatness and uniformity of the formed layer can be improved.

[Electron acceptor compounds]

From the viewpoint of reducing resistance, the composition for organic electroluminescent elements preferably further contains an electron-accepting compound. Particularly when the composition for an organic electroluminescent element is used to form a hole injection layer, it is preferable to contain an electron-accepting compound.

The electron-accepting compound is preferably a compound having oxidizing power and the ability to accept one electron from the above-mentioned polymer. Specifically, a compound having an electron affinity of 4 eV or more is preferred, and a compound having an electron affinity of 5 eV or more is more preferred.

Examples of such electron-accepting compounds include triarylboron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, and salts of arylamines and Lewis acids. One or two or more compounds selected from the group formed.

Specific examples include onium salts substituted with organic groups such as 4-isopropyl-4'-methyldiphenyl iodonium (pentafluorophenyl) borate and triphenyl sulfonium tetrafluoroborate (International Publication No. 2005/089024), (International Publication No. 2017/164268); iron (III) chloride (Japanese Patent Application Publication No. 11-251067), ammonium peroxodisulfate and other high atomic valence inorganic compounds; tetracyanoethylene Cyano compounds such as ginseng (pentafluorophenyl) borane (Japanese Patent Application Publication No. 2003-31365) and other aromatic boron compounds; fullerene derivatives and iodine, etc.

The composition for organic electroluminescent elements may contain one of the above-mentioned electron acceptor compounds alone, or may contain two or more types in any combination and ratio.

When the composition for organic electroluminescent elements contains an electron-accepting compound, the content of the electron-accepting compound in the composition for organic electroluminescent elements is usually 0.0005 mass % or more, preferably 0.001 mass % or more, and usually The content is 20 mass% or less, preferably 10 mass% or less. In addition, the electron-accepting compound is relatively strong compared to the polymer in the composition for organic electroluminescent devices. The combined ratio is usually 0.5 mass% or more, preferably 1 mass% or more, more preferably 3 mass% or more, and usually 80 mass% or less, preferably 60 mass% or less, more preferably 40 mass% or less.

If the content of the electron-acceptor compound in the composition for organic electroluminescent elements is more than the above-mentioned lower limit, the electron acceptor will accept electrons from the polymer to reduce the resistance of the formed organic layer, so it is preferable; if It is preferably below the above upper limit because the formed organic layer is less likely to have defects and uneven film thickness.

[cationic free compound]

The composition for organic electroluminescence elements may further contain a cationic radical compound.

As the cationic radical compound, an ionic compound formed from a cationic radical of a chemical species that removes one electron from a hole-transporting compound, and a conjugated anion is preferred. When the cationic radical is derived from a hole-transporting polymer compound, the cationic radical has a structure in which one electron is removed from the repeating unit of the polymer compound.

Furthermore, the cationic radical is preferably a chemical species in which one electron has been removed from the hole-transporting compound described below. From the viewpoints of amorphousness, visible light transmittance, heat resistance, solubility, etc., the most suitable chemical species as a hole-transporting compound is a chemical species that removes one electron from a preferred compound.

Here, the cationic radical compound can be produced by mixing a hole-transporting compound described later and an electron-accepting compound mentioned above. That is, by mixing a hole transporting compound and an electron accepting compound, electrons move from the hole transporting compound to the electron accepting compound, thereby generating cationic radicals from the hole transporting compound. A cationic ionic compound formed with a conjugated anion.

When the composition for organic electroluminescent elements of the present invention contains a cationic radical compound, the content of the cationic radical compound in the composition for organic electroluminescent elements is usually 0.0005 mass% or more, preferably 0.001 mass% or more, and It is usually 40 mass% or less, preferably 20 mass% or less. If the content of the cationic radical compound is more than the lower limit, the formed organic layer will have low resistance, so it is preferable; if it is less than the upper limit, the formed organic layer will be less prone to defects and uneven film thickness, so it is less likely to occur. Better.

In addition, the composition for organic electroluminescence elements may contain, in addition to the above-mentioned components, components contained in the composition for forming a hole injection layer or the composition for forming a hole transport layer described below in the amounts described below.

<Organic electroluminescent element>

The organic electroluminescent element of the present invention is an organic electroluminescent element having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate. In the organic electroluminescent element according to the first aspect of the present invention, the organic layer has a layer containing the above-mentioned polymer a or a polymer in which the polymer a is cross-linked. In the organic electroluminescent element according to 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 contains the above polymer a or is made of The polymer a is a cross-linked polymer, and the light-emitting layer contains the above-mentioned material having a partial structure represented by formula (CzP). An organic electroluminescent element according to an 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 materials contained in the hole transport layer and the light-emitting layer All contain materials (compounds) having a partial structure represented by the formula (CzP) above the carbazole ring. In an embodiment of the third aspect, the material having a partial structure represented by the formula (CzP) contained in the hole transport layer is preferably the above-mentioned material. Polymer b or a cross-linked polymer of the above-mentioned polymer b, or the above-mentioned polymer c or a cross-linked polymer of the above-mentioned polymer c.

Various conditions and aspects in the organic electroluminescent devices of the above embodiments can be combined arbitrarily. Specific descriptions of the manufacturing methods and characteristics applicable to these organic electroluminescent devices will be described later.

The manufacturing method of the organic electroluminescent element in the embodiment of the present invention is not particularly limited. It is preferably manufactured by a method including the following steps: using the above-mentioned composition for organic electroluminescent element, and wet film formation A film forming step that forms at least one layer constituting the organic layer. When the organic layer includes a plurality of layers, a known method may be used for laminating the plurality of layers.

In the organic electroluminescent element, the organic layer has a hole injection layer and a hole transport layer. Preferably, at least one of these hole injection layers and hole transport layers is a layer formed by a wet film forming method ( The organic layer formed by the film-forming step); the particularly preferred organic layer has a hole injection layer, a hole transport layer and a luminescent layer, and all of these hole injection layers, hole transport layers and luminescent layers are made of moisture. The layer formed by the film-forming method.

The "wet film forming method" in this embodiment refers to a method using, for example, spin coating, dip coating, die coating, rod coating, blade coating, roll coating, spray coating, capillary coating, etc. As a film forming method, that is, as a coating method, the coating film is dried using wet film forming methods such as cloth method, inkjet method, nozzle printing method, screen printing method, gravure printing method, and quick-drying printing method. And the method of film formation. Among these film forming methods, spin coating, spray coating, inkjet, nozzle printing, etc. are preferred.

As an example of the structure of the organic electroluminescent element, a schematic diagram (cross-section) of an example of the structure of the organic electroluminescent element 10 is shown in FIG. 1 . In Figure 1, 1 represents the substrate, 2 represents the anode, 3 represents the hole injection layer, 4 represents the hole transport layer, 5 represents the light emitting layer, 6 represents the hole blocking layer, 7 represents the electron transport layer, and 8 represents the electron injection layer. 9 represents the cathode.

Hereinafter, an example of an embodiment of the layer structure of an organic electroluminescent element and its general formation method will be described with reference to FIG. 1 .

[Substrate]

The substrate 1 becomes the support of the organic electroluminescent element, and usually a quartz or glass plate, a metal plate or metal foil, a plastic film or sheet, etc. are used. Among these, a glass plate, a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polyester is preferred. In order to prevent the organic electroluminescent element from being easily degraded due to external air, the substrate is preferably made of a material with high gas barrier properties. Therefore, especially when using materials with low gas barrier properties such as synthetic resin substrates, it is preferable to provide a dense silicon oxide film on at least one side of the substrate to improve the gas barrier properties.

[anode]

The anode 2 is responsible for injecting holes into the layer on the side of the light-emitting layer 5.

The anode 2 usually uses metals such as aluminum, gold, silver, nickel, palladium, and platinum; metal oxides such as indium and/or tin oxides; halide metals such as copper iodide; carbon black and poly(3-methylthiophene) , polypyrrole, polyaniline and other conductive polymers.

The anode 2 is usually formed by dry methods such as sputtering and vacuum evaporation. In addition, when forming the anode using metal particles such as silver, copper iodide and other particles, carbon black, conductive metal oxide particles, conductive polymer powder, etc., it can also be dispersed in an appropriate binder resin solution. , and formed by coating on the substrate. Also, for conducting electricity In the case of conductive polymers, electrolytic polymerization can also be used to directly form a thin film on the substrate, or a conductive polymer can be coated on the substrate to form an anode (Appl. Phys. Lett., Vol. 60, page 2711, 1992).

The anode 2 usually has a single-layer structure, but may also have a laminated structure as appropriate. When the anode 2 has a laminated structure, different conductive materials can also be laminated on the first-layer anode.

The thickness of the anode 2 can be determined according to the required transparency and material. Especially when high transparency is required, a thickness with a visible light transmittance of 60% or more is preferred, and a thickness of 80% or more is more preferred. The thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less. On the other hand, when transparency is not required, the thickness of the anode 2 can be set arbitrarily according to the required strength, etc. In this case, the anode 2 can also be set to the same thickness as the substrate.

When other layers are formed on the surface of the anode 2, impurities on the anode 2 can be removed by applying ultraviolet/ozone, oxygen plasma, argon plasma, etc. treatments before film formation, and their free potential can be adjusted to increase the potential in advance. The hole is injectable, so it is better.

[Hole injection layer]

The layer responsible for 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. Furthermore, when there are two or more layers responsible for transporting holes from the anode 2 side to the light-emitting layer 5 side, the layer closest to the anode side is called the hole injection layer 3 . From the viewpoint of enhancing the function of transporting holes from the anode 2 to the light-emitting layer 5 side, it is preferable to form the hole injection layer 3 . When forming the hole injection layer 3, the hole injection layer 3 is usually formed on the anode 2.

The film thickness of the hole injection layer 3 is usually 1 nm or more, preferably 5 nm or more, and usually 1000 nm or less, preferably 500 nm or less.

The hole injection layer can be formed by vacuum evaporation or wet film formation. From the viewpoint of superior film-forming properties, it is preferable to use a wet film-forming method.

The hole injection layer 3 preferably contains a hole transport compound, and more preferably contains a hole transport compound and an electron acceptor compound. More preferably, the hole injection layer contains a cationic radical compound, and particularly preferably, the hole injection layer contains a cationic radical compound and a hole transporting compound.

The general method of forming the hole injection layer will be described below. However, in the organic electroluminescent element of the present invention, the hole injection layer is preferably formed by a wet film forming method using a composition for organic electroluminescent elements. .

[Hole transport compound]

The composition for forming a hole injection layer usually contains a hole transporting compound that becomes the hole injection layer 3 . Moreover, in the case of a wet film forming method, a solvent is usually further contained. The composition for forming the hole injection layer is preferably one that has high hole transport properties and can efficiently transport injected holes. Therefore, it is preferable that the hole mobility is large and that impurities that become traps are less likely to be generated during manufacturing or use. Moreover, it is preferable that it has excellent stability, a small dissociation potential, and high transparency to visible light. Especially when the hole injection layer is in contact with the light-emitting layer, it is preferably one that does not reduce the light emitted from the light-emitting layer, or that does not form an exciplex with the light-emitting layer to reduce the luminous efficiency.

As a hole-transporting compound, a compound having a dissociation potential of 4.5 eV to 6.0 eV is preferred from the viewpoint of a charge injection barrier from the anode to the hole injection layer. Examples of the hole-transporting compound include aromatic amine compounds, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzylbenzene compounds, and tertiary compounds linked by a benzene group. Amine compounds, hydrazone compounds, silazane compounds, quinacridone compounds, etc.

Among the above-described exemplary compounds, from the viewpoint of amorphousness and visible light transmittance, aromatic amine compounds are preferred, and aromatic tertiary amine compounds are more preferred. Here, the term "aromatic tertiary amine compound" refers to a compound having an aromatic tertiary amine structure, and also includes compounds having a group derived from an aromatic tertiary amine.

The type of the aromatic tertiary amine compound is not particularly limited. From the viewpoint of easily utilizing the surface smoothing effect to obtain uniform light emission, it is preferable to use a polymer compound (connected by repeating units) with a weight average molecular weight of 1,000 or more and 1,000,000 or less. polymeric compound).

The hole injection layer 3 preferably contains the above-mentioned electron acceptor compound or the above-mentioned cationic radical compound because the conductivity of the hole injection layer can be improved by oxidation of the hole-transporting compound.

Cations derived from polymer compounds such as PEDOT/PSS (Adv. Mater., 2000, Vol. 12, page 481) or aniline green hydrochloride (J. Phys. Chem., 1990, Vol. 94, page 7716) Free radical compounds can also be produced by oxidative polymerization (dehydrogenation polymerization).

Oxidative polymerization here refers to chemical or electrochemical oxidation of monomers using peroxodisulfate or the like in an acidic solution. In the case of this oxidative polymerization (dehydrogenation polymerization), a monomer is oxidized to become a polymer, and an anion derived from an acidic solution is used as a conjugated anion, thereby removing one electron from the repeating unit of the polymer. Cationic radicals.

[Formation of hole injection layer using wet film formation method]

When the hole injection layer 3 is formed by a wet film forming method, it is usually mixed with a solvent (solvent for the hole injection layer) that can be dissolved to become the material of the hole injection layer to prepare a film-forming composition (hole injection layer). injection layer forming composition), and then apply the hole injection layer forming composition on It is formed by forming a film on the layer corresponding to the layer below the hole injection layer (usually the anode) and drying it.

The concentration of the hole-transporting compound in the composition for forming the hole injection layer can be arbitrary as long as the effect of the present invention is not significantly impaired. From the perspective of film thickness uniformity, the lower the better; and , On the other hand, from the viewpoint that defects are less likely to occur in the hole injection layer, the higher the thickness, the better. Specifically, it is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and particularly preferably 0.5 mass% or more; on the other hand, it is preferably 70 mass% or less, more preferably 60 mass% or less, and particularly preferably 50 mass%. mass% or less.

Examples of the solvent include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, and the like.

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

Examples of the ester-based solvent include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.

Examples of the aromatic hydrocarbon solvent include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, Cyclohexylbenzene, methylnaphthalene, etc.

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

In addition to these, dimethyl styrene, etc. can also be used.

The hole injection layer 3 is formed by a wet film forming method. Usually, after preparing the hole injection layer forming composition, it is formed on a layer corresponding to the lower layer of the hole injection layer 3 (usually the anode 2). Coating to form a film and drying.

The hole injection layer 3 is usually dried by heating or reduced pressure drying after the film is formed.

[Formation of hole injection layer by vacuum evaporation method]

When the hole injection layer 3 is formed by vacuum evaporation, one or more of the constituent materials of the hole injection layer 3 (the above-mentioned hole transport compounds, electron acceptor compounds, etc.) are usually installed. Put it into a crucible set in a vacuum container (when two or more materials are used, they are usually put into separate crucibles), exhaust the vacuum container to about 10 ^-4 Pa with a vacuum pump, and then heat the crucible (use 2 When more than two kinds of materials are used, each crucible is usually heated) and the evaporation amount of the material in the crucible is controlled while evaporating (when two or more materials are used, the evaporation amount is usually controlled independently to evaporate). A hole injection layer is formed on the anode on the substrate placed opposite to the crucible. Furthermore, when two or more kinds of materials are used, a hole injection layer can be formed by putting the mixture into a crucible, heating it, and evaporating it.

The degree of vacuum during evaporation is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1×10 ^-6 Torr (0.13×10 ^-4 Pa) or more, and 9.0×10 ^-6 Torr (12.0× 10 ^-4 Pa) or less. The evaporation speed is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 Å/second or more and 5.0 Å/second or less. The film-forming temperature during evaporation is not limited as long as the effect of the present invention is not significantly impaired, but is preferably 10°C or more and 50°C or less.

In addition, the hole injection layer 3 may be cross-linked similarly to the hole transport layer 4 described later.

[hole transport layer]

The hole transport layer 4 is a layer responsible for transporting holes from the anode 2 side to the light emitting layer 5 side. In this embodiment, the hole transport layer 4 is in contact with the light-emitting layer 5, and the hole transport layer 4 is a layer containing a material having a partial structure represented by formula (CzP). When forming the hole transport layer 4 , the hole transport layer 4 is usually formed between the anode 2 and the light-emitting layer 5 . In addition, when the hole injection layer 3 is present, it is formed between the hole injection layer 3 and the light-emitting layer 5 .

The film thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, and on the other hand, it is usually 300 nm or less, preferably 100 nm or less.

The hole transport layer 4 may be formed by vacuum evaporation or wet film formation. From the viewpoint of excellent film-forming properties, it is preferably formed by a wet film-forming method.

A general method of forming a hole transport layer will be described below. However, in organic electroluminescent devices, the hole transport layer is preferably formed by a wet film-forming method using a composition for organic electroluminescent devices.

In an organic electroluminescent element, the hole transport layer containing a material having a partial structure represented by formula (CzP) may also contain a hole transporting compound other than a material having a partial structure represented by formula (CzP).

The hole transport layer 4 usually contains a hole transport compound. The hole transporting compound contained in the hole transporting layer 4 is preferably the above-mentioned polymer, or when the above-mentioned polymer has a crosslinkable group, it is a crosslinked polymer. Furthermore, in addition to polymers, preferred examples of the hole transporting compounds include: 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl Aromatic diamines containing two or more tertiary amines and two or more condensed aromatic rings substituted with nitrogen atoms (Japanese Patent Application Laid-Open No. 5-234681); 4,4',4"-see (1 -Naphthylphenyl Aromatic amine compounds with a starburst structure such as triphenylamine (J. Lumin., Vol. 72-74, page 985, 1997); aromatic amines formed from triphenylamine tetramers Compounds (Chem. Commun., page 2175, 1996); 2,2',7,7'-bis(diphenylamino)-9,9'-spirobisulfan and other spiro compounds (Synth. Metals, Volume 91, page 209, 1997); carbazole derivatives such as 4,4'-N,N'-dicarbazolebiphenyl, etc. In addition, for example, polyvinylcarbazole, polyvinyltriphenylamine (Japanese Patent Application Laid-Open No. 7-53953), polyarylene ether terine containing tetraphenylbenzidine (Polym. Adv. Tech. , Volume 7, Page 33, 1996), etc.

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

When the hole transport layer is formed by a wet film forming method, generally the hole injection layer is replaced with the hole injection layer forming composition in the same manner as when the hole injection layer is formed by a wet film forming method. The transport layer forming composition is formed.

When the hole transport layer is formed by a wet film forming method, usually the composition for forming the hole transport layer further contains a solvent. The solvent used in the hole transport layer forming composition may be the same solvent as the solvent used in the hole injection layer forming composition.

The concentration of the hole transporting compound in the hole transport layer forming composition can be set to the same range as the concentration of the hole transporting compound in the hole injection layer forming composition.

When the hole transport layer is formed by a wet film forming method, it can be formed in the same manner as the hole injection layer film forming method.

[Formation of hole transport layer using vacuum evaporation method]

When the hole transport layer is formed by vacuum evaporation, generally, similarly to the case where the hole injection layer is formed by vacuum evaporation, instead of the hole injection layer forming composition, a hole transport layer forming composition is used. The composition can then be formed. Vacuum degree, evaporation speed and temperature during evaporation The film formation conditions, such as the film formation conditions, etc., can be carried out according to the same conditions as those used in the vacuum evaporation of the above-mentioned hole injection layer.

[Light-emitting layer]

The light-emitting layer 5 is a layer responsible for the function of being excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 9 to emit light when an electric field is applied between a pair of electrodes. The luminescent layer 5 is a layer formed between the anode 2 and the cathode 9. The luminescent layer is formed between the hole injection layer and the cathode when the anode has a hole injection layer; when there is a hole transport layer on the anode , is formed between the hole transport layer and the cathode.

The film thickness of the light-emitting layer 5 can be arbitrary as long as the effect of the present invention is not significantly impaired. From the viewpoint of the film being less likely to cause defects, the thicker is better. On the other hand, from the viewpoint of easily forming a low driving voltage From a perspective, the thinner, the better. Therefore, it is preferably 3 nm or more, and more preferably 5 nm or more. On the other hand, it is generally preferably 200 nm or less, and more preferably 100 nm or less.

The luminescent layer 5 preferably contains a host material having at least one of hole transporting properties or electron transporting properties, such as a luminescent material described below or a compound having a partial structure represented by the above formula (CzP). Particularly preferably, the luminescent layer 5 contains at least one of A material with luminescent properties (luminescent material), and preferably contains a material with charge transport properties (host material).

As the luminescent material, a phosphorescent luminescent material or a fluorescent luminescent material can be used.

In the organic electroluminescent element according to the embodiments of 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 materials having a partial structure represented by formula (CzP).

When the light-emitting layer is a phosphorescent light-emitting layer, the following materials are preferred as the phosphorescent light-emitting material.

<Phosphorescent luminescent material>

Phosphorescent luminescent materials refer to materials that emit light from an excited triplet state. For example, metal complex compounds containing Ir, Pt, Eu, etc. are representative examples, and those containing metal complex compounds as material structures are preferred.

Among the metal complexes, examples of phosphorescent organic metal complexes that emit light via a triplet state include, for example, compounds selected from the long-period periodic table (hereinafter, unless otherwise specified, the so-called “periodic table” refers to Long-period periodic table) A Wier network complex or an organic metal complex compound in which metals from Groups 7 to 11 are central metals. As such a phosphorescent material, a compound represented by the following formula (201) or a compound represented by the formula (205) is preferred, and a compound represented by the formula (201) is more preferred.

Ring A1 represents an aromatic hydrocarbon ring structure that may have a substituent or an aromatic heterocyclic structure that may have a substituent.

Ring A2 represents an aromatic heterocyclic structure that may have a substituent.

R ²⁰¹ and R ²⁰² each independently have a structure shown in formula (202), and "*" in formula (202) represents a bond with ring A1 or ring A2. R ²⁰¹ and R ²⁰² may be the same or different. When R ²⁰¹ and R ²⁰² exist in the plural, they may be the same or different.

Ar ²⁰¹ and Ar ²⁰³ each independently represent an aromatic hydrocarbon ring structure that may have a substituent, or an aromatic heterocyclic structure that may have a substituent.

Ar ²⁰² represents an aromatic hydrocarbon ring structure that may have a substituent, an aromatic heterocyclic structure that may have a substituent, or an aliphatic hydrocarbon structure that may have a substituent.

The substituents bonded to ring A1, the substituents bonded to ring A2, or the substituents bonded to ring A1 and the substituents bonded to ring A2 may also bond to each other to form a ring.

B ²⁰¹ -L ²⁰⁰ -B ²⁰² represent anionic bidentate ligands. B ²⁰¹ and B ²⁰² independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may also be atoms constituting a ring. L ²⁰⁰ represents a single bond, or an atomic group that together with B ²⁰¹ and B ²⁰² forms a bidentate ligand. When plural numbers B ²⁰¹ -L ²⁰⁰ -B ²⁰² exist, they may be the same or different.

i1 and i2 independently represent integers from 0 to 12.

i3 is an integer greater than 0 with the upper limit of the number that can be substituted for Ar ²⁰² .

j is an integer greater than 0 with the upper limit of the number that can be substituted for Ar ²⁰¹ .

k1 and k2 are each independently an integer greater than or equal to 0 with the upper limit of the number of substitutions possible for ring A1 and ring A2.

v is an integer between 1 and 3.

Unless otherwise specified, the groups in the formulas (201) and (202) are preferably substituents selected from the following substituent group Z2.

<Substituent group Z2>

‧Alkyl group, preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 8 carbon atoms, particularly preferably one with 1 to 6 carbon atoms alkyl.

‧The alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and even more preferably an alkoxy group having 1 to 6 carbon atoms.

‧Aryloxy group, preferably an aryloxy group with a carbon number of 6 to 20, more preferably an aryloxy group with a carbon number of 6 to 14, even more preferably an aryloxy group with a carbon number of 6 to 12, particularly preferably an aryloxy group with a carbon number of 6 to 12 6 aryloxy group.

‧Heteroaryloxy group, preferably a heteroaryloxy group with 3 to 20 carbon atoms, more preferably a heteroaryloxy group with 3 to 12 carbon atoms.

‧Alkylamino group, preferably an alkylamino group having 1 to 20 carbon atoms, more preferably an alkylamino group having 1 to 12 carbon atoms.

‧Arylamine group, preferably an arylamine group having 6 to 36 carbon atoms, more preferably an arylamine group having 6 to 24 carbon atoms.

‧Aralkyl group, preferably an aralkyl group having 7 to 40 carbon atoms, more preferably an aralkyl group having 7 to 18 carbon atoms, even more preferably an aralkyl group having 7 to 12 carbon atoms.

‧Heteroaralkyl group, preferably a heteroaralkyl group with 7 to 40 carbon atoms, more preferably a heteroaralkyl group with 7 to 18 carbon atoms.

‧Alkenyl group, preferably an alkenyl group with 2 to 20 carbon atoms, more preferably an alkenyl group with 2 to 12 carbon atoms, even more preferably an alkenyl group with 2 to 8 carbon atoms, particularly preferably one with 2 to 6 carbon atoms alkenyl.

‧Alkynyl group, preferably an alkynyl group with 2 to 20 carbon atoms, more preferably an alkynyl group with 2 to 12 carbon atoms.

‧Aryl group, preferably an aryl group with 6 to 30 carbon atoms, more preferably an aryl group with 6 to 24 carbon atoms, even more preferably an aryl group with 6 to 18 carbon atoms, particularly preferably 6 to 14 carbon atoms Aryl.

‧Heteroaryl group, preferably a heteroaryl group with a carbon number of 3 to 30, more preferably a heteroaryl group with a carbon number of 3 to 24, even more preferably a heteroaryl group with a carbon number of 3 to 18, particularly preferably a heteroaryl group with a carbon number of 3 to 18 3~14 heteroaryl groups.

‧Alkyl silyl group, preferably an alkyl silyl group with an alkyl carbon number of 1 to 20, more preferably an alkyl silyl group with an alkyl carbon number of 1 to 12.

‧Arylsilyl group, preferably an arylsilyl group with an aryl carbon number of 6 to 20, more preferably an arylsilyl group with an aryl carbon number of 6 to 14.

‧Alkyl carbonyl group, preferably an alkyl carbon group having 2 to 20 carbon atoms.

‧Aromatic carbonyl group, preferably an aromatic carbonyl group with 7 to 20 carbon atoms.

The above groups may also be one or more hydrogen atoms substituted by fluorine atoms, or one or more hydrogen atoms substituted by deuterium atoms.

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

‧Hydrogen atom, deuterium atom, fluorine atom, cyano group or -SF5.

(Preferred group among substituent group Z2)

Among these substituent groups Z2, preferred are an alkyl group, an alkoxy group, an aryloxy group, an arylamine group, an aralkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkylsilyl group, an arylsilyl group, and the like. A group in which more than one hydrogen atom of the group is replaced by a fluorine atom, a fluorine atom, a cyano group, or -SF5; more preferably, it is an alkyl group, an arylamine group, an aralkyl group, an alkenyl group, an aryl group, a heteroaryl group, and the like. A group in which more than one hydrogen atom of the group is replaced by a fluorine atom, a fluorine atom, a cyano group or -SF5; more preferably, it is an alkyl group, an alkoxy group, an aryloxy group, an arylamine group, an aralkyl group, an alkenyl group, an aryl group, or an alkyl group. base, heteroaryl, alkylsilyl, arylsilyl; particularly preferably alkyl, arylamine, aralkyl, alkenyl, aryl, heteroaryl; most preferably alkyl, arylamine, aralkyl base, aryl, heteroaryl.

These substituent group Z2 may further have a substituent selected from the substituent group Z2 as a substituent. The preferred group, more preferred group, further preferred group, particularly preferred group, and optimum group of the substituent that may be contained are the same as the preferred group in the substituent group Z2.

Ring A1 represents an aromatic hydrocarbon ring structure that may have a substituent or an aromatic heterocyclic structure that may have a substituent.

As the aromatic hydrocarbon ring, an aromatic hydrocarbon ring having 6 to 30 carbon atoms is preferred, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a triphenyl ring, an ethane naphthalene ring, 1,2 -Benzene ring, fluorine ring.

The aromatic heterocyclic ring is preferably an aromatic heterocyclic ring having 3 to 30 carbon atoms containing any one of a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, and more preferably a furan ring, a benzofuran ring, or a thiophene ring. , benzothiophene ring.

The ring A1 is preferably a benzene ring, a naphthalene ring, or a fluorine ring, particularly preferably a benzene ring or a fluorine ring, and most preferably a benzene ring.

Ring A2 represents an aromatic heterocyclic structure that may have a substituent.

環、三

環、咪唑環、

唑環、噻唑環、苯并噻唑環、苯并

唑環、苯并咪唑環、喹啉環、異喹啉環、喹

啉環、喹唑啉環、

啶環、啡啶環；更佳為吡啶環、吡

環、嘧啶環、咪唑環、苯并噻唑環、苯并

唑環、喹啉環、異喹啉環、喹

啉環、喹唑啉環；進而更佳為吡啶環、咪唑環、苯并噻唑環、喹啉環、異喹啉環、喹

啉環、喹唑啉環；最佳為吡啶環、咪唑環、苯并噻唑環、喹啉環、喹

啉環、喹唑啉環。 The aromatic heterocyclic ring is preferably an aromatic heterocyclic ring having 3 to 30 carbon atoms containing any one of a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom. Specific examples thereof include a pyridine ring, a pyrimidine ring, a pyridine ring,

ring, three

ring, imidazole ring,

Azole ring, thiazole ring, benzothiazole ring, benzo

Azole ring, benzimidazole ring, quinoline ring, isoquinoline ring, quinoline

pholine ring, quinazoline ring,

pyridine ring, phenanthridine ring; more preferably pyridine ring, pyridine ring

ring, pyrimidine ring, imidazole ring, benzothiazole ring, benzo

Azole ring, quinoline ring, isoquinoline ring, quinoline

pholine ring, quinazoline ring; more preferably, pyridine ring, imidazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, quinoline ring

pholine ring, quinazoline ring; the best ones are pyridine ring, imidazole ring, benzothiazole ring, quinoline ring, quinazoline ring

Phenoline ring, quinazoline ring.

啉環)、(苯環-喹唑啉環)、(苯環-咪唑環)、(苯環-苯并噻唑環)。 As a preferred combination of ring A1 and ring A2, if expressed in terms of (ring A1-ring A2), it is (benzene ring-pyridine ring), (benzene ring-quinoline ring), (phenyl ring-quinoline ring)

pholine ring), (benzene ring-quinazoline ring), (benzene ring-imidazole ring), (benzothiazole ring).

The substituents that ring A1 and ring A2 may have can be selected arbitrarily, and preferably one or a plurality of substituents are selected from the above-mentioned substituent group Z2.

Ar ²⁰¹ and Ar ²⁰³ each independently represent an aromatic hydrocarbon ring structure that may have a substituent, or an aromatic heterocyclic structure that may have a substituent.

Ar ²⁰² represents an aromatic hydrocarbon ring structure that may have a substituent, an aromatic heterocyclic structure that may have a substituent, or an aliphatic hydrocarbon structure that may have a substituent.

When any one of Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ has an aromatic hydrocarbon ring structure that may have a substituent, the aromatic hydrocarbon ring structure is preferably an aromatic hydrocarbon ring having 6 to 30 carbon atoms. Specifically, Preferably, they are benzene ring, naphthalene ring, anthracene ring, triphenyl ring, ethanenaphthalene ring, 1,2-benzoacenaphthylene ring, and fluorine ring; more preferably, they are benzene ring, naphthalene ring, and fluorine ring; most preferably benzene ring.

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

When any one of Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ is a benzene ring which may have a substituent, it is preferable that at least one benzene ring is bonded to an adjacent structure at the ortho or meta position, and more preferably at least one benzene ring is bonded to an adjacent structure at the ortho or meta position. Rings are structurally bonded by meta positions and adjacent ones.

環、三

環、咪唑環、

唑環、噻唑環、苯并噻唑環、苯并

唑環、苯并咪唑環、喹啉環、異喹啉環、喹

啉環、喹唑啉環、

啶環、啡啶環、咔唑環、二苯并呋喃環、二苯并噻吩環；更佳為吡啶環、嘧啶環、三

環、咔唑環、二苯并呋喃環、二苯并噻吩環。 When any one of Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ is an aromatic heterocyclic structure that may have a substituent, the aromatic heterocyclic structure preferably contains any one of a nitrogen atom, an oxygen atom, or a sulfur atom. An aromatic heterocyclic ring having 3 to 30 carbon atoms as a heteroatom; specific examples include pyridine ring, pyrimidine ring, pyridine ring,

ring, three

ring, imidazole ring,

Azole ring, thiazole ring, benzothiazole ring, benzo

Azole ring, benzimidazole ring, quinoline ring, isoquinoline ring, quinoline

pholine ring, quinazoline ring,

pyridine ring, phenanthridine ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring; more preferably, pyridine ring, pyrimidine ring, trisulfide ring

Ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring.

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

When Ar ² is an aliphatic hydrocarbon structure that may have a substituent, it is an aliphatic hydrocarbon structure having a linear, branched chain or cyclic structure, preferably having a carbon number of 1 or more and 24 or less, more preferably a carbon number The number of carbon atoms is 1 or more and 12 or less, and more preferably, the carbon number is 1 or more and 8 or less.

i1 represents an integer from 0 to 12, preferably 1 to 12, more preferably 1 to 8, and further preferably 1 to 6. By setting this range, it is expected that solubility and charge transport properties will be improved.

i3 preferably represents an integer from 0 to 5, more preferably 0 to 2, and even more preferably 0 or 1.

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

k1 and k2 preferably represent an integer from 0 to 3, preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1.

The substituents that Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ may have can be selected arbitrarily. Preferably, one or a plurality of substituents are selected from the above-mentioned substituent group Z2. Preferably, if there is the above-mentioned substituent group Z2, more Preferred ones are hydrogen atoms, alkyl groups, and aryl groups, particularly preferred ones are hydrogen atoms and aryl groups, and most preferred ones are unsubstituted (hydrogen atoms).

Among the structures represented by the above formula (202), a material having the following structure is preferred. It has a structure in which a benzene ring is connected to a group. That is, Ar ²⁰¹ is a benzene ring structure, i1 is 1 to 6, and at least one of the benzene rings is bonded to an adjacent structure in the ortho or meta position. By having this structure, it is expected that the solubility will be improved and the charge transport properties will be improved.

Ring A1 or ring A2 has a structure of an aromatic hydrocarbon group or an aromatic heterocyclic group bonded to an alkyl group or an aryl group, that is, Ar ²⁰¹ is an aromatic hydrocarbon structure or an aromatic heterocyclic structure, and i1 is 1~ 6. Ar ²⁰² is an aliphatic hydrocarbon structure, i2 is 1 to 12, preferably 3 to 8, Ar ²⁰³ is a benzene ring structure, and i3 is 0 or 1. Ar ²⁰¹ preferably has the above aromatic hydrocarbon structure, more preferably has a structure in which 1 to 5 benzene rings are connected, and still more preferably has 1 benzene ring. By having this structure, it is expected that the solubility will be improved and the charge transport properties will be improved.

A structure in which a dendrimer is bonded to ring A1 or ring A2. For example, Ar ²⁰¹ and Ar ²⁰² are benzene ring structures, Ar ²⁰³ is a biphenyl or terphenyl structure, i1 and i2 are 1 to 6, i3 is 2, and j is 2. By having this structure, it is expected that the solubility will be improved and the charge transport properties will be improved.

B ²⁰¹ -L ²⁰⁰ -B ²⁰² represent anionic bidentate ligands. B ²⁰¹ and B ²⁰² independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may also be atoms constituting a ring. L ²⁰⁰ represents a single bond, or an atomic group that together with B ²⁰¹ and B ²⁰² forms a bidentate ligand. When plural numbers B ²⁰¹ -L ²⁰⁰ -B ²⁰² exist, they may be the same or different.

Among the structures shown in B ²⁰¹ -L ²⁰⁰ -B ²⁰² , the structure shown in the following formula (203) or (204) is preferred.

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

[Chemical 65]

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

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

[Chemical 66]

[Chemical 67]

[Chemical 68]

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

In formula (205), M ² represents a metal, and T represents a carbon atom or a nitrogen atom. R ⁹² ~ R ⁹⁵ each independently represent a substituent. Among them, when T is a nitrogen atom, R ⁹⁴ and R ⁹⁵ are absent.

In formula (205), M ² represents metal. As a specific example, the metal selected from Groups 7 to 11 of the periodic table can be exemplified by the above-mentioned metals. Among them, preferred examples include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum or gold, and particularly preferred examples include divalent metals such as platinum and palladium.

In formula (205), R ⁹² and R ⁹³ independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, a cyano group, an amine group, a hydroxyl group, an alkoxycarbonyl group, a carboxyl group, and an alkoxy group. group, alkylamino group, aralkylamine group, haloalkyl group, hydroxyl group, aryloxy group, aromatic hydrocarbon group or aromatic heterocyclic group.

In addition, when T is a carbon atom, R ⁹⁴ and R ⁹⁵ each independently represent the substituent shown as the same example as R ⁹² and R ⁹³ . In addition, when T is a nitrogen atom, R ⁹⁴ or R ⁹⁵ directly bonded to T does not exist. Moreover, R ⁹² to R ⁹⁵ may further have a substituent. As the substituent, the above-mentioned substituent may be used. Furthermore, among R ⁹² to R ⁹⁵ , any two or more groups may be connected to each other to form a ring.

The molecular weight of the phosphorescent material is preferably 5,000 or less, more preferably 4,000 or less, and particularly preferably 3,000 or less. In addition, the molecular weight of the phosphorescent material is usually 800 or more, preferably 1,000 or more, and more preferably 1,200 or more. By having this molecular weight range, the phosphorescent light-emitting materials are uniformly mixed with the charge transport material without agglomeration, and it is considered that a light-emitting layer with high luminous efficiency can be obtained.

Due to the high Tg, melting point, decomposition temperature, etc., the phosphorescent luminescent material and the formed luminescent layer have superior heat resistance, and are less prone to film quality degradation or material heating due to gas generation, recrystallization, molecular migration, etc. In view of the increase in impurity concentration associated with decomposition, etc., the molecular weight of the phosphorescent light-emitting material is preferably larger. On the other hand, from the viewpoint of easy purification of the organic compound, the molecular weight of the phosphorescent light-emitting material is preferably smaller.

In an organic electroluminescent element using a polymer as a charge transport 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 host material is preferably The following materials.

<Host material (compound)>

As the host material (compound) of the light-emitting layer, those having the above formula (CzP) or formula (CzP-2) can be used. Furthermore, when the luminescent material or other host material has the formula (CzP), a host material that does not have the formula (CzP) or the formula (CzP-2) can also be used appropriately. At this time, the skeleton, molecular weight, substituents, etc. are the same as above.

In an organic electroluminescent element in which a polymer is used as a charge transport material for forming at least one of a hole injection layer and a hole transport layer, and the light-emitting layer is a fluorescent light-emitting material, the following blue material is preferred: Fluorescent luminescent materials.

The luminescent material for the blue fluorescent luminescent layer is not particularly limited, but is preferably a compound represented by the following formula (211).

In the above formula (211), Ar ²⁴¹ represents an aromatic hydrocarbon condensed ring structure that may have a substituent, and Ar ²⁴² and Ar ²⁴³ independently represent an alkyl group, an aromatic hydrocarbon group, or these bonded structures that may have a substituent. base.

n41 is 1~4.

、苝等。 Ar ²⁴¹ preferably represents a condensed ring structure of an aromatic hydrocarbon having 10 to 30 carbon atoms. Specific examples of the structure include naphthalene, ethanonaphthalene, anthracene, phenanthrene, 1,2-benzoacenaphthylene, pyrene, and pyrene. Tetraphenyl,

, perylene, etc.

、苝。進而更 佳為碳數16~18之芳香族烴縮合環構造，具體構造可舉例如1,2-苯并苊、芘、

。 More preferably, it is an aromatic hydrocarbon condensed ring structure having 12 to 20 carbon atoms. Specific structures include, for example, ethane naphthalene, fluorine, anthracene, phenanthrene, 1,2-benzoacenaphthene, pyrene, pyrene, tetraphenyl,

, perylene. More preferably, it is an aromatic hydrocarbon condensed ring structure with 16 to 18 carbon atoms. Specific examples of the structure include 1,2-benzoacenaphthene, pyrene,

.

n41 is 1~4, better 1~3, better 1~2, best 2.

The substituent that 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 even more preferably a substituent group Z2. Preferred groups are hydrocarbyl groups.

In an organic electroluminescent element using a polymer as a charge transport material for forming at least one of a hole injection layer and a hole transport layer, when the light emitting layer is a phosphorescent light emitting material, the host material is preferably as follows: Material.

The host material for the blue fluorescent light-emitting layer is not particularly limited, but is preferably a compound represented by the following formula (212).

[In the above formula (212), R ²⁴¹ and R ²⁴² each independently have the structure shown in the formula (213), R ²⁴³ represents a substituent, and when R ²⁴³ is a plural number, it can be the same or different, and n43 is 0 to 8. ]

Ar ²⁴⁴ and Ar ²⁴⁵ independently represent an aromatic hydrocarbon structure that may have a substituent, or a heteroaromatic ring structure that may also have a substituent; when Ar ²⁴⁴ and Ar ²⁴⁵ exist in plural, they may be the same or different; n44 is 1~5, n45 is 0~5.

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

Ar ²⁴⁵ is preferably an aromatic hydrocarbon structure belonging to a monocyclic or condensed ring having 6 to 30 carbon atoms, which may have a substituent, or an aromatic heterocyclic ring belonging to a condensed ring having 6 to 30 carbon atoms, which may have a substituent. Structure; more preferably, it may be an aromatic hydrocarbon structure that has a substituent and belongs to a monocyclic or condensed ring with 6 to 12 carbon atoms, or it may have an aromatic heterocyclic structure that has a substituent and belongs to a fused ring with 12 carbon atoms.

n44 is preferably 1 to 3, more preferably 1 or 2.

n45 is preferably 0~3, more preferably 0~2.

The substituent that R ²⁴³ , Ar ²⁴⁴ , and Ar ²⁴⁵ may have is 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 Preferable substituent groups Z are hydrocarbon groups.

The molecular weight of the luminescent material for the blue fluorescent luminescent 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 more, and more preferably 400 or more.

[Formation of light-emitting layer by wet film formation method]

The formation method of the luminescent layer can be a vacuum evaporation method or a wet film formation method. From the viewpoint of superior film formation, the wet film formation method is preferred, and the spin coating method and the inkjet method are more preferred. . Especially when using a composition for an organic electroluminescent element to form a hole injection layer or a hole transport layer that serves as a lower layer of the light-emitting layer, it is easier to perform lamination using a wet film-forming method, so it is preferable to use a wet film-forming method. . When the light-emitting layer is formed by a wet film-forming method, it is usually the same as the above-mentioned wet film-forming method for forming the hole injection layer. Instead of the hole injection layer forming composition, a material that can be dissolved to form the light-emitting layer is used. The composition for forming a light-emitting layer is prepared by mixing a solvent (a solvent for the light-emitting layer).

Examples of the solvent include, in addition to the ether solvents, ester solvents, aromatic hydrocarbon solvents, and amide solvents listed for the formation of the hole injection layer, alkane solvents, halogenated aromatic hydrocarbon solvents, Aliphatic alcohol solvents, alicyclic alcohol solvents, aliphatic ketone solvents, alicyclic ketone solvents, etc. Specific examples of the solvent are listed below, but they are not limited to these as long as the effects of the present invention are not impaired.

Examples include 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, phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethyl Aromatic ether solvents such as anisole and diphenyl ether; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-benzoate Aromatic ester solvents such as butyl ester; toluene, xylene, mesitylene, cyclohexylbenzene, tetralin, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4 -Aromatic hydrocarbon solvents such as diisopropylbenzene, cyclohexylbenzene, and methylnaphthalene; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; n-decyl Alkane solvents such as alkane, cyclohexane, ethylcyclohexane, decalin, and dicyclohexane; halogenated aromatic hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene; aliphatic solvents such as butanol and hexanol Alcohol-based solvents; alicyclic alcohol-based solvents such as cyclohexanol and cyclooctanol; alicyclic ketone-based solvents such as methyl ethyl ketone and dibutanone; alicyclic ketones such as cyclohexanone, cyclooctanone, and fentanone Department of solvents, etc. Among these, alkane-based solvents and aromatic hydrocarbon-based solvents are particularly preferred.

[Hole blocking layer]

A hole blocking layer 6 may be provided between the light emitting layer 5 and the electron injection layer 8 described below. The hole blocking layer 6 is a layer laminated on the light-emitting layer 5 so as to be in contact with the interface on the cathode 9 side of the light-emitting layer 5 .

The hole blocking layer 6 has the function of preventing holes moving from the anode 2 from reaching the cathode 9 and transporting the electrons injected from the cathode 9 to the direction of the light-emitting layer 5 with high efficiency. Physical properties required for the material constituting the hole blocking layer 6 include, for example, high electron mobility and low hole mobility, a large energy gap (difference between HOMO and LUMO), and a high excited triplet energy level (T1). .

Examples of hole blocking layer materials that satisfy such conditions include bis(2-methyl-8-quinolyl)(phenol)aluminum, bis(2-methyl-8-quinolyl)(triphenyl) Bis(2-methyl-8-quinolyl)aluminum-μ-side oxy-bis-(2-methyl-8-quinolyl)aluminum Metal complexes such as dinuclear metal complexes; styrene-based compounds such as stilbene biphenyl derivatives (Japanese Patent Application Publication No. 11-242996); 3-(4-biphenyl)-4-phenyl-5 -(4- Triazole derivatives such as 3-butylphenyl)-1,2,4-triazole (Japanese Patent Application Laid-Open No. 7-41759); phenanthroline derivatives such as bathocuproline (Japanese Patent Application Publication No. 10-79297 Gazette), etc. In addition, compounds having at least one pyridine ring substituted at positions 2, 4, and 6 described in International Publication No. 2005/022962 are also preferred hole blocking layer materials.

The formation method of the hole blocking layer 6 is not limited. Therefore, it can be formed by wet film forming method, evaporation method, or other methods.

The film thickness of the hole blocking layer 6 is arbitrary as long as the effect of the present invention is not significantly impaired. It is usually 0.3nm or more, preferably 0.5nm or more, and usually 100nm or less, preferably 50nm or less.

[Electron transport layer]

The electron transport layer 7 is disposed 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 using a compound that can efficiently transport electrons injected from the cathode 9 toward the light-emitting layer 5 between electrodes to which an electric field is applied. The electron transport compound used as the electron transport layer 7 must be a compound that has high electron injection efficiency from the cathode 9 or the electron injection layer 8, has high electron mobility, and can efficiently transport the injected electrons.

二唑衍生物、二苯乙烯基聯苯衍生物、矽諾魯衍生物、3-羥基黃酮金屬錯合體、5-羥基黃酮金屬錯合體、苯并

唑金屬錯合體、苯并噻唑金屬錯合體、參苯并咪唑苯(美國專利第5645948號說明書)；喹

啉化合物(日本專利特開平6- 207169號公報)；菲咯啉衍生物(日本專利特開平5-331459號公報)；2-第三丁基-9,10-N,N’-二氰基蒽醌二亞胺、n型氫化非晶質碳化矽、n型硫化鋅、n型硒化鋅等。 Specific examples of the electron transport compound used in the electron transport layer include metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Application Publication No. Sho 59-194393); 10-hydroxybenzo h] Metal complex of quinoline,

Oxidazole derivatives, distyrylbiphenyl derivatives, silanol derivatives, 3-hydroxyflavone metal complex, 5-hydroxyflavone metal complex, benzo

Azole metal complex, benzothiazole metal complex, ginseng benzimidazolbenzene (US Patent No. 5645948 specification); quinine

Phenoline compounds (Japanese Patent Laid-Open No. 6-207169); phenanthroline derivatives (Japanese Patent Laid-Open No. 5-331459); 2-tert-butyl-9,10-N,N'-dicyano Anthraquinone diimide, n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type zinc selenide, etc.

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

The electron transport layer 7 is formed by being laminated on the hole blocking layer 6 using a wet film forming method or a vacuum evaporation method as described above. Vacuum evaporation method is usually used.

[Electron injection layer]

The electron injection layer 8 functions to efficiently inject 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, the material forming the electron injection layer 8 is preferably a metal with a low work function. For example, alkali metals such as sodium and cesium; alkaline earth metals such as barium and calcium; and the like can be used. The film thickness is generally preferably from 0.1 nm to 5 nm.

Furthermore, organic electron transport materials represented by nitrogen-containing heterocyclic compounds such as hexaphenanthroline or metal complexes such as aluminum complexes of 8-hydroxyquinoline are doped with sodium, potassium, cesium, lithium, rubidium, etc. Alkali metals (described in Japanese Patent Application Laid-Open No. 10-270171, Japanese Patent Application Publication No. 2002-100478, Japanese Patent Application Publication No. 2002-100482, etc.) are preferred because they can achieve electron injection, improved transport properties, and excellent film quality.

The film thickness of the electron injection layer 8 is usually 5 nm or more, preferably 10 nm or more, and is usually 200 nm or less, preferably 100 nm or less.

The electron injection layer 8 is formed by laminating the light emitting layer 5 or the hole blocking layer 6 or the electron transport layer 7 above it by using a wet film forming method or a vacuum evaporation method.

The details in the case of the wet film formation method are the same as in the case of the aforementioned light-emitting layer.

[cathode]

The cathode 9 functions to inject electrons into the layer on the side of the light-emitting layer 5 (electron injection layer, light-emitting layer, etc.).

As the material of the cathode 9, the materials used for the above-mentioned anode 2 can be used. However, on the premise of efficient electron injection, it is better to use a metal with a low work function. For example, tin, magnesium, indium, calcium, aluminum can be used. , silver and other metals or their alloys, etc. Specific examples include low work function alloy electrodes such as magnesium-silver alloys, magnesium-indium alloys, and aluminum-lithium alloys.

From the perspective of the stability of the device, it is better to laminate a metal layer with a high work function and stable to the atmosphere on the cathode to protect the cathode made of a metal with a low work function. Examples of metals to be laminated include aluminum, silver, copper, nickel, chromium, gold, platinum and other metals.

The film thickness of the cathode is usually the same as that of the anode.

[Other layers]

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

[Other component composition]

The organic electroluminescent element of the present invention can also have a structure opposite to the above description, that is, a cathode, an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer, a hole transport layer, and an electron layer are sequentially stacked on a substrate. Hole injection layer, anode.

When an organic electroluminescent element is applied to an organic electroluminescent device, it can be used as a single organic electroluminescent element, or a plurality of organic electroluminescent elements can be arranged in an array. It can be used in a structure in which the anode and the cathode are arranged in an X-Y matrix.

<Organic EL display device>

An organic EL display device (organic electroluminescence element display device) according to another embodiment of the present invention includes the above-mentioned organic electroluminescence element. There are no special restrictions on the type or structure of the organic EL display device, and organic electroluminescent elements can be used to assemble according to common methods.

For example, an organic EL display device can be formed according to the method described in "Organic EL Display" (Ohm Co., Ltd., published on August 20, 2016, written by Seishi Toto, Chihaya Adachi, and Hideyuki Murata).

<Organic EL lighting>

An organic EL lighting (organic electroluminescent element lighting) according to another embodiment of the present invention includes the above-mentioned organic electroluminescent element. There are no special restrictions on the type and structure of organic EL lighting, and organic electroluminescent components can be used to assemble according to common methods.

[Example]

Hereinafter, the present invention will be described in more detail using exemplary embodiments. 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]

[Chemical 73]

Under nitrogen flow, fill compound 1 (10.3g, 36.58mmol), compound 2 (5.2g, 24.39mmol), potassium phosphate (13.0g, 60.98mmol), toluene (60ml), ethanol (30ml) and water (30ml). Put it in a flask, completely replace the system with nitrogen and heat it to 60°C.

Bis(triphenylphosphine)palladium(II) dichloride (0.086g, 0.122mmol) was added, and the mixture was stirred at 60°C for 3 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified over activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 85/15) to obtain compound 3 (4.4 g, yield 55.8%).

[Synthesis of compound 4]

Under nitrogen flow, add 50 ml of dimethyl styrene, compound 3 (4.4 g, 13.6 mmol), bis(bipinacol) borate (4.2 g, 16.34 mmol), and potassium acetate (4.0) into a 200 ml flask. g, 40.83mmol), stir at 60°C for 30 minutes. Thereafter, 1,1'-bis(diphenylphosphino)ferrocene-dichloropalladium(II)-dichloromethane [PdCl ₂ (dppf)CH ₂ Cl ₂ ] (0.56g, 0.68mmol) was added, React at 85°C for 4 hours.

Pure water was dropped and the reaction solution was filtered under reduced pressure. The filtrate was extracted with toluene, dried with anhydrous magnesium sulfate and crudely refined with activated clay. The crude product was purified by column chromatography (developing solution: hexane/ethyl acetate = 90/10) to obtain compound 4 (5.0 g, yield 98%).

[Synthesis of compound 6]

Under nitrogen flow, fill compound 4 (5.0g, 13.5mmol), compound 5 (6.48g, 14.46mmol), potassium phosphate (8.8g, 41.31mmol), toluene (40ml), ethanol (20ml) and water (20ml). Put it in a flask, completely replace the system with nitrogen and heat it to 60°C.

Bis(triphenylphosphine)palladium(II) dichloride (0.048g, 0.069mmol) was added, and the mixture was stirred at 60°C for 2 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified over activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 85/15) to obtain compound 6 (6.3 g, yield 81.0%).

[Synthesis of compound 7]

Combine 3-nitrophenylboronic acid (30.1g, 180.3mmol), 1-bromo-3-iodobenzene (56.0g, 197.94mmol), potassium phosphate (95.5g, 450mmol), toluene (350ml), and ethanol. Fill the flask with alcohol (150ml) and water (225ml), fully replace the system with nitrogen and heat it to 60°C. Add 4(triphenylphosphine)palladium(0) (5.2g, 4.5mmol) and stir at 85°C for 5 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified over activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 3/1) to obtain compound 7 (20.3 g, yield 41%).

[Synthesis of compound 8]

烷、化合物7(20.3g、72.99mmol)、雙(聯頻哪醇)硼酸酯(22.2g、89.6mmol)、醋酸鉀(35.9g、365.8mmol)，依60℃攪拌30分鐘。其後，加入1,1’-雙(二苯基膦基)二茂鐵-二氯鈀(II)-二氯甲烷[PdCl₂(dppf)CH₂Cl₂](1.8g、2.19mmol)，依85℃反應3.5小時。 Under nitrogen flow, add 260 ml of 1,4-bis to a 500 ml flask.

Alkane, compound 7 (20.3g, 72.99mmol), bis(pinopinacol) borate (22.2g, 89.6mmol), potassium acetate (35.9g, 365.8mmol), stir at 60°C for 30 minutes. Thereafter, 1,1'-bis(diphenylphosphino)ferrocene-dichloropalladium(II)-dichloromethane [PdCl ₂ (dppf)CH ₂ Cl ₂ ] (1.8g, 2.19mmol) was added, React at 85°C for 3.5 hours.

Pure water was dropped and the reaction solution was filtered under reduced pressure. The filtrate was extracted with toluene, dried with anhydrous magnesium sulfate and crudely refined with activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 1/1) to obtain compound 8 (19.1 g, yield 84%).

[Synthesis of compound 9]

[Chemical 78]

Fill a flask with compound 6 (3.6g, 6.4mmol), compound 8 (2.3g, 7.03mmol), potassium phosphate (4.1g, 19.21mmol), toluene (40ml), ethanol (20ml) and water (10ml). The system was fully replaced with nitrogen and heated to 60°C. Add 4(triphenylphosphine)palladium(0) (0.2g, 0.19mmol) and stir at 85°C for 3.5 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified over activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 1/1) to obtain compound 9 (3.5 g, yield 80.2%).

[Synthesis of compound 10]

Under nitrogen flow, add 350 ml of tetrahydrofuran, 20 ml of ethanol, compound 9 (3.5 g, 5.13 mmol), and palladium/carbon (10%, about 55% moisture, 0.4 g) into a 500 ml flask, and stir at 50°C for 10 minute. Thereafter, hydrazine monohydrate (1.8 g) was dropped and the reaction was carried out at the same temperature for 3 hours.

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

[Synthesis of compound 12]

Under nitrogen flow, combine compound 11 (5.0g, 9.27mmol), phenylboronic acid (1.2g, 9.46mmol), potassium phosphate (5.9g, 27.8mmol), toluene (30ml), ethanol (15ml) and water (14ml). Fill the flask, fully replace the system with nitrogen and heat it to 65°C.

Bis(triphenylphosphine)palladium(II) dichloride (0.033g, 0.046mmol) was added, and the mixture was stirred at 65°C for 3 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified over activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 85/15) to obtain compound 12 (4.1 g, yield 90.3%).

[Synthesis of compound 13]

Under nitrogen flow, add 35 ml of dimethyl styrene, compound 12 (4.1 g, 8.38 mmol), bis(bipinacol) borate (3.2 g, 12.6 mmol), and potassium acetate (2.5 g, 25.1 mmol), stir at 60°C for 30 minutes. Thereafter, 1,1'-bis(diphenylphosphino)ferrocene-dichloropalladium(II)-dichloromethane [PdCl ₂ (dppf)CH ₂ Cl ₂ ] (0.34g, 0.42mmol) was added, React at 85°C for 3 hours.

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

[Synthesis of compound 14]

Under nitrogen flow, compound 13 (4.5g, 8.39mmol), 3-bromo-9-(4-iodophenyl)-9H-carbazole (3.95g, 8.81mmol), potassium phosphate (4.5g, 20.98mmol) , toluene (30ml), ethanol (10ml) and water (10.5ml) were filled into the flask, the system was fully replaced with nitrogen and heated to 65°C.

Bis(triphenylphosphine)palladium(II) dichloride (0.030g, 0.042mmol) was added, and the mixture was stirred at 65°C for 3 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified over activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 75/25) to obtain compound 14 (2.2 g, yield 35.9%).

[Synthesis of compound 15]

[Chemical 83]

Next, compound 14 (2.2g, 3.01mmol), compound 8 (1.2g, 3.61mmol), potassium phosphate (1.6g, 7.5mmol), toluene (10ml), ethanol (5ml) and water (4ml) were filled in flask, replace the system with sufficient nitrogen and heat it to 60°C. Quadrat(triphenylphosphine)palladium(0) (0.1g, 0.09mmol) was added, and the mixture was stirred at 85°C for 4 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified over activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 50/50) to obtain compound 15 (1.75 g, yield 68.5%).

[Synthesis of compound 16]

Under nitrogen flow, add 20 ml of tetrahydrofuran, 10 ml of ethanol, compound 15 (1.75 g, 2.06 mmol), and palladium/carbon (10%, about 55% moisture, 0.18g) into a 100 ml flask, and stir at 52°C. 10 minutes. Thereafter, hydrazine monohydrate (0.7g) was added, and the reaction was carried out at the same temperature for 8 hours.

The reaction solution was filtered under reduced pressure through water-wet diatomaceous earth, and the filtrate was concentrated and purified by recrystallization from ethanol to obtain compound 16 (0.9 g, yield 53.3%).

[Synthesis of compound 17]

Under nitrogen flow, add 4-bromophenol (11.6g, 67.21mmol), 4,4'-difluorodiphenylketone (6.67g, 30.55mmol), and 100ml of N,N'-dimethyl in a 300ml flask. Formamide and potassium acetate (16.9g, 122.29mmol) were stirred at 140°C for 3 hours. Thereafter, the reaction solution at 40°C was added to 500 ml of pure water, stirred for 10 minutes and filtered under reduced pressure. The filtrate was suspended and washed in the order of ethanol and methanol, filtered, and dried to obtain compound 17 (12.6 g, Yield 78.6%).

[Synthesis of compound 19]

In a 1L flask, add 270ml of toluene, 135ml of ethanol, compound 18 (20.0g, 44.8mmol), 50.72g of 5-bromo-2-iodotoluene (179.3mmol), and potassium phosphate aqueous solution (2M, that is, 2 mol/L concentration )191ml, and the solution was degassed under vacuum and replaced with nitrogen. Heat under nitrogen flow and stir for 30 minutes. Thereafter, 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, treated with MgSO ₄ and activated clay, the toluene solution was heated to reflux, the insoluble matter was filtered, and recrystallized to obtain compound 19 as a colorless solid (yield 14.2g, yield 60.2%).

[Synthesis of compound 20]

Compound 20 was synthesized by the same method as the synthesis of compound 19 by replacing 5-bromo-2-iodotoluene with 1-bromo-4-iodobenzene.

[Synthesis of compound 22]

Under nitrogen flow, compound 21 (17.8g, 33.0mmol), 4-(9H-carbazol-9-yl)phenylboronic acid (9.5g, 33.0mmol), potassium phosphate (21.0g, 99.0mmol), toluene ( 100ml), ethanol (50ml) and water (50ml) were filled into the flask, the system was fully replaced with nitrogen and heated to 65°C.

Bis(triphenylphosphine)palladium(II) dichloride (0.12g, 0.17mmol) was added, and the mixture was stirred at 65°C for 3 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified over activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 80/20) to obtain compound 22 (18.4 g, yield 85.2%).

[Synthesis of compound 23]

Under nitrogen flow, add 100 ml of dimethyl styrene, compound 22 (18.2 g, 27.8 mmol), bis(bipinacol) borate (10.6 g, 41.7 mmol), and potassium acetate (8.2) into a 300 ml flask. g, 83.4mmol), stir at 60°C for 30 minutes. Thereafter, 1,1'-bis(diphenylphosphino)ferrocene-dichloropalladium(II)-dichloromethane [PdCl ₂ (dppf)CH ₂ Cl ₂ ] (2.3g, 2.78mmol) was added, React at 85°C for 4.5 hours.

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

[Synthesis of compound 24]

Compound 23 (5.3g, 7.49mmol), 3-bromo-9-(4-iodophenyl)-9H-carbazole (3.3g, 7.34mmol), potassium phosphate (4.2g, 19.82mmol), toluene (30ml ), ethanol (15ml) and water (10ml) were filled into the flask, the system was fully replaced with nitrogen and heated to 65°C.

Bis(triphenylphosphine)palladium(II) dichloride (0.052g, 0.073mmol) was added, and the mixture was stirred at 65°C for 3 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified over activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 75/25) to obtain compound 24 (4.8 g, yield 76.0%).

[Synthesis of compound 26]

Next, compound 24 (4.6g, 5.13mmol), compound 25 (2.2g, 6.67mmol), potassium phosphate (2.1g, 15.4mmol), toluene (24ml), ethanol (8ml), and water (8ml) were filled in flask, replace the system with sufficient nitrogen and heat it to 60°C. Add 4(triphenylphosphine)palladium(0) (0.18g, 0.154mmol) and stir at 85°C for 3.5 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified over activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 60/40) to obtain compound 26' (3.9 g, yield 74.9%).

[Chemical 92]

Under nitrogen flow, add 40 ml of tetrahydrofuran, 40 ml of ethanol, compound 26' (3.9 g, 3.84 mmol), and palladium/carbon (10%, about 55% water-wet, 0.29g) into a 300 ml flask at 52°C. Stir for 10 minutes. Thereafter, hydrazine monohydrate (1.3g) was added, and the reaction was carried out at the same temperature for 5 hours.

The reaction solution was filtered under reduced pressure through water-wet diatomaceous earth, and the filtrate was concentrated and purified by recrystallization from ethanol to obtain compound 26 (3.3 g, yield 87.2%).

[Synthesis of compound 27]

Next, compound 3-bromo-3'-iodo-1,1-biphenyl (29.4g, 81.9mmol), commercially available compound 26 (20.0g, 81.9mmol), potassium phosphate (2M aqueous solution, 103g, 205mmol) Fill the flask with toluene (200ml) and ethanol (100ml), fully replace the system with nitrogen and heat it to 60°C. Quadrat(triphenylphosphine)palladium(0) (2.37g, 2.05mmol) was added, and the mixture was stirred at 85°C for 6 hours. Add water to the reaction solution and extract with toluene. Pour the organic layer into anhydrous sulfur The magnesium acid is dried and roughly refined with activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 950/50) to obtain compound 27 (23.1 g, yield 81%).

[Synthesis of compound 28]

Fill compound 27 (23.1g, 66.1mmol), commercially available 3-aminophenylboronic acid (9.8g, 63.0mmol), potassium phosphate (2M aqueous solution, 79g, 158mmol), toluene (160ml), and ethanol (80ml). Put it in a flask, fully replace the system with nitrogen and heat it to 60°C. Add 4(triphenylphosphine)palladium(0) (1.85g, 1.6mmol) and stir at 85°C for 4 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified over activated clay. The crude product was purified by column chromatography (developing solution: hexane/ethyl acetate = 8/2) to obtain compound 28 (22.2 g, yield 92.9%).

[Synthesis of compound 30]

Compound 29 was used instead of compound 26, and compound 30 was synthesized according to the same method as the synthesis of compound 27.

[Synthesis of compound 31]

Compound 30 was used instead of compound 27, and compound 31 was synthesized according to the same method as the synthesis of compound 28.

[Synthesis of compound 32]

硼烷(4.5g、8.39mmol)、3-溴-9-(4-碘苯基)-9H-咔唑(3.95g、8.81mmol)、磷酸鉀(4.5g、20.98mmol)、甲苯(30ml)、乙醇(10ml)及水(10.5ml)填裝於燒瓶，將系統內充分以氮取代並加溫至65℃。 Under a stream of nitrogen, commercially available 2-(9,9-dimethyl-9H-quin-2-yl)-4,4,5,5-tetramethyl-1,3,2-di

Borane (4.5g, 8.39mmol), 3-bromo-9-(4-iodophenyl)-9H-carbazole (3.95g, 8.81mmol), potassium phosphate (4.5g, 20.98mmol), toluene (30ml) , ethanol (10ml) and water (10.5ml) were filled into the flask, the system was fully replaced with nitrogen and heated to 65°C.

Bis(triphenylphosphine)palladium(II) dichloride (0.030g, 0.042mmol) was added, and the mixture was stirred at 65°C for 3 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried over anhydrous magnesium sulfate And use activated clay for rough refining. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 75/25) to obtain compound 32 (2.2 g, yield 35.9%).

[Synthesis of compound 33]

Next, compound 32 (2.2g, 3.01mmol), compound 8 (1.2g, 3.61mmol), potassium phosphate (1.6g, 7.5mmol), toluene (10ml), ethanol (5ml), and water (4ml) were filled in flask, fully replace the system with nitrogen and heat it to 60°C. Quadrat(triphenylphosphine)palladium(0) (0.1g, 0.09mmol) was added, and the mixture was stirred at 85°C for 4 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified over activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 50/50) to obtain compound 33 (1.75 g, yield 68.5%).

[Synthesis of compound 34]

[Chemical 99]

Under nitrogen flow, add 20 ml of tetrahydrofuran, 10 ml of ethanol, compound 33 (1.75 g, 2.06 mmol), and palladium/carbon (10%, about 55% moisture, 0.18g) into a 100 ml flask, and stir at 52°C. 10 minutes. Thereafter, hydrazine monohydrate (0.7g) was added, and the reaction was carried out at the same temperature for 8 hours.

The reaction solution was filtered under reduced pressure through water-wet diatomaceous earth, and the filtrate was concentrated and purified by recrystallization from ethanol to obtain compound 34 (0.9 g, yield 53.3%).

[Synthesis of compound 35]

3-Bromo-9-phenyl-9H-carbazole (3.6g, 6.4mmol), compound 8 (2.3g, 7.03mmol), potassium phosphate (4.1g, 19.21mmol), toluene (40ml), ethanol (20ml) ) and water (10 ml) were filled into the flask, the system was fully replaced with nitrogen and heated to 60°C. Add 4(triphenylphosphine)palladium(0) (0.2g, 0.19mmol) and stir at 85°C for 3.5 hours. Add water to the reaction solution and extract with toluene. The organic layer was dried with anhydrous magnesium sulfate and refined with activated clay. system. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 1/1) to obtain compound 35 (3.5 g, yield 80.2%).

[Synthesis of compound 36]

Under nitrogen flow, add 350 ml of tetrahydrofuran, 20 ml of ethanol, compound 35 (3.5 g, 5.13 mmol), and palladium/carbon (10%, about 55% moisture, 0.4 g) into a 500 ml flask, and stir at 50°C. 10 minutes. Thereafter, hydrazine monohydrate (1.8g) was added, and the reaction was carried out at the same temperature for 3 hours.

The reaction solution was filtered under reduced pressure through water-wet diatomaceous earth, and the filtrate was concentrated, washed with methanol and refined to obtain compound 36 (3.0 g, yield 91%).

<Example 1>

[Synthesis of Polymer 1]

According to the following reaction formula, polymer 1 is synthesized.

[Chemical 102]

Filling compound 19 (1.8g, 3.4mmol), 2-amino-9,9-dihexylfluoride (1.89g, 5.4mmol), compound 10 (0.883g, 1.4mmol), sodium tert-butoxide (2.51g , 26.1mmol) and toluene (32g, 37ml), fully replace the system with nitrogen and heat it to 60°C (solution A1).

To a solution of ginseng (dibenzylideneacetone) dipalladium complex (0.062g, 0.07mmol) in 11 ml of toluene, add [4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos) (0.14g, 0.5mmol), heated to 60°C (solution B1).

In a nitrogen flow, solution B1 was added to solution A1, and a heating and reflux reaction was performed for 1.0 hours. After confirming that compound 19 disappeared, compound 20 (1.49 g, 2.95 mmol) was added. After heating and refluxing for 2 hours, benzene bromide (0.66 g, 4.2 mmol) was added, and heating and refluxing reaction was performed for 2 hours. The reaction solution was allowed to cool, 73 ml of toluene was added, and the mixture was dripped into an ethanol/water (500 ml/90 ml) solution to obtain a blocked crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and Reprecipitate with ammonia and ethanol. The filtered polymer was purified by column chromatography to obtain the target polymer 1 (2.2 g). The molecular weight of the obtained polymer 1 is 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]

Polymer 2 was synthesized according to the following reaction formula.

Filling compound 19 (1.8g, 3.4mmol), 2-amino-9,9-dihexylfluoride (1.3g, 3.7mmol), compound 10 (1.99g, 3.0mmol), sodium tert-butoxide (2.51g , 26.1mmol) and toluene (32g, 37ml), fully replace the system with nitrogen and heat it to 60°C (solution A2).

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

In a nitrogen flow, solution B2 was added to solution A2, and a heating and reflux reaction was performed for 1.0 hours. After confirming that compound 19 disappeared, compound 20 (1.51 g, 2.99 mmol) was added. After heating and refluxing for 2 hours, benzene bromide (0.66 g, 4.2 mmol) was added, and heating and refluxing reaction was performed for 2 hours. The reaction solution was allowed to cool, 73 ml of toluene was added, and the mixture was dripped into an ethanol/water (500 ml/90 ml) solution to obtain a capped crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ethanol containing ammonia water. The filtered polymer was purified by column chromatography to obtain the target polymer 2 (2.6 g). The molecular weight of the obtained polymer 2 is 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]

Polymer 3 was synthesized according to the following reaction formula.

[Chemical 104]

Filled with compound 19 (1.2g, 2.25mmol), 2-amino-9,9-dihexylquinone (1.056g, 3.02mmol), compound 16 (0.739g, 0.90mmol), compound 31 (0.233g, 0.59mmol) ), sodium tertbutoxide (1.67g, 17.4mmol) and toluene (30g, 35ml), fully replace the system with nitrogen and heat it to 60°C (solution A3).

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

In a nitrogen flow, solution B3 was added to solution A3, and a heating and reflux reaction was performed for 1.0 hours. After confirming that compound 19 disappeared, compound 17 (0.91 g, 1.74 mmol) was added. After heating and refluxing for 2 hours, benzene bromide (0.83 g, 5.3 mmol) was added, and heating and refluxing reaction was performed for 2 hours. The reaction solution was allowed to cool and dropped into an ethanol/water (200ml/20ml) solution to obtain a blocked crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and Reprecipitate with ammonia and ethanol. The filtered polymer was purified by column chromatography to obtain the target polymer 3 (1.2 g). The molecular weight of the obtained polymer 3 is 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 reaction formula.

Filled with compound 19 (2.0g, 3.76mmol), 2-amino-9,9-dihexylbenzene (1.79g, 5.12mmol), compound 28 (0.60g, 1.66mmol), compound 34 (0.45g, 0.75mmol) ), sodium tertbutoxide (2.78g, 28.93mmol) and toluene (52g, 60ml), fully replace the system with nitrogen and heat it to 60°C (solution A4).

To a solution of ginseng(dibenzylideneacetone)dipalladium complex (0.069g, 0.075mmol) in 11.9 ml of toluene, add [4-(N,N-dimethylamino)phenyl]di-tert-butyl Amphos (0.16g, 0.6mmol), heated to 60°C (solution B4).

In a nitrogen flow, solution B4 was added to solution A4, and a heating and reflux reaction was performed for 1.0 hours. After confirming that compound 19 disappeared, compound 20 (1.33 g, 2.6 mmol) was added. After heating and refluxing for 2 hours, benzene bromide (1.77 g, 11.3 mmol) was added, and heating and refluxing reaction was performed for 2 hours. The reaction solution was cooled and dropped into an ethanol/water (315 ml/50 ml) solution to obtain a blocked crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ethanol containing ammonia water. The filtered polymer was purified by column chromatography to obtain the target polymer 4 (2.8 g). The molecular weight of the obtained polymer 4 is 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 reaction formula.

[Chemical 106]

Filling compound 19 (1.7g, 3.19mmol), 2-amino-9,9-dihexylbenzoate (1.12g, 3.20mmol), compound 34 (1.93g, 3.19mmol), sodium tert-butoxide (2.37g , 24.66mmol) and toluene (34g, 39ml), fully replace the system with nitrogen and heat it to 60°C (solution A5).

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

In a nitrogen flow, solution B5 was added to solution A5, and a heating and reflux reaction was performed for 1.0 hours. After confirming that compound 19 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, benzene bromide (0.65 g, 4.14 mmol) was added, and heating and refluxing reaction was performed for 2 hours. After the reaction solution was allowed to cool, 58 ml of toluene was added and dripped into an ethanol/water (270 ml/43 ml) solution to obtain a capped crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and Reprecipitate with ammonia and ethanol. The filtered polymer was purified by column chromatography to obtain the target polymer 5 (2.7 g). The molecular weight of the obtained polymer 5 is as follows.

Weight average molecular weight (Mw)=38840

Number average molecular weight (Mn)=28990

Dispersion (Mw/Mn)=1.34

[Insolubilization experiment]

The polymer prepared in the Example was used to conduct an insolubilization experiment on cyclohexylbenzene and methyl benzoate. Polymers 1, 2 and 5 were dissolved in anisole to prepare a coating composition. Use the coating composition to produce a 110nm~130nm film on a glass slide substrate by spin coating. Furthermore, the film was heat-treated at 230°C for 30 minutes. Thereafter, the thickness of each film was measured at room temperature.

Furthermore, each membrane was rinsed with cyclohexylbenzene or butyl benzoate, respectively. The rinsing treatment was performed by dropping 130 μl of the solvent onto the coating film, leaving it to stand for 90 seconds, and then rotating the substrate. The rinsed film is heated together with the slide substrate, and the film thickness of the residual film on the slide substrate is measured. Table 1 shows the ratio of the film thickness before and after the rinse treatment (insolubilization rate).

As shown in Table 1, the organic films of polymers 1, 2, and 5 after heat treatment will not dissolve in cyclohexylbenzene or butyl benzoate, indicating that wet film formation is possible.

<Experiment II>

<Example 6>

[Synthesis of Polymer 6]

Polymer 6 was synthesized according to the following reaction formula.

Filling compound 19 (1.3g, 2.44mmol), 2-amino-9,9-dihexylfluoride (0.79g, 2.25mmol), compound 36 (1.08g, 2.64mmol), sodium tert-butoxide (1.81g , 18.83mmol) and toluene (23g, 27ml), fully replace the system with nitrogen and heat it to 60°C (solution A6).

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

In a nitrogen flow, solution B6 was added to solution A6, and a heating and reflux reaction was performed for 1.0 hours. After confirming that compound 19 disappeared, compound 20 (1.12 g, 2.22 mmol) was added. After heating and refluxing for 2 hours, benzene bromide (0.35 g, 2.23 mmol) was added, and heating and refluxing reaction was performed for 2 hours. The reaction solution was allowed to cool, 57 ml of toluene was added, and the solution was added dropwise to ethanol/water (240 ml/50 ml) to obtain a capped crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ethanol containing ammonia water. The filtered polymer was purified by column chromatography to obtain the target polymer 6 (1.8 g). The molecular weight of the obtained polymer 6 is 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]

Polymer 7 was synthesized according to the following reaction formula.

[Chemical 108]

Filling compound 19 (1.5g, 2.8mmol), 2-amino-9,9-dihexylfluoride (0.59g, 1.7mmol), 2-amino-9,9-dimethylfluoride (0.59g, 2.8 mmol), compound 28 (1.11g, 1.1mmol), sodium tert-butoxide (2.09g, 21.7mmol) and toluene (24g, 27.7ml), replace the system with sufficient nitrogen and heat it to 60°C (solution A3) .

To a solution of ginseng(dibenzylideneacetone)dipalladium complex (0.052g, 0.06mmol) in 3.3 ml of toluene, add [4-(N,N-dimethylamino)phenyl]di-tert-butyl Amphos (0.12g, 0.5mmol), heated to 60°C (solution B3).

In a nitrogen flow, solution B3 was added to solution A3, and a heating and reflux reaction was performed for 1.0 hours. After confirming that compound 19 disappeared, compound 20 (1.30 g, 2.6 mmol) was added. Heating and refluxing for 2 hours After this time, benzene bromide (0.44 g, 2.8 mmol) was added, and heating and refluxing reaction were performed for 2 hours. The reaction solution was allowed to cool, 40 ml of toluene was added, and the mixture was dripped into an ethanol/water (500 ml/90 ml) solution to obtain a blocked crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ethanol containing ammonia water. The filtered polymer was purified by column chromatography to obtain the target polymer 7 (1.7 g). The molecular weight of the obtained polymer 7 is as follows.

Weight average molecular weight (Mw)=40000

Number average molecular weight (Mn)=29600

Dispersion (Mw/Mn)=1.35

[Component Example]

The following shows the results of evaluating the performance of devices produced using polymers 1, 5, 6, and 7 and polymer HT-1. The present invention is not limited to the following examples, and may be arbitrarily modified and implemented without departing from the gist of the present invention.

<Example 8>

Make an organic electroluminescent device according to the following method.

For a glass substrate where a transparent conductive film of indium tin oxide (ITO) is deposited to a thickness of 50 nm (manufactured by Samyong Vacuum Co., Ltd., a sputtered film product), a 2 mm pattern is patterned using normal photolithography techniques and hydrochloric acid etching. Wide stripes form the anode. The substrate thus patterned to form ITO is sequentially cleaned by ultrasonic waves with a surfactant aqueous solution, washed with ultrapure water, and ultrasonicated with ultrapure water. After washing with wave cleaning and ultrapure water, it is dried with compressed air, and finally cleaned with ultraviolet ozone.

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

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

Next, 100 parts by mass of the charge transporting polymer compound having the following polymer 5 was dissolved in cyclohexylbenzene to prepare a 1.5 wt% solution.

[Chemical 110]

Spin-coat this solution on the above-mentioned substrate coated with the hole injection layer in a glove box, and dry it using a heating plate in a nitrogen glove box at 230°C for 30 minutes to form a uniform film with a thickness of 25 nm. , to form a hole transport layer.

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

Spin-coat this solution on the above-mentioned substrate coated with the hole transport layer in a glove box, and dry it using a heating plate in a nitrogen glove box at 120°C for 20 minutes to form a uniform film with a film thickness of 40 nm. , to form a luminescent layer.

The substrate with the light-emitting layer formed on it was placed in a vacuum evaporation device, and the exhaust in the device was reduced to 2×10 ^-4 Pa or less.

Next, the following structural formula (HB-1) and 8-hydroxyquinoline lithium were co-evaporated on the light-emitting layer at a film thickness ratio of 2:3 by vacuum evaporation at a speed of 1Å/second to form a film Hole blocking layer 30nm thick.

Next, a 2 mm wide stripe-shaped shadow mask used as a mask for cathode evaporation is closely adhered to the substrate in a manner orthogonal to the ITO stripes of the anode, and is placed in another vacuum evaporation device. Then, as a cathode, aluminum is heated with a molybdenum boat to form an aluminum layer with a film thickness of 80 nm at a vapor deposition rate of 1 to 8.6 Å/second to form a cathode. As described above, an organic electroluminescent element having a light-emitting area portion of 2 mm×2 mm size was obtained.

<Example 9>

An element was produced in the same manner as in Example 1 except that the hole transport layer was made of polymer 1.

[Chemical 113]

<Comparative example 1>

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

[Evaluation of components]

The characteristics of the obtained organic electroluminescent devices of Examples 1-2 and Comparative Example 1 are shown in Table 2. The relative luminous efficiency is measured as the current luminous efficiency (cd/A) when light is emitted at a brightness of 1000 cd/ ^m2 . The relative value is obtained by dividing the current luminous efficiency of the example by the current luminous efficiency of the comparative example. Let the comparison be For example, the relative value is set to 100. When it exceeds 100, it means that the current luminous efficiency is high. The relative voltage is measured as the voltage (V) when light is emitted at a current density of 10 mA/cm ² , and is the difference (V) with the voltage of Comparative Example 1 as a reference. A negative value indicates a low voltage. It can be seen that the organic electrostatic device provided with the hole transport layer containing the polymer according to the first aspect of the present invention has improved efficiency and lower voltage than the organic electrostatic device of the comparative example.

<Example 10>

In addition to setting the hole transport layer to polymer 5 and setting the composition of the light-emitting layer to (H-2): (H-3): (D-2)=60:40:15, a film with a film thickness of 75nm, The other components were produced in the same manner as in Example 1. (H-2), (H-3) and (D-2) are as shown below.

<Comparative example 2>

The device was produced in the same manner as in Example 3 except that the hole transport layer was (HT-1).

[Evaluation of components]

The characteristics of the obtained organic electroluminescent devices of Example 10 and Comparative Example 2 are shown in Table 3. The relative current efficiency and relative voltage are synonymous with Table 2. As shown in the results in Table 3, it can be seen that the organic electroluminescent element having the hole transport layer and the light-emitting layer of the present invention including the second gist has improved efficiency and lower voltage compared to the organic electroluminescent element of the comparative example.

<Example 11>

In addition to setting the hole injection layer as (P1): (HI-1)=100:20, a film with a film thickness of 60 nm, the hole transport layer is a film of polymer 5 with a film thickness of 25 nm, and the luminescent layer consists of The device was produced in the same manner as in Example 1 except for a film with a film thickness of 70 nm of (H-4): (H-5): (D-2) = 60:40:15. (H-4) and (H-5) are as shown below.

<Comparative Example 3>

In addition to setting the hole transport layer to polymer 6 and setting the composition of the light-emitting layer to (H-6): (H-7): (D-2) = 60:40:15, a film with a film thickness of 70 nm, Otherwise, the device was produced in the same manner as in Example 4. (H-6) and (H-7) are as shown below.

<Reference Example 1>

The device was produced in the same manner as in Example 4 except that the hole transport layer was made of polymer 6 and the composition of the light-emitting layer was the same as in Example 4.

<Reference example 2>

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

[Evaluation of components]

The characteristics of the obtained organic electroluminescent devices of Example 10 and Reference Example 1 are shown in Table 4. The relative current efficiency is measured as the current efficiency (cd/A) when light is emitted with a luminance of 1000 cd/m ² , and is the relative value to that when Reference Example 1 is set to 100. The relative voltage is measured as the voltage (V) when light is emitted at a current density of 10 mA/cm ² , and is the difference (V) between the voltage when using the voltage of Reference Example 1 as a reference. As shown in the results in Table 4, it can be seen that the efficiency of the organic electrostatic device containing the polymer according to the first aspect of the present invention is improved in the hole transport layer.

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

The characteristics of the obtained organic electroluminescent devices of Example 10 and Reference Example 2 are shown in Table 6. The relative current efficiency is measured as the current efficiency (cd/A) when light is emitted with a luminance of 1000 cd/m ² , and is the relative value to that when Reference Example 2 is set to 100. The relative voltage is measured as the voltage (V) when light is emitted at a current density of 10 mA/cm ² and is the difference (V) with the voltage of Reference Example 2 as a reference. As shown in the results in Table 6, it can be seen that the efficiency of an organic electrostatic device containing a polymer according to the first aspect of the present invention is improved when the hole transport layer includes a light-emitting layer that satisfies the second aspect of the present invention.

The characteristics of the obtained organic electroluminescent devices of Example 10, Reference Example 1, and Comparative Example 3 are shown in Table 7. The relative current efficiency is measured as the current efficiency (cd/A) when light is emitted with a luminance of 1000 cd/m ² , and is the relative value to that of Comparative Example 3 when it is set to 100. The relative voltage is measured as the voltage (V) when light is emitted at a current density of 10 mA/cm ² and is the difference (V) with the voltage of Comparative Example 3 as a reference. As shown in the results in Table 7, it can be seen that the luminous efficiency of the organic electroluminescent device containing the polymer according to the first aspect of the present invention is improved in the hole transport layer. At the same time, from the comparison of Comparative Example 3, Example 10 and Reference Example 1, it can be seen that The luminous efficiency of the organic electroluminescent element that satisfies the third gist of the present invention is improved.

<Example 12>

[Synthesis of Polymer 8]

Polymer 8 was synthesized according to the following reaction formula.

[Chemical 118]

Filled with compound 19 (1.5g, 2.8mmol), 2-amino-9,9-dihexylquinone (1.245g, 3.6mmol), compound 28 (0.342g, 0.9mmol), compound 26 (1.11g, 1.1mmol) ), sodium tertbutoxide (2.09g, 21.7mmol) and toluene (24g, 27.7ml), fully replace the system with nitrogen and heat it to 60°C (solution A8).

To a solution of ginseng(dibenzylideneacetone)dipalladium complex (0.052g, 0.06mmol) in 3.3 ml of toluene, add [4-(N,N-dimethylamino)phenyl]di-tert-butyl Amphos (0.12g, 0.5mmol), heated to 60°C (solution B8).

In a nitrogen flow, solution B8 was added to solution A8, and a heating and reflux reaction was performed for 1.0 hours. After confirming that compound 19 disappeared, compound 20 (1.22 g, 2.4 mmol) was added. After heating and refluxing for 2 hours, benzene bromide (1.24 g, 7.9 mmol) was added, and heating and refluxing reaction was performed for 2 hours. The reaction solution was allowed to cool, 40 ml of toluene was added, and the mixture was dripped into an ethanol/water (500 ml/90 ml) solution to obtain a blocked crude polymer.

The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ethanol containing ammonia water. The filtered polymer was purified by column chromatography to obtain the target polymer 8 (2.1 g). The molecular weight of the obtained polymer 8 is as follows.

Weight average molecular weight (Mw)=39800

Number average molecular weight (Mn)=29920

Dispersion (Mw/Mn)=1.33

[Determination of the excited singlet energy level (S1) and excited triplet energy level (T1) of polymers]

Each polymer 1 and polymer 8 were dissolved in 2-methyltetrahydrofuran to prepare a solution with a concentration of 1% by weight. The fluorescence and phosphorescence spectra of this solution sample were measured using a fluorescence spectrophotometer (Hitachi Fluorescence Spectrophotometer F-4500) at an excitation wavelength of 350 nm and under cooling conditions of liquid nitrogen. In the obtained fluorescence emission spectrum and phosphorescence emission spectrum, the S1 energy level and the T1 energy level are obtained from the peak wavelength of the emission peak located on the shortest wavelength side. The measurement results are shown in Table 8.

Compared with the polymer 8 whose terminal Ar ⁵ is carbazole, the non-carbazole polymer 1 shows a higher T1 energy level. This is thought to be because when there is one carbazole, the conjugation length becomes shorter compared to the case where two carbazoles are conjugated to each other, so the molecular energy gap becomes wider and the T1 level becomes higher. Because T1 is high, energy from the light-emitting layer is not easily transferred to the hole transport layer, and it is thought that an organic EL element with high luminous efficiency can be realized.

[Confirm electronic status through calculation]

Through calculation, confirm the electronic states of the following polymer units 1 to 5.

The electronic state is calculated using the software Gaussian 09, Revision B.01 (see below). At this time, as the quantum chemical calculation method, density functional theory (Density Functional Theory) is used, B3LYP is used as the functional function, and 6-31G is used as the basis function to perform structural optimization calculation of the base state. The expression of HOMO and LUMO (function value 0.03a.u.) is performed using the software MolStudio R4.0 Rev 2.0 Pprogram (NEC Corporation).

The results of this calculation are shown in Figures 2 to 4. As can be seen from Figures 2 and 3, polymer units 1 and 2 are HOMO present near N of the main chain, and LUMO locally present at the terminal side of the side chain. In addition, it can be seen from Figure 4 that the HOMO system exists near N in the main chain in units 3 to 5, and the LUMO system exists in Ar ⁵ of formula (1). The more rings, they are distributed closer to the terminal side than the carbazole ring. , showing local existence.

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

[Polymer unit 1]

[Polymer unit 2]

[Polymer units 3, 4, 5]

<Experiment III>

<Example 13>

Make an organic electroluminescent device according to the following method.

For a glass substrate where a transparent conductive film of indium tin oxide (ITO) is deposited to a thickness of 130nm (manufactured by Samyong Vacuum Co., Ltd., a sputtered film product), a 2mm pattern is patterned using normal photolithography techniques and hydrochloric acid etching. Wide stripes form the anode. The substrate thus patterned with ITO is washed sequentially by ultrasonic cleaning with a surfactant aqueous solution, ultrasonic cleaning with ultrapure water, ultrasonic cleaning with ultrapure water, and ultrapure water washing. Compressed air is used to dry it, and finally ultraviolet ozone cleaning is performed.

As a composition for forming a hole injection layer, 100 parts by weight of a hole transporting polymer having a repeating structure of the following formula (P1) and 10 parts by weight of a compound represented by the following formula (HI-1) were dissolved in ethyl benzoate. Ester, prepare a composition of 3.0wt%.

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

Next, 100 parts by mass of the charge transporting polymer having the following polymer 7 was dissolved in cyclohexylbenzene to prepare a 3.0 wt% solution.

Spin-coat this solution on the above-mentioned substrate coated with the hole injection layer in a glove box, and dry it using a heating plate in a nitrogen glove box at 230°C for 30 minutes to form a uniform film with a thickness of 40 nm. , to form a hole transport layer.

Next, as a material for 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 mass of the following structural formula (D-2) were weighed and dissolved. In cyclohexylbenzene, make a 7.8wt% solution.

Spin-coat this solution on the above-mentioned substrate coated with the hole transport layer in a glove box, and dry it using a heating plate in a nitrogen glove box at 130°C for 20 minutes to form a uniform film with a film thickness of 80 nm. , to form a luminescent layer.

The substrate with the light-emitting layer formed on it was placed in a vacuum evaporation device, and the inside of the device was evacuated to 2×10 ^-4 Pa or less.

Next, the following structural formula (HB-1) and 8-hydroxyquinoline lithium were co-evaporated on the light-emitting layer at a film thickness ratio of 2:3 by vacuum evaporation at a speed of 1Å/second to form a film Hole blocking layer 30nm thick.

Next, a 2 mm wide stripe-shaped shadow mask used as a mask for cathode evaporation is closely adhered to the substrate in a manner orthogonal to the ITO stripes of the anode, and is placed in another vacuum evaporation device. Then, as a cathode, aluminum is heated with a molybdenum boat to form an aluminum layer with a film thickness of 80 nm at a vapor deposition rate of 1 to 8.6 Å/second to form a cathode. As described above, an organic electroluminescent element having a light-emitting area portion of 2 mm×2 mm size was obtained.

This device contains a material with the formula (Cz-P) as a partial structure in the hole transport layer and the light-emitting layer.

<Comparative Example 4>

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

[Evaluation of components]

Table 9 shows the evaluation results of the voltage and drive life of the organic electroluminescent elements obtained in Example 13 and Comparative Example 4. The voltage is measured at 10 mA/cm ² when energized. Using the voltage of the element of Comparative Example 4 as a reference, the difference between the voltage of the element of Example 13 and the voltage of the element of Comparative Example 4 is obtained, and is set as the relative voltage [V] . Furthermore, the element was driven at 40 mA/cm ² and the 15% brightness decay life (LT85) was measured, and the ratio when the 15% decay life of Comparative Example 4 was used as a standard and set to 1 was determined as the relative life. These are shown in Table 9. As shown in the results in Table 9, it can be seen that in the organic electroluminescent element using a material containing the formula (CzP) as a partial structure in both the hole transport layer (HTL) and the light emitting layer (EML), the voltage is low , long life.

<Example 14>

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

<Comparative example 5>

The device was produced in the same manner as in Example 13 except that the composition of the light-emitting layer was set to (H-8): (H-9): (D-2) = 40:60:20.

<Comparative Example 6>

The rest is the same as in Example 13 except that the hole transport layer is set to HT-2 and the composition of the light-emitting layer is set to (H-8): (H-9): (D-2) = 40:60:20. Make components.

[Evaluation of components]

For the organic electroluminescent elements obtained in Example 14, Comparative Example 5, and Comparative Example 6, the relative voltage and relative lifetime were determined in the same manner as in Example 13 and Comparative Example 4. At this time, Comparative Example 6 is used as a standard. These are shown in Table 10. As shown in the results in Table 10, it was found that an organic electroluminescent element using a material containing formula (CzP) as a partial structure in both the hole transport layer and the light-emitting layer has low voltage and long life.

As mentioned above, the present invention has been described based on specific embodiments. However, each embodiment is only an example and does not limit the scope of the present invention. Each embodiment described in this specification can be variously modified within the scope that does not deviate from the gist of the invention, and can be combined with features described in other embodiments within the scope of implementation.

1:Substrate

2:Anode

3: Hole injection layer

4: Hole transport layer

5: Luminous layer

6: Hole blocking layer

7:Electron transport layer

8:Electron injection layer

9:Cathode

10: Organic electroluminescent components

Claims (22)

A polymer containing repeating units represented by the following formula (1);

(In formula (1), G represents an aromatic hydrocarbon group that may have a substituent; an aromatic heterocyclic group that may also have a substituent; or a C atom, an N atom, a B atom or a P atom; Ar ² ~ Ar ⁴ respectively Independently means a divalent aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or an aromatic hydrocarbon group that may have a substituent or an aromatic heterocyclic group that may have a substituent directly Or a plurality of divalent groups connected via a linking group; Ar ⁵ represents an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or an aromatic group that may have a substituent. The base of a hydrocarbon group and an aromatic heterocyclic group that may have a substituent is a monovalent group connected directly or via a plurality of connecting groups; Ar ⁶ represents a hydrogen atom or a substituent; "-*" in Ar ¹ is represented by the formula ( 1) The bonding position between middle and G). The polymer of claim 1, wherein the above-mentioned G is an N atom. The polymer of claim 1 or 2, wherein Ar ⁵ is represented by any one of the following a-1 to e-4;

(In a-1 to e-4, "-*" represents the bonding position with Ar ^4. When there are plural "-*"s, any one of them represents the bonding position with Ar ⁴ ). The polymer of claim 1 or 2, wherein the above formula (1) is a repeating unit represented by any one of the following formulas (2)-1 to (2)-3; [Chemical 3]

(In formula (2)-1 to formula (2)-3, Ar ¹ is the same as Ar ¹ in the above 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 ~ R ⁴ independently represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, Or an aralkyl group that may have a substituent; R ⁵ to R ⁷ and R ¹¹ to R ¹⁴ independently represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or an alkoxy group that may have a substituent. Aralkyl group, or aromatic hydrocarbon group that may also have a substituent; a and b are each independently an integer from 0 to 4; c1 and c2 are each independently an integer from 1 to 3; d1 and d2 are each independently an integer from 0 to 4 ; when R ¹ , R ² , R ³ and R ⁴ are plural in the repeating unit, R ¹ , R ² , R ³ and R ⁴ may be the same or different). The polymer of claim 1 or 2, which further contains repeating units represented by any one of the following (3)-1~(3)-3;

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

The organic electroluminescent element according to Claim 13, wherein the material contained in the above-mentioned light-emitting layer containing a compound having a partial structure represented by the above formula (CzP) has at least either hole transporting property or electron transporting property. The main material or the luminescent material. Such as the organic electroluminescent element of claim 14, wherein the skeleton of the above-mentioned host material has an aromatic structure, an aromatic amine structure, a triarylamine structure, a dibenzofuran structure, a naphthalene structure, a phenanthrene structure, a phthalocyanine structure, and a porphyrin structure. Phenoline structure, thiophene structure, benzylphenyl structure, fluorine structure, quinacridone structure, triphenyl structure, carbazole structure, pyrene structure, anthracene structure, phenanthroline structure, quinoline structure, pyridine structure, pyrimidine structure, three

structure,

An oxadiazole structure or an imidazole structure, or one having any one of a carbazole structure, a dibenzofuran structure, a triarylamine structure, a naphthalene structure, a phenanthrene structure, and a pyrene structure. The organic electroluminescent element according to any one of claims 13 to 15, wherein the compound having the partial structure represented by the above formula (CzP) contained in the above-mentioned light-emitting layer is any of the following formulas (14) to (16) A low molecular compound represented by one, and the molecular weight of the low molecular compound is 5,000 or less; [Chemical 6]

(In formulas (14) to (16), A is a partial structure shown in the above formula (CzP), and may also have a substituent; B represents a single bond or any partial structure; when A exists in plural, they may be the same or different; when B exists in plural form, it can be the same or different; na, nb and nc respectively independently represent integers above 1 and below 5). The organic electroluminescent element of claim 16, wherein the low molecular compound represented by the above formula (14) is a low molecular compound represented by the following formula (17); [Chemical 7]

(In the above formula (17), Q represents a nitrogen atom or any one of the trivalent substituents represented by any one of the following structural formulas (18-1) to (18-3); Xb ¹ , Yb ¹ and Zb ¹ each independently represent a divalent hydrocarbon aromatic ring group having 6 to 30 carbon atoms that may have a substituent, or a divalent heteroaromatic ring group having 3 to 30 carbon atoms that may have a substituent; in Xb ¹ , When Yb ¹ and Zb ¹ exist in plural, they may be the same or different; A is a partial structure shown in the above formula (CzP), and may also have a substituent, and A when present in plural may be the same or different; p12 , q12 and r12 independently represent integers above 0 and below 6; q13 and r13 independently represent 0 or 1; Yb ² when q13 is 0 and Zb ² when r13 is 0 independently represent hydrogen atoms, and may also have substitutions The base has a monovalent hydrocarbon aromatic ring group with 6 to 30 carbon atoms, or a monovalent heteroaromatic ring group with 3 to 30 carbon atoms that may have a substituent; when q13 is 1, Yb ² is a direct bond; r13 is 1 At this time, Zb ² is a direct bond; in formulas (18-1) ~ (18-3), the three * in a structural formula respectively represent the bonding position with any base of Xb ¹ , Yb ¹ or Zb ¹ )

The organic electroluminescent element of claim 16, wherein the low molecular compound represented by the above formula (16) is a low molecular compound represented by the 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 that may have a substituent, or a divalent hydrocarbon aromatic ring group having 3 to 30 carbon atoms that may have a substituent. Heteroaromatic ^ring group ^; Heteroaromatic ring group; when Xc ¹ and Yc ¹ exist in plural, they may be the same or different; A is a partial structure shown in the above formula (CzP), and may also have a substituent; s11 and t11 independently represent 0 or more and An integer below 6; nc represents an integer above 1 and below 5). The organic electroluminescent device of claim 17, wherein the low molecular compound represented by the above formula (17) is a compound represented by any one of the following formulas (17-1) to (17-6); [Chemical 10 ]

[Chemical 11]

(In the above general formulas (17-1) ~ (17-6), p12' represents an integer from 1 to 5; q12' and r12' independently represent an integer from 0 to 5; p14 is 12; q14 is When q13 is 1, it is 12, and there is no case where q13 is 0; r14 is 12 when r13 is 1, and there is no case where r13 is 0; q15 and r15 are independently 4 or 5 respectively; R ³¹ and R ³² are respectively independently a hydrogen atom or a substituent; Xb ¹ , Yb ¹ , Zb ¹ , q13 and r13 are respectively the same as the above formula (17)). The organic electroluminescent element of claim 18, wherein the low molecular compound represented by the above formula (19) is a compound represented by the following formula (19-1);

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