JP2013087216A - Crosslinked type polymer, and organic electroluminescent element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinked type polymer suitable for forming a thin film by an application method, and suitable as a material for electronic use.SOLUTION: The crosslinked type polymer is a polymer containing structural units expressed by formulas (A) and (B). P is a group derived from a compound expressed by Formula (P), in the Formula (A). Lrepresents a connection group. Q is a group derived from a compound expressed by Formula (Q), in the Formula (B). Lrepresents a connection group. At least one out of c members of the Qs and d members of Ls has a crosslinking group, in the Formula (B).

Description

  The present invention relates to a cross-linked polymer and an organic electroluminescence device (organic EL device) using the same.

Organic EL elements are self-luminous and have no viewing angle dependency, and can be surface-emitting and thinned. Therefore, application to displays such as televisions and mobile phones, lighting, and the like are being studied.
The organic EL element has a configuration in which a thin film of an organic compound is sandwiched between a cathode and an anode. Thin film forming methods are roughly classified into vapor deposition methods and coating methods. The vapor deposition method is a method of forming a thin film on a substrate in a vacuum mainly using a low molecular compound, and commercialization has preceded. On the other hand, the coating method is a method of forming a thin film on a substrate using a solution, such as ink jet or printing, and the use efficiency of the material is high, and it is suitable for large area and high definition. This is an indispensable technique for EL displays.

  The vacuum deposition method using low-molecular materials is extremely low in material utilization efficiency, and the larger the size, the more the shadow mask will bend, which makes it difficult to deposit on a large substrate. There is a problem that it is difficult to manufacture a display device using an EL substrate. In addition, the manufacturing cost increases.

On the other hand, a polymer material can form a uniform film by applying a solution dissolved in an organic solvent, and is represented by an inkjet method or a printing method using this. A coating method can be used. Therefore, the utilization efficiency of the material can be increased to nearly 100%. In addition, since it can easily cope with substrates of various shapes from small substrates to large substrates, the manufacturing cost of the element can be greatly reduced.
However, in general, the coating method is not suitable for a stacked element, and there is a problem that it is not easy to improve the performance of the element.

The reason why the coating method is not suitable for the laminate type is that the layer formed earlier is dissolved when the layers are stacked. Specifically, in a coated laminated organic light emitting device, the hole injection layer and the hole transport layer must be insoluble in the solvent used when forming the light emitting layer.
Therefore, at present, many organic EL devices using a coating method form a hole injection layer with an aqueous dispersion of polythiophene: polystyrene sulfonic acid (PEDOT: PSS), and a light emitting layer with an aromatic system such as toluene. It is limited to a two-layer structure in which film formation is performed using an organic solvent. This is because the PEDOT: PSS layer does not dissolve in toluene, and thus such a two-layer structure can be produced.
Therefore, for example, it was not applicable when a hole transport layer was formed on a hole injection layer and a light emitting layer was further formed.

For the hole injection layer, as represented by PEDOT / PSS, a water-soluble or alcohol-soluble material is often used. Therefore, the hole transport material is deposited and laminated on the hole injection layer using an organic solvent other than water or alcohol such as toluene, xylene, dioxane, cyclohexanone.
Here, it has been proposed to use a thermal or photocrosslinking polymer as a hole transport material (see Patent Document 1). However, the photo-crosslinking type material is deteriorated by light and has a problem that the hole transport property, the light emission efficiency, and the element lifetime are lowered. There is a problem that holes may occur.
In addition, there is a problem in that even if the film does not shrink after thermal crosslinking, it may be dissolved in a film-forming solvent used for laminating the light-emitting layer (see Patent Documents 2-4).

  In addition, there is a technique in which a material in which a polymerizable substituent is bonded to a low molecular weight compound is used, and after coating it, the solubility in the coating solvent for other layers is lowered to form a multilayer structure. (For example, refer to Patent Document 5). However, since low molecular weight compounds tend to crystallize themselves, there is a problem that it is difficult to form a high-quality thin film.

JP 2006-257196 A JP 2008-63327 A JP 2009-283509 A JP 2011-82052 A JP 2006-279007 A

  An object of the present invention is to provide a crosslinked polymer suitable for forming a thin film by a coating method and suitable as an electronic material.

  As a result of intensive studies, the present inventors have found that a crosslinked polymer having a structural unit derived from carbazole or a compound similar to carbazole (P and Q groups described later) can form a high-quality thin film stably and easily. In addition, the present inventors have found that this material is useful as an electronic material by changing the solubility due to a crosslinking reaction by heat or the like, thereby completing the present invention.

［式（Ａ）中、Ｐは下記式（Ｐ）で表される化合物に由来する基である。

（式中、Ａ_１はそれぞれ独立に、窒素原子又はＣＲ_２である。
Ｘ_１は、単結合、Ｏ、Ｓ、ＣＲ_２Ｒ_３又はＮＲ_２である。
Ｒ_１〜Ｒ_３は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の環形成炭素数３〜１０のシクロアルキル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数３〜３０のヘテロアリール基、置換もしくは無置換のアリールアミノ基又はアリールシリル基である。）
ａは２〜５の整数であり、（Ｐ）ａは、上記（Ｐ）基がａ個連続して結合していることを表す。ａ個のＰはそれぞれ独立であり、また、Ｐ同士の結合位置は限定されない。
Ｌ_１は連結基を表す。
ｂは、０〜５の整数であり、（Ｌ_１）ｂは、ｂが２以上である場合、Ｌ_１がｂ個連続して結合したことを表す。この場合、ｂ個のＬ_１はそれぞれ独立であり、また、Ｌ_１同士が結合する位置は限定されない。
式（Ａ）において、ＰとＬ_１の結合位置は限定されない。
式（Ｂ）中、Ｑは下記式（Ｑ）で表される化合物に由来する基である。

（式中、Ａ_２はそれぞれ独立に、窒素原子又はＣＲ_６である。
Ｘ_２は、単結合、Ｏ、Ｓ、ＣＲ_６Ｒ_７又はＮＲ_６である。
Ｒ_５〜Ｒ_７は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の環形成炭素数３〜１０のシクロアルキル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数３〜３０のヘテロアリール基、置換もしくは無置換のアリールアミノ基、アリールシリル基、又は架橋性基である。）
ｃは２〜５の整数であり、（Ｑ）ｃは、上記（Ｑ）基がｃ個連続して結合していることを表す。ｃ個のＱはそれぞれ独立であり、また、Ｑ同士の結合位置は限定されない。
Ｌ_２はそれぞれ独立に、置換もしくは無置換の炭素数１〜２０のアルキレン基、置換もしくは無置換の環形成炭素数３〜１０のシクロアルキレン基、置換もしくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、置換もしくは無置換の環形成原子数３〜３０の芳香族複素環基、置換もしくは無置換のアリールアミン残基、アリールシリレン基、又は架橋性基である。
ｄは、０〜５の整数であり、（Ｌ_１）ｄは、ｄが２以上である場合、Ｌ_２がｄ個連続して結合していることを表す。この場合、ｄ個のＬ_２はそれぞれ独立であり、また、Ｌ_２同士が結合する位置は限定されない。
式（Ｂ）において、ＱとＬ_２の結合位置は限定されない。
式（Ｂ）において、ｃ個のＱ及びｄ個のＬ_２のうち、少なくとも１つは、架橋性基を有する。］
２．前記Ｐ又はＱが、置換又は無置換のカルバゾールの残基である１に記載の重合体。
３．ａ個連続した置換もしくは無置換のカルバゾール残基において隣接するカルバゾール残基同士の結合位置、又は、ｃ個連続した置換もしくは無置換のカルバゾール残基において隣接するカルバゾール残基同士の結合位置が、それぞれ、３位−３’位、３位−２’位、及び、２位−２’位から選ばれた一種である２に記載の重合体。
４．下記の構造１及び構造２の少なくとも一方を有する、２又は３に記載の重合体。
構造１：前記（Ｐ）ａ中の１つの置換又は無置換のカルバゾール残基と、Ｌ_１との結合位置が、該カルバゾール残基の９位、３位又は２位である。
構造２：前記（Ｑ）ｃ中の１つの置換又は無置換のカルバゾール残基と、Ｌ_２との結合位置が、該カルバゾール残基の９位、３位又は２位である。
５．下記の構造３及び構造４の少なくとも一方を有する、２〜４のいずれかに記載の重合体。
構造３：前記（Ｐ）ａ中の１つの置換又は無置換のカルバゾール残基と、Ｌ_２との結合位置が、該カルバゾール残基の９位、３位又は２位である。
構造４：前記（Ｑ）ｃ中の１つの置換又は無置換のカルバゾール残基と、Ｌ_１との結合位置が、該カルバゾール残基の９位、３位又は２位である。
６．前記ａ又はｃが、それぞれ２又は３である１〜５のいずれかに記載の重合体。
７．下記式（１）〜（７）のいずれかで表される１〜６のいずれかに記載の重合体。

（各式中、Ｒ_１、Ｒ_２、Ｒ_５、Ｒ_６、Ｌ_１及びＬ_２は、前記式（Ａ）及び（Ｂ）のＲ_１、Ｒ_２、Ｒ_５、Ｒ_６、Ｌ_１及びＬ_２と同様である。
ｍ及びｎはそれぞれ、重合体に占める各構造単位の含有率（モル比）を表し、ｍは０．０１〜０．９９、ｎは０．０１〜０．９９であり、ｍ＋ｎ＝１である。
ｌは、０又は１である。）
８．下記式（８）〜（２５）のいずれかで表される７に記載の重合体。

（各式中、Ｒ_１、Ｒ_２、Ｒ_５、Ｒ_６、Ｌ_１及びＬ_２は、前記式（Ａ）及び（Ｂ）のＲ_１、Ｒ_２、Ｒ_５、Ｒ_６、Ｌ_１及びＬ_２と同様である。
ｍ及びｎはそれぞれ、重合体に占める各構造単位の含有率（モル比）を表し、ｍは０．０１〜０．９９、ｎは０．０１〜０．９９であり、ｍ＋ｎ＝１である。）
９．前記式（１）〜（２５）で表される各重合体の、Ｒ_５の少なくとも１つ又はＲ_６の少なくとも１つが架橋性基であり、Ｌ_２は架橋性基ではない、７又は８の重合体。
１０．前記架橋性基が、下記式（３１）〜（４２）で示される基から選択される基である１〜９のいずれかに記載の重合体。

１１．前記式（１）〜（２１）で表される各重合体のＬ_２の少なくとも１つが架橋性基であり、Ｒ_５及びＲ_６が架橋性基ではない７又は８の重合体。
１２．前記架橋性基であるＬ_２が、下記式（４３）〜（４６）で示される基から選択される基である１１に記載の重合体。

（式（４５）及び（４６）において、ｏは、１〜１０の整数である。）
１３．前記式（１）〜（２５）で表される各重合体の、Ｒ_１、Ｒ_２、Ｒ_５及びＲ_６の少なくとも１つが、下記式（５１）〜（５５）で表される基から選択される基である８〜１２のいずれかに記載の重合体。

（式中、Ｒ_１１〜Ｒ_２３は、それぞれ独立に、置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の環形成炭素数３〜１０のシクロアルキル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の炭素数１〜２０のアルコキシ基、置換もしくは無置換の環形成炭素数３〜１０のシクロアルコキシ基、置換もしくは無置換の環形成炭素数６〜３０のアリールオキシ基、置換もしくは無置換の炭素数７〜４０のアラルキル基、置換もしくは無置換の環形成原子数３〜３０のヘテロアリール基、置換アミノ基、置換シリル基、ハロゲン原子、ニトロ基、シアノ基又はヒドロキシル基である。
ａ、ｃ、ｄ、ｆ、ｇ、及びｉは、それぞれ独立に、０〜４の整数である。
ｂ、ｅ、ｈ及びｊは、それぞれ独立に、０〜３の整数である。
Ｔ_１〜Ｔ_５はそれぞれ独立に、単結合、置換もしくは無置換の環形成炭素数６〜５０の芳香族炭化水素環基又は環形成原子数３〜３０の芳香族複素環基である。）
１４．上記１〜１３のいずれかに記載の重合体及び溶媒を含む塗布液。
１５．前記溶媒の少なくとも１種が有機溶媒である１４に記載の塗布液。
１６．上記１４又は１５に記載の塗布液を用いて湿式成膜する電子素子の製造方法。
１７．前記電子素子が、電界発光素子、光電変換素子又はトランジスタである１６に記載の電子素子の製造方法。
１８．前記電子素子が、有機エレクトロルミネッセンス素子である１６又は１７に記載の電子素子の製造方法。
１９．陽極と陰極と、前記陽極と陰極の間に、発光層を含む１層以上の有機薄膜層を有し、
前記有機薄膜層の少なくとも１層が１〜１３のいずれかに記載の重合体を含む有機エレクトロルミネッセンス素子。
２０．前記有機薄膜層の少なくとも１層が正孔注入層又は正孔輸送層である１９に記載の有機エレクトロルミネッセンス素子。
２１．前記正孔注入層又は正孔輸送層が発光層と接している２０に記載の有機エレクトロルミネッセンス素子。
２２．前記発光層が湿式成膜法により成膜された１９〜２１のいずれかに記載の有機エレクトロルミネッセンス素子。 According to the present invention, the following polymers and the like are provided.
1. A polymer containing structural units represented by the following formulas (A) and (B).

[In formula (A), P is a group derived from a compound represented by the following formula (P).

(In the formula, each A ₁ is independently a nitrogen atom or CR ₂ .
X ₁ is a single bond, O, S, CR ₂ R ₃ or NR ₂ .
R _{1 to} R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted group. An aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 ring atoms, a substituted or unsubstituted arylamino group, or an arylsilyl group. )
a is an integer of 2 to 5, and (P) a represents that a number of the (P) groups are bonded continuously. The a P's are independent from each other, and the bonding position between the P's is not limited.
L ₁ represents a linking group.
b is an integer from 0 to 5, _(L 1) b, when b is 2 or more, indicating _{that L 1} is bonded b pieces continuously. In this case, b pieces of L ₁ are independent from each other, and the position at which L ₁ is bonded is not limited.
In the formula (A), the bonding position of P and L ₁ is not limited.
In the formula (B), Q is a group derived from a compound represented by the following formula (Q).

(In the formula, each A ₂ is independently a nitrogen atom or CR ₆ .
X ₂ is a single bond, O, S, CR ₆ R ₇ or NR ₆ .
R _{5 to} R ₇ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted group. An aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 ring atoms, a substituted or unsubstituted arylamino group, an arylsilyl group, or a crosslinkable group. )
c is an integer of 2 to 5, and (Q) c represents that c (Q) groups are bonded in succession. The c Qs are independent of each other, and the bonding positions of the Qs are not limited.
L ₂ each independently represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 ring carbon atoms, or a substituted or unsubstituted ring carbon atom having 6 to 30 carbon atoms. An aromatic hydrocarbon ring group, a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms, a substituted or unsubstituted arylamine residue, an arylsilylene group, or a crosslinkable group.
d is an integer from 0 to 5, _(L 1) d, when d is 2 or more, indicating _{that L 2} is bonded d items sequentially. In this case, the d pieces of L ₂ are independent from each other, and the position at which L ₂ is bonded is not limited.
In the formula (B), the bonding position of Q and L ₂ is not limited.
In formula (B), at least one of c Q and d L ₂ has a crosslinkable group. ]
2. 2. The polymer according to 1, wherein P or Q is a residue of a substituted or unsubstituted carbazole.
3. a bonding position between adjacent carbazole residues in a consecutive substituted or unsubstituted carbazole residues, or a bonding position between adjacent carbazole residues in c consecutive substituted or unsubstituted carbazole residues, 3. The polymer according to 2, which is a kind selected from the 3-position, 3′-position, 3-position-2′-position, and 2-position-2′-position.
4). 4. The polymer according to 2 or 3, having at least one of the following structure 1 and structure 2.
Structure 1: The bonding position between one substituted or unsubstituted carbazole residue in (P) a and L ₁ is the 9-position, 3-position or 2-position of the carbazole residue.
Structure 2: The bonding position between one substituted or unsubstituted carbazole residue in (Q) c and L ₂ is the 9th, 3rd or 2nd position of the carbazole residue.
5. The polymer in any one of 2-4 which has at least one of the following structure 3 and structure 4.
Structure 3: The bonding position between one substituted or unsubstituted carbazole residue in (P) a and L ₂ is the 9th, 3rd or 2nd position of the carbazole residue.
Structure 4: The bonding position between one substituted or unsubstituted carbazole residue in (Q) c and L ₁ is the 9th, 3rd or 2nd position of the carbazole residue.
6). The polymer in any one of 1-5 whose said a or c is 2 or 3, respectively.
7). The polymer in any one of 1-6 represented by either of following formula (1)-(7).

_{(Wherein, R 1, R 2, R} 5, R 6, L 1 and _{L 2, R} 1 in the formula (A) and _{(B), R 2, R} 5, R 6, L 1 and L _Same as ₂ .
m and n each represent the content (molar ratio) of each structural unit in the polymer, m is 0.01 to 0.99, n is 0.01 to 0.99, and m + n = 1. .
l is 0 or 1. )
8). 8. The polymer according to 7, which is represented by any one of the following formulas (8) to (25).

_{(Wherein, R 1, R 2, R} 5, R 6, L 1 and _{L 2, R} 1 in the formula (A) and _{(B), R 2, R} 5, R 6, L 1 and L _Same as ₂ .
m and n each represent the content (molar ratio) of each structural unit in the polymer, m is 0.01 to 0.99, n is 0.01 to 0.99, and m + n = 1. . )
9. In each of the polymers represented by the formulas (1) to (25), at least one of R ₅ or at least one of R ₆ is a crosslinkable group, and L ₂ is not a crosslinkable group. Polymer.
10. The polymer according to any one of 1 to 9, wherein the crosslinkable group is a group selected from groups represented by the following formulas (31) to (42).

11. Each at least one polymer of L ₂ is a bridging group, the polymer of R ₅ and R ₆ are crosslinkable not group 7 or 8 of the formula (1) to (21).
12 12. The polymer according to 11, wherein L _{2 as the} crosslinkable group is a group selected from groups represented by the following formulas (43) to (46).

(In formulas (45) and (46), o is an integer of 1 to 10.)
13. In the polymers represented by the formulas (1) to (25), at least one of R ₁ , R ₂ , R ₅ and R ₆ is selected from the groups represented by the following formulas (51) to (55). The polymer in any one of 8-12 which is a group made.

(In the formula, R _{11 to} R ₂₃ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, substituted or unsubstituted. An aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 10 ring carbon atoms, a substituted or unsubstituted ring formation Aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 ring atoms, substituted amino group, substituted silyl group, halogen An atom, a nitro group, a cyano group or a hydroxyl group.
a, c, d, f, g, and i are each independently an integer of 0 to 4;
b, e, h, and j are each independently an integer of 0 to 3.
T _{1 to} T ₅ are each independently a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 50 ring carbon atoms or an aromatic heterocyclic group having 3 to 30 ring atoms. )
14 The coating liquid containing the polymer and solvent in any one of said 1-13.
15. 15. The coating solution according to 14, wherein at least one of the solvents is an organic solvent.
16. 16. A method for producing an electronic device, wherein a wet film is formed using the coating solution according to 14 or 15 above.
17. 17. The method for producing an electronic device according to 16, wherein the electronic device is an electroluminescent device, a photoelectric conversion device or a transistor.
18. The method for producing an electronic element according to 16 or 17, wherein the electronic element is an organic electroluminescence element.
19. Having one or more organic thin film layers including a light emitting layer between the anode and the cathode and the anode and the cathode;
The organic electroluminescent element in which at least 1 layer of the said organic thin film layer contains the polymer in any one of 1-13.
20. 20. The organic electroluminescence device according to 19, wherein at least one of the organic thin film layers is a hole injection layer or a hole transport layer.
21. 21. The organic electroluminescence device according to 20, wherein the hole injection layer or the hole transport layer is in contact with the light emitting layer.
22. The organic electroluminescent element according to any one of 19 to 21, wherein the light emitting layer is formed by a wet film forming method.

  ADVANTAGE OF THE INVENTION According to this invention, it is suitable for formation of the thin film by the apply | coating method, and can provide the crosslinked polymer suitable as an electronic material.

The polymer of the present invention is characterized by containing structural units represented by the following formulas (A) and (B).

In the formulas (A) and (B), P and Q are groups derived from carbazole or a compound similar to carbazole, and L ₁ and L ₂ are linking groups. The structural unit of the above formula (A) does not have a crosslinkable group, and the structural unit of the above formula (B) has one or more crosslinkable groups. When the polymer of the present invention has the structural units represented by the formulas (A) and (B), the surface flatness of the film obtained by crosslinking after film formation is increased. Moreover, the tolerance to the organic solvent used for coating is increased.

In the above formula (A), P is a group derived from a compound represented by the following formula (P).

In formula (P), A ₁ is a nitrogen atom or CR ₂ respectively.
X ₁ is a single bond, O, S, CR ₂ R ₃ or NR ₂ .
R _{1 to} R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted group. An aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 ring atoms, or a substituted or unsubstituted arylamino group.
At least one of R _{1 to} R ₃ in the formula (P) is a single bond that binds to another group such as P or L ₁ .

a is an integer of 2 to 5, and 2 or 3 is preferable. (P) a represents that a number of the (P) groups are continuously bonded. The a P's are independent from each other, and the bonding position between the P's is not limited.
L ₁ represents a linking group. L ₁ is preferably each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 ring carbon atoms, or a substituted or unsubstituted ring forming carbon atom. It is an aromatic hydrocarbon ring group having 6 to 30 atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms, a substituted or unsubstituted arylamine residue, or an arylsilylene group. Moreover, it is the group which connected these groups 2 or more. In this case, each group may be the same or different.

b is an integer from 0 to 5, _(L 1) b, when b is 2 or more, indicating _{that L 1} is bonded b pieces continuously. In this case, b pieces of L ₁ are independent from each other, and the position at which L ₁ is bonded is not limited.
In the formula (A), the bonding position of P and L ₁ is not limited.

In the formula (B), Q is a group derived from a compound represented by the following formula (Q).

In the formula, A ₂ is a nitrogen atom or CR ₆ , respectively.
X ₂ is a single bond, O, S, CR ₆ R ₇ or NR ₆ .
R _{5 to} R ₇ are each independently a group or a crosslinkable group similar to R _{1 to} R ₃ described above.

c is an integer of 2 to 5, and 2 or 3 is preferable. (Q) c represents that c (Q) groups are bonded in succession. The c Qs are independent of each other, and the bonding positions of the Qs are not limited.
L ₂ is each independently a group or a crosslinkable group similar to L ₁ described above.
d is an integer from 0 to 5, _(L 2) d, when d is 2 or more, indicating _{that L 2} is bonded d items sequentially. In this case, the d pieces of L ₂ are independent from each other, and the position at which L ₂ is bonded is not limited.
In the formula (B), the bonding position of Q and L ₂ is not limited.
In formula (B), at least one of c Q and d L ₂ has a crosslinkable group.

The polymer of the present invention only needs to have the above-described structural units (A) and (B), and the structure derived from other structural units, for example, α-olefins, as long as the effects of the present invention are not impaired. You may have a unit.
A polymer in which the structural units (A) and (B) are alternately bonded is preferable. An example (AB) in which the structural units (A) and (B) are alternately bonded is shown below. The following example corresponds to -ABAB-.

In the present invention, the P or Q group is preferably a substituted or unsubstituted carbazole residue.
In addition, in a consecutive substituted or unsubstituted carbazole residues, bonding positions between adjacent carbazole residues, or in c consecutive substituted or unsubstituted carbazole residues, bonding positions between adjacent carbazole residues. Are preferably selected from the 3-position, 3'-position, 3-position-2'-position, or 2-position-2'-position, respectively. As an example, two P bonding forms are shown below.

Moreover, it is preferable to have at least one of the following structure 1 and structure 2.
Structure 1: The bonding position between one substituted or unsubstituted carbazole residue in (P) a and L ₁ is the 9-position, 3-position or 2-position of the carbazole residue.
Structure 2: The bonding position between one substituted or unsubstituted carbazole residue in (Q) c and L ₂ is the 9th, 3rd or 2nd position of the carbazole residue.
Furthermore, it is preferable to have at least one of the following structure 3 and structure 4.
Structure 3: The bonding position between one substituted or unsubstituted carbazole residue in (P) a and L ₂ is the 9th, 3rd or 2nd position of the carbazole residue.
Structure 4: The bonding position between one substituted or unsubstituted carbazole residue in (Q) c and L ₁ is the 9th, 3rd or 2nd position of the carbazole residue.
As an example of the above, the bonding position between the carbazole residue and L ₁ is shown below.

Moreover, it is preferable that at least 1 of said R < ₁ > -R < ₃ > and at least 1 of R < ₅ > -R < ₇ > are groups selected from the group represented by following formula (51)-(55).

In the formula, each of R _{11 to} R ₂₃ is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted group. Aryl group having 6 to 30 ring carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkoxy group having 3 to 10 ring carbon atoms, substituted or unsubstituted ring forming carbon An aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 ring atoms, a substituted amino group, a substituted silyl group, and a halogen atom , A nitro group, a cyano group or a hydroxyl group.
a, c, d, f, g, and i are each independently an integer of 0 to 4;
b, e, h, and j are each independently an integer of 0 to 3.

R ₁₇ is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, or a substituted or unsubstituted ring carbon number 6 to 30. Or a substituted or unsubstituted heteroaryl group having 3 to 30 ring atoms.
T _{1 to} T ₅ are each independently a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 50 ring carbon atoms, or an aromatic heterocyclic group having 3 to 30 ring atoms.

Hereinafter, examples of each group of the above-described formula will be described.
The “hydrogen atom” in the present application includes a deuterium atom and a tritium atom. The “ring-forming carbon” means a carbon atom constituting a saturated ring, an unsaturated ring, or an aromatic ring, and the “ring-forming atom” includes a hetero ring (including a saturated ring, an unsaturated ring, and an aromatic ring). ) Is a carbon atom and a hetero atom.

  Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl group. N-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, n-undecanyl group, n-dodecanyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl Group, 2-hydroxyisobutyl group, 1,2-dihydroxyethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, etc. Preferably, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl Group, n- pentyl group, n- hexyl, n- heptyl, n- octyl, n- nonyl, and the like.

Further, the alkylene group of L ₁ and L ₂ (alkane residue) include residues corresponding to the alkyl group described above.

  Examples of the substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group, cyclohexylethyl group, 4-fluorocyclohexyl group, A 1-adamantyl group, a 2-adamantyl group, a 1-norbornyl group, a 2-norbornyl group and the like can be mentioned, and a cyclopentyl group and a cyclohexyl group are preferable.

In addition, examples of the cycloalkylene group (cycloalkane residue) of L ₁ and L ₂ include residues corresponding to the above-described cycloalkyl groups.

  Examples of the substituted or unsubstituted aryl group having 6 to 50 (preferably 6 to 30) ring-forming carbon atoms (monovalent aromatic hydrocarbon group) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, 1- Anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9- Naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, p-terphenyl-4-yl group, p -Terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group Group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl- 1-naphthyl group, 4-methyl-1-anthryl group, 4′-methylbiphenyl-4-yl group, 4 ″ -t-butyl-p-terphenyl-4-yl group, fluoren-1-yl group, fluorene Examples include 2-yl group, fluoren-3-yl group, and fluoren-4-yl group.

  Among them, a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4- Yl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, fluorene- 2-yl group and fluoren-3-yl group, more preferably phenyl group, 1-naphthyl group, 2-naphthyl group, m-tolyl group, p-tolyl group, fluoren-2-yl group, fluorene-3 -An yl group.

  Examples of the divalent or higher valent group of the aromatic hydrocarbon ring group include groups derived by removing a hydrogen atom from the above-described aryl group.

  Examples of the substituted or unsubstituted heteroaryl group having 3 to 30 ring atoms (monovalent aromatic heterocyclic group) include 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl Group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl Group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group Group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, 2-dibenzofuranyl group, 4- Dibenzofuranyl group, quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4- Isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3- Carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, 1-phenanthridinyl group, 2-phenanthridinyl group, 3-phenanthridyl Group, 4-phenanthridinyl group, 6-phenanthridinyl group, 7-phenanthridinyl group, 8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1,7-phenanthrolin-2-yl group, 1,7-phenanthroline-3-yl group, 1, 7-phenanthroline-4-yl group, 1,7-phenanthroline-5-yl group, 1,7-phenanthroline-6-yl group, 1,7-phenanthroline-8-yl group, 1,7-phenanthroline-9- Yl group, 1,7-phenanthroline-10-yl group, 1,8-phenanthroline-2-yl group, 1,8-phenanthroline-3-yl group, 1,8-phenanthro Rin-4-yl group, 1,8-phenanthroline-5-yl group, 1,8-phenanthroline-6-yl group, 1,8-phenanthroline-7-yl group, 1,8-phenanthroline-9-yl group 1,8-phenanthroline-10-yl group, 1,9-phenanthroline-2-yl group, 1,9-phenanthroline-3-yl group, 1,9-phenanthroline-4-yl group, 1,9-phenanthroline -5-yl group, 1,9-phenanthroline-6-yl group, 1,9-phenanthroline-7-yl group, 1,9-phenanthroline-8-yl group, 1,9-phenanthroline-10-yl group, 1,10-phenanthroline-2-yl group, 1,10-phenanthroline-3-yl group, 1,10-phenanthroline-4-yl group, 1,10-phenanthroline-5 Yl group, 2,9-phenanthroline-1-yl group, 2,9-phenanthroline-3-yl group, 2,9-phenanthroline-4-yl group, 2,9-phenanthroline-5-yl group, 2,9 -Phenanthroline-6-yl group, 2,9-phenanthroline-7-yl group, 2,9-phenanthroline-8-yl group, 2,9-phenanthroline-10-yl group, 2,8-phenanthroline-1-yl Group, 2,8-phenanthroline-3-yl group, 2,8-phenanthroline-4-yl group, 2,8-phenanthroline-5-yl group, 2,8-phenanthroline-6-yl group, 2,8- Phenanthroline-7-yl group, 2,8-phenanthroline-9-yl group, 2,8-phenanthroline-10-yl group, 2,7-phenanthroline-1-yl group, 2,7 Phenanthroline-3-yl group, 2,7-phenanthroline-4-yl group, 2,7-phenanthroline-5-yl group, 2,7-phenanthroline-6-yl group, 2,7-phenanthroline-8-yl group 2,7-phenanthroline-9-yl group, 2,7-phenanthroline-10-yl group, 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group 4-phenothiazinyl group, 10-phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 10-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group, 5- Oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl Group, 2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group, 2-methylpyrrol-3-yl group, 2-methylpyrrol-4-yl group, 2-methylpyrrol-5-yl Group, 3-methylpyrrol-1-yl group, 3-methylpyrrol-2-yl group, 3-methylpyrrol-4-yl group, 3-methylpyrrol-5-yl group, 2-t-butylpyrrole-4 -Yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl- 3-indolyl group, 2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group, 2-t-butyl-3-indolyl group, 4-t-butyl-3-indolyl group, 2 -Thienyl group, 3-thienyl group, -Benzothiophenyl group, 3-thiophenyl group, 4-thiophenyl group, 5-thiophenyl group, 6-thiophenyl group, 7-thiophenyl group, 1-isothiophenyl group, 3-isothiophenyl group, 4-isothiophenyl Group, 5-isothiophenyl group, 6-isothiophenyl group, 7-isothiophenyl group, 2-dibenzothiophenyl group, 4-dibenzothiophenyl group and the like.

  Preferably, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group, 2-dibenzothiophenyl group, 4-dibenzothiophenyl group.

  Examples of the divalent or higher valent group of the aromatic heterocyclic group include groups derived by removing a hydrogen atom from the above-described heteroaryl group.

Examples of the substituted amino group include a substituted or unsubstituted mono- or dialkylamino group, or a substituted or unsubstituted mono- or diarylamino group.
Examples of the alkylamino group or dialkylamino group include those in which the alkyl moiety is the alkyl group described above.
Examples of the arylamino group include a diarylamino group and an alkylarylamino group. Examples of the alkyl group and aryl group bonded to the nitrogen atom include the above-described aryl group and alkyl group.
In addition, examples of the arylamine residue of L ₁ and L ₂ include a triarylamine residue and an alkylarylamine residue. Examples of the alkyl group and aryl group bonded to the nitrogen atom include the above-described aryl group and alkyl group.

Substituted silyl groups include silyl groups substituted with alkyl and / or aryl. Examples of the alkyl group and aryl group bonded to the silicon atom include the above-described aryl group and alkyl group. The alkyl groups substituted on the silyl group may be the same or different. Similarly, the aryl groups substituted on the silyl group may be the same or different.
Specifically, the trialkylsilyl group includes a trimethylsilyl group, a vinyldimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a propyldimethylsilyl group, a tributylsilyl group, a t-butyldimethylsilyl group, a tripentylsilyl group, a tripentylsilyl group, A heptylsilyl group, a trihexylsilyl group, etc. are mentioned. A trimethylsilyl group and a triethylsilyl group are preferable.
Examples of the arylsilyl group include an alkylarylsilyl group and a triarylsilyl group. Examples of the triarylsilyl group include a triphenylsilyl group and a trinaphthylsilyl group. A triphenylsilyl group is preferred. Examples of the alkylarylsilyl group include a dimethylphenylsilyl group, a diethylphenylsilyl group, a diphenylmethylsilyl group, and an ethyldiphenylsilyl group. A diphenylmethylsilyl group and an ethyldiphenylsilyl group are preferred.

  A C1-C20 alkoxy group is represented as -OY and the example of said alkyl group is mentioned as an example of Y. The alkoxy group is, for example, a methoxy group or an ethoxy group.

  A cycloalkoxy group having 3 to 10 ring carbon atoms is represented as -OY, and examples of Y include the above-described cycloalkyl groups. The cycloalkoxy group is, for example, a cyclopentyloxy group or a cyclohexyloxy group.

  The aryloxy group having 6 to 30 ring carbon atoms is represented as -OY, and examples of Y include the above aromatic hydrocarbon rings. The aryloxy group is, for example, a phenoxy group.

  The aralkyl group having 7 to 40 carbon atoms is represented by -Y-Z. Examples of Y include alkylene examples corresponding to the above alkyl groups, and examples of Z include the above aryl groups. It is done. The aryl part of the aralkyl group preferably has 6 to 30 carbon atoms. The alkyl moiety preferably has 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. For example, a benzyl group, a phenylethyl group, and a 2-phenylpropan-2-yl group.

  As a halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are mentioned, Preferably it is a fluorine atom.

As the substituent for each of the above groups, each independently a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, or a ring-forming carbon number of 3 A cycloalkyl group having 20 to 20 carbon atoms, a trialkylsilyl group having an alkyl group having 1 to 20 carbon atoms, a triarylsilyl group having an aryl group having 6 to 24 ring carbon atoms, an alkyl group having 1 to 20 carbon atoms, and ring formation An alkylarylsilyl group having an aryl group having 6 to 24 carbon atoms, an aryl group having 6 to 24 ring carbon atoms, a heteroaryl group having 5 to 24 ring atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, or It is a cyano group. Specific examples include the aryl group, alkyl group, cycloalkyl group, trialkylsilyl group, triarylsilyl group, alkylarylsilyl group, heteroaryl group, alkoxy group, halogen atom, and cyano group. Furthermore, these groups may have a similar substituent.
Examples of the alkenyl group include a substituent having an unsaturated bond in the molecule of the alkyl group described above.

In the present invention, the crosslinkable group means a group having a “part having crosslinkability” by heat, light, acid, electron beam or the like such as a known unsaturated double bond, epoxy group, or okitacene. Examples of the crosslinkable group include the following.

In said each formula, n represents the integer of 0-10.
R _X represents a hydrogen atom, an alkyl group, or a halogen. As an alkyl group, a C1-C20 thing is mentioned, Especially preferably, it is a C1-C4 alkyl group.
R _Y represents a hydrogen atom, an alkyl group, an amino group, an aryl group, a halogen atom, an amide group or a carbonyl group. As an alkyl group, a C1-C20 thing is mentioned, Especially preferably, it is a C1-C4 alkyl group.

Specifically, groups selected from the groups represented by the following formulas (31) to (42) are preferable.

（式（４５）及び（４６）において、ｏは、１〜１０の整数である。） Incidentally, the crosslinking group also includes groups bonded to the crosslinkable group in the linking group exemplified above L ₁ and L _2. Of these, a group selected from the groups represented by the following formulas (43) to (46) is preferable.

(In formulas (45) and (46), o is an integer of 1 to 10.)

  The polymers of the present invention are preferably those represented by the following formulas (1) to (7). Especially, what is represented by following formula (8)-(25) is preferable. In addition, in the following formula, in order to express the bonding state of the structural units A and B and the content ratio in the polymer, it is described as a block copolymer for convenience, but only the block copolymer is described. It is not shown. The polymer of the present invention is not limited to a block copolymer, and includes a random copolymer (for example, -ABBABBBAAABA-) and the like.

In the formulas _{above, R 1, R 2, R} 5, R 6, L 1 and _{L 2, R} 1, _{R 2} in the formula (A) and _{(B), R 5, R} 6, L 1 and is the same as that of L _2.
m and n each represent the content (molar ratio) of each structural unit in the polymer, m is 0.01 to 0.99, n is 0.01 to 0.99, and m + n = 1. .
l is 0 or 1.

In the present invention, a polymer in which at least one of R ₅ or at least one of R ₆ of each polymer represented by the above formulas (1) to (25) is a crosslinkable group is more preferable. In this case, L ₂ may be a crosslinkable group, but not all L ₂ may be crosslinkable groups.
Further, it is preferable that the formula (1) to at least one of L ₂ of each polymer represented by (21) is a polymer which is crosslinkable group. In this case, R ₅ and R ₆ may be crosslinkable groups, but not all R ₅ and R ₆ may be crosslinkable groups.

In addition, at least one of R ₁ , R ₂ , R ₅ and R ₆ of each polymer represented by the formulas (1) to (25) is a group represented by the above-described formulas (51) to (55). Is preferably a group selected from:

There is no restriction | limiting in particular in the molecular weight of the polymer of this invention, From the oligomer more than a dimer to an ultra high molecular body is contained.
The polymer has a number average molecular weight (Mn), preferably 10 ³ to 10 ⁸ , more preferably 5 × 10 ³ to 10 ⁶ . Further, a weight average molecular weight (Mw), preferably from ¹⁰ 3 to 10 ^8, more preferably from 5 × ¹⁰ 3 to 10 ^6. The molecular weight distribution represented by Mw / Mn is not particularly limited, but is preferably 10 or less, and more preferably 3 or less.

If the molecular weight of the polymer is too large, it becomes impossible to form a uniform film in device fabrication due to gelation. On the other hand, if the molecular weight is too small, it may be difficult to control the solubility.
The number average molecular weight and the weight average molecular weight can be determined by calibration with standard polystyrene using size exclusion chromatography (SEC).

The polymer of the present invention is obtained by polymerizing a polymerizable monomer corresponding to each group of P, Q, L ₁ and L ₂ of the structural units A and B.
The polymerization method is not particularly limited, but the Suzuki polymerization method in which a dihalide derivative corresponding to each of the above groups and a diboronic acid derivative or a boronic acid ester derivative are coupled with a palladium catalyst is desirable. The halogen of the dihalide derivative is more preferably Br or I than Cl. The coupling partner of the dihalide derivative is more preferably a boronic acid ester derivative than the boronic acid. In particular, boronic acid ester derivatives, dipinacol ester derivatives, and di-1,3-propanediol derivatives are preferable.

In the polymer of the present invention, the molar ratio between the structural unit A and the structural unit B is preferably 0.01 to 0.99, respectively. Adjustments may be made so that the thermosetting properties required for the polymer are obtained within this range. When the content of the structural unit B having a thermally crosslinkable group increases, the crosslinkability of the polymer also increases.
More preferably, the molar ratio of the structural unit A is 0.85 to 0.99, and particularly preferably 0.95 to 0.99.

Specific examples of the polymer of the present invention [compounds (1-1) to (196-18)] are shown below. However, the polymer of the present invention is not limited to these.
In the following tables, H is a hydrogen atom, and H-1 to H-18, H-29, and H-30 represent the following groups. m and n each represent the content (molar ratio) of each structural unit in the polymer, m is 0.01 to 0.99, n is 0.01 to 0.99, and m + n = 1. .
Similarly to the above formulas (1) to (25), in the following formula, in order to express the bonding state of the structural units A and B and the content of the polymer in the polymer, for convenience, like a block copolymer Although described, it does not represent only block copolymers.

  The polymer of the present invention can form a thin film by a coating method. As the coating method, a wet film forming method is preferably used. Specifically, letterpress printing method, intaglio printing method, planographic printing method, stencil printing method, printing method combining these and offset printing method, inkjet printing method, dispenser spin coating method, bar coating method, dip coating method Spray coating method, slit coating method, roll coating method, cap coating method, gravure roll coating method, meniscus coating method and the like can be applied. In particular, when fine patterning is required, a relief printing method, an intaglio printing method, a lithographic printing method, a stencil printing method, a printing method combining these and an offset printing method, an inkjet printing method, a dispenser coating, and the like are preferable. Alternatively, a method may be used in which the polymer is formed on the transfer precursor substrate by the dry or wet film formation method described above, and then transferred onto a wiring substrate having a target electrode by laser light or heat press. Film formation by these methods can be performed under conditions well known to those skilled in the art, and details thereof are omitted.

The coating liquid used for the coating method contains the polymer of the present invention and a solvent. The polymer in the coating solution may be dissolved or dispersed in the solvent.
The solvent is preferably an organic solvent, and examples of the organic solvent include chloroform, chlorobenzene, chlorotoluene, chloroxylene, chloroanisole, dichloromethane, dichlorobenzene, dichlorotoluene, dichloroethane, trichloroethane, trichlorobenzene, trichloromethylbenzene, and bromobenzene. , Chlorinated solvents such as dibromobenzene and bromoanisole, ether solvents such as tetrahydrofuran, dioxane, dioxolane, oxazole, methylbenzoxazole, benzoisoxazole, furan, furazane, benzofuran, dihydrobenzofuran, ethylbenzene, diethylbenzene, triethylbenzene, trimethyl Benzene, trimethoxybenzene, propylbenzene, isopropylbenzene, diisopropyl Benzene, dibutylbenzene, amylbenzene, dihexylbenzene, cyclohexylbenzene, tetramethylbenzene, dodecylbenzene, benzonitrile, acetophenone, methylacetophenone, methoxyacetophenone, toluic acid ethyl ester, toluene, ethyltoluene, methoxytoluene, dimethoxytoluene, trimethoxy Toluene, isopropyltoluene, xylene, butylxylene, isopropylxylene, anisole, ethylanisole, dimethylanisole, trimethylanisole, propylanisole, isopropylanisole, butylanisole, methylethylanisole, anetholeanisyl alcohol, methylbenzoate, ethylbenzoate, Propyl benzoate, butyl benzoate, diphenyl ether, Aromatic hydrocarbon solvents such as tilphenyl ether, benzyl methyl ether, benzyl ethyl ether, methylenedioxybenzene, methylnaphthalene, tetrahydronaphthalene, aniline, methylaniline, ethylaniline, butylaniline, biphenyl, methylbiphenyl, isopropylbiphenyl, Aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, tetradecane, decalin, isopropylcyclohexane, acetone , Ketone solvents such as methyl ethyl ketone, cyclohexanone, acetophenone, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate, phenyl acetate, ethylene glycol Polyhydric alcohols such as ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and the like Examples include derivatives, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. . These organic solvents can be used alone or in combination.

  Among these, from the viewpoint of solubility, film formation uniformity, viscosity characteristics, etc., at least toluene, xylene, ethylbenzene, amylbenzene, anisole, 4-methoxytoluene, 2-methoxytoluene, 1,2-dimethoxybenzene, mesitylene , Tetrahydronaphthalene, cyclohexylbenzene, 2,3-dihydrobenzofuran, cyclohexanone, and methylcyclohexanone are preferably included.

In addition, a viscosity adjusting agent, a surface tension adjusting agent, a crosslinking reaction initiator, and a crosslinking reaction catalyst may be added to the film-forming solution as necessary. For the viscosity modifier, surface tension modifier, crosslinking reaction initiator, and crosslinking reaction catalyst, select one that does not affect the device characteristics even if it remains in the film, or the film is formed in the film formation process. What can be removed from inside is desirable.
In the present invention, it is preferable that at least one polymer is contained in the solvent and the polymer is dispersed or dissolved to form a dispersion or solution.

  After the film formation, the polymer thin film can be formed by drying by vacuum or heating and removing the solvent. The resulting film can be completely insolubilized by light irradiation or heating (for example, about 250 ° C.) to crosslink the polymer.

  When forming a thin film, a reaction initiator such as an antioxidant or a polymerization initiator that does not affect the performance of the organic EL element, such as a phosphorus-based antioxidant, may be blended. Moreover, you may mix | blend another compound (for example, acceptor material mentioned later) etc. according to a use.

A method of curing the polymer by crosslinking (polymerization) is not particularly limited, and examples thereof include radical polymerization, ionic polymerization, living polymerization, radical living polymerization, and coordination polymerization.
Examples of the initiator for the radical polymerization method include azo compounds and peroxides, and azobisisobutyronitrile (AIBN), azobisisobutyric acid diester derivatives, and dibenzoyl peroxide (BPO) are preferable.
As the initiator for cationic polymerization, various strong acids (p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc.) and Lewis acids are preferable.
It is also possible to polymerize by light irradiation and / or heat treatment.

The polymer of the present invention can form a thin film by a coating method, and the resulting film has a hole transporting property. Therefore, it is useful as an electronic material. For example, it can be used for an electronic element such as an electroluminescence element, a photoelectric conversion element, or a transistor.
In particular, it is suitable as a material for an organic electroluminescence element, particularly a material (hole transport layer, hole injection layer, etc.) used in a hole transport region between an anode and a light emitting layer.

In the organic EL device of the present invention, one or more organic thin film layers including at least a light emitting layer are sandwiched between a cathode and an anode. And at least 1 layer of an organic thin film layer contains the polymer of this invention.
In this invention, it has an organic thin film layer between an anode and a light emitting layer, and it is preferable that this layer is an organic thin film layer containing the polymer of this invention. Examples of the layer formed in the hole transport region include a hole transport layer and a hole injection layer.
In addition, the hole injection layer or the hole transport layer is preferably in contact with the light emitting layer. In this case, the light emitting layer can be formed by a wet film forming method following the hole injection layer or the hole transport layer.

  In the present invention, the polymer is more preferably contained as a main component of at least one of a hole transport layer and a hole injection layer. Specifically, in the hole transport layer or the hole injection layer, the content of the polymer of the present invention is preferably 51 to 100% by weight.

  Furthermore, it is preferable that at least one of the hole transport layer and the hole injection layer contains an acceptor material. In particular, the layer in contact with the anode is preferably contained. Inclusion of the acceptor material increases the hole density in the hole injecting / transporting layer and increases the hole mobility, thereby reducing the driving voltage of the resulting organic EL device and improving the carrier balance. To extend the service life.

The acceptor material is preferably an organic compound having an electron-withdrawing substituent or an electron-deficient ring.
Examples of the electron-withdrawing substituent include halogen, CN-, carbonyl group, arylboron group and the like.

  Examples of electron-deficient rings include 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 2-imidazole, 4-imidazole, 3-pyrazole, 4-pyrazole, pyridazine, and pyrimidine. , Pyrazine, cinnoline, phthalazine, quinazoline, quinoxaline, 3- (1,2,4-N) -triazolyl, 5- (1,2,4-N) -triazolyl, 5-tetrazolyl, 4- (1-O, 3-N) -oxazole, 5- (1-O, 3-N) -oxazole, 4- (1-S, 3-N) -thiazole, 5- (1-S, 3-N) -thiazole, 2 A compound selected from the group consisting of -benzoxazole, 2-benzothiazole, 4- (1,2,3-N) -benzotriazole, and benzimidazole, Not be limited to these.

As typical element structures of the organic EL element of the present invention, the following structures (1) to (13) can be exemplified.
(1) Anode / light emitting layer / cathode (2) Anode / hole injection layer / light emitting layer / cathode (3) Anode / light emitting layer / electron injection layer / cathode (4) Anode / hole injection layer / light emitting layer / electron Injection layer / cathode (5) Anode / organic semiconductor layer / light emitting layer / cathode (6) Anode / organic semiconductor layer / electron barrier layer / light emitting layer / cathode (7) Anode / organic semiconductor layer / light emitting layer / adhesion improving layer / Cathode (8) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode (9) Anode / insulating layer / light emitting layer / insulating layer / cathode (10) Anode / inorganic semiconductor layer / insulating layer / Light emitting layer / insulating layer / cathode (11) Anode / organic semiconductor layer / insulating layer / light emitting layer / insulating layer / cathode (12) Anode / insulating layer / hole injection layer / hole transport layer / light emitting layer / insulating layer / Cathode (13) Anode / insulating layer / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode

  Of these, the configuration (8) is preferably used, but is not limited thereto.

  In the organic EL device of the present invention, known members can be used for the constituent members other than the organic thin film layer containing the polymer of the present invention. For example, the light emitting layer preferably contains a styrylamine compound, an arylamine compound, or a fluoranthene compound.

Forming other than the organic thin film layer containing the polymer of the present invention is a wet film forming method such as a vacuum film forming method such as vacuum deposition, sputtering, plasma, ion plating, or a wet film forming method such as a coating method or a printing method. A known method such as the above can be applied.
The thickness of each layer is not particularly limited, but must be set to an appropriate thickness. If the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too thin, pinholes and the like are generated, and sufficient light emission luminance cannot be obtained even when an electric field is applied. The normal film thickness is suitably in the range of 5 nm to 10 μm, but more preferably in the range of 10 nm to 0.2 μm.

  After insolubilization of the polymer of the present invention, in the case of further laminating it, any of the dry film formation method and the wet film formation method can be used as described above, but the wet film formation method is particularly preferably used. it can. As the means for laminating this upper layer, there are a relief printing method, an intaglio printing method, a lithographic printing method, a stencil printing method, a printing method combining these and an offset printing method, an ink jet printing method, a dispenser spin coating method, a bar coating method. The method, dip coating method, spray coating method, slit coating method, roll coating method, cap coating method, gravure roll coating method, meniscus coating method, etc. can be applied.

  An organic EL device is produced by forming an anode, a light emitting layer, a hole injection / transport layer as required, and an electron injection / transport layer as necessary, and further forming a cathode by various materials and layer forming methods. be able to. Moreover, an organic EL element can also be produced from the cathode to the anode in the reverse order.

Example 1
The following polymer P-1 was synthesized.

(1) Synthesis of monomer M-1

(A) Synthesis of Intermediate M-1-1 Under a nitrogen atmosphere, 100 mL of N, N-dimethylformamide (DMF) was added to 10.0 g (59.8 mmol) of carbazole in a 500 mL three-necked flask with a cooling tube, and ice water Cooled to 0 ° C. in a bath. After cooling, a solution prepared by dissolving 10.6 g (59.8 mmol) of N-bromosuccinimide (NBS) in 100 mL of DMF was slowly added dropwise. After completion of the dropwise addition, the ice-water bath was removed, the temperature was returned to room temperature, and the mixture was stirred for 8 hours.

  The reaction solution was dropped into water to precipitate a solid, and a precipitate was obtained by filtration. The obtained crude product was purified by silica gel chromatography (toluene), and the obtained solid was dried under reduced pressure to obtain 12.2 g (yield 83%) of a white solid.

^The white powder obtained was identified as Intermediate M-1-1 by ¹ H-NMR spectrum and field desorption mass spectrum (hereinafter, FD-MS) analysis.

(B) Synthesis of Intermediate M-1-2 Under a nitrogen atmosphere, in a 300 mL three-necked flask with a condenser tube, M-1-1 6.0 g (24.3 mmol), iodobenzene 5.4 g (26.7 mmol), CuI1. To 4 g (7.29 mmol), trans-cyclohexanediamine 0.8 g (7.29 mmol) and potassium phosphate 10.3 g (48.6 mmol) was added 120 mL of dioxane, and the mixture was heated at reflux for 8 hours.

After completion of the reaction, the solvent was removed by removing under reduced pressure. Thereafter, 100 mL of dichloromethane and 100 mL of water were added to extract the target product, and the organic layer was taken out. MgSO ₄ was added to the extracted organic layer for drying, and MgSO ₄ was removed by filtration. The solvent was removed under reduced pressure, and the resulting crude product was purified by silica gel chromatography (toluene: hexane = 1: 10). When the obtained solid was dried under reduced pressure, 6.7 g (yield 85%) of a white solid was obtained.

^The white powder obtained was identified as Intermediate M-1-2 by ¹ H-NMR spectrum and FD-MS analysis.

(C) Synthesis of Intermediate M-1-3 In a 300 mL three-necked flask with a condenser tube under a nitrogen atmosphere, 4.0 g (12.5 mmol) of M-1-2 and 2.8 g (15.0 mmol) of triisopropyl borate Then, 60 mL of dehydrated tetrahydrofuran (THF) was added and stirred, and cooled to −78 ° C. in a methanol / dry ice bath. After cooling, 38 mL (60.9 mmol) of n-butyllithium (1.61M) was slowly added dropwise, and the mixture was stirred for 1 hour after cooling. Next, it returned to room temperature and stirred for 7 hours. After completion of the reaction, 10 mL of methanol was added dropwise, and 30 mL of 1N HCl aqueous solution was further added dropwise. Methylene chloride and water were added, the target product was extracted, and the organic layer was taken out. MgSO ₄ was added to the organic layer for drying, and MgSO ₄ was removed by filtration. The solvent was removed under reduced pressure and isolated by column chromatography to obtain 2.1 g (yield 60%) of a white solid. ^The white powder obtained was identified as Intermediate M-1-3 by ¹ H-NMR spectrum and FD-MS analysis.

(D) Synthesis of Intermediate M-1-4 In a 300 mL three-necked flask with a cooling tube in a nitrogen atmosphere, M-1-1 4 g (10.0 mmol), M-1-3 3.7 g (10.0 mmol) , Pd (PPh ₃ ) ₄ 0.2 g (0.2 mol), sodium carbonate 2.1 g (20.0 mmol), dimethyl ether (DME) 40 mL, and water 20 mL were added, and the mixture was refluxed and stirred for 8 hours. After completion of the reaction, the solvent was removed by removing under reduced pressure. Thereafter, 100 mL of dichloromethane and 100 mL of water were added to extract the target product, and the organic layer was taken out. MgSO ₄ was added to the extracted organic layer for drying, and MgSO ₄ was removed by filtration. The solvent was removed under reduced pressure, and the resulting crude product was purified by silica gel chromatography. When the obtained solid was dried under reduced pressure, 3.0 g (yield 74%) of a white solid was obtained.

^The white powder obtained was identified as Intermediate M-1-4 by ¹ H-NMR spectrum and FD-MS analysis.

(E) Synthesis of Intermediate M-1-5 Under a nitrogen atmosphere, M-1-4 2.5 g (6.1 mmol), 4- (4-bromophenyl) -dibenzofuran 2.0 g (6.1 mmol), CuI To 0.4 g (1.8 mmol), trans-cyclohexanediamine, and 2.6 g (12.2 mmol) of potassium phosphate, 30 mL of dioxane was added and heated while refluxing for 8 hours.

After completion of the reaction, the solvent was removed by removing under reduced pressure. Thereafter, 100 mL of dichloromethane and 100 mL of water were added to extract the target product, and the organic layer was taken out. MgSO ₄ was added to the extracted organic layer for drying, and MgSO ₄ was removed by filtration. The solvent was removed under reduced pressure, and the resulting crude product was purified by silica gel chromatography. When the obtained solid was dried under reduced pressure, 2.8 g (yield 70%) of a white solid was obtained.

^The white powder obtained was identified as Intermediate M-1-5 by ¹ H-NMR spectrum and FD-MS analysis.

(F) Synthesis of M-1 Under a nitrogen atmosphere, 40 mL of DMF was added to 2.5 g (3.8 mmol) of M-1-5 and cooled to 0 ° C. in an ice water bath.

  After cooling, a solution prepared by dissolving 1.4 g (8.0 mmol) of N-bromosuccinimide in 40 mL of DMF was slowly added dropwise. After completion of dropping, the ice water bath was removed, the temperature was returned to room temperature, and the mixture was stirred for 8 hours. The reaction solution was dropped into water to precipitate a solid, which was collected by suction filtration.

  The obtained crude product was purified by silica gel chromatography, and the obtained solid was dried under reduced pressure to obtain 2.5 g (yield 80%) of a white solid.

^The white powder obtained was identified as M-1 by ¹ H-NMR spectrum and FD-MS analysis.

(2) Synthesis of monomer M-2

(A) Synthesis of intermediate M-2-1 Using intermediate M-1-4 and 4-bromo-1,2-dihydrocyclobutabenzene, the same method as the synthesis of intermediate M-1-2 Was synthesized. The target product was obtained in a yield of 5.6 g (yield 86%). ^The powder was identified as M-2-1 by ¹ H-NMR spectrum and FD-MS analysis.

(B) Synthesis | combination of M-2 It synthesize | combined by the method similar to the synthesis | combination of the intermediate body M-1 using the intermediate body M-2-1. The target product was obtained in a yield of 4.4 g (yield 78%). ^The powder was identified as M-2 by ¹ H-NMR spectrum and FD-MS analysis.

(3) Synthesis of polymer P-1

Under nitrogen atmosphere, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-di-n-octylfluorene (4.1 g) (6. 2 mmol), M-1 5.0 g (6.2 mmol), M-2 0.2 g (0.3 mmol), palladium acetate [Pd (OAc) ₂ ] 0.01 g (0.04 mmol), tri (o-tolyl) ) Add phosphine [P (o-Tol) ₃ ] 0.06 g (0.2 mmol), potassium phosphate 6.6 g (30.9 mmol), dioxane 50 mL, toluene 12 mL, water 11 mL, and heat while refluxing for 16 hours. did.

After completion of the reaction, the solvent was removed by removing under reduced pressure. 150 mL of toluene and 100 mL of water were added to extract the target product, and the organic layer was taken out. MgSO ₄ was added to the extracted organic layer for drying, and MgSO ₄ was removed by filtration. The solvent was concentrated under reduced pressure, and the concentrate was filtered through silica gel. The collected solution was concentrated under reduced pressure and added dropwise to methanol to precipitate a solid. The solid was collected by filtration and dried under reduced pressure.

Under a nitrogen atmosphere, this crude product, 0.3 g (1.9 mmol) of bromobenzene, 0.03 g (0.04 mmol) of Pd (OAc) _2, 0.01 g (0.05 mmol) of P (t-Bu) ₃ Then, potassium phosphate (2.0 g, 9.5 mmol) and toluene (50 mL) were added, and the mixture was heated under reflux for 8 hours. Next, 0.2 g (1.9 mmol) of phenylboronic acid was added and further heated for 8 hours.

After completion of the reaction, 100 mL of water was added to extract the target product, and the organic layer was taken out. MgSO ₄ was added to the extracted organic layer for drying, and MgSO ₄ was removed by filtration. The collected filtrate was filtered through silica gel. The collected solution was concentrated, sodium diethyldithiacarbamate aqueous solution was added, and the mixture was stirred at 80 ° C. for 8 hours. After cooling, the organic layer was washed with water, and the resulting solution was added dropwise to methanol and collected by filtration to obtain a precipitate.

This precipitate was dissolved in toluene and purified by passing through a silica gel column. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 5.3 g of polymer P-1.
The polystyrene equivalent number average molecular weight of P-1 was 7.8 × 10 ³ , and the polystyrene equivalent weight average molecular weight was 2.4 × 10 ⁴ .

In the present application, the molecular weight and molecular weight distribution were measured under the following conditions.
100 μl of a solution prepared by dissolving 10 mg of a sample in 10 ml of THF was injected. The flow rate was 1 ml / min and the column temperature was set to 40 ° C. Tosoh HLC-8220 was used as the size exclusion chromatography (SEC) apparatus. As the detector, a differential refraction (RI) detector or an ultraviolet-visible (UV) detector was used. Two TSKgel GMH-XL and one TSKgel G2000-XL manufactured by Tosoh were used as the columns, and TSK standard polystyrene manufactured by Tosoh was used as the standard sample polystyrene.

Example 2
The following polymer P-2 was synthesized.

(1) Synthesis of monomer M-3

(A) Synthesis of Intermediate M-3-1 Except that NBS was changed to N-iodosuccinimide (NIS), synthesis was performed in the same manner as the synthesis of Intermediate M-1-1. The target product was obtained in a yield of 5.6 g (yield 79%). ^The powder was identified as M-3-1 by ¹ H-NMR spectrum and FD-MS analysis.

(B) Synthesis of Intermediate M-3-2 The synthesis was performed in the same manner as the synthesis of Intermediate M-1-1 except that Intermediate M-3-1 was used. The target product was obtained in a yield of 3.7 g (82% yield). ^The powder was identified as M-3-2 by ¹ H-NMR spectrum and FD-MS analysis.

(C) Synthesis of Intermediate M-3-3 The intermediate M-3-2 and the intermediate M-1-3 were used and synthesized in the same manner as the synthesis of the intermediate M-1-4. The target product was obtained in a yield of 5.2 g (76% yield). ^The powder was identified as M-3-3 by ¹ H-NMR spectrum and FD-MS analysis.

(D) Synthesis of M-3 The intermediate M-3-3 and 1-bromo-4-iodobenzene were used and synthesized in the same manner as the synthesis of the intermediate M-1-2. The target product was obtained in a yield of 4.9 g (yield 66%). ^The powder was identified as M-3 by ¹ H-NMR spectrum and FD-MS analysis.

(2) Synthesis of monomer M-4

(A) Synthesis of Intermediate M-4-1 Using carbazole and bromocyclobutabenzene, the intermediate M-1-2 was synthesized in the same manner as the intermediate M-1-2. The target product was obtained in a yield of 7.9 g (yield 90%). ^The powder was identified as M-4-1 by ¹ H-NMR spectrum and FD-MS analysis.

(B) Synthesis of Intermediate M-4-2 Intermediate M-4-1 was used and synthesized in the same manner as the synthesis of intermediate M-1-1. The target product was obtained in a yield of 6.8 g (yield 77%). ^The powder was identified as M-4-2 by ¹ H-NMR spectrum and FD-MS analysis.

(C) Synthesis of Intermediate M-4-3 Intermediate M-4-2 was used and synthesized in the same manner as intermediate M-1-3. The target product was obtained in a yield of 5.5 g (yield 75%). ^The powder was identified as M-4-3 by ¹ H-NMR spectrum and FD-MS analysis.

(D) Synthesis of Intermediate M-4-4 Intermediate M-3-2 and intermediate M-4-3 were used and synthesized in the same manner as intermediate M-1-4. The target product was obtained in a yield of 6.1 g (yield 60%). ^The powder was identified as M-4-4 by ¹ H-NMR spectrum and FD-MS analysis.

(E) Synthesis of M-4 Using the intermediate M-4-4 and 1-bromo-4-iodobenzene, the synthesis was performed in the same manner as the synthesis of the intermediate M-1-2. The target product was obtained in a yield of 5.3 g (yield 77%). ^The powder was identified as M-4 by ¹ H-NMR spectrum and FD-MS analysis.

(3) Synthesis of polymer P-2

Using 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-di-n-octylfluorene, M-3 and M-4 And synthesized in the same manner as P-1. The target product was obtained in a yield of 5.2 g. The polystyrene equivalent number average molecular weight of P-2 was 1.2 × 10 ⁴ , and the polystyrene equivalent weight average molecular weight was 3.5 × 10 ⁴ .

Example 3
The following polymer P-3 was synthesized.

(1) Synthesis of monomer M-5

(A) Synthesis of Intermediate M-5-1 Under a nitrogen stream, 18.3 g (100 mmol) of 4-bromo-1,2-dihydrocyclobutabenzene was added 300 mL of dehydrated THF, cooled to −78 ° C., and n- 130 mL of butyl lithium hexane solution (1.58M) was added dropwise. After stirring for 1 hour, 16.5 mL of 1,6-diiodohexane was slowly added dropwise, the temperature was raised to room temperature over 1 hour, and the reaction was further continued for 2 hours. A 10% diluted hydrochloric acid solution was added and stirred, and the organic layer was extracted. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The obtained solid was purified by silica gel chromatography and dried under reduced pressure to obtain 12.6 g (yield 37%) of a colorless liquid. ^The powder was identified as M-5-1 by ¹ H-NMR spectrum and FD-MS analysis.

(B) Synthesis of M-5 Under a nitrogen stream, 120 mL of dehydrated THF was added to 12.5 g (38.6 mmol) of 2,7-dibromofluorene, cooled to −78 ° C., and an LDA hexane / THF solution (1.11 M). Was added dropwise. After stirring for 1 hour, 21.7 g of M-5-1 dissolved in 60 mL of dehydrated THF was slowly added dropwise, the temperature was raised to room temperature over 1 hour, and the reaction was further continued for 2 hours.

A 10% dilute hydrochloric acid solution was added and stirred, methylene chloride was added to extract the target product, and the organic layer was taken out. MgSO ₄ was added to the organic layer for drying, and MgSO ₄ was removed by filtration. The solvent was removed under reduced pressure and isolated by column chromatography to obtain 12.2 g (yield 45%) of a white solid. ^The white powder obtained was identified as M-5 by ¹ H-NMR spectrum and FD-MS analysis.

(2) Synthesis of monomer M-6

(A) Synthesis of Intermediate M-6-1 Using 2-bromo-dibenzofuran, synthesis was performed in the same manner as the synthesis of Intermediate M-1-3. The target product was obtained in a yield of 6.1 g (yield 63%). ^The powder was identified as M-6-1 by ¹ H-NMR spectrum and FD-MS analysis.

(B) Synthesis of Intermediate M-6-2 Under a nitrogen stream, 10 g (59.8 mmol) of 9-H-carbazole was added and dissolved in 75 ml of chloroform, and then cooled to 0 ° C. in an ice water bath. Next, a solution obtained by slowly dispersing 38.8 g (239.2 mmol) of FeCl _{3 in} about 60 ml of chloroform was dropped. After dropping, the temperature was returned to room temperature and stirred for 24 hours. The reaction solution was added dropwise to a large amount of methanol to precipitate a solid. The solid was collected by filtration. Then, it was repeatedly washed with a large amount of methanol and water and collected by filtration to obtain 7.8 g of solid (yield 82%). ^The white powder obtained was identified as M-6-2 by ¹ H-NMR spectrum and FD-MS analysis.

(C) Synthesis of Intermediate M-6-3 Intermediate M-6-2 was used and synthesized in the same manner as Intermediate M-2. The target product was obtained in a yield of 4.1 g (56% yield). ^The powder was identified as M-6-3 by ¹ H-NMR spectrum and FD-MS analysis.

(D) Synthesis of M-6 Using the intermediate M-6-1 and the intermediate M-6-3, the synthesis was performed in the same manner as the synthesis of the intermediate M-1-4. The target product was obtained in a yield of 3.4 g (yield 48%). ^The powder was identified as M-6 by ¹ H-NMR spectrum and FD-MS analysis.

(3) Synthesis of polymer P-3

Under a nitrogen atmosphere, 9,9-dioctyl-2,7-dibromofluorene 5.8 g (10.0 mmol), M-5 0.4 g (0.5 mmol), M-6 7.0 g (10.5 mmol), Tris (Dibenzylideneacetone) dipalladium (0) [Pd ₂ (dba) ₃ ] 0.2 g (0.2 mmol), P (t-Bu) ₃ 0.06 g (0.3 mmol), t-butoxy sodium 3.0 g 40 mL of xylene was added to (31.5 mmol) and heated while refluxing for 20 hours.

After completion of the reaction, the solvent was removed by removing under reduced pressure. The target product was extracted by adding 100 mL of water, and the organic layer was taken out. MgSO ₄ was added to the extracted organic layer for drying, and MgSO ₄ was removed by filtration. The solvent was concentrated under reduced pressure, and the concentrate was filtered through silica gel. The collected solution was concentrated under reduced pressure and added dropwise to methanol to precipitate a solid. The solid was collected by suction filtration and dried under reduced pressure.

Under a nitrogen atmosphere, this crude product and 0.5 g (3.2 mmol) of bromobenzene, 0.04 g (0.2 mmol) of Pd (OAc) _2, 0.06 g (0.3 mmol) of P (t-Bu) ₃ , 40 mL of toluene was added to 1.1 g (5.2 mmol) of potassium phosphate, and the mixture was heated while refluxing for 8 hours. Next, 0.4 g (3.2 mmol) of phenylboronic acid was added and further heated for 8 hours.

After completion of the reaction, 100 mL of water was added to extract the target product, and the organic layer was taken out. MgSO ₄ was added to the extracted organic layer for drying, and MgSO ₄ was removed by filtration. The collected filtrate was filtered through silica gel. The collected solution was concentrated, sodium diethyldithiacarbamate aqueous solution was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the organic layer was washed with water, and the resulting solution was added dropwise to methanol and collected by filtration to obtain a precipitate.

This precipitate was dissolved in toluene and purified by passing through a silica gel column. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 7.3 g of polymer P-3. P-3 had a polystyrene equivalent number average molecular weight of 0.9 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 2.8 × 10 ⁴ .

Example 4
The following polymer P-4 was synthesized.

(1) Synthesis of monomer M-7

(A) Synthesis of Intermediate M-7-1 Using 9-phenylcarbazole, it was synthesized by the same method as the synthesis of M-2. The target product was obtained in a yield of 2.9 g (yield 73%). ^The powder was identified as M-7-1 by ¹ H-NMR spectrum and FD-MS analysis.

(B) Synthesis of Intermediate M-7-2 Using carbazole and 2-bromo-dibenzofuran, synthesis was performed in the same manner as the synthesis of Intermediate M-1-2. The target product was obtained in a yield of 4.0 g (yield 68%). ^The powder was identified as M-7-2 by ¹ H-NMR spectrum and FD-MS analysis.

(C) Synthesis of Intermediate M-7-3 Intermediate M-7-2 was used and synthesized in the same manner as Intermediate M-1-1. The target product was obtained in a yield of 3.2 g (yield 59%). ^The powder was identified as M-7-3 by ¹ H-NMR spectrum and FD-MS analysis.

(D) Synthesis of Intermediate M-7-4 Intermediate M-7-3 was used and synthesized in the same manner as intermediate M-1-3. The target product was obtained in a yield of 5.4 g (yield 66%). ^The powder was identified as M-7-4 by ¹ H-NMR spectrum and FD-MS analysis.

(E) Synthesis of Intermediate M-7-5 Intermediate M-7-4 and Intermediate M-7-1 were used and synthesized in the same manner as Intermediate M-1-4. The target product was obtained in a yield of 2.7 g (yield 61%). ^The powder was identified as M-7-5 by ¹ H-NMR spectrum and FD-MS analysis.

(F) Synthesis of M-7 Using the intermediate M-7-5, the synthesis was performed in the same manner as the synthesis of the monomer M-2. The target product was obtained in a yield of 3.9 g (56% yield). ^The powder was identified as M-7 by ¹ H-NMR spectrum and FD-MS analysis.

(2) Synthesis of monomer M-8

(A) Synthesis of Intermediate M-8-1 Intermediate M-4-1 was used and synthesized in the same manner as the synthesis of monomer M-2. The target product was obtained in a yield of 5.3 g (yield 85%). ^The powder was identified as M-8-1 by ¹ H-NMR spectrum and FD-MS analysis.

(B) Synthesis of Intermediate M-8-2 Intermediate M-8-1 and Intermediate M-7-4 were used and synthesized in the same manner as Intermediate M-1-4. The target product was obtained in a yield of 3.8 g (yield 58%). ^The powder was identified as M-8-2 by ¹ H-NMR spectrum and FD-MS analysis.

(C) Synthesis of M-8 The intermediate M-8-2 was used and synthesized in the same manner as the synthesis of M-2. The target product was obtained in a yield of 4.2 g (yield 60%). ^The powder was identified as M-8 by ¹ H-NMR spectrum and FD-MS analysis.

(3) Synthesis of polymer P-4

Using 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-di-n-octylfluorene, M-7, M-8 And synthesized in the same manner as P-1. The target product was obtained in a yield of 3.3 g. The polymer P-4 had a polystyrene equivalent number average molecular weight of 1.8 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 4.0 × 10 ⁴ .

Example 5
The following polymer P-5 was synthesized.

(1) Synthesis of monomer M-9

(A) Synthesis of intermediate M-9-1 Using carbazole and 3-bromo-dibenzofuran, intermediate M-9-0 synthesized by a method similar to the synthesis of intermediate M-1-2 was used. Then, it was synthesized by the same method as the synthesis of intermediate M-2. The target product was obtained in a yield of 4.6 g (yield 87%). ^The powder was identified as M-9-1 by ¹ H-NMR spectrum and FD-MS analysis.

(B) Synthesis of Intermediate M-9-2 Intermediate M-9-9-1 was used and synthesized in the same manner as Intermediate M-1-3. The target product was obtained in a yield of 1.9 g (43% yield). ^The powder was identified as M-9-2 by ¹ H-NMR spectrum and FD-MS analysis.

(C) Synthesis of M-9 The intermediate M-9-2 was used and synthesized in the same manner as the synthesis of the intermediate M-1-4. The target product was obtained in a yield of 3.5 g (56% yield). ^The powder was identified as M-9 by ¹ H-NMR spectrum and FD-MS analysis.

(2) Synthesis of polymer P-5

It was synthesized in the same manner as P-3 using 2,7-dibromo-9,9-di-n-octylfluorene, M-5 and M-9. The target product was obtained in a yield of 6.2 g. The polymer P-5 had a polystyrene equivalent number average molecular weight of 1.9 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 3.8 × 10 ⁴ .

Example 6
The following polymer P-6 was synthesized.

(1) Synthesis of monomer M-10

(A) Synthesis of Intermediate M-10-1 Intermediate M-10-2 was used and synthesized in the same manner as Intermediate M-1-1. The target product was obtained in a yield of 3.5 g (yield 66%). ^The powder was identified as M-10-1 by ¹ H-NMR spectrum and FD-MS analysis.

(B) Synthesis of M-10 Using the intermediate M-10-1 and the intermediate M-7-4, the synthesis was performed in the same manner as the synthesis of the intermediate M-1-4. The target product was obtained in a yield of 4.9 g (yield 72%). ^The powder was identified as M-10 by ¹ H-NMR spectrum and FD-MS analysis.

(2) Synthesis of monomer M-11

(A) Synthesis of Intermediate M-11-1 Intermediate M-4-1 was used and synthesized in the same manner as Intermediate M-1-1. The target product was obtained in a yield of 3.9 g (yield 70%). ^The powder was identified as M-11-1 by ¹ H-NMR spectrum and FD-MS analysis.

(B) Synthesis of Intermediate M-11-2 Intermediate M-11-1 was used and synthesized in the same manner as intermediate M-1-3. The target product was obtained in a yield of 4.4 g (52% yield). ^The powder was identified as M-11-1 by ¹ H-NMR spectrum and FD-MS analysis.

(C) Synthesis of M-11 Using the intermediate M-10-1 and the intermediate M-11-2, the synthesis was performed in the same manner as the synthesis of the intermediate M-1-4. The target product was obtained in a yield of 2.3 g (yield 67%). ^The powder was identified as M-11 by ¹ H-NMR spectrum and FD-MS analysis.

(3) Synthesis of polymer P-6

It was synthesized in the same manner as P-3 using 2,7-dibromo-9,9-di-n-octylfluorene, M-10, M-11. The target product was obtained in a yield of 4.6 g. The polymer P-6 had a polystyrene equivalent number average molecular weight of 1.5 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 3.3 × 10 ⁴ .

Example 7
The following polymer P-7 was synthesized.

(1) Synthesis of monomer M-12

(A) Synthesis of Intermediate M-12-1 Intermediate M-7-3 and Intermediate M-7-4 were used and synthesized in the same manner as Intermediate M-1-4. The target product was obtained in a yield of 3.6 g (82% yield). ^The powder was identified as M-12-1 by ¹ H-NMR spectrum and FD-MS analysis.

(B) Synthesis of Intermediate M-12-2 Intermediate M-12-1 was used and synthesized in the same manner as Intermediate M-1-1. The target product was obtained in a yield of 3.5 g (yield 66%). ^The powder was identified as M-12-2 by ¹ H-NMR spectrum and FD-MS analysis.

(C) Synthesis of Intermediate M-12-3 Intermediate M-12-2 was used and synthesized in the same manner as intermediate M-1-3. The target product was obtained in a yield of 4.1 g (62% yield). ^The powder was identified as M-12-3 by ¹ H-NMR spectrum and FD-MS analysis.

(D) Synthesis of Intermediate M-12-4 Intermediate M-12-3 and intermediate M-3-2 were used and synthesized in the same manner as intermediate M-1-4. The target product was obtained in a yield of 1.8 g (yield 76%). ^The powder was identified as M-12-4 by ¹ H-NMR spectrum and FD-MS analysis.

(E) Synthesis of M-12 Using the intermediate M-12-4 and 1-bromo-4-iodobenzene, the synthesis was performed in the same manner as the synthesis of the intermediate M-1-2. The target product was obtained in a yield of 2.7 g (yield 70%). ^The powder was identified as M-12 by ¹ H-NMR spectrum and FD-MS analysis.

(2) Synthesis of monomer M-13

Under a nitrogen stream, 3.7 g (5.3 mmol) of M-5, 4.1 g (31.8 mmol) of bispinacolatodiboron, 1,1′-bis (diphenylphosphino) ferrocene-palladium (II) dichloride-dichloromethane The complex [PdCl ₂ (dppf) · CH ₂ Cl ₂ ] 0.5 g (0.6 mmol), potassium acetate 3.1 g (31.8 mmol) and dehydrated DMSO were added, and the mixture was refluxed at 80 ° C. for 28 hours. After cooling, 25 mL of water was added to extract the target product, and the organic layer was taken out. MgSO ₄ was added to the extracted organic layer for drying, and MgSO ₄ was removed by filtration. The solvent was removed under reduced pressure, and the resulting crude product was purified by silica gel chromatography. The obtained solid was dried under reduced pressure to obtain 2.7 g (yield 64%) of a white solid. ^The powder was identified as M-13 by ¹ H-NMR spectrum and FD-MS analysis.

(3) Synthesis of polymer P-7

Using 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-di-n-octylfluorene, M-12, M-13 And synthesized in the same manner as P-1. The target product was obtained in a yield of 5.5 g. The polymer P-7 had a polystyrene equivalent number average molecular weight of 1.0 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 2.5 × 10 ⁴ .

Example 8
Polymer P-8 was synthesized according to the following scheme.

Using 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-di-n-octylfluorene, M-1, M-13 And synthesized in the same manner as P-1. The target product was obtained in a yield of 5.2 g. The number average molecular weight in terms of polystyrene of the polymer P-8 was 3.8 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 1.6 × 10 ⁴ .

Comparative Example 1
Polymer P-9 was synthesized according to the following scheme.

(1) Synthesis of monomer M-14 (a) Synthesis of intermediate M-14-1 In a 300 mL three-necked flask with a condenser tube under a nitrogen atmosphere, 6.0 g (35.4 mmol) of diphenylamine and bromobenzocyclobutene 6. 5 g (35.4 mmol), Pd (OAc) ₂ 0.2 g (0.9 mmol), P (t-Bu) ₃ 0.3 g (1.4 mmol), t-butoxy sodium 6.8 g (70.8 mmol) Toluene 100mL was added and it heated, making it recirculate | reflux for 8 hours.
After completion of the reaction, the solvent was removed by removing under reduced pressure. Thereafter, 100 mL of dichloromethane and 100 mL of water were added to extract the target product, and the organic layer was taken out. MgSO ₄ was added to the extracted organic layer for drying, and MgSO ₄ was removed by filtration. The solvent was removed under reduced pressure, and the resulting crude product was purified by silica gel chromatography. When the obtained solid was dried under reduced pressure, 7.2 g (yield 88%) of a white solid was obtained.

^The white powder obtained was identified as Intermediate M-14-1 by ¹ H-NMR spectrum and FD-MS analysis.

(B) Synthesis of M-14 Using the intermediate M-14-1, synthesis was performed in the same manner as the synthesis of the intermediate M-1-1. The target product was obtained in a yield of 4.8 g (68% yield). ^The powder was identified as M-14 by ¹ H-NMR spectrum and FD-MS analysis.

(2) Synthesis of P-9 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-di-n-octylfluorene, di It was synthesized in the same manner as P-1 using (4-bromophenyl) phenylamine, M-14. The target product was obtained in a yield of 5.6 g. The polymer P-9 had a polystyrene equivalent number average molecular weight of 7.8 × 10 ³ and a polystyrene equivalent weight average molecular weight of 2.4 × 10 ⁴ .

Comparative Example 2
The following polymer P-10 was synthesized.

(1) Synthesis of monomer M-16

Under a nitrogen atmosphere, 9,9-dioctyl-2,7-dibromofluorene 10.0 g (18.2 mmol), aniline 1.7 g (18.2 mmol), Pd ₂ (dba) 30.6 g (0.6 mmol), ( ±) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl (rac-BINAP) 1.7 g (0.8 mmol), t-butoxy sodium 5.0 g (72.8 mmol), toluene 500 mL was added and heated at reflux for 16 hours.

After completion of the reaction, the solvent was removed by removing under reduced pressure. The target product was extracted by adding 100 mL of water, and the organic layer was taken out. MgSO ₄ was added to the extracted organic layer for drying, and MgSO ₄ was removed by filtration. The solvent was removed under reduced pressure, and the resulting crude product was purified by silica gel chromatography. When the obtained solid was dried under reduced pressure, 6.8 g (yield 65%) of a white solid was obtained. ^The white powder obtained was identified as Intermediate M-16 by ¹ H-NMR spectrum and FD-MS analysis.

(2) Synthesis of monomer M-17

(2) Synthesis of monomer M-17 (a) Synthesis of intermediate M-17-1 Synthesis was performed in the same manner as the synthesis of intermediate M-1-4 using the above compound. The target product was obtained in a yield of 7.8 g (68% yield). ^The powder was identified as M-17-1 by ¹ H-NMR spectrum and FD-MS analysis.

(B) Synthesis of M-17 Using the intermediate M-17-1, synthesis was performed in the same manner as the synthesis of M-16. The target product was obtained in a yield of 5.8 g (yield 63%). ^The powder was identified as M-17 by ¹ H-NMR spectrum and FD-MS analysis.

(3) Synthesis of polymer P-10

Using 4,4′-dibromobiphenyl, M-16, and M-17, synthesis was performed in the same manner as for P-3. The target product was obtained in a yield of 4.5 g. The polymer P-10 had a polystyrene equivalent number average molecular weight of 1.3 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 3.6 × 10 ⁴ .

Example 9 (Production and evaluation of organic EL device)
A glass substrate with an ITO transparent electrode having a thickness of 25 mm × 75 mm × 1.1 mm (manufactured by Geomatic Co., Ltd.) was ultrasonically cleaned in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. On the glass substrate with a transparent electrode after cleaning, a film of polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT: PSS) used for the hole injection layer by spin coating is formed to a thickness of 10 nm, and the hole injection layer is formed. (PSS is an acceptor).
Subsequently, the xylene solution (1.0 wt%) of the polymer P-1 obtained in Example 1 was formed into a film with a film thickness of 25 nm by a spin coat method. Next, this was dried at 120 ° C. under reduced pressure for 1 hour to form a hole transport layer.
Further, the following compound EM1 having a film thickness of 40 nm was deposited to form a film. At the same time, an amine compound D1 having the following styryl group was deposited as a light emitting molecule so that the weight ratio of EM1 and D1 was 95: 5, thereby forming a light emitting layer.
The following Alq was deposited on this film to a thickness of 10 nm by vapor deposition. This layer functions as an electron injection layer.
Thereafter, Li (Li source: manufactured by Saesgetter Co.), which is a reducing dopant, and Alq were vapor-deposited, and an Alq: Li film (film thickness: 10 nm) was formed as an electron injection layer (cathode). Metal Al was vapor-deposited on the Alq: Li film to form a metal cathode, which was sealed with glass in nitrogen to produce an organic EL device.

  A current was passed through the produced organic EL device to evaluate luminous efficiency and lifetime. The results are shown in Table 197.

（Ｍｅはメチル基である。） Example 10
An organic EL device was prepared and evaluated in the same manner as in Example 9 except that the following arylamine compound D2 was used instead of the amine compound D1 having a styryl group as the material of the light emitting layer. The results are shown in Table 197.

(Me is a methyl group.)

Comparative Example 3
Table 197 shows the results obtained by producing and evaluating an organic EL device in the same manner as in Example 9, except that P-9 obtained in Comparative Example 1 was used instead of P-1 as the hole transport material.

Comparative Example 4
An organic EL device was prepared and evaluated in the same manner as in Example 9 except that P-10 obtained in Comparative Example 2 was used instead of P-1 as the hole transport material. The results are shown in Table 197.

  From the results of Examples 9 to 10 and Comparative Examples 3 to 4, the organic EL device using the biscarbazole polymer of the present invention has a luminous efficiency, compared with the organic EL device using the comparative compound that is an aromatic amine derivative. It can be seen that the life is excellent.

Example 11 (Organic EL device fabrication and evaluation)
A glass substrate with an ITO transparent electrode having a thickness of 25 mm × 75 mm × 1.1 mm (manufactured by Geomatic Co., Ltd.) was ultrasonically cleaned in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. On the glass substrate with a transparent electrode after cleaning, a film of polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT: PSS) used for the hole injection layer by spin coating is formed to a thickness of 10 nm, and the hole injection layer is formed. (PSS is an acceptor).
Next, a xylene solution (1.0 wt%) of the polymer P-1 obtained in Example 1 was formed into a film having a film thickness of 25 nm by a spin coating method, dried and thermally cured at 230 ° C. for 30 minutes, A hole transport layer was formed.
Next, a xylene solution (1.0 wt%) in which the compound EM1 (host) and the amine compound D1 (dopant) having a styryl group are mixed at a solid content weight ratio of 95: 5 is spin-coated to 40 nm. A light emitting layer was formed by drying at 150 ° C. for 30 minutes.
On this film, Alq was deposited to a thickness of 10 nm by vapor deposition. This layer functions as an electron injection layer. Thereafter, Li (Li source: manufactured by Saesgetter Co.), which is a reducing dopant, and Alq were vapor-deposited, and an Alq: Li film (film thickness: 10 nm) was formed as an electron injection layer (cathode). Metal Al was vapor-deposited on the Alq: Li film to form a metal cathode, which was sealed with glass in nitrogen to produce an organic EL device.
A current was passed through the produced organic EL device to evaluate the performance. The results are shown in Table 198.

Example 12
An organic EL device was prepared and evaluated in the same manner as in Example 11 except that the polymer P-2 obtained in Example 2 was used instead of P-1 as the hole transport material. The results are shown in Table 198.

Example 13
An organic EL device was prepared and evaluated in the same manner as in Example 11 except that the polymer P-3 obtained in Example 3 was used instead of P-1 as the hole transport material. The results are shown in Table 198.

Example 14
An organic EL device was prepared and evaluated in the same manner as in Example 11 except that the polymer P-4 obtained in Example 4 was used instead of P-1 as the hole transport material. The results are shown in Table 198.

Example 15
An organic EL device was prepared and evaluated in the same manner as in Example 11 except that the polymer P-5 obtained in Example 5 was used instead of P-1 as the hole transport material. The results are shown in Table 198.

Example 16
An organic EL device was prepared and evaluated in the same manner as in Example 11 except that the polymer P-6 obtained in Example 6 was used instead of P-1 as the hole transport material. The results are shown in Table 198.

Example 17
An organic EL device was prepared and evaluated in the same manner as in Example 11 except that the polymer P-7 obtained in Example 7 was used instead of P-1 as the hole transport material. The results are shown in Table 198.

Example 18
An organic EL device was prepared and evaluated in the same manner as in Example 11 except that the polymer P-8 obtained in Example 8 was used instead of P-1 as the hole transport material. The results are shown in Table 198.

Example 19
An organic EL device was prepared and evaluated in the same manner as in Example 11 except that the arylamine compound D2 was used in place of the amine compound D1 having a styryl group as the material for the light emitting layer. The results are shown in Table 198.

Comparative Example 5
An organic EL device was prepared and evaluated in the same manner as in Example 11 except that P-9 obtained in Comparative Example 1 was used instead of P-1 as the hole transport material. The results are shown in Table 198.

Comparative Example 6
An organic EL device was prepared and evaluated in the same manner as in Example 11 except that P-10 obtained in Comparative Example 2 was used instead of P-1 as the hole transport material. The results are shown in Table 198.

From the results of Examples 11 to 19 and Comparative Examples 5 and 6, the organic EL device using the biscarbazole polymer of the present invention is higher in luminous efficiency than the organic EL device using the comparative compound that is an aromatic amine derivative. It can be seen that the life is excellent.
It was also confirmed that excellent performance was obtained even when the hole injection layer, the hole transport layer, and the light emitting layer were formed by wet film formation.

  The polymer of the present invention is useful as an electronic material. In particular, it is suitable as a material for an organic electroluminescence element, particularly a material used in a hole transport region between an anode and a light emitting layer.

Claims (22)

A polymer containing structural units represented by the following formulas (A) and (B).

[In formula (A), P is a group derived from a compound represented by the following formula (P).

(In the formula, each A ₁ is independently a nitrogen atom or CR ₂ .
X ₁ is a single bond, O, S, CR ₂ R ₃ or NR ₂ .
R _{1 to} R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted group. An aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 ring atoms, a substituted or unsubstituted arylamino group, or an arylsilyl group. )
a is an integer of 2 to 5, and (P) a represents that a number of the (P) groups are bonded continuously. The a P's are independent from each other, and the bonding position between the P's is not limited.
L ₁ represents a linking group.
b is an integer from 0 to 5, _(L 1) b, when b is 2 or more, indicating _{that L 1} is bonded b pieces continuously. In this case, b pieces of L ₁ are independent from each other, and the position at which L ₁ is bonded is not limited.
In the formula (A), the bonding position of P and L ₁ is not limited.
In the formula (B), Q is a group derived from a compound represented by the following formula (Q).

(In the formula, each A ₂ is independently a nitrogen atom or CR ₆ .
X ₂ is a single bond, O, S, CR ₆ R ₇ or NR ₆ .
R _{5 to} R ₇ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted group. An aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 ring atoms, a substituted or unsubstituted arylamino group, an arylsilyl group, or a crosslinkable group. )
c is an integer of 2 to 5, and (Q) c represents that c (Q) groups are bonded in succession. The c Qs are independent of each other, and the bonding positions of the Qs are not limited.
L ₂ each independently represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 ring carbon atoms, or a substituted or unsubstituted ring carbon atom having 6 to 30 carbon atoms. An aromatic hydrocarbon ring group, a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 ring atoms, a substituted or unsubstituted arylamine residue, an arylsilylene group, or a crosslinkable group.
d is an integer from 0 to 5, _(L 1) d, when d is 2 or more, indicating _{that L 2} is bonded d items sequentially. In this case, the d pieces of L ₂ are independent from each other, and the position at which L ₂ is bonded is not limited.
In the formula (B), the bonding position of Q and L ₂ is not limited.
In formula (B), at least one of c Q and d L ₂ has a crosslinkable group. ]   The polymer according to claim 1, wherein P or Q is a residue of a substituted or unsubstituted carbazole.   a bonding position between adjacent carbazole residues in a consecutive substituted or unsubstituted carbazole residues, or a bonding position between adjacent carbazole residues in c consecutive substituted or unsubstituted carbazole residues, The polymer according to claim 2, which is a kind selected from the 3-position, 3'-position, 3-position-2'-position, and 2-position-2'-position. The polymer according to claim 2 or 3, which has at least one of the following structure 1 and structure 2.
Structure 1: The bonding position between one substituted or unsubstituted carbazole residue in (P) a and L ₁ is the 9-position, 3-position or 2-position of the carbazole residue.
Structure 2: The bonding position between one substituted or unsubstituted carbazole residue in (Q) c and L ₂ is the 9th, 3rd or 2nd position of the carbazole residue. The polymer in any one of Claims 2-4 which has at least one of the following structure 3 and the structure 4.
Structure 3: The bonding position between one substituted or unsubstituted carbazole residue in (P) a and L ₂ is the 9th, 3rd or 2nd position of the carbazole residue.
Structure 4: The bonding position between one substituted or unsubstituted carbazole residue in (Q) c and L ₁ is the 9th, 3rd or 2nd position of the carbazole residue.   Said a or c is 2 or 3, respectively, The polymer in any one of Claims 1-5. The polymer in any one of Claims 1-6 represented by either of following formula (1)-(7).

_{(Wherein, R 1, R 2, R} 5, R 6, L 1 and _{L 2, R} 1 in the formula (A) and _{(B), R 2, R} 5, R 6, L 1 and L _Same as ₂ .
m and n each represent the content (molar ratio) of each structural unit in the polymer, m is 0.01 to 0.99, n is 0.01 to 0.99, and m + n = 1. .
l is 0 or 1. ) The polymer of Claim 7 represented by either of following formula (8)-(25).

_{(Wherein, R 1, R 2, R} 5, R 6, L 1 and _{L 2, R} 1 in the formula (A) and _{(B), R 2, R} 5, R 6, L 1 and L _Same as ₂ .
m and n each represent the content (molar ratio) of each structural unit in the polymer, m is 0.01 to 0.99, n is 0.01 to 0.99, and m + n = 1. . ) In each polymer represented by the formulas (1) to (25), at least one of R ₅ or at least one of R ₆ is a crosslinkable group, and L ₂ is not a crosslinkable group. 8. Polymer of 8. The polymer according to any one of claims 1 to 9, wherein the crosslinkable group is a group selected from groups represented by the following formulas (31) to (42).

Each at least one polymer of L ₂ is a bridging group, the polymer according to claim 7 or 8 R ₅ and R ₆ is not a crosslinking group represented by the formula (1) to (21). The polymer according to claim 11, wherein L ₂ which is the crosslinkable group is a group selected from groups represented by the following formulas (43) to (46).

(In formulas (45) and (46), o is an integer of 1 to 10.) In the polymers represented by the formulas (1) to (25), at least one of R ₁ , R ₂ , R ₅ and R ₆ is selected from the groups represented by the following formulas (51) to (55). The polymer according to any one of claims 8 to 12, which is a group to be formed.

(In the formula, R _{11 to} R ₂₃ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, substituted or unsubstituted. An aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 10 ring carbon atoms, a substituted or unsubstituted ring formation Aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 ring atoms, substituted amino group, substituted silyl group, halogen An atom, a nitro group, a cyano group or a hydroxyl group.
a, c, d, f, g, and i are each independently an integer of 0 to 4;
b, e, h, and j are each independently an integer of 0 to 3.
T _{1 to} T ₅ are each independently a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 50 ring carbon atoms or an aromatic heterocyclic group having 3 to 30 ring atoms. )   The coating liquid containing the polymer and solvent in any one of Claims 1-13.   The coating liquid according to claim 14, wherein at least one of the solvents is an organic solvent.   The manufacturing method of the electronic element which carries out wet film-forming using the coating liquid of Claim 14 or 15.   The method of manufacturing an electronic device according to claim 16, wherein the electronic device is an electroluminescent device, a photoelectric conversion device, or a transistor.   The method of manufacturing an electronic device according to claim 16 or 17, wherein the electronic device is an organic electroluminescence device. Having one or more organic thin film layers including a light emitting layer between the anode and the cathode and the anode and the cathode;
The organic electroluminescent element in which at least 1 layer of the said organic thin film layer contains the polymer in any one of Claims 1-13.   The organic electroluminescence device according to claim 19, wherein at least one of the organic thin film layers is a hole injection layer or a hole transport layer.   The organic electroluminescence device according to claim 20, wherein the hole injection layer or the hole transport layer is in contact with the light emitting layer.   The organic electroluminescent element according to any one of claims 19 to 21, wherein the light emitting layer is formed by a wet film forming method.