JP2013133359A - Polymer compound, and organic el element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer compound capable of obtaining an organic EL element of excellent brightness life.SOLUTION: The polymer compound includes at least one structural unit selected from the group comprising structural units expressed by a naphthalene structural unit and a fluorene structural unit, and a nitrogen containing heterocyclic constitutional unit, and further includes a constitutional unit of Formula (5) or (6) in its terminal part, or a constitutional unit containing an unsaturated group adjacent to an organic hydrocarbon group or an organic heterocyclic group in a principal chain, in its block copolymer part. In the Formula, Rrepresents alkyl group or the like; Arrepresents a phenylene group or the like; m represents 0 or 1; prepresents an integer of 0 or more; prepresents an integer of 1 or more; and Y represents a coupling position to other constitutional unit.

Description

  The present invention relates to a polymer compound and an organic EL device using the same.

  In recent years, organic EL displays using organic electroluminescence elements (hereinafter referred to as organic EL elements) have attracted attention as next-generation displays. This organic EL element includes organic layers such as a light emitting layer and a charge transport layer. The organic EL element may be obtained using a low molecular organic material or may be obtained using a high molecular organic material. When a polymer organic material is used as a main material, a large-sized organic EL display is manufactured because a uniform film can be easily formed when a coating method such as an ink jet printing method or a spin coating method is used. In this case, it has been proposed to use a polymer organic material for an organic EL element (Patent Document 1 and Patent Document 2).

JP-A-8-209120 JP 2003-155476 A

  When a conventional organic polymer material is used for an organic EL element, it cannot be said that the luminance life of the organic EL element is sufficient.

  Therefore, an object of the present invention is to provide a polymer compound useful for producing an organic EL device having excellent luminance life. Another object of the present invention is to provide an organic EL device using the polymer compound.

  That is, the present invention provides the following polymer compounds.

[1] A polymer having at least one structural unit selected from the group consisting of structural units represented by formula (1), formula (2) and formula (3), and a structural unit represented by formula (4) A compound comprising:
The polymer compound further has a terminal structural unit represented by the formula (5) or the formula (6), or a block polymerization unit represented by the formula (12), the formula (13), or the formula (14). It has at least 1 structural unit chosen from the group which consists of a structural unit represented, The high molecular compound characterized by the above-mentioned.

（式中、
Ｒ^１１およびＲ^１２は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、アルコキシ基またはアリールオキシ基を表し、これらの基は置換基を有していてもよく、複数存在するＲ^１１およびＲ^１２は同一であっても異なっていてもよい。
Ｒ^ｘおよびＲ^ｙは、それぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基表し、これらの基は置換基を有していてもよく、互いに結合して環構造を形成していてもよい。）

(Where
R ¹¹ and R ¹² each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group or an aryloxy group, and these groups may have a substituent. In addition, a plurality of R ¹¹ and R ¹² may be the same or different.
R ^x and R ^y each independently represent a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent and are bonded to each other to form a ring structure May be formed. )

（式中、
Ｘは、Ｏ、Ｓ、Ｃ（Ｒ^３）_２またはＮＲ^２を表し、
Ｒ^１、Ｒ^２、およびＲ^３は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、アルコキシ基またはアリールオキシ基を表し、これらの基は置換基を有していてもよく、複数存在するＲ^１は同一であっても異なっていてもよく、Ｒ^２が複数存在した場合、これらは同一であっても異なっていてもよく、Ｒ^３が複数存在した場合、これらは同一でも異なっていてもよい。）

(Where
X represents O, S, C (R ³ ) ₂ or NR ² ;
R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group, or an aryloxy group, and these groups have a substituent. A plurality of R ¹ may be the same or different, and when a plurality of R ² are present, they may be the same or different, and a plurality of R ³ were present. In these cases, they may be the same or different. )

（式中、
Ａｒ^２は、フェニレン基、ナフチレン基、アントラセンジイル基、フルオレンジイル基またはフェナンスレンジイル基を表し、これらの基は置換基を有していてもよく、Ａｒ^２が複数存在する場合、これらは同一であっても異なっていてもよい。
Ａｒ^３は、アリーレン基または２価の芳香族複素環基を表し、これらの基は置換基を有していてもよく、Ａｒ^３が複数存在する場合、これらは同一であっても異なっていてもよい。
Ｒ^４は、水素原子、アルキル基、アリール基、アルケニル基、アルキニル基またはハロゲン原子を表し、これらの基は置換基を有していてもよく、複数存在するＲ^４は同一であっても異なっていてもよい。
ｍは、０または１を表し、複数存在するｍは同一でも異なっていてもよい。
ｐ^１は、０以上の整数を表し、ｐ^２は、１以上整数を表す。
Ｙは、高分子化合物の他の構成単位との結合位置を表す。）

(Where
Ar ² represents a phenylene group, a naphthylene group, an anthracenediyl group, a fluorenediyl group, or a phenanthrene diyl group, and these groups may have a substituent, and when a plurality of Ar ² are present, May be the same or different.
Ar ³ represents an arylene group or a divalent aromatic heterocyclic group, and these groups may have a substituent, and when a plurality of Ar ³ are present, they may be the same or different. Also good.
R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a halogen atom, and these groups may have a substituent, and a plurality of R ⁴ may be the same or different. It may be.
m represents 0 or 1, and a plurality of m may be the same or different.
p ¹ represents an integer of 0 or more, ^{p 2} represents an integer of 1 or more.
Y represents a bonding position with another structural unit of the polymer compound. )

（式中、
Ａｒ^１１は、アリーレン基または２価の芳香族複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^１２は、フェニレン基、ナフチレン基、アントラセンジイル基、フルオレンジイル基またはフェナンスレンジイル基を表し、これらの基は置換基を有していてもよい。
Ａｒ^１３は、３価の芳香族炭化水素基または３価の芳香族複素環基を表し、これらの基は置換基を有していてもよい。
Ｒ^１４は、水素原子、アルキル基、アリール基、アルケニル基、アルキニル基またはハロゲン原子を表し、これらの基は置換基を有していてもよく、複数存在するＲ^１４は同一でも異なっていてもよい。
ｎは、０または１を表し、ｐ^３は、０または１を表す。）
［２］ 前記高分子化合物の全構成単位に対する、前記式（５）、式（６）、式（１２）、式（１３）および式（１４）で表される構成単位の合計が０．０１〜１５モル％である、［１］に記載の高分子化合物。
［３］ 前記高分子化合物の末端部の構成単位が、式（９）、式（１０）または式（１１）で表される、請求項１または２に記載の高分子化合物。

(Where
Ar ¹¹ represents an arylene group or a divalent aromatic heterocyclic group, and these groups optionally have a substituent.
Ar ¹² represents a phenylene group, a naphthylene group, an anthracenediyl group, a fluorenediyl group, or a phenanthrene diyl group, and these groups may have a substituent.
Ar ¹³ represents a trivalent aromatic hydrocarbon group or a trivalent aromatic heterocyclic group, and these groups may have a substituent.
R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a halogen atom, and these groups may have a substituent, and a plurality of R ¹⁴ may be the same or different. Good.
n represents 0 or 1, and p ³ represents 0 or 1. )
[2] The total of the structural units represented by the formula (5), the formula (6), the formula (12), the formula (13), and the formula (14) with respect to all the structural units of the polymer compound is 0.01. The polymer compound according to [1], which is ˜15 mol%.
[3] The polymer compound according to claim 1 or 2, wherein a structural unit at a terminal portion of the polymer compound is represented by the formula (9), the formula (10), or the formula (11).

（式中、
Ｒ^５およびＲは、水素原子、アルキル基、アリール基、アルケニル基、アルキニル基、またはハロゲン原子を表し、これらの基は置換基を有していてもよく、複数存在するＲ^５およびＲは同一であっても異なっていてもよい。
但し、Ｒのうちの一つは高分子化合物の他の構成単位との結合位置を表す。）
［４］ 前記高分子化合物のブロック重合部として、式（１５）で表される構成単位を有する、［１］または［２］に記載の高分子化合物。

(Where
R ⁵ and R represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or a halogen atom, and these groups may have a substituent, and a plurality of R ⁵ and R are the same Or different.
However, one of R represents a bonding position with another structural unit of the polymer compound. )
[4] The polymer compound according to [1] or [2], having a structural unit represented by the formula (15) as a block polymerization portion of the polymer compound.

（式中、
Ｒ^１５は、水素原子、アルキル基、アリール基、アルケニル基、アルキニル基またはハロゲン原子を表し、これらの基は置換基を有していてもよく、複数存在するＲ^１５は同一でも異なっていてもよい。）
［５］ フェニレン誘導体、ビフェニレン誘導体、ジヒドロフェナンスレン誘導体、アリールアミン誘導体およびフェナンスレン誘導体からなる群から選ばれる少なくとも１つの誘導体から、環を構成する炭素原子に結合した水素原子２個を除いた２価の基を、
構成単位としてさらに有する、［１］〜［４］のいずれかに一項に記載の高分子化合物。
［６］ 環を構成する窒素原子、酸素原子、硫黄原子、ケイ素原子、リン原子および炭素原子の合計が５個〜１４個である芳香族複素環式化合物であって、該芳香族複素環式化合物の環を構成する炭素原子に結合した水素原子２個を除いた２価の基を、
構成単位としてさらに有する、［１］〜［５］のいずれか一項に記載の高分子化合物。
［７］ 陽極、陰極および発光層を有する有機発光素子であって、
該発光層に、［１］〜［５］のいずれか一項に記載の高分子化合物を含有する、有機ＥＬ素子。
［８］ 陽極、陰極、発光層および電荷輸送層を有する有機発光素子であって、
該電荷輸送層に、［１］〜［５］いずれか一項に記載の高分子化合物を含有する、有機ＥＬ素子。

(Where
R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a halogen atom, and these groups may have a substituent, and a plurality of R ¹⁵ may be the same or different. Good. )
[5] 2 in which two hydrogen atoms bonded to carbon atoms constituting a ring are removed from at least one derivative selected from the group consisting of a phenylene derivative, a biphenylene derivative, a dihydrophenanthrene derivative, an arylamine derivative, and a phenanthrene derivative. A valent group,
The polymer compound according to any one of [1] to [4], which is further included as a structural unit.
[6] An aromatic heterocyclic compound having a total of 5 to 14 nitrogen atoms, oxygen atoms, sulfur atoms, silicon atoms, phosphorus atoms and carbon atoms constituting the ring, the aromatic heterocyclic compounds A divalent group excluding two hydrogen atoms bonded to carbon atoms constituting the ring of the compound,
The polymer compound according to any one of [1] to [5], which is further included as a structural unit.
[7] An organic light emitting device having an anode, a cathode, and a light emitting layer,
The organic EL element which contains the high molecular compound as described in any one of [1]-[5] in this light emitting layer.
[8] An organic light emitting device having an anode, a cathode, a light emitting layer and a charge transport layer,
An organic EL device containing the polymer compound according to any one of [1] to [5] in the charge transport layer.

  According to the polymer compound of the present invention, an organic EL device having excellent luminance life can be obtained. Moreover, according to the preferable form of the high molecular compound of this invention, the organic EL element excellent in luminous efficiency is obtained.

  Hereinafter, terms commonly used in this specification will be described with examples as necessary.

  The “structural unit” means a unit structure existing in one or more polymer compounds. The “structural unit” is divided into a “structural unit” at the terminal portion of the polymer compound and a “structural unit” other than the terminal portion, and the “structural unit” other than the terminal portion is a “repeating unit” (that is, It is preferable that it is contained in the polymer compound as a unit structure present in two or more.

The term “C _{x to} C _y ” (x and y are positive integers satisfying x <y) is the number of carbon atoms of the partial structure corresponding to the functional group name described immediately after this term, It means x to y. That is, when the organic group described immediately after “C _{x to} C _y ” is an organic group named by combining a plurality of functional group names (for example, C _{x to} C _y alkoxyphenyl group), It means that the number of carbon atoms of the partial structure corresponding to the functional group name (for example, alkoxy) described immediately after “C _{x to} C _y ” among the functional group names is _x to _y . For example, “C ₁ -C ₁₂ alkyl group” means an alkyl group having 1 to 12 carbon atoms, and “C ₁ -C ₁₂ alkoxyphenyl group” has “1 to 12 carbon atoms”. It means a phenyl group having an “alkoxy group”.

The alkyl group may have a substituent, and may be any of a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and a cycloalkyl group. As the alkyl group, a linear alkyl group or a cyclic alkyl group is preferable, and an unsubstituted alkyl group or an alkyl group substituted with a halogen atom or the like is preferable.
The number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-15, and still more preferably 1-12. Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, and a hexyl group. Cyclohexyl group, 2-ethylhexyl group, heptyl group, octyl group, 3,7-dimethyloctyl group, nonyl group, decyl group, dodecyl group, arylalkyl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group , Perfluorohexyl group, perfluorooctyl group and the like.

  The aryl group is a remaining atomic group obtained by removing one hydrogen atom bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon, and may have a substituent. As the aryl group, an aryl group consisting only of an aromatic ring, an unsubstituted aryl group, or an aryl group substituted with a halogen atom or an alkoxy group is preferable. As the aryl group, a group having a benzene ring, a group having a condensed ring, two or more benzene rings and / or condensed rings, a single bond or a divalent organic group (for example, an alkylene group such as a vinylene group) Examples include a bonded group.

The number of carbon atoms of the aryl group is preferably 6 to 60, more preferably 6 to 30, and still more preferably 6 to 16. The aryl group which may have a substituent, a phenyl _group, C 1 _{-C 12} alkoxyphenyl _group, C 1 _{-C 12} alkylphenyl group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 2-fluorenyl group, pentafluorophenyl group, biphenyl _group, C 1 _{-C 12} alkoxy biphenylyl group, and _C 1 _{-C 12} alkyl biphenylyl group, and among them, phenyl _group, C 1 _{-C 12} alkoxyphenyl _group, C 1 _{-C 12} alkylphenyl group, biphenyl _group, C 1 _{-C 12} alkoxy biphenylyl group or _C 1 _{-C 12} alkyl biphenylyl group, are preferred.

A monovalent aromatic heterocyclic group is a remaining atomic group obtained by removing one hydrogen atom bonded to an atom constituting an aromatic heterocyclic ring from an aromatic heterocyclic compound, and has a substituent. Good. The monovalent aromatic heterocyclic group is preferably an unsubstituted monovalent aromatic heterocyclic group or a monovalent aromatic heterocyclic group substituted with a substituent such as an alkyl group. The number of carbon atoms of the monovalent aromatic heterocyclic group is preferably 4 to 60, more preferably 4 to 30, even more preferably 4 to 14, particularly preferably, without including the number of carbon atoms of the substituent. Is 4-9. An aromatic heterocyclic compound is not only a carbon atom but also an oxygen atom, sulfur atom, nitrogen atom, phosphorus atom, boron atom, silicon as an element constituting a ring among aromatic cyclic compounds having a cyclic structure. An atom, a selenium atom, a tellurium atom, an arsenic atom, or other heteroatom atoms. The aromatic heterocyclic group may monovalent optionally having a substituent, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, a carbazolyl group, an indolyl group, quinolyl group and isoquinolyl group, and among them a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, or _C 1 _{-C 12} alkyl pyridyl group are preferable.

The alkoxy group may have a substituent, and may be any of a linear alkoxy group, a branched alkoxy group, and a cyclic alkoxy group. As the alkoxy group, a linear alkoxy group or a cyclic alkoxy group is preferable, and an alkoxy group substituted with an unsubstituted alkoxy group, a halogen atom, an alkoxy group or the like is preferable.
The number of carbon atoms of the alkoxy group is preferably 1-20, more preferably 1-15, and still more preferably 1-12. Examples of the alkoxy group which may have a substituent include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy Group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, dodecyloxy group, arylalkoxy group, trifluoromethoxy group, pentafluoro Examples include an ethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, a perfluorooctyloxy group, a methoxymethyloxy group, and a 2-methoxyethyloxy group.

The number of carbon atoms of the aryloxy group is preferably 6 to 60, more preferably 6 to 30, and still more preferably 6 to 16. The aryloxy group which may have a substituent, a phenoxy _group, C 1 _{-C 12} alkoxy phenoxy _group, C 1 _{-C 12} alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, and penta fluorophenyl group, and among them _C 1 _{-C 12} alkoxy phenoxy group, or a _C 1 _{-C 12} alkylphenoxy group are preferable.

  The alkenyl group may have a substituent, and may be any of a linear alkenyl group, a branched alkenyl group, and a cyclic alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 15, and still more preferably 2 to 10. Examples of the alkenyl group which may have a substituent include vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group and 1-hexenyl. Group, 2-hexenyl group, 1-octenyl group, arylalkenyl group and the like.

  The alkynyl group may have a substituent, and may be any of a linear alkynyl group, a branched alkynyl group, and a cyclic alkynyl group. The number of carbon atoms in the alkynyl group is preferably 2 to 20, more preferably 2 to 15, and still more preferably 2 to 10. Examples of the alkynyl group which may have a substituent include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group and 1-hexynyl. Group, 2-hexynyl group, 1-octynyl group, arylalkynyl group and the like.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  An arylene group means an atomic group obtained by removing two hydrogen atoms bonded to carbon atoms constituting an aromatic ring from an aromatic hydrocarbon, including those having an independent benzene ring or condensed ring, and having a substituent. You may do it. The number of carbon atoms of the arylene group is preferably 6 to 60, more preferably 6 to 48, still more preferably 6 to 30, and particularly preferably 6 to 16, excluding the number of carbon atoms of the substituent. It is a piece. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the arylene group include phenylene groups such as 1,4-phenylene group, 1,3-phenylene group, and 1,2-phenylene group; biphenylylene groups such as 2,7-biphenylylene group and 3,6-biphenylylene group; 4-naphthalenediyl group, 1,5-naphthalenediyl group, naphthalenediyl group such as 2,6-naphthalenediyl group; 1,4-anthracenediyl group, 1,5-anthracenediyl group, 2,6-anthracenediyl group Anthracenediyl group such as 9,10-anthracenediyl group; Phenanthenediyl group such as 2,7-phenanthrenediyl group; 1,7-naphthacenediyl group, 2,8-naphthacenediyl group, 5,12-naphthacenediyl Naphthacenediyl groups such as groups; fluorenediyl groups such as 2,7-fluorenediyl group and 3,6-fluorenediyl group Groups: 1,6-pyrenediyl group, 1,8-pyrenediyl group, 2,7-pyrenediyl group, pyrenediyl group such as 4,9-pyrenediyl group; 3,9-perylenediyl group, 3,10-perylenediyl group, etc. And perylenediyl groups. Of these, a phenylene group which may have a substituent and a fluorenediyl group which may have a substituent are preferable.

  The divalent aromatic heterocyclic group is an atomic group obtained by removing two hydrogen atoms bonded to atoms constituting an aromatic heterocyclic ring from an aromatic heterocyclic compound, and has a substituent. Good. The divalent aromatic heterocyclic group is preferably an unsubstituted divalent aromatic heterocyclic group or a divalent aromatic heterocyclic group substituted with a substituent such as an alkyl group. The number of carbon atoms of the divalent aromatic heterocyclic group is preferably 4 to 60, more preferably 4 to 16, more preferably 4 to 12, excluding the number of carbon atoms of the substituent. Particularly preferred is 4-9. Examples of the divalent aromatic heterocyclic group include pyridinediyl groups such as 2,5-pyridinediyl group and 2,6-pyridinediyl group; bipyridines such as 2,2′-bipyridine-4,4′-diyl group. Diyl group; thiophene diyl group such as 2,5-thiophenediyl group; frangyl group such as 2,5-furandiyl group; triazinediyl group such as 2,4-triazinediyl group; 2,6-quinolinediyl group and the like Quinoline diyl group; isoquinoline diyl group such as 1,4-isoquinoline diyl group and 1,5-isoquinoline diyl group; quinoxaline diyl group such as 5,8-quinoxaline diyl group; 2,1,3-benzothiadiazole-4,7- 2,1,3-benzothiadiazole diyl group such as diyl group; benzothiazole diyl group such as 4,7-benzothiazole diyl group; Zorujiiru group, carbazole-diyl group such as a 3,6-carbazolediyl group; dibenzosilole-diyl group such as and 2,7 dibenzosilole-diyl group. Of these, a pyridinediyl group which may have a substituent, a triazinediyl group which may have a substituent, and a carbazole diyl group which may have a substituent are preferable.

  A trivalent aromatic hydrocarbon group means an atomic group formed by removing three hydrogen atoms bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon, and having an independent benzene ring or condensed ring And may have a substituent. The number of carbon atoms of the trivalent aromatic hydrocarbon group is preferably 6 to 60, more preferably 6 to 48, and still more preferably 6 to 30, excluding the number of carbon atoms of the substituent. Particularly preferably, the number is 6 to 16. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the trivalent aromatic hydrocarbon group include 1,3,5-benzenetriyl group, benzenetriyl group such as 1,2,4-benzenetriyl group; 1,2,6-naphthalenetriyl group, Naphthalenetriyl groups such as 1,2,7-naphthalenetriyl group, 2,4,7-naphthalenetriyl group; 1,3,10-anthracentriyl group, 1,4,6-anthracentriyl group, 1,8,10-anthracentriyl group, 2,9,10-anthracentriyl group, 2,6,9-anthracentriyl group, etc .; 2,7,9-phenanthrenetriyl group A phenanthrene triyl group such as 2,6,7-fluorenetriyl group; and a pyrenetriyl group such as 1,6,8-pyrenetriyl group, 2,7,8-pyrenetriyl group, etc. Can be mentioned. Of these, a benzenetriyl group which may have a substituent and a fluorenetriyl group which may have a substituent are preferable.

  The trivalent aromatic heterocyclic group is a remaining atomic group obtained by removing three hydrogen atoms bonded to an atom constituting an aromatic heterocyclic ring from an aromatic heterocyclic compound, and has a substituent. Good. The trivalent aromatic heterocyclic group is preferably an unsubstituted trivalent aromatic heterocyclic group or a trivalent aromatic heterocyclic group substituted with a substituent such as an alkyl group. The number of atoms of the trivalent aromatic heterocyclic group is preferably 4 to 60, more preferably 4 to 16, more preferably 4 to 12, and particularly preferably, not including the number of atoms of the substituent. Is 4-9. Examples of the trivalent aromatic heterocyclic group include pyridinetriyl groups such as 2,4,5-pyridinetriyl group and 2,4,6-pyridinetriyl group; and 2,4,6-triazinetriyl. Groups and the like.

  Unless otherwise specified, the term “substituent” represents the above alkyl group, aryl group, monovalent aromatic heterocyclic group, alkoxy group, aryloxy group, alkenyl group, alkynyl group and halogen atom, Among them, a halogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 1 to 12 carbon atoms, a linear alkoxyl group having 1 to 12 carbon atoms, carbon A branched alkoxyl group having 1 to 12 atoms, a linear alkenyl group having 1 to 12 carbon atoms, a branched alkenyl group having 1 to 12 carbon atoms, and the like are preferable.

  Hereinafter, preferred embodiments of the polymer compound and the organic EL device of the present invention will be described in detail.

The polymer compound of the present invention comprises at least one structural unit selected from the group consisting of structural units represented by formula (1), formula (2) and formula (3), and a structure represented by formula (4) A polymer compound having a unit,
The polymer compound further has a terminal structural unit represented by the formula (5) or the formula (6), or a block polymerization unit represented by the formula (12), the formula (13), or the formula (14). It has at least 1 structural unit chosen from the group which consists of a structural unit represented.

（式中、
Ｒ^１１およびＲ^１２は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、アルコキシ基またはアリールオキシ基を表し、これらの基は置換基を有していてもよく、複数存在するＲ^１１およびＲ^１２は同一であっても異なっていてもよい。
Ｒ^ｘおよびＲ^ｙは、それぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基表し、これらの基は置換基を有していてもよく、互いに結合して環構造を形成していてもよい。）

(Where
R ¹¹ and R ¹² each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group or an aryloxy group, and these groups may have a substituent. In addition, a plurality of R ¹¹ and R ¹² may be the same or different.
R ^x and R ^y each independently represent a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent and are bonded to each other to form a ring structure May be formed. )

（式中、
Ｘは、Ｏ、Ｓ、Ｃ（Ｒ^３）_２またはＮＲ^２を表し、
Ｒ^１、Ｒ^２およびＲ^３は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、アルコキシ基またはアリールオキシ基を表し、これらの基は置換基を有していてもよく、複数存在するＲ^１は同一であっても異なっていてもよく、Ｒ^２が複数存在した場合、これらは同一であっても異なっていてもよく、Ｒ^３が複数存在した場合、これらは同一でも異なっていてもよい。）

(Where
X represents O, S, C (R ³ ) ₂ or NR ² ;
R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group or an aryloxy group, and these groups have a substituent. A plurality of R ¹ may be the same or different, and when a plurality of R ² are present, they may be the same or different, and when a plurality of R ³ are present These may be the same or different. )

（式中、
Ａｒ^２は、フェニレン基、ナフチレン基、アントラセンジイル基、フルオレンジイル基またはフェナンスレンジイル基を表し、これらの基は置換基を有していてもよく、Ａｒ^２が複数存在する場合、これらは同一であっても異なっていてもよい。
Ａｒ^３は、アリーレン基または２価の芳香族複素環基を表し、これらの基は置換基を有していてもよく、Ａｒ^３が複数存在する場合、これらは同一であっても異なっていてもよい。
Ｒ^４は、水素原子、アルキル基、アリール基、アルケニル基、アルキニル基またはハロゲン原子を表し、これらの基は置換基を有していてもよく、複数存在するＲ^４は同一であっても異なっていてもよい。
ｍは、０または１を表し、複数存在するｍは同一でも異なっていてもよい。
ｐ^１は、０以上の整数を表し、ｐ^２は、１以上整数を表す。
Ｙは、高分子化合物の他の構成単位との結合位置を表す。）

(Where
Ar ² represents a phenylene group, a naphthylene group, an anthracenediyl group, a fluorenediyl group, or a phenanthrene diyl group, and these groups may have a substituent, and when a plurality of Ar ² are present, May be the same or different.
Ar ³ represents an arylene group or a divalent aromatic heterocyclic group, and these groups may have a substituent, and when a plurality of Ar ³ are present, they may be the same or different. Also good.
R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a halogen atom, and these groups may have a substituent, and a plurality of R ⁴ may be the same or different. It may be.
m represents 0 or 1, and a plurality of m may be the same or different.
p ¹ represents an integer of 0 or more, ^{p 2} represents an integer of 1 or more.
Y represents a bonding position with another structural unit of the polymer compound. )

（式中、
Ａｒ^１１は、アリーレン基または２価の芳香族複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^１２は、フェニレン基、ナフチレン基、アントラセンジイル基、フルオレンジイル基またはフェナンスレンジイル基を表し、これらの基は置換基を有していてもよい。
Ａｒ^１３は、３価の芳香族炭化水素基または３価の芳香族複素環基を表し、これらの基は置換基を有していてもよい。
Ｒ^１４は、水素原子、アルキル基、アリール基、アルケニル基、アルキニル基またはハロゲン原子を表し、これらの基は置換基を有していてもよく、複数存在するＲ^１４は同一でも異なっていてもよい。
ｎは、０または１を表し、ｐ^３は、０または１を表す。）

(Where
Ar ¹¹ represents an arylene group or a divalent aromatic heterocyclic group, and these groups optionally have a substituent.
Ar ¹² represents a phenylene group, a naphthylene group, an anthracenediyl group, a fluorenediyl group, or a phenanthrene diyl group, and these groups may have a substituent.
Ar ¹³ represents a trivalent aromatic hydrocarbon group or a trivalent aromatic heterocyclic group, and these groups may have a substituent.
R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a halogen atom, and these groups may have a substituent, and a plurality of R ¹⁴ may be the same or different. Good.
n represents 0 or 1, and p ³ represents 0 or 1. )

  According to the polymer compound of the present invention, an organic EL device having an excellent luminance life can be obtained.

As one of the factors that a sufficient luminance life cannot be obtained in a conventional organic EL device using a polymer compound, it is considered that excited triplet energy not related to light emission causes a decrease in light emission efficiency of the organic EL device. It is done. On the other hand, in the organic EL device using the polymer compound of the present invention, it is possible to quickly remove the excited triplet energy not involved in the light emission, and it is considered that a sufficient luminance lifetime is obtained.
More specifically, the structural unit of the terminal part represented by Formula (5) and Formula (6), and the structural unit of the block polymerization part represented by Formula (12), Formula (13), and Formula (14) Are considered to function as acceptors for excited triplet energy not involved in light emission.
Further, in the polymer compound of the present invention, since the structural unit that functions as the accepting portion for the excited triplet energy is arranged at the terminal portion or the block polymerization portion, an organic EL device having excellent luminous efficiency can be obtained. It is thought that.

  The structural units represented by the formula (1), formula (2) and formula (3) will be described.

In the structural units represented by the formula (1) and the formula (2), R ¹¹ represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group or an aryloxy group, and This group may have a substituent. Among these, R ¹¹ is preferably a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent.

  The structural unit represented by the formula (1) is preferably a structural unit represented by the following formula (C-1) to formula (C-5) from the viewpoint of luminance life, It is more preferable that it is a structural unit represented by 3)-Formula (C-5).

  The structural unit represented by the formula (2) is preferably a structural unit represented by the following formula (C-6) and formula (C-7) from the viewpoint of luminance life.

In the structural unit represented by the formula (3), R ¹² represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group or an aryloxy group, and these groups are substituents. You may have. Among these, R ¹² is preferably a hydrogen atom and an alkyl group, and more preferably a hydrogen atom.

R ^x and R ^y in the formula (3) are a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent from the viewpoint of luminance lifetime. An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable.
Further, R ^x and R ^y are preferably different from each other. As a combination of R ^x and R ^y , R ^x is an alkyl group which may have a substituent, and R ^y has a substituent. It is preferably an aryl group that may be used.
R ^x and R ^y may be bonded to each other to form a ring structure. For example, when R ^x and R ^y are aryl groups that may have a substituent, the aryl groups may be linked to each other. A structure may be formed to have a spirobifluorene skeleton as the structure represented by the formula (3).

  The structural unit represented by the formula (3) is preferably a structural unit represented by the following formula (F-1) from the viewpoint of luminance life.

（式中、Ｒ^ｘ及びＲ^ｙは前記と同じ意味を表す。）

(Wherein R ^x and R ^y represent the same meaning as described above.)

Examples of the structural unit represented by the formula (F-1) include structural units represented by the following formulas (F-2) to (F-11). From the viewpoint of luminance life, the formula (F− 2) to a structural unit represented by Formula (F-9), more preferably a structural unit represented by Formula (F-3) to Formula (F-9), and Formula (F-9). It is more preferable that it is a structural unit represented by -7)-Formula (F-9).

  Next, the structural unit represented by the formula (4) will be described.

X in the formula (4) represents O, S, C (R ³ ) ₂ or NR ^2, and among these, X is preferably O or S, that is, represented by the formula (4). The structural unit is preferably a structural unit represented by the following formula (C-11) and formula (C-12).

（式中、Ｒ^１およびＲ^２は前記と同じ意味を表す。）

(Wherein R ¹ and R ² represent the same meaning as described above.)

R ¹ in Formula (4), Formula (C-11), and Formula (C-12) represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group, or an aryloxy group. These groups may have a substituent. Among these, R ¹ is preferably a hydrogen atom and an alkyl group which may have a substituent, and more preferably a hydrogen atom.

R ² in the above formula (4) represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group or an aryloxy group, and these groups may have a substituent. . Among these, R ² is preferably a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and may have a substituent. More preferred is an aryl group.

  The structural unit represented by the formula (C-11) is preferably a structural unit represented by the following formula (C-13) to formula (C-17) from the viewpoint of luminous efficiency. More preferred are structural units represented by C-16) and formula (C-17).

  The structural unit represented by the formula (C-12) is preferably a structural unit represented by the following formula (C-18) to formula (C-22) from the viewpoint of luminous efficiency. It is preferable that it is a structural unit represented by C-21) and a formula (C-22).

  Next, the structural unit of the terminal part of a high molecular compound represented by the said Formula (5) and Formula (6) is demonstrated.

Ar ² in the formulas (5) and (6) represents a phenylene group, a naphthylene group, an anthracenediyl group, a fluorenediyl group, or a phenanthrene diyl group, and these groups may have a substituent. Good. Among these, from the viewpoint of luminous efficiency, Ar ² includes a phenylene group which may have a substituent, a naphthylene group which may have a substituent, and an anthracenediyl which may have a substituent. It is preferably a fluorenediyl group which may have a group and a substituent, and may be a phenylene group which may have a substituent, a naphthylene group which may have a substituent and a fluorenediyl group. More preferably.

Ar ³ in the formulas (5) and (6) represents an arylene group or a divalent aromatic heterocyclic group, and these groups may have a substituent. Among these, Ar ³ is preferably an arylene group which may have a substituent, and more preferably a phenylene group which may have a substituent.

R ⁴ in the formulas (5) and (6) represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or a halogen atom, and these groups may have a substituent. Among these, R ⁴ is preferably a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent.
Furthermore, R ⁴ may form an aliphatic ring structure or an aromatic ring structure with R ⁴ together with Ar ² or with Ar ³ .

  Y in the formula (5) and formula (6) represents a binding site with the other structural unit of the polymer compound, and the structural unit at the terminal portion of the polymer compound and other units at the position of Y in the formula Indicates that the structural unit is connected.

In the formula (5), m represents 0 or 1. When m is 0 and p ¹ described later is 0, at least one R ⁴ is preferably an aryl group which may have a substituent.

P ^{1 in the} formula (5) represents an integer of 0 or more. p ¹ is preferably 0 or 1, and more preferably 0.

  The structural unit represented by the formula (5) is represented by the formula (9), the formula (10), the formula (11), and the formula (T-3) to the formula (T-16) from the viewpoint of luminance life. The structural unit is preferably, and the formula (9), formula (10), and formula (11) are more preferable.

R ⁵ and R in Formula (9), Formula (10), Formula (11), and Formula (T-3) to Formula (T-16) are a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkynyl group. Alternatively, it represents a halogen atom, and these groups may have a substituent. However, one of R is Y. Among these, R ⁵ and R are preferably a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, from the viewpoint of luminous efficiency. It is more preferable that it is a phenyl group which may have an atom or a substituent.

As the structural unit represented by the formula (5),
A structural unit represented by the formula (T-51) which is a preferred form of the formula (9) is preferred, and a structural unit represented by the formula (T-52) which is a preferred form of the formula (10). preferable.

（式中、Ｙは前記と同じ意味を表す。）

(In the formula, Y represents the same meaning as described above.)

Ar ^{2 in the} above formulas (5) and (6) may form an aliphatic ring structure or an aromatic ring structure together with Ar ³ .

  In the formula (6), m represents 0 or 1.

P ^{2 in the} formula (6) represents an integer of 1 or more. p ² is preferably 1.

  The structural unit represented by the formula (6) is preferably a structural unit represented by the formula (T-31), the formula (T-32), and the formula (T-33).

  The structural units represented by the formula (12), formula (13) and formula (14) contained in the block polymerization part of the polymer compound of the present invention will be described.

Ar ¹¹ in the formula (12), formula (13) and formula (14) represents an arylene group or a divalent aromatic heterocyclic group, and these groups may have a substituent. Among these, Ar ¹¹ is preferably an arylene group which may have a substituent, and more preferably a phenylene group which may have a substituent.

Ar ¹² in the formula (12), the formula (13) and the formula (14) represents a phenylene group, a naphthylene group, an anthracenediyl group, a fluorenediyl group or a phenanthrene diyl group, and these groups have a substituent. You may have. Among these, Ar ¹² has a phenylene group which may have a substituent, a naphthylene group which may have a substituent, an anthracenediyl group which may have a substituent, and a substituent. It is preferably a fluorenediyl group which may be used.

Ar ¹³ in the formula (14) represents a trivalent aromatic hydrocarbon group or a trivalent aromatic heterocyclic group, and these groups may have a substituent. Among these, as Ar ¹³ , a trivalent aromatic hydrocarbon group which may have a substituent is preferable, and a 1,3,5-benzenetriyl group which may have a substituent is more preferable. preferable.

R ¹⁴ in the formula (12), formula (13) and formula (14) represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a halogen, and these groups have a substituent. Also good. Among these, R ¹⁴ is preferably a hydrogen atom, an alkyl group which may have a substituent and an aryl group which may have a substituent, and has a hydrogen atom and a substituent. More preferably, it may be an aryl group.

R ¹⁴ in Formula (12), Formula (13), and Formula (14) may form an aliphatic ring structure or an aromatic ring structure together with R ¹⁴ , Ar ¹¹ , or Ar ^12. good. Ar ¹¹ in the formula (13) and the formula (14) may form an aliphatic ring structure or an aromatic ring structure together with Ar ¹² .

  N in the formula (12), formula (13) and formula (14) represents 0 or 1.

The structural unit represented by the formula (12) is preferably a structural unit represented by the formula (15) and the formula (B-2) to the formula (B-9).

（式中、Ｒ^ｘ、Ｒ^ｙは、前記と同じ意味を表す。Ｒ^１５は、水素原子、アルキル基、アリール基、アルケニル基、アルキニル基またはハロゲンを表し、これらの基は置換基を有していてもよく、複数存在Ｒ^１５は同一であっても異なっていてもよい。）

(Wherein R ^x and R ^y represent the same meaning as described above. R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a halogen, and these groups have a substituent. And the plural R ¹⁵ may be the same or different.)

R ¹⁵ in Formula (15) and Formula (B-2) to Formula (B-9) is a hydrogen atom, an alkyl group that may have a substituent, and an aryl group that may have a substituent. It is preferable that

  As the structural unit represented by the formula (12), a structural unit represented by the formula (B-21) which is a preferred form of the formula (15) is preferable.

  The structural unit represented by the formula (13) is preferably a structural unit represented by the formula (B-11) to the formula (B-13).

  As the structural unit represented by the formula (13), the formula (B-22) which is a preferred form of the formula (B-11) and the formula (B) which is a preferred form of the formula (B-12). The structural unit represented by -23) is preferred.

  The structural unit represented by the formula (14) is preferably a structural unit represented by the formula (B-14) to the formula (B-17).

  As the structural unit represented by the formula (14), the formula (B-24) which is a preferred form of the formula (B-14) and the formula (B-25) which is a preferred form of the formula (B-15). ) And Formula (B-26), Formula (B-27) which is a preferred form of Formula (B-16), and Formula (B-28) which is a preferred form of Formula (B-17). The structural unit is preferred.

  Next, other structural units possessed by the polymer compound of the present invention will be described.

The polymer compound of the present invention may further have other structural units other than the formulas (1) to (6), the formula (12), and the formula (13).
As other structural units, two hydrogen atoms bonded to carbon atoms constituting the ring from at least one derivative selected from the group consisting of phenylene derivatives, biphenylene derivatives, dihydrophenanthrene derivatives, arylamine derivatives and phenanthrene derivatives It is preferably a divalent group excluding.
Another structural unit is an aromatic heterocyclic compound having a total of 5 to 14 nitrogen atoms, oxygen atoms, sulfur atoms, silicon atoms, phosphorus atoms and carbon atoms constituting the ring, The divalent group is preferably a divalent group excluding two hydrogen atoms bonded to carbon atoms constituting the ring of the aromatic heterocyclic compound.

  As the other structural unit, from the viewpoint of luminance lifetime, the formula (C-31) to the formula (C-36), the formula (C-41) to the formula (C-46), and the formula (C-51) to the formula The structural unit represented by (C-63) is preferable, and the formula (C-31) to the formula (C-36), the formula (C-41) to the formula (C-45), and the formula (C-51) to the formula The structural unit represented by (C-58) is more preferable, and the structural unit represented by formula (C-31) to formula (C-35) and formula (C-41) to formula (C-45) Further preferred.

（式中、Ｒ^２、Ｒ^５、Ｒ^ｘおよびＲ^ｙは、前記と同じ意味を表す。）

(In the formula, R ² , R ⁵ , R ^x and R ^y represent the same meaning as described above.)

The manufacturing method of the high molecular compound which has the terminal part of the structural unit represented by the said Formula (5) or Formula (6) is demonstrated.
(I) A method in which a constituent unit of a terminal part having one polymerizable group and a constituent unit other than the terminal part are simultaneously mixed in a reaction vessel to cause a polymerization reaction.
(Ii) Further, as another method, a method having a first step of polymerizing structural units other than the terminal portion and a second step of reacting the structural units of the terminal portion.
The polymer compound of the present invention can be produced by any of the production methods (i) and (ii) above.
In the production method of (i) or (ii) above, when the structural unit at the terminal portion of the polymer compound is not sufficiently substituted with the structural unit represented by formula (5) or formula (6), You may have the 3rd process replaced with a terminal part. As the terminal part used in the third step, for example, the terminal group described in JP-A-9-45478 may be used in addition to the terminal part according to the present invention.

  Next, the manufacturing method of the high molecular compound which has a structural unit represented by Formula (12), Formula (13), or Formula (14) as a block polymerization part of this invention is demonstrated.

<1. Block copolymer>
The polymer compound of the present invention has a structural unit represented by the above formula (12), formula (13) or formula (14) as a block polymerization part, but the polymer compound having a block polymerization part is “block type”. Sometimes called "copolymer".
In the present specification, the block type copolymer includes a part of a polymer compound having a specific structural unit chain structure (hereinafter referred to as a block polymerization part), and is included in the block polymerization part. The chain structure of the structural units has at least one structural or arrangement characteristic that does not substantially exist in a portion other than the block polymerization portion.

  In addition, the block type copolymer includes those in which a plurality of block polymerization portions are present and the block polymerization portions adjacent to each other have different configurations. That is, adjacent block polymerization parts are composed of a chain structure of different structural units, or even a block polymerization part composed of the same kind of structural units has a different composition ratio or chain structure.

  For example, the block copolymer is a polymer compound in which a specific block polymerization portion and a portion where the specific block polymerization portions are joined differ in structure or arrangement. In addition, for example, a block copolymer is a polymer compound having a difference in configuration or arrangement between a specific block polymerization portion and another block polymerization portion.

  In the block-type copolymer, the constitution of the block polymerization portion may be that the content of the constitutional unit, the arrangement pattern of the constitutional unit, and the average chain length can be estimated, and the constitution of the block polymerization portion can be completely calculated or specified. It does not have to be.

  This will be specifically described below. Block polymerization represented by Block 1 is represented by [Ma], [Mb], and [Mc] as the structural unit of Block 1 that is the block polymerization unit, and [Mx] and [My] as the structural unit of Block 2 that is the block polymerization unit. A block copolymer is obtained by combining a part and a block polymerization part represented by Block2.

  Here, na, nb, nc, nx, and ny represent the number of repetitions of the unit structure, na and nx represent an integer of 1 or more, and nb, nc, and ny represent an integer of 0 or more. The block polymerization part represented by Block 1 may contain other structural units other than Ma, Mb, and Mc, and the block polymerization part represented by Block 2 may contain other units other than Mx and My. A structural unit may be included. As a preferred form, the sum of na + nb + nc is 5 or more, and further, the sum of nx + ny is 2 or more. In a more preferred form, the sum of na + nb + nc is 8 or more, and the sum of nx + ny is 2 or more. It is.

  Specific examples of the block copolymer include formula (1-6), formula (1-7), formula (1-8)), formula (1-9) and the like.

（式中、ｗ^０は１以上の整数、ｗ^１は０または１、ｗ^２は０または１を表す。）

(W ⁰ represents an integer of 1 or more, w ¹ represents 0 or 1, and w ² represents 0 or 1.)

As a preferred form of the polymer compound having a block polymerization portion of the present invention,
For example, in the formula (1-6) to the formula (1-9),
The structural unit constituting Block 1 is represented by the formula (4) and at least one structural unit selected from the group consisting of the structural units represented by the formula (1), formula (2) and formula (3). And does not include the structural units of the formula (12) and the formula (13),
The structural unit constituting Block 2 includes the structural unit represented by Formula (12), Formula (13), and / or Formula (14), and does not include the structural unit represented by Formula (4). Things.

  The manufacturing method of the high molecular compound which has a structural unit of the said Formula (12), Formula (13), or Formula (14) as a block polymerization part of this invention is demonstrated.

<2. Manufacturing method of block polymerization section>
The following (i) to (v) can be mentioned as a method for producing a block polymerization part of a polymer compound having the structural unit of the formula (12), formula (13) or formula (14) as the block polymerization part. .
(I) A first step of synthesizing Block 1 by polymerizing structural units constituting Block 1, and Block 2 having a structure different from that of Block 1 and capable of being polymerized with Block 1 The monomer of the structural unit to be added is polymerized to obtain a polymer compound which is a block copolymer represented by the formula (1-6), formula (1-7) or formula (1-8). A method having a second step.
(Ii) A first step of synthesizing Block2 by polymerizing structural units constituting Block2, and Block1 having a structure different from that of Block2 and capable of being polymerized with Block2. The monomer of the structural unit to be added is polymerized to obtain a polymer compound which is a block copolymer represented by the formula (1-6), formula (1-7) or formula (1-8). A method having a second step.
(Iii) A first step of polymerizing the structural units constituting Block 1 to synthesize Block 1, a separate second step of polymerizing the structural units constituting Block 2 to synthesize Block 2, and the Block 1 It has a third step of polymerizing Block 2 to obtain a polymer compound which is a block copolymer represented by the formula (1-6), formula (1-7) or formula (1-8). Method.
(Iv) The block type co-weight represented by the above formula (1-6), formula (1-7) or formula (1-8) by any one of the methods (i), (ii) or (iii) above A first step of obtaining a coalescence, and a monomer of a structural unit constituting Block 3 which is a block polymerization portion having a structure different from that of Block 1 and Block 2 and capable of being polymerized together with Block 1 and Block 2 are polymerized, The method which has a 2nd process of obtaining the high molecular compound which is a block type copolymer represented by Formula (1-9).
(V) A first step of polymerizing the structural units constituting Block 1 to synthesize Block 1; a second step of separately polymerizing the structural units constituting Block 2 to synthesize Block 2; A block type copolymer represented by the above formula (1-9) is obtained by polymerizing the third step of obtaining Block 3 by polymerizing the structural units of Block 3 and Block 1, Block 2, and Block 3. A method comprising a fourth step of obtaining a molecular compound.

<3. Manufacturing method of terminal part>
The method for producing the terminal portion of the polymer compound having the structural unit of the formula (12), formula (13) or formula (14) as the block polymerization portion will be described.
The structural unit at the end may be a structural unit represented by the above formula (5) or formula (6), or may be another structural unit. In addition to the exemplified structure in the present invention, for example, end groups described in JP-A-9-45478 may be used.

  As a polymerization method of the polymer compound of the present invention, the respective structural units may be polymerized at once, or may be divided and reacted as necessary. One polymerization method is condensation polymerization, but the polymerization can be performed by other methods. As the polymerization form, a Suzuki coupling reaction (Chem. Rev., Vol. 95, p. 2457 (1995)) using a suitable catalyst or a suitable base, a method using a Grignard reaction (Kyoritsu) Publication, Polymer Functional Material Series Vol. 2, Polymer Synthesis and Reaction (2), pages 432 to 433), Method of Polymerization by Yamamoto Polymerization (Prog. Polym. Sci.), 17th Volume, pages 1153-1205, 1992).

  In the polymer compound of the present invention, the polystyrene equivalent weight average molecular weight is preferably in the range of 5,000 to 1,000,000, and more preferably in the range of 10,000 to 500,000. The polystyrene-converted weight average molecular weight can be evaluated by, for example, gel permeation chromatography (hereinafter sometimes referred to as GPC).

In the polymer compound of the present invention, the total of the constituent units selected from the group consisting of the constituent units represented by the formula (1), formula (2) and formula (3) is the total constituent unit constituting the polymer compound. From 100 mol%, it is 10 mol% to 99 mol%, and from the viewpoint of luminous efficiency, it is preferably a ratio of 20 mol% to 95 mol%, more preferably 30 mol% to 95 mol%. It is a ratio.
The structural unit represented by the formula (4) is 0.5 mol% to 50 mol% with respect to 100 mol% of all structural units constituting the polymer compound, and preferably 1 from the viewpoint of luminous efficiency. The ratio is from mol% to 30 mol%, more preferably from 1 mol% to 10 mol%.
The sum of the structural units selected from the group consisting of the structural units represented by the formula (5), formula (6), formula (12), formula (13) and formula (14) is the total of the constituents of the polymer compound. The amount is preferably 0.005 to 15 mol%, more preferably 0.005 to 10 mol%, and more preferably 0.01 to 6 mol% with respect to 100 mol% of the structural unit. More preferably.

  The method for evaluating the total molar ratio of the structural units represented by the formula (5), formula (6), formula (12), formula (13) and formula (14) is evaluated based on physical properties characteristic of the structure. Examples thereof include H-NMR measurement. Also, a method for measuring the molar extinction coefficient and fluorescence intensity of the monomer in advance and evaluating the absorption quantity and fluorescence intensity using a calibration curve. Or you may calculate from the preparation amount ratio of the raw material used for superposition | polymerization of a high molecular compound, but it can evaluate not only these methods.

As an organic EL element, the organic EL element which consists of an anode, a cathode, and a light emitting layer is mentioned, for example. The organic EL device may further include a charge transport layer and a charge injection layer described later between the anode and the light emitting layer, and further include a charge transport layer and a charge injection layer described below between the cathode and the light emitting layer. You may have. The light emitting layer means a layer having a function of emitting light in the organic EL element. The charge transport layer means a hole transport layer having a function of transporting holes and an electron transport layer having a function of transporting electrons. Accordingly, examples of the organic EL element include an organic EL element in which a hole transport layer is further provided between the anode and the light emitting layer, and an organic EL element in which an electron transport layer is further provided between the cathode and the light emitting layer. It may be an organic EL device in which both a hole transport layer and an electron transport layer are provided.
The fluorescent light-emitting polymer of the present invention can be suitably used as a material used for the light emitting layer. This is because an excellent luminance life can be obtained. Moreover, the fluorescent light-emitting polymer of the present invention can also be suitably used as a material used for the charge transport layer. This is because excellent charge transportability can be obtained.

Examples of the structure of such an organic EL element include the following structures a) to d).
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that the layers are laminated adjacent to each other. The same has the same meaning hereinafter.)

When the organic EL element has a hole transport layer, the hole transport layer usually contains a hole transport material (a high molecular weight compound, a low molecular weight compound).
Among the hole transport materials, high molecular weight compounds include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, triphenyldiamine. Examples include derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, and the like.
Among the hole transport materials, examples of the low molecular weight compound include pyrazoline derivatives, arylamine derivatives, and triphenyldiamine derivatives. The low molecular weight compound is preferably used by being dispersed in a polymer binder.

  As the polymer binder, a compound that does not extremely inhibit charge transport and does not strongly absorb visible light is preferable. For example, poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p- Phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  As a method of forming the hole transport layer, when a low molecular weight compound is used, a method of forming a film from a mixed solution with a polymer binder is exemplified. In the case of using a high molecular weight compound, a method by film formation from a solution is exemplified.

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing the hole transport material is preferable. Solvents include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorinated solvents such as chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, toluene, xylene, mesitylene, Aromatic hydrocarbon solvents such as ethylbenzene, n-hexylbenzene, cyclohexylbenzene, anisole, 4-methylanisole, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane Aliphatic hydrocarbon solvents such as n-decane, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate, ethylene glycol, ethylene glycol Polyhydric alcohols such as butyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, methanol, ethanol Examples thereof include alcohol solvents such as propanol, isopropanol and cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. A solvent may be used individually by 1 type, or may use 2 or more types together.

  For film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method Coating methods such as a printing method, an offset printing method, an inkjet printing method, a capillary coating method, and a nozzle coating method can be used.

  The thickness of the hole transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate values. Usually, the thickness is 1 nm to 1 μm, preferably 2 to 500 nm. More preferably, it is 5 to 200 nm.

When the organic EL element has an electron transport layer, the electron transport layer usually contains an electron transport material (a high molecular weight compound, a low molecular weight compound).
Examples of electron transport materials include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyl Examples include dicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes containing 8-hydroxyquinoline or derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, and the like.

  As a method for forming the electron transport layer, when a low molecular weight compound is used, a vacuum deposition method from a powder or a method by film formation from a solution or a molten state is exemplified. In the case of using a high molecular weight compound, a method of film formation from a solution or a molten state is exemplified. In the method by film formation from a solution or a molten state, the above polymer binder may be used in combination.

  The solvent used for film formation from a solution is preferably a solvent capable of dissolving or uniformly dispersing the electron transport material and / or the polymer binder. As the solvent, the same solvents as those exemplified in the section of the hole transport layer can be used.

  For film formation from a solution or a molten state, a method similar to the method exemplified in the section of the hole transport layer can be used.

  The thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate values. Usually, the thickness is 1 nm to 1 μm, preferably 2 to 500 nm. More preferably, it is 5-200 nm.

  In order to improve adhesion to the electrode and charge injection from the electrode, a charge injection layer or an insulating layer (usually 0.5 to 4.0 nm in average thickness adjacent to the electrode, hereinafter the same) Examples of the layer having an effect of lowering the driving voltage of the light emitting element include a hole injection layer having a function of injecting holes from the anode and an electron injection layer in which electrons are injected from the cathode. It is done.

Examples of the structure of such an organic EL element include the following structures e) to k).
e) Anode / light-emitting layer / electron transport layer / electron injection layer / cathode f) Anode / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode g) Anode / hole injection layer / hole transport layer / Light emitting layer / cathode h) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode i) anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode j) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode k) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

The fluorescent light-emitting polymer of the present invention can be used in any layer constituting the organic layer. Preferably, it is used for a positive hole transport layer, a light emitting layer, or an electron transport layer, More preferably, it is used for a light emitting layer. A sufficient luminance life can be obtained by using the fluorescent light-emitting polymer of the present invention for a light-emitting layer, and good hole transport can be achieved by using the fluorescent light-emitting polymer of the present invention for a hole transport layer or an electron transport layer. This is because the property or the electron transport property is obtained.
The fluorescent polymer of the present invention may be used in two or more organic layers selected from a hole transport layer, a light emitting layer, and an electron transport layer.

  The thickness of the light emitting layer may be selected so that the driving voltage and the light emission efficiency are moderate values, but is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm. Particularly preferably, the thickness is 5 nm to 100 nm.

  A preferred embodiment is a structure of an organic EL element selected from the above b) to k). A more preferable form is an organic EL element structure selected from the above d) to k).

  When the fluorescent light-emitting polymer of the present invention is used in any one of the light-emitting layer, the hole transport layer, and the electron transport layer, in addition to the fluorescent light-emitting polymer of the present invention, coatability, charge transportability, light emission Depending on the purpose such as improvement of the form, low molecules, oligomers, and other polymer compounds may be added and used.

  Lamination and film formation of each layer can be performed by either a vacuum vapor deposition method or a solution coating method. For lamination and film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method Application methods such as spray coating, screen printing, flexographic printing, offset printing, inkjet printing, and nozzle coating can be used.

  In the EL element configuration of b) to k) above, when two or more layers are laminated by a coating method, after the first layer is laminated, the second layer solution (sometimes referred to as a coating solution) is used. A layer forming method in which the first layer does not dissolve is preferable. For example, there is a method in which a hole transport layer is formed by a coating method, the hole transport layer is heated and insolubilized in an organic solvent used for preparing a light emitting layer, and then a light emitting layer is formed. The heating temperature is usually 150 to 300 ° C. The heating time is usually 1 minute to 1 hour. In this case, when a component that has not been insolubilized by heating is removed, the hole transport layer may be rinsed with a solvent used for forming the light emitting layer after heating and before forming the light emitting layer. When the solvent insolubilization by heating is sufficiently performed, the above rinsing can be omitted. In order to sufficiently insolubilize the solvent by heating, it is preferable to use a compound having a polymerizable group in the molecule as the high molecular weight compound used in the hole transport layer. The number of polymerizable groups is preferably 5 mol% or more based on the number of structural units in the molecule.

  The substrate in the organic EL element may be any substrate that can form an electrode and does not change chemically when forming an organic layer, and a substrate made of a material such as glass, plastic, polymer film, or silicon. Can be mentioned. When an opaque substrate is used, the opposite electrode is preferably transparent or translucent.

  Examples of the material for the anode include a conductive metal oxide film and a translucent metal thin film. Specifically, a conductive compound made of indium oxide, zinc oxide, tin oxide, and a composite thereof such as indium tin oxide (hereinafter referred to as ITO), indium zinc oxide, or the like is used. Film, NESA, gold, platinum, silver, and copper, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. As the anode, an organic transparent conductive film such as polyaniline and a derivative thereof, polythiophene and a derivative thereof may be used. Further, the anode may have a laminated structure of two or more layers.

  The thickness of the anode can be selected in consideration of light transmittance and electric conductivity, and is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 40 to 500 nm.

  In order to facilitate charge injection, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or an insulating layer made of a metal oxide, a metal fluoride, or an organic insulating material may be provided on the anode. Good.

  Materials used for the hole injection layer include phenylamine compounds, starburst amine compounds, phthalocyanine compounds, oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide, amorphous carbon, polyaniline, and derivatives thereof. And conductive polymers such as polythiophene and derivatives thereof.

  When the hole injection layer is a conductive polymer or the polymer compound of the above-described embodiment, in order to improve the electrical conductivity, the hole injection layer may include polystyrene sulfonate ions, Anions such as alkylbenzene sulfonate ions and camphor sulfonate ions may be doped.

  The material of the cathode is preferably a material having a low work function, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, Metals such as samarium, europium, terbium, ytterbium, alloys of two or more of them, or one or more of them, and of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin An alloy with one or more kinds, graphite, a graphite intercalation compound, or the like is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy. The cathode may have a laminated structure of two or more layers.

  When the cathode has a laminate structure of two or more layers, a laminate structure of a metal, metal oxide, metal fluoride, or an alloy thereof and a metal such as aluminum, silver, or chromium is preferable.

  The thickness of the cathode may be adjusted in consideration of electric conductivity and durability, and is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 to 500 nm.

  Examples of the method for producing the cathode include a vacuum deposition method, a sputtering method, and a laminating method in which a metal thin film is thermocompression bonded. In addition, a layer made of a conductive polymer, a metal oxide, or a metal fluoride, a layer having an average thickness of 2 nm or less made of an organic insulating material may be provided between the cathode and the organic layer. A protective layer for protecting the light emitting element may be attached. In order to stably use the light emitting element for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the light emitting element from the outside.

  Hereinafter, although the further detail of this invention is demonstrated based on an Example and a comparative example, this invention is not limited to a following example.

[Method for measuring number average molecular weight and weight average molecular weight]
In this example, the polystyrene-equivalent number average molecular weight and weight average molecular weight were determined by gel permeation chromatography (GPC, Shimadzu Corporation, trade name: LC-10Avp). The polymer compound to be measured was dissolved in tetrahydrofuran to a concentration of about 0.5% by weight, and 30 μL was injected into GPC. Tetrahydrofuran was used for the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As for the column, two TSKgel SuperHM-H (manufactured by Tosoh) and one TSKgel SuperH2000 (manufactured by Tosoh) were connected in series. A UV detector (detection wavelength 254 nm) was used as the detector.

[NMR measurement]
The NMR measurement of the monomer was performed under the following conditions.
Apparatus: Nuclear magnetic resonance apparatus, INOVA300 (trade name), manufactured by Varian Inc. Measurement solvent: Deuterated chloroform or deuterated tetrahydrofuran Sample concentration: About 1% by mass
Measurement temperature: 25 ° C

[LC-MS measurement]
The measurement of LC-MS was performed by the following method. The measurement sample was dissolved in chloroform or tetrahydrofuran to a concentration of about 2 mg / mL, and 1 μL was injected into LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD). For the mobile phase of LC-MS, ion-exchanged water, acetonitrile, tetrahydrofuran or a mixed solution thereof was used, and acetic acid was added as necessary. The column used was L-column 2 ODS (3 μm) (manufactured by Chemicals Evaluation and Research Institute, inner diameter: 2.1 mm, length: 100 mm, particle size: 3 μm).

<Polymerization Example 1: Synthesis of polymer compound 1>

  In an inert atmosphere, the following formula:

で表される化合物Ａ（２．６８８２ｇ、２．９６ｍｍｏｌ）、下記式：

Compound A (2.6882 g, 2.96 mmol) represented by the following formula:

で表される化合物Ｂ（０．４２４５ｇ、０．７５ｍｍｏｌ）、下記式：

Compound B (0.4245 g, 0.75 mmol) represented by the following formula:

で表される化合物Ｃ（１．６３９６ｇ、１．８０ｍｍｏｌ）、下記式：

Compound C (1.6396 g, 1.80 mmol) represented by the following formula:

で表される化合物Ｄ（０．２３７７ｇ、０．４５ｍｍｏｌ）、ジクロロビス（トリフェニルホスフィン）パラジウム（２．１ｍｇ）およびトルエン（６２ｍｌ）を混合し、１０５℃に加熱した。得られた反応溶液に、２０重量％水酸化テトラエチルアンモニウム水溶液（１０ｍｌ）を滴下し、４．５時間還流させた。反応後、そこに、フェニルボロン酸（３６．８ｍｇ）およびジクロロビス（トリフェニルホスフィン）パラジウム（２．１ｍｇ）を加え、更に１６．５間還流させた。次いで、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、８０℃で２時間撹拌した。得られた混合物を冷却後、水（４０ｍｌ）で２回、３重量％酢酸水溶液（４０ｍｌ）で２回、水（４０ｍｌ）で２回洗浄し、得られた溶液をメタノール（５００ｍＬ）に滴下、ろ取することで沈殿物を得た。

Embedded image Compound D (0.2377 g, 0.45 mmol), dichlorobis (triphenylphosphine) palladium (2.1 mg) and toluene (62 ml) were mixed and heated to 105 ° C. To the resulting reaction solution, a 20 wt% tetraethylammonium hydroxide aqueous solution (10 ml) was added dropwise and refluxed for 4.5 hours. After the reaction, phenylboronic acid (36.8 mg) and dichlorobis (triphenylphosphine) palladium (2.1 mg) were added thereto, and the mixture was further refluxed for 16.5. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the resulting mixture, it was washed twice with water (40 ml), twice with a 3% by weight aqueous acetic acid solution (40 ml) and twice with water (40 ml), and the resulting solution was added dropwise to methanol (500 mL). A precipitate was obtained by filtration.

This precipitate was dissolved in toluene (100 mL) and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol (500 ml) and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 3.12 g of polymer compound 1. The number average molecular weight of polystyrene conversion of the high molecular compound 1 was 7.8 * 10 < ⁴ >, and the weight average molecular weight of polystyrene conversion was 2.6 * 10 < ⁵ >.

  The polymer compound 1 has the following formula in terms of the theoretical value obtained from the quantitative ratio of the raw materials used:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、および下記式：

And the following formula:

で表される構成単位とを、５０：１２．５：３０：７．５のモル比で構成されてなる共重合体である。

Is a copolymer constituted by a molar ratio of 50: 12.5: 30: 7.5.

<Polymerization Example 2: Synthesis of Polymer Compound 2>

  In an inert atmosphere, the following formula:

で表される化合物Ｅ（２．２７４９ｇ、２．９７ｍｍｏｌ）、化合物Ｂ（０．３２９０ｇ、０．６０ｍｍｏｌ）、下記式：

Compound E (2.2749 g, 2.97 mmol), Compound B (0.3290 g, 0.60 mmol) represented by the following formula:

で表される化合物Ｆ（１．２３７５ｇ、１．９２ｍｍｏｌ）、下記式：

Compound F (1.2375 g, 1.92 mmol) represented by the following formula:

で表される化合物Ｇ（０．１３３０ｇ、０．１８ｍｍｏｌ）、下記式：

Compound G (0.1330 g, 0.18 mmol) represented by the following formula:

で表される化合物Ｈ（０．３２９５ｇ、０．３０ｍｍｏｌ）、ジクロロビス（トリフェニルホスフィン）パラジウム（２．１ｍｇ）およびトルエン（７６ｍＬ）を混合し、１０５℃に加熱した。得られた反応溶液に、２０質量％水酸化テトラエチルアンモニウム水溶液（１０ｍＬ）を滴下し、２時間還流させた。反応後、そこに、フェニルボロン酸（３７ｍｇ）、ジクロロビス（トリフェニルホスフィン）パラジウム（２．１ｍｇ）、トルエン（６ｍＬ）および２０質量％水酸化テトラエチルアンモニウム水溶液（１０ｍｌ）を加え、さらに１４．５時間還流させた。次いで、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、８０℃で２時間撹拌した。得られた混合物を冷却後、有機層を、水（３９ｍｌ）で２回、３質量％酢酸水溶液（３９ｍｌ）で２回、水（３９ｍｌ）で２回洗浄し、得られた溶液をメタノール（５００ｍＬ）に滴下、ろ取することで沈殿物を得た。この沈殿物をトルエンに溶解させ、アルミナカラム、シリカゲルカラムを順番に通すことにより精製した。得られた溶液をメタノール（４６６ｍｌ）に滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、高分子化合物２（２．４２ｇ）を得た。高分子化合物２のポリスチレン換算の数平均分子量は１．０×１０^５であり、ポリスチレン換算の重量平均分子量は２．９×１０^５であった。

Embedded image Compound H (0.3295 g, 0.30 mmol), dichlorobis (triphenylphosphine) palladium (2.1 mg) and toluene (76 mL) were mixed and heated to 105 ° C. To the obtained reaction solution, a 20 mass% tetraethylammonium hydroxide aqueous solution (10 mL) was added dropwise and refluxed for 2 hours. After the reaction, phenylboronic acid (37 mg), dichlorobis (triphenylphosphine) palladium (2.1 mg), toluene (6 mL) and 20% by mass tetraethylammonium hydroxide aqueous solution (10 ml) were added thereto, and further 14.5 hours. Refluxed. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the resulting mixture, the organic layer was washed twice with water (39 ml), twice with 3% by weight aqueous acetic acid (39 ml) and twice with water (39 ml), and the resulting solution was washed with methanol (500 mL). ) Was added dropwise and collected by filtration to obtain a precipitate. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol (466 ml) and stirred, and then the resulting precipitate was collected by filtration and dried to obtain polymer compound 2 (2.42 g). The polymer compound 2 had a polystyrene-equivalent number average molecular weight of 1.0 × 10 ⁵ and a polystyrene-equivalent weight average molecular weight of 2.9 × 10 ⁵ .

  The polymer compound 2 has the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、および下記式：

And the following formula:

で表される構成単位とを、５０：１０：３２：３：５のモル比で構成されてなる共重合体である。

Is a copolymer constituted by a molar ratio of 50: 10: 32: 3: 5.

<Example 1: Synthesis of polymer compound 3>

  Under an inert atmosphere, Compound E (2.300 g, 3.00 mmol), Compound B (0.329 g, 0.60 mmol), Compound F (1.237 g, 1.92 mmol), Compound G (0.133 g, 0.30 mmol). 18 mmol), Compound H (0.329 g, 0.30 mmol), the following formula:

で表される化合物Ｉ（０．０１７３ｇ、０．０７ｍｍｏｌ、シグマアルドリッチ社製）、ジクロロビス（トリフェニルホスフィン）パラジウム（２．１ｍｇ）およびトルエン（７２ｍＬ）を混合し、１０５℃に加熱した。得られた反応溶液に２０質量％水酸化テトラエチルアンモニウム水溶液（１０ｍＬ）を滴下し、３．５時間還流させた。反応後、そこに、フェニルボロン酸（３７ｍｇ）、ジクロロビス（トリフェニルホスフィン）パラジウム（２．１ｍｇ）、トルエン（６ｍＬ）および２０質量％水酸化テトラエチルアンモニウム水溶液（１０ｍｌ）を加え、さらに１９時間還流させた。次いで、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、８０℃で２時間撹拌した。得られた混合物を冷却後、有機層を、水（４０ｍｌ）で２回、３質量％酢酸水溶液（４０ｍｌ）で２回、水（４０ｍｌ）で２回洗浄し、得られた溶液をメタノール（４７１ｍＬ）に滴下、ろ取することで沈殿物を得た。この沈殿物をトルエンに溶解させ、アルミナカラム、シリカゲルカラムを順番に通すことにより精製した。得られた溶液をメタノール（３２７ｍｌ）に滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、高分子化合物３（２．５８ｇ）を得た。高分子化合物３のポリスチレン換算の数平均分子量は５．０×１０^４であり、ポリスチレン換算の重量平均分子量は１．４×１０^５であった。

Embedded image Compound I (0.0173 g, 0.07 mmol, manufactured by Sigma-Aldrich), dichlorobis (triphenylphosphine) palladium (2.1 mg), and toluene (72 mL) were mixed and heated to 105 ° C. A 20 mass% tetraethylammonium hydroxide aqueous solution (10 mL) was added dropwise to the resulting reaction solution, and the mixture was refluxed for 3.5 hours. After the reaction, phenylboronic acid (37 mg), dichlorobis (triphenylphosphine) palladium (2.1 mg), toluene (6 mL) and a 20% by mass tetraethylammonium hydroxide aqueous solution (10 ml) were added thereto, and the mixture was further refluxed for 19 hours. It was. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the resulting mixture, the organic layer was washed twice with water (40 ml), twice with 3% by mass acetic acid aqueous solution (40 ml) and twice with water (40 ml), and the resulting solution was washed with methanol (471 mL). ) Was added dropwise and collected by filtration to obtain a precipitate. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol (327 ml) and stirred, and then the resulting precipitate was collected by filtration and dried to obtain polymer compound 3 (2.58 g). The polymer compound 3 had a polystyrene-equivalent number average molecular weight of 5.0 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 1.4 × 10 ⁵ .

  The polymer compound 3 has the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、および下記式：

And the following formula:

で表される構成単位とを、５０：１０：３２：３：５のモル比で有し、末端構造が下記式：

The terminal unit is represented by the following formula: in a molar ratio of 50: 10: 32: 3: 5.

で表される構造を有する共重合体である。

It is a copolymer which has a structure represented by these.

<Example 2: Synthesis of polymer compound 4>

Under an inert atmosphere, Compound E (2.300 g, 3.00 mmol), Compound B (0.329 g, 0.60 mmol), Compound F (1.237 g, 1.92 mmol), Compound G (0.133 g, 0.30 mmol). 18 mmol), Compound H (0.329 g, 0.30 mmol), Compound I (0.0173 g, 0.07 mmol), dichlorobis (triphenylphosphine) palladium (2.1 mg) and toluene (72 mL) Heated. A 20% by mass aqueous tetraethylammonium hydroxide solution (10 mL) was added dropwise to the resulting reaction solution, and the mixture was refluxed for 4 hours. After the reaction, phenylboronic acid (37 mg), dichlorobis (triphenylphosphine) palladium (2.1 mg), toluene (6 mL) and 20% by mass tetraethylammonium hydroxide aqueous solution (10 ml) were added thereto, and the mixture was further refluxed for 17 hours. It was. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the resulting mixture, the organic layer was washed twice with water (39 ml), twice with 3% by mass acetic acid aqueous solution (39 ml) and twice with water (39 ml), and the resulting solution was washed with methanol (469 mL). ) Was added dropwise and collected by filtration to obtain a precipitate. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol (327 ml) and stirred, and then the resulting precipitate was collected by filtration and dried to obtain polymer compound 4 (2.57 g). The polymer compound 4 had a polystyrene-equivalent number average molecular weight of 9.8 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 2.5 × 10 ⁵ .

  The polymer compound 4 has the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、および下記式：

And the following formula:

で表される構成単位とを、５０：１０：３２：３：５のモル比で有する末端構造が下記式：

The terminal structure having a molar ratio of 50: 10: 32: 3: 5 is represented by the following formula:

で表される構造を有する共重合体である。

It is a copolymer which has a structure represented by these.

<Example 3: Synthesis of polymer compound 5>

Under an inert atmosphere, Compound E (1.803 g, 2.35 mmol), Compound B (0.329 g, 0.60 mmol), Compound F (0.851 g, 1.32 mmol), Compound G (0.133 g, 0.35 mmol). 18 mmol), Compound H (0.329 g, 0.30 mmol), dichlorobis (triphenylphosphine) palladium (2.1 mg) and toluene (53 mL) were mixed and heated to 105 ° C. A 20% by mass aqueous tetraethylammonium hydroxide solution (10 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 2.5 hours. The polystyrene-equivalent number average molecular weight at this time was 4.2 × 10 ⁴ , and the polystyrene-equivalent weight average molecular weight was 1.4 × 10 ⁵ .
Compound A (0.558 g, 0.62 mmol), the following formula:

で表される化合物Ｊ（０．２０３ｇ、０．６０ｍｍｏｌ）およびトルエン（１８ｍＬ）を加え、さらに２．５時間還流させた。反応後、そこに、フェニルボロン酸（３６ｍｇ）、ジクロロビス（トリフェニルホスフィン）パラジウム（２．１ｍｇ）、トルエン（８ｍＬ）および２０質量％水酸化テトラエチルアンモニウム水溶液（１０ｍｌ）を加え、さらに１８時間還流させた。次いで、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、８０℃で２時間撹拌した。得られた混合物を冷却後、有機層を、水（３９ｍｌ）で２回、３質量％酢酸水溶液（３９ｍｌ）で２回、水（３９ｍｌ）で２回洗浄し、得られた溶液をメタノール（４６６ｍＬ）に滴下、ろ取することで沈殿物を得た。この沈殿物をトルエンに溶解させ、アルミナカラム、シリカゲルカラムを順番に通すことにより精製した。得られた溶液をメタノール（４６６ｍｌ）に滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、高分子化合物５（２．５５ｇ）を得た。高分子化合物５のポリスチレン換算の数平均分子量は８．４×１０^４であり、ポリスチレン換算の重量平均分子量は２．６×１０^５であった。

Compound J (0.203 g, 0.60 mmol) and toluene (18 mL) represented by the formula were added, and the mixture was further refluxed for 2.5 hours. After the reaction, phenylboronic acid (36 mg), dichlorobis (triphenylphosphine) palladium (2.1 mg), toluene (8 mL) and 20% by mass tetraethylammonium hydroxide aqueous solution (10 ml) were added thereto, and the mixture was further refluxed for 18 hours. It was. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the resulting mixture, the organic layer was washed twice with water (39 ml), twice with 3% by mass acetic acid aqueous solution (39 ml) and twice with water (39 ml), and the resulting solution was washed with methanol (466 mL). ) Was added dropwise and collected by filtration to obtain a precipitate. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol (466 ml) and stirred, and then the resulting precipitate was collected by filtration and dried to obtain polymer compound 5 (2.55 g). The polymer compound 5 had a polystyrene-equivalent number average molecular weight of 8.4 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 2.6 × 10 ⁵ .

  The polymer compound 5 has the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、および下記式：

And the following formula:

で表される構成単位とを、［４０：１０：２２：３：５］−ｂ−［１０：１０］のモル比で構成されてなるブロック型共重合体である。

Is a block copolymer composed of a molar ratio of [40: 10: 22: 3: 5] -b- [10:10].

<Synthesis Example 1: Synthesis of Compound K>

  Under a nitrogen atmosphere, Compound 1 (25.0 g), [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethylene adduct (0.24 g) and tert-butyl methyl ether (410 mL) were added. At a temperature of 10 ° C. or lower, 2-ethylhexylmagnesium bromide (173 mL of 1 mol / L diethyl ether solution) was added dropwise and stirred at room temperature for 4 hours. After completion of the reaction, the reaction solution was poured into a mixed solution of water and 2N hydrochloric acid, the aqueous layer was extracted with ethyl acetate, and the obtained organic layer was washed with an aqueous sodium chloride solution. The washed organic layer was dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: hexane) to obtain 21.3 g of Compound 2 as a pale yellow oil.

MS (ESI, positive): [M ⁺ ] 353
¹ H-NMR (300 MHz, CDCl ₃ ); δ (ppm) = 0.75-1.00 (12H, m), 1.10-1.50 (16H, m), 1.69-1.85 ( 2H, m), 2.90-3.05 (4H, m), 7.24-7.38 (3H, m), 7.35-7.44 (3H, m), 7.90-7. 95 (3H, m).

  Compound 2 (21.3 g), bis (pinacolato) diboron (4,4,4 ′, 4 ′, 5,5,5 ′, 5′-octamethyl-2,2′-bi-1,3 under nitrogen atmosphere , 2-dioxaborolane) (46.0 g), bis (1,5-cyclooctadiene) di-μ-methoxydiiridium (I) (0.24 g) (manufactured by Sigma-Aldrich), 4,4′-di tert -Butyl-2,2'-dipyridyl (0.19 g) and dioxane (140 mL) were charged, and the mixture was stirred at 100 ° C for 3 hours. After cooling the obtained reaction liquid, dioxane was distilled off under reduced pressure, methanol was added to the residue, and the precipitated solid was collected by filtration and dried. This solid was dissolved in toluene, activated clay was added, and the mixture was stirred at 60 ° C. for 30 minutes. Thereafter, the obtained mixture was filtered while hot in a filter pre-coated with silica gel, and the filtrate was concentrated under reduced pressure. Methanol was added to the resulting concentrated residue, and the precipitated solid was collected by filtration and dried to obtain 28.0 g of Compound K as a white powder solid.

LC-MS (ESI, positive): [M ⁺ ] 605
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm): 0.85-0.95 (12H, m), 1.24-1.50 (16H, m), 1.6-1.85 ( 2H, m), 2.90-3.18 (4H, m), 7.60 (2H, s), 8.47 (2H, s).

<Synthesis Example 2: Synthesis of Compound L>

  The reaction vessel was placed in an argon atmosphere, and 3-n-hexyl bromobenzene (111.1 g) and tetrahydrofuran were added to prepare a homogeneous solution, which was cooled to -75 ° C. To this solution was added 2.5M n-butyllithium / hexane solution (1 molar equivalent to 1-bromo-3,5-di-n-hexylbenzene) (176 ml) at -75 ° C over 1.5 hours. The solution was added dropwise, and the solution was further stirred at -70 ° C for 1.5 hours. Next, a solution consisting of 2,7-dibromofluorenone (142 g) and tetrahydrofuran was added dropwise at -75 ° C over 1 hour, and the reaction solution was allowed to warm to room temperature and stirred for 4 hours. Next, the solution was cooled to 0 ° C., slowly added with acetone and 2 mol% aqueous hydrochloric acid and stirred, then warmed to room temperature and allowed to stand at room temperature. Next, the reaction mixture was filtered, the filtrate was concentrated, hexane and water were added and stirred, and the aqueous layer was removed from the oil layer which was allowed to stand and liquid-separated. A saturated saline solution was added to the oil layer and stirred, and the aqueous layer was removed from the oil layer which was allowed to stand and separate. Magnesium sulfate was added to the oil layer and stirred, and the filtrate obtained by filtration was concentrated. Subsequently, it refine | purified by the silica gel column chromatography using hexane and a dichloromethane as a developing solvent, and the compound 3 (162g) was obtained.

  The reaction vessel was placed under an argon stream, and compound 3 (162 g) and trifluoroacetic acid (245 ml) were added. Trimethylsilane (115 ml) was added dropwise to the solution over 30 minutes and stirred overnight at room temperature. Next, the reaction solution was cooled to 10 ° C., hexane and distilled water were added, and the mixture was stirred for 1 hour. Then, the aqueous layer which was allowed to stand and separated was removed from the oil layer. Subsequently, water was added and stirred, and the aqueous layer which was allowed to stand and liquid-separated was removed from the oil layer. A saturated saline solution was added to the oil layer and stirred, and the aqueous layer was removed from the oil layer which was allowed to stand and separate. Magnesium sulfate was added to the oil layer and stirred, and the filtrate obtained by filtration was concentrated. Subsequently, the mixture was purified by silica gel column chromatography using hexane and dichloromethane as developing solvents, and concentrated to remove the solvent. Subsequently, the compound 4 (138g) was obtained by wash | cleaning with methanol.

  The reaction vessel was placed under an argon stream, and compound 4 (138 g), 1-bromooctane (75.4 ml), methyl trioctyl ammonium chloride (trade name: Aliquat (registered trademark) 336, manufactured by Sigma-Aldrich) (1.2 g) And 40% potassium hydroxide (60 ml) was added and stirred at 85 ° C. overnight. Next, the reaction solution was cooled to room temperature, dichloromethane and distilled water were added, and the mixture was stirred for 1 hour. The aqueous layer which was allowed to stand and separated was removed from the oil layer. Subsequently, water was added and stirred, and the aqueous layer which was allowed to stand and liquid-separated was removed from the oil layer. A saturated saline solution was added to the oil layer and stirred, and the aqueous layer was removed from the oil layer which was allowed to stand and separate. Magnesium sulfate was added to the oil layer and stirred, and the filtrate obtained by filtration was concentrated. Subsequently, the mixture was purified by silica gel column chromatography using hexane and dichloromethane as developing solvents, and concentrated to remove the solvent. Subsequently, reprecipitation using methanol and dichloromethane was performed to obtain Compound L (145 g).

<Polymerization Example 3: Synthesis of Polymer Compound 6>

Under an inert atmosphere, Compound K (1.1969 g, 1.98 mmol), Compound L (1.0737 g, 1.80 mmol), Compound H (0.2197 g, 0.20 mmol), dichlorobis (triphenylphosphine) palladium (1 .4 mg) and toluene (47 mL) were mixed and heated to 105 ° C. A 20% by weight aqueous tetraethylammonium hydroxide solution (6.6 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 3.5 hours. After the reaction, phenylboronic acid (24 mg), 20 wt% tetraethylammonium hydroxide aqueous solution (6.6 mL) and dichlorobis (triphenylphosphine) palladium (1.4 mg) were added thereto, and the mixture was refluxed for 16.5 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the resulting mixture, the reaction solution was washed twice with water, twice with a 3 wt% aqueous acetic acid solution and twice with water, and the resulting solution was added dropwise to methanol and collected by filtration. Got. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.12 g of polymer compound 6. The polymer compound 6 had a polystyrene-equivalent number average molecular weight of 7.5 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 2.7 × 10 ⁵ .

  The polymer compound 6 has the following formula according to the theoretical value obtained from the amount ratio of the raw materials used:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位とが、５０：４５：５のモル比で構成されてなる共重合体である。

Is a copolymer having a molar ratio of 50: 45: 5.

<Example 4: Synthesis of polymer compound 7)

  Under an inert atmosphere, Compound K (1.195 g, 1.98 mmol), Compound L (1.074 g, 1.80 mmol), Compound H (0.220 g, 0.20 mmol), dichlorobis (triphenylphosphine) palladium (1 .4 mg) and toluene (47 mL) were mixed and heated to 105 ° C. A 20 wt% tetraethylammonium hydroxide aqueous solution (6.6 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 3 hours and 20 minutes. After the reaction, there is the following formula:

で表される化合物Ｍ（４６ｍｇ、和光純薬社製）、２０重量％水酸化テトラエチルアンモニウム水溶液（６．６ｍＬ）およびジクロロビス（トリフェニルホスフィン）パラジウム（１．４ｍｇ）を加え、１４時間還流させた。次いで、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、８０℃で２時間撹拌した。得られた反応液を冷却後、該反応液を、水で２回、３重量％酢酸水溶液で２回、水で２回洗浄し、得られた溶液をメタノールに滴下し、ろ取することで沈殿物を得た。この沈殿物をトルエンに溶解させ、アルミナカラム、シリカゲルカラムを順番に通すことにより精製した。得られた溶液をメタノールに滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、高分子化合物７を１．３２ｇ得た。高分子化合物７のポリスチレン換算の数平均分子量は９．８×１０⁴であり、ポリスチレン換算の重量平均分子量は２．８×１０⁵であった。

Compound M (46 mg, manufactured by Wako Pure Chemical Industries Ltd.), 20 wt% tetraethylammonium hydroxide aqueous solution (6.6 mL) and dichlorobis (triphenylphosphine) palladium (1.4 mg) were added, and the mixture was refluxed for 14 hours. . Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the obtained reaction solution, the reaction solution was washed twice with water, twice with a 3% by weight aqueous acetic acid solution and twice with water, and the obtained solution was dropped into methanol and filtered. A precipitate was obtained. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.32 g of polymer compound 7. The polymer compound 7 had a polystyrene-equivalent number average molecular weight of 9.8 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 2.8 × 10 ⁵ .

  The polymer compound 7 has the following formula:

で表される構成単位、下記式：

A structural unit represented by the following formula:

で表される構成単位、および下記式：

And the following formula:

で表される構成単位とが、５０：４５：５のモル比で構成されてなり、下記式：

Is constituted by a molar ratio of 50: 45: 5, and the following formula:

で表される末端構造を有する共重合体であった。

It was a copolymer which has the terminal structure represented by these.

<Comparative example 1: Preparation and evaluation of organic EL element C1>
AQ-1200 (manufactured by Plextronics), which is a polythiophene / sulfonic acid-based hole injecting agent, is formed on a glass substrate with an ITO film having a thickness of 45 nm by sputtering to a thickness of 50 nm by spin coating. Heated on plate at 170 ° C. for 15 minutes.

  Next, a xylene solution 1 in which the polymer compound 1 was dissolved in a xylene solvent at a concentration of 0.5% by mass was prepared. A xylene solution 1 was deposited to a thickness of 20 nm by spin coating. Then, it heated at 180 degreeC for 60 minute (s) on the hotplate in nitrogen atmosphere.

Next, a xylene solution 2 in which the polymer compound 2 was dissolved in a xylene solvent at a concentration of 1.2% by mass was prepared. A xylene solution 2 was deposited to a thickness of 60 nm by spin coating. Then, it heated at 130 degreeC for 10 minute (s) on the hotplate in nitrogen atmosphere. Then, about 3 nm of sodium fluoride and then about 80 nm of aluminum were vapor-deposited as a cathode, and the organic EL element C1 was produced. In addition, after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.

When voltage was applied to the obtained organic EL element C1, fluorescence emission having an emission spectrum peak at 460 nm derived from the polymer compound 2 was obtained from the organic EL element C1. The maximum luminous efficiency of the organic EL element C1 was 10.1 cd / A. When the initial luminance was set to 5000 cd / m ² and the time until the initial luminance decreased by 40% (that is, 60% of the initial luminance) was measured, it was 10 hours. The results are shown in Table 1.

<Example 5: Production and evaluation of organic EL element 1>
The organic EL element 1 is a xylene in which the polymer compound 2 in the production of the organic EL element C1 is changed to the polymer compound 3 and the polymer compound 3 is dissolved in a xylene solvent at a concentration of 1.2% by mass. It was prepared in the same manner except that Solution 3 was used. When voltage was applied to the obtained organic EL device 1, fluorescence emission having an emission spectrum peak at 460 nm derived from the polymer compound 3 was obtained from the organic EL device 1. The maximum luminous efficiency of the organic EL element 1 was 8.7 cd / A. When the initial luminance was set to 5000 cd / m ² and the time until the initial luminance decreased by 40% (that is, 60% of the initial luminance) was measured, it was 51 hours. The results are shown in Table 1.
<Example 6: Production and evaluation of organic EL element 2>
The organic EL element 2 is a xylene obtained by changing the polymer compound 2 to the polymer compound 4 in the preparation of the organic EL element C1 and dissolving the polymer compound 4 at a concentration of 1.2% by mass in a xylene solvent. It was prepared in the same manner except that Solution 4 was used. When voltage was applied to the obtained organic EL element 2, fluorescence emission having an emission spectrum peak at 460 nm derived from the polymer compound 4 was obtained from the organic EL element 2. The maximum light emission efficiency of the organic EL element 2 was 9.7 cd / A. The initial luminance was set to 5000 cd / m ² and the time until the initial luminance was reduced by 40% (that is, 60% of the initial luminance) was 49 hours. The results are shown in Table 1.
<Example 7: Production and evaluation of organic EL element 3>
The organic EL element 3 is a xylene in which the polymer compound 2 in the production of the organic EL element C1 is changed to the polymer compound 5 and the polymer compound 5 is dissolved at a concentration of 1.0 mass% in a xylene solvent. It was prepared in the same manner except that Solution 5 was used. When voltage was applied to the obtained organic EL device 3, fluorescence emission having an emission spectrum peak at 465 nm derived from the polymer compound 5 was obtained from the organic EL device 3. The maximum light emission efficiency of the organic EL element 3 was 10.4 cd / A. The initial luminance was set to 5000 cd / m ^2, and the time until the initial luminance decreased by 40% (that is, 60% of the initial luminance) was 56 hours. The results are shown in Table 1.

  From Table 1, the organic EL device using the polymer compound 3, the polymer compound 4 and the polymer compound 5 showed an excellent luminance life as compared with the organic EL device using the polymer compound 2.

<Comparative Example 2: Production and evaluation of organic EL element C2>
The organic EL element C2 is a xylene in which the polymer compound 2 in the production of the organic EL element C1 is changed to the polymer compound 6 and the polymer compound 6 is dissolved at a concentration of 1.2% by mass in a xylene solvent. A similar method was used except that the solution 6 was used. When voltage was applied to the obtained organic EL element C2, fluorescence emission having an emission spectrum peak at 465 nm derived from the polymer compound 6 was obtained from the organic EL element C2. The maximum light emission efficiency of the organic EL element C2 was 10.8 cd / A. The initial luminance was set to 5000 cd / m ^2, and the time until the initial luminance decreased by 40% (that is, 60% of the initial luminance) was measured and found to be 72 hours. The results are shown in Table 2.

<Example 8: Production and evaluation of organic EL element 4>
The organic EL element 4 is a xylene obtained by changing the polymer compound 2 to the polymer compound 7 in the production of the organic EL element C1 and dissolving the polymer compound 7 at a concentration of 1.2% by mass in a xylene solvent. A similar method was used except that the solution 7 was used. When voltage was applied to the obtained organic EL element 4, fluorescence emission having an emission spectrum peak at 465 nm derived from the polymer compound 7 was obtained from the organic EL element 4. The maximum luminous efficiency of the organic EL element 4 was 10.2 cd / A. The initial luminance was set to 5000 cd / m ^2, and the time until the initial luminance decreased by 40% (that is, 60% of the initial luminance) was measured and found to be 98 hours. The results are shown in Table 2.

  From Table 2, the organic EL device using the polymer compound 7 showed an excellent luminance life as compared with the organic EL device using the polymer compound 6.

Claims (8)

A polymer compound having at least one structural unit selected from the group consisting of structural units represented by formula (1), formula (2) and formula (3) and a structural unit represented by formula (4). And
The polymer compound further has a terminal structural unit represented by the formula (5) or the formula (6), or a block polymerization unit represented by the formula (12), the formula (13), or the formula (14). It has at least 1 structural unit chosen from the group which consists of a structural unit represented, The high molecular compound characterized by the above-mentioned.

(Where
R ¹¹ and R ¹² each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group or an aryloxy group, and these groups may have a substituent. In addition, a plurality of R ¹¹ and R ¹² may be the same or different.
R ^x and R ^y each independently represent a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent and are bonded to each other to form a ring structure May be formed. )

(Where
X represents O, S, C (R ³ ) ₂ or NR ² ;
R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group or an aryloxy group, and these groups have a substituent. A plurality of R ¹ may be the same or different, and when a plurality of R ² are present, they may be the same or different, and when a plurality of R ³ are present These may be the same or different. )

(Where
Ar ² represents a phenylene group, a naphthylene group, an anthracenediyl group, a fluorenediyl group, or a phenanthrene diyl group, and these groups may have a substituent, and when a plurality of Ar ² are present, May be the same or different.
Ar ³ represents an arylene group or a divalent aromatic heterocyclic group, and these groups may have a substituent, and when a plurality of Ar ³ are present, they may be the same or different. Also good.
R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a halogen atom, and these groups may have a substituent, and a plurality of R ⁴ may be the same or different. It may be.
m represents 0 or 1, and a plurality of m may be the same or different.
p ¹ represents an integer of 0 or more, ^{p 2} represents an integer of 1 or more.
Y represents a bonding position with another structural unit of the polymer compound. )

(Where
Ar ¹¹ represents an arylene group or a divalent aromatic heterocyclic group, and these groups optionally have a substituent.
Ar ¹² represents a phenylene group, a naphthylene group, an anthracenediyl group, a fluorenediyl group, or a phenanthrene diyl group, and these groups may have a substituent.
Ar ¹² represents a trivalent aromatic hydrocarbon group or a trivalent aromatic heterocyclic group, and these groups may have a substituent.
R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a halogen atom, and these groups may have a substituent, and a plurality of R ¹⁴ may be the same or different. Good.
n represents 0 or 1, and p ³ represents 0 or 1. )   The total of the structural units represented by the formula (5), the formula (6), the formula (12), the formula (13) and the formula (14) with respect to all the structural units of the polymer compound is 0.01 to 15 mol. The polymer compound according to claim 1, which is%. The high molecular compound of Claim 1 or 2 with which the structural unit of the terminal part of the said high molecular compound is represented by Formula (9), Formula (10), or Formula (11).

(Where
R ⁵ and R represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or a halogen atom, and these groups may have a substituent, and a plurality of R ⁵ and R are the same Or different.
However, one of R represents a bonding position with another structural unit of the polymer compound. ) The high molecular compound of Claim 1 or 2 which has a structural unit represented by Formula (15) as a block polymerization part of the said high molecular compound.

(Where
R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a halogen atom, and these groups may have a substituent, and a plurality of R ¹⁵ may be the same or different. Good. ) Two hydrogen atoms bonded to the carbon atoms constituting the ring were removed from at least one derivative selected from the group consisting of phenylene derivatives, biphenylene derivatives, dihydrophenanthrene derivatives, phenylene vinylene derivatives, arylamine derivatives and phenanthrene derivatives. Divalent groups
The polymer compound according to claim 1, further comprising as a structural unit. An aromatic heterocyclic compound having a total of 5 to 14 nitrogen atoms, oxygen atoms, sulfur atoms, silicon atoms, phosphorus atoms and carbon atoms constituting the ring, wherein the ring of the aromatic heterocyclic compound A divalent group excluding two hydrogen atoms bonded to the carbon atoms constituting
The polymer compound according to claim 1, further comprising as a structural unit. An organic light emitting device having an anode, a cathode and a light emitting layer,
The organic EL element which contains the high molecular compound as described in any one of Claims 1-5 in this light emitting layer. An organic light emitting device having an anode, a cathode, a light emitting layer and a charge transport layer,
An organic EL device containing the polymer compound according to any one of claims 1 to 5 in the charge transport layer.