JP2016044228A - High molecular weight compound and light emitting element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high molecular weight compound excellent in crosslinking property.SOLUTION: There is provided the high molecular weight compound containing a constitutional unit having a group represented by the formula (1). (1), where R, R, R, Rand Rare each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group or a monovalent heterocyclic group and these groups may have a substituent, nA represent an integer of 0 to 5, Lrepresents an alkylene group, a cycloalkylene group, an arylene group, a bivalent heterocyclic group, a group represented by -NR'-, an oxygen atom or a sulfur atom, there groups may have a substituent, R' represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group and these groups may have a substituent.SELECTED DRAWING: None

Description

  The present invention relates to a polymer compound and a light emitting device using the same.

  An organic electroluminescence element (hereinafter also referred to as “light-emitting element”) has high luminous efficiency and low driving voltage, and thus can be suitably used for display applications, and has attracted attention in recent years. This light-emitting element includes organic layers such as a light-emitting layer and a charge transport layer. By using a polymer compound, an organic layer can be formed by a coating method typified by an ink jet printing method. Therefore, a polymer compound used for manufacturing a light-emitting element has been studied.

  As a material used for a hole transport layer of a light-emitting element, Patent Document 1 discloses a polymer compound including a structural unit derived from an arylamine and a structural unit derived from an aromatic hydrocarbon having a benzocyclobutane structure. And used for a hole transport layer of a light-emitting element. Benzocyclobutane functions as a bridging group. Therefore, it is possible to form a hole transport layer substantially insoluble in the solvent by forming a film of the polymer compound by a coating method and then crosslinking benzocyclobutane by heating or the like. A light emitting layer or the like can be laminated on the hole transport layer by a coating method.

JP 2008-106241 A

  However, the polymer compound described in Patent Document 1 is not always sufficient in crosslinkability.

  Therefore, an object of the present invention is to provide a polymer compound having excellent crosslinkability. Another object of the present invention is to provide a composition containing the polymer compound and a light-emitting device obtained using the polymer compound. It is another object of the present invention to provide a compound useful for producing the polymer compound.

  The present invention first provides a polymer compound containing a structural unit having a group represented by the following formula (1).

［式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基または１価の複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^２とＲ^３、Ｒ^３とＲ^４、Ｒ^４とＲ^５は、互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。
ｎＡは０〜５の整数を表す。
Ｌ^Ａは、アルキレン基、シクロアルキレン基、アリーレン基、２価の複素環基、−ＮＲ’−で表される基、酸素原子または硫黄原子を表し、これらの基は置換基を有していてもよい。Ｒ’は、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。Ｌ^Ａが複数存在する場合、それらは同一でも異なっていてもよい。］

[Where:
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group or monovalent heterocyclic group These groups may have a substituent. R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.
nA represents an integer of 0 to 5.
L ^A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, the group represented by -NR'-, an oxygen atom or a sulfur atom, these groups have a substituent Also good. R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. When a plurality of ^LA are present, they may be the same or different. ]

  The present invention secondly provides a compound represented by the following formula (2M) or (2'M).

［式中、
Ａｒ^１は、芳香族炭化水素基または複素環基を表し、これらの基は置換基を有していてもよい。
ｎは１〜４の整数を表す。
Ｑ^１は、前記式（１）で表される基を表す。Ｑ^１が複数存在する場合、それらは同一でも異なっていてもよい。
Ｚ^１およびＺ^２は、それぞれ独立に、下記の置換基Ａ群または置換基Ｂ群から選ばれる基を表す。］

[Where:
Ar ¹ represents an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent.
n represents an integer of 1 to 4.
Q ¹ represents a group represented by the formula (1). When a plurality of Q ¹ are present, they may be the same or different.
Z ¹ and Z ² each independently represent a group selected from the following substituent group A or substituent group B. ]

［式中、
ｍＡは０〜５の整数を表し、ｍは１〜４の整数を表し、ｃは０または１を表す。ｍＡが複数存在する場合、それらは同一でも異なっていてもよい。
Ａｒ^３は、芳香族炭化水素基、複素環基、または、少なくとも１種の芳香族炭化水素環と少なくとも１種の複素環とが直接結合した基を表し、これらの基は置換基を有していてもよい。
Ａｒ^２およびＡｒ^４は、それぞれ独立に、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^２、Ａｒ^３およびＡｒ^４はそれぞれ、当該基が結合している窒素原子に結合している当該基以外の基と、直接または酸素原子もしくは硫黄原子を介して結合して、環を形成していてもよい。
Ｋ^Ａは、アルキレン基、シクロアルキレン基、アリーレン基、２価の複素環基、−ＮＲ’’−で表される基、酸素原子または硫黄原子を表し、これらの基は置換基を有していてもよい。Ｒ’’は、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。Ｋ^Ａが複数存在する場合、それらは同一でも異なっていてもよい。
Ｑ^２は、前記式（１）で表される基、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。但し、少なくとも１つのＱ^２は、前記式（１）で表される基である。
Ｚ^３およびＺ^４は、それぞれ独立に、下記の置換基Ａ群から選ばれる基または置換基Ｂ群から選ばれる基を表す。］

[Where:
mA represents an integer of 0 to 5, m represents an integer of 1 to 4, and c represents 0 or 1. When a plurality of mA are present, they may be the same or different.
Ar ³ represents an aromatic hydrocarbon group, a heterocyclic group, or a group in which at least one aromatic hydrocarbon ring and at least one heterocyclic ring are directly bonded, and these groups have a substituent. It may be.
Ar ² and Ar ⁴ each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
Ar ² , Ar ^3, and Ar ⁴ are each bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded, directly or via an oxygen atom or sulfur atom, to form a ring. It may be.
K ^A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, -NR '' -, a group represented by an oxygen atom or a sulfur atom, these groups have a substituent May be. R ″ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. When a plurality of K ^A are present, they may be the same or different.
Q ² represents a group represented by the formula (1), a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. . However, at least one Q ² is a group represented by the formula (1).
Z ³ and Z ⁴ each independently represent a group selected from the following substituent group A or a group selected from substituent group B. ]

<Substituent group A>
Chlorine atom, bromine atom, iodine atom, —O—S (═O) ₂ R ^C1 (wherein R ^C1 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups have a substituent. A group represented by:
<Substituent group B>
-B in (OR ^C2) ₂ (wherein, R ^C2 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, these groups may have a substituent. There exist a plurality of R ^C2 is Groups which may be the same or different and may be linked to each other to form a ring structure together with the oxygen atoms to which they are bonded.
A group represented by —BF ₃ Q ′ (wherein Q ′ represents Li, Na, K, Rb or Cs);
-A group represented by MgY '(wherein Y' represents a chlorine atom, a bromine atom or an iodine atom);
A group represented by —ZnY ″ (wherein Y ″ represents a chlorine atom, a bromine atom or an iodine atom); and
-Sn (R ^C3) ₃ (wherein, R ^C3 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, these groups may have a substituent. More existing R ^C3 is The groups may be the same or different and may be linked to each other to form a ring structure together with the tin atoms to which they are bonded.

  Third, the present invention provides at least one selected from the group consisting of the above-described polymer compound, a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material, an antioxidant, and a solvent. And a composition containing the following materials.

  Fourthly, the present invention provides a light emitting device obtained using the above polymer compound.

  According to the present invention, a polymer compound having excellent crosslinkability can be provided. Moreover, according to this invention, the light emitting element obtained using the composition containing this high molecular compound and this high molecular compound can be provided. Furthermore, according to the present invention, a compound useful for producing the polymer compound can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

<Explanation of common terms>
Terms commonly used in this specification have the following meanings unless otherwise specified.

  Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, i-Pr represents an isopropyl group, and t-Bu represents a tert-butyl group.

  The hydrogen atom may be a deuterium atom or a light hydrogen atom.

  In the formula representing the metal complex, the solid line representing the bond with the central metal means a covalent bond or a coordinate bond.

The “polymer compound” means a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ .

“Low molecular weight compound” means a compound having no molecular weight distribution and a molecular weight of 1 × 10 ⁴ or less.

  “Structural unit” means one or more units present in a polymer compound.

The “alkyl group” may be linear or branched. The carbon atom number of a linear alkyl group is 1-50 normally without including the carbon atom number of a substituent, Preferably it is 3-30, More preferably, it is 4-20. The number of carbon atoms of the branched alkyl group is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20, not including the number of carbon atoms of the substituent.
The alkyl group may have a substituent, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isoamyl group, 2-ethylbutyl group, Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, 3-propylheptyl group, decyl group, 3,7-dimethyloctyl group, 2-ethyloctyl group, 2-hexyldecyl group, dodecyl group, and these Examples include groups in which the hydrogen atom in the group is substituted with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, etc., for example, a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorobutyl group, Fluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, 3- (4-methylphenyl) propyl group, 3- (3,5-di-hexyl group Ruphenyl) propyl group and 6-ethyloxyhexyl group.
The number of carbon atoms of the “cycloalkyl group” is usually 3 to 50, preferably 3 to 30 and more preferably 4 to 20 without including the number of carbon atoms of the substituent.
The cycloalkyl group may have a substituent, and examples thereof include a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.

“Aryl group” means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The carbon atom number of an aryl group is 6-60 normally without including the carbon atom number of a substituent, Preferably it is 6-20, More preferably, it is 6-10.
The aryl group may have a substituent, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2 -Pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and hydrogen atoms in these groups Are groups substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, or the like.

The “alkoxy group” may be linear or branched. The number of carbon atoms of a linear alkoxy group is 1-40 normally without including the carbon number of a substituent, Preferably it is 4-10. The number of carbon atoms of the branched alkoxy group is usually 3 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent.
The alkoxy group may have a substituent, for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, tert-butyloxy group, pentyloxy group, hexyloxy group, Heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, and the hydrogen atom in these groups is a cycloalkyl group, an alkoxy group, And a group substituted with a cycloalkoxy group, an aryl group, a fluorine atom, or the like.
The number of carbon atoms of the “cycloalkoxy group” is usually 3 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent.
The cycloalkoxy group may have a substituent, and examples thereof include a cyclohexyloxy group.

The number of carbon atoms of the “aryloxy group” is usually 6 to 60, preferably 7 to 48, not including the number of carbon atoms of the substituent.
The aryloxy group may have a substituent, for example, a phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, 1- Examples include a pyrenyloxy group and a group in which a hydrogen atom in these groups is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom or the like.

“P-valent heterocyclic group” (p represents an integer of 1 or more) is a p-group of hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from a heterocyclic compound. This means the remaining atomic group excluding the hydrogen atom. Among the p-valent heterocyclic groups, this is an atomic group obtained by removing p hydrogen atoms from an aromatic heterocyclic compound directly bonded to carbon atoms or heteroatoms constituting the ring. A “p-valent aromatic heterocyclic group” is preferable.
`` Aromatic heterocyclic compounds '' are oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole, etc. A compound in which the ring itself exhibits aromaticity and a heterocyclic ring such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, and benzopyran itself does not exhibit aromaticity, but the aromatic ring is condensed to the heterocyclic ring. Means a compound.

The number of carbon atoms of the monovalent heterocyclic group is usually 2 to 60, preferably 4 to 20, not including the number of carbon atoms of the substituent.
The monovalent heterocyclic group may have a substituent, for example, thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidinyl group, quinolinyl group, isoquinolinyl group, pyrimidinyl group, triazinyl group, and these And a group in which the hydrogen atom in the group is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or the like.

  “Halogen atom” refers to a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The “amino group” may have a substituent, and a substituted amino group is preferable. As a substituent which an amino group has, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group is preferable.
Examples of the substituted amino group include a dialkylamino group, a dicycloalkylamino group, and a diarylamino group.
Examples of the amino group include dimethylamino group, diethylamino group, diphenylamino group, bis (4-methylphenyl) amino group, bis (4-tert-butylphenyl) amino group, bis (3,5-di-tert- Butylphenyl) amino group.

The “alkenyl group” may be linear or branched. The number of carbon atoms of a linear alkenyl group is 2-30 normally without including the carbon atom number of a substituent, Preferably it is 3-20. The number of carbon atoms of the branched alkenyl group is usually 3 to 30, and preferably 4 to 20, not including the number of carbon atoms of the substituent.
The number of carbon atoms of the “cycloalkenyl group” is usually 3 to 30, preferably 4 to 20, not including the number of carbon atoms of the substituent.
The alkenyl group and the cycloalkenyl group may have a substituent, for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, Examples include a pentenyl group, a 1-hexenyl group, a 5-hexenyl group, a 7-octenyl group, and a group in which these groups have a substituent.

The “alkynyl group” may be linear or branched. The carbon atom number of an alkynyl group is 2-20 normally without including the carbon atom of a substituent, Preferably it is 3-20. The number of carbon atoms of the branched alkynyl group is usually 4 to 30, preferably 4 to 20, not including the carbon atom of the substituent.
The number of carbon atoms of the “cycloalkynyl group” is usually 4 to 30, preferably 4 to 20, not including the carbon atom of the substituent.
The alkynyl group and cycloalkynyl group may have a substituent, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4- Examples include a pentynyl group, 1-hexynyl group, 5-hexynyl group, and groups in which these groups have a substituent.

The “arylene group” means an atomic group remaining after removing two hydrogen atoms directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The carbon atom number of an arylene group is 6-60 normally without including the carbon atom number of a substituent, Preferably it is 6-30, More preferably, it is 6-18.
The arylene group may have a substituent, for example, phenylene group, naphthalenediyl group, anthracenediyl group, phenanthrene diyl group, dihydrophenanthenediyl group, naphthacene diyl group, fluorenediyl group, pyrenediyl group, perylene diyl group, Examples include chrysenediyl groups and groups in which these groups have substituents, and groups represented by formula (A-1) to formula (A-20) are preferable. The arylene group includes a group in which a plurality of these groups are bonded.

［式中、ＲおよびＲ^aは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表す。複数存在するＲおよびＲ^aは、各々、同一でも異なっていてもよく、Ｒ^a同士は互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。］

[Wherein, R and R ^a each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R and R ^a may be the same or different, and R ^a may be bonded to each other to form a ring together with the atoms to which each is bonded. ]

The number of carbon atoms of the divalent heterocyclic group is usually 2 to 60, preferably 3 to 20 and more preferably 4 to 15 without including the number of carbon atoms of the substituent.
The divalent heterocyclic group may have a substituent, for example, pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilol, phenoxazine, phenothiazine, acridine, Divalent acridine, furan, thiophene, azole, diazole, and triazole include divalent groups obtained by removing two hydrogen atoms from hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring, and preferably Is a group represented by formula (AA-1) to formula (AA-34). The divalent heterocyclic group includes a group in which a plurality of these groups are bonded.

［式中、ＲおよびＲ^aは、前記と同じ意味を表す。］

[Wherein, R and R ^a represent the same meaning as described above. ]

The “crosslinking group” is a group capable of generating a new bond by being subjected to heat treatment, ultraviolet irradiation treatment, radical reaction, etc., preferably, the formula (XL-1) of the crosslinking group A group It is a crosslinking group represented by (XL-17).
(Crosslinking group A group)

［式中、
Ｒ^ＸＬは、メチレン基、酸素原子または硫黄原子を表し、ｎ^ＸＬは、０〜５の整数を表す。Ｒ^ＸＬが複数存在する場合、それらは同一でも異なっていてもよく、ｎ^ＸＬが複数存在する場合、それらは同一でも異なっていてもよい。
＊は結合位置を表す。
これらの架橋基は置換基を有していてもよい。］

[Where:
R ^XL represents a methylene group, an oxygen atom or a sulfur atom, and n ^XL represents an integer of 0 to 5. When a plurality of R ^XL are present, they may be the same or different, and when a plurality of n ^XL are present, they may be the same or different.
* Represents a bonding position.
These crosslinking groups may have a substituent. ]

  “Substituent” means a halogen atom, cyano group, alkyl group, cycloalkyl group, aryl group, monovalent heterocyclic group, alkoxy group, cycloalkoxy group, aryloxy group, amino group, substituted amino group, alkenyl group. Represents a cycloalkenyl group, an alkynyl group or a cycloalkynyl group. The substituent may be a crosslinking group.

  <Polymer compound of the present invention>

[Group Represented by Formula (1)]
The high molecular compound of this invention contains the structural unit which has group represented by Formula (1).

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and more preferably, because the cross-linking property of the polymer compound of the present invention is more excellent. It is an alkyl group, and these groups may have a substituent.

The substituent which the group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ may have is preferably an alkyl group, a cycloalkyl group or an aryl group.

  nA is preferably an integer of 0 to 3, more preferably 0 or 1, and even more preferably 1, since the crosslinkability of the polymer compound of the present invention is more excellent.

L ^A, since the crosslinking of the polymer compound of the present invention is more excellent, preferably an alkylene group, a cycloalkylene group, an arylene group or a divalent heterocyclic group, more preferably an alkylene group or an arylene group, More preferably, it is an alkylene group, and these groups may have a substituent.

Alkylene group represented by L ^A is not including the carbon atom number of substituent is usually 1 to 10, preferably 1 to 8, more preferably 1-6. Cycloalkylene group represented by L ^A is not including the carbon atom number of substituent is usually 3 to 10.
The alkylene group and the cycloalkylene group may have a substituent, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group, and an octylene group.

Arylene group represented by L ^A may have a substituent, for example, o- phenylene, m- phenylene, p- phenylene, and the like.

L ^A substituent optionally be included in the group represented by is preferably an alkyl group, a cycloalkyl group or an aryl group.

When a plurality of L ^A are present, they may be the same or different, but are preferably the same group or atom since the production of the polymer compound of the present invention is facilitated.

If L ^A there are a plurality, at least two L ^A may be a group represented by -NR'-, but preferably not adjacent groups represented by -NR'-.

When a plurality of L ^A are present, two or more L ^A may be an oxygen atom or a sulfur atom, but these atoms are preferably not adjacent to each other.

  Examples of the group represented by the formula (1) include groups represented by the formula (1-1) to the formula (1-32), and the crosslinkability of the polymer compound of the present invention is more preferable. And groups represented by formulas (1-1), (1-4), (1-6), (1-8), (1-20), (1-23) and (1-26) More preferably, they are groups represented by formulas (1-1), (1-4) and (1-6).

［式中、Ｐｈはフェニル基を表し、＊は結合位置を表す。］

[Wherein Ph represents a phenyl group, and * represents a bonding position. ]

  The structural unit having a group represented by formula (1) is preferably a structural unit represented by formula (2) described later, but may be a structural unit represented by the following.

［式中、Ｑ^１は、前記式（１）で表される基を表す。］

[Wherein, Q ¹ represents a group represented by the formula (1). ]

[Structural Unit Represented by Formula (2)]
The structural unit having a group represented by the formula (1) is preferably a structural unit represented by the formula (2) because the crosslinkability of the polymer compound of the present invention is more excellent.

［式中、
Ａｒ^１は、芳香族炭化水素基または複素環基を表し、これらの基は置換基を有していてもよい。
ｎは１〜４の整数を表す。
Ｑ^１は、前記式（１）で表される基を表す。Ｑ^１が複数個存在する場合、それらは同一でも異なっていてもよい。］

[Where:
Ar ¹ represents an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent.
n represents an integer of 1 to 4.
Q ¹ represents a group represented by the formula (1). When a plurality of Q ¹ are present, they may be the same or different. ]

Ar ¹ is preferably an aromatic hydrocarbon group which may have a substituent since the cross-linking property of the polymer compound of the present invention is more excellent.

The number of carbon atoms of the aromatic hydrocarbon group represented by Ar ¹ is usually 6 to 60, preferably 6 to 30 and more preferably 6 to 18 without including the number of carbon atoms of the substituent. is there.
The arylene group portion excluding n substituents of the aromatic hydrocarbon group represented by Ar ¹ is preferably a group represented by the formula (A-1) to the formula (A-20), More preferably, a group represented by formula (A-1), formula (A-2), formula (A-6) to formula (A-10), formula (A-19) or formula (A-20) And more preferably a group represented by the formula (A-1), the formula (A-2), or the formula (A-9), and these groups optionally have a substituent.

The number of carbon atoms of the heterocyclic group represented by Ar ¹ is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18 without including the number of carbon atoms of the substituent.
The divalent heterocyclic group moiety excluding n substituents of the heterocyclic group represented by Ar ¹ is preferably a group represented by the formula (AA-1) to the formula (AA-34). is there.

Ar ¹ preferably has a benzene ring which may have a substituent, a fluorene ring which may have a substituent, and a substituent because the polymer compound of the present invention is more excellent in crosslinkability. A hydrogen atom (2 + n) directly bonded to a carbon atom constituting the ring from an optionally substituted naphthalene ring, an optionally substituted phenanthrene ring, or an optionally substituted dihydrophenanthrene ring More preferably, from a benzene ring which may have a substituent, a fluorene ring which may have a substituent, or a naphthalene ring which may have a substituent. , A group excluding (2 + n) hydrogen atoms directly bonded to the carbon atoms constituting the ring, and more preferably, directly bonded to the carbon atoms constituting the ring from an optionally substituted benzene ring Hydrogen atom There are groups excluding (2 + n).

The aromatic hydrocarbon group and heterocyclic group represented by Ar ¹ may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and an aryloxy group. Group, halogen atom, monovalent heterocyclic group and cyano group.

  n is preferably 1 or 2 because it facilitates the synthesis of the polymer compound of the present invention.

Q ¹ represents a group represented by the formula (1). When a plurality of Q ¹ are present, they may be the same or different, but they are preferably the same group because production of the polymer compound of the present invention is facilitated.

  The content of the structural unit represented by the formula (2) is preferably 2 to 90 mol with respect to the total content of the structural units contained in the polymer compound since the stability of the polymer compound of the present invention is excellent. %, More preferably 2 to 70 mol%, still more preferably 3 to 50 mol%.

  As a structural unit represented by Formula (2), the structural unit represented by Formula (2-1)-Formula (2-12) is mentioned, for example, Preferably Formula (2-1)-Formula (2) is mentioned. -9), more preferably a structural unit represented by the formula (2-1) to the formula (2-3), and more preferably a formula (2-1). Is a structural unit.

［式中、Ｑ^１は前記と同じ意味を表す。］

[Wherein Q ¹ represents the same meaning as described above. ]

  As for the structural unit represented by Formula (2), only 1 type may be contained in the high molecular compound, and 2 or more types may be contained.

[Structural Unit Represented by Formula (2 ′)]
The structural unit having a group represented by the formula (1) is preferably a structural unit represented by the formula (2 ′) because the crosslinkability of the polymer compound of the present invention is more excellent.

［式中、
ｍＡは０〜５の整数を表し、ｍは１〜４の整数を表し、ｃは０または１の整数を表す。ｍＡが複数存在する場合、それらは同一でも異なっていてもよい。
Ａｒ^３は、芳香族炭化水素基、複素環基、または、少なくとも１種の芳香族炭化水素環と少なくとも１種の複素環が直接結合した基を表し、これらの基は置換基を有していてもよい。
Ａｒ^２およびＡｒ^４は、それぞれ独立に、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^２、Ａｒ^３およびＡｒ^４はそれぞれ、当該基が結合している窒素原子に結合している当該基以外の基と、直接または酸素原子もしくは硫黄原子を介して結合して、環を形成していてもよい。
Ｋ^Ａは、アルキレン基、シクロアルキレン基、アリーレン基、２価の複素環基、−ＮＲ’’−で表される基、酸素原子または硫黄原子を表し、これらの基は置換基を有していてもよい。Ｒ’’は、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。Ｋ^Ａが複数存在する場合、それらは同一でも異なっていてもよい。
Ｑ^２は、架橋基Ａ群から選ばれる架橋基、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。但し、少なくとも１つのＱ^２は、前記式（１）で表される基である。］

[Where:
mA represents an integer of 0 to 5, m represents an integer of 1 to 4, and c represents an integer of 0 or 1. When a plurality of mA are present, they may be the same or different.
Ar ³ represents an aromatic hydrocarbon group, a heterocyclic group, or a group in which at least one aromatic hydrocarbon ring and at least one heterocyclic ring are directly bonded, and these groups have a substituent. May be.
Ar ² and Ar ⁴ each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
Ar ² , Ar ^3, and Ar ⁴ are each bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded, directly or via an oxygen atom or sulfur atom, to form a ring. It may be.
K ^A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, -NR '' -, a group represented by an oxygen atom or a sulfur atom, these groups have a substituent May be. R ″ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. When a plurality of K ^A are present, they may be the same or different.
Q ² represents a bridging group selected from the bridging group A, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. However, at least one Q ² is a group represented by the formula (1). ]

  mA is preferably 0 or 1, and more preferably 1, because the crosslinkability of the polymer compound of the present invention is more excellent.

  m is preferably 1 because it facilitates the synthesis of the polymer compound of the present invention.

  c is preferably 0 because it facilitates the synthesis of the polymer compound of the present invention.

Ar ³ is preferably an aromatic hydrocarbon group because the cross-linking property of the polymer compound of the present invention is more excellent.

The definition and example of the arylene group part excluding m substituents of the aromatic hydrocarbon group represented by Ar ³ are the same as the definition and example of the arylene group represented by Ar ^X2 in formula (X) described later. It is.

The definition and examples of the divalent group excluding m substituents of a group in which at least one aromatic hydrocarbon ring represented by Ar ³ and at least one heterocycle are directly bonded are shown in the formula ( The definition and examples of the divalent group in which at least one arylene group represented by Ar ^X2 in X) and at least one divalent heterocyclic group are directly bonded are the same.

Ar ² and Ar ⁴ are preferably an arylene group because the polymer compound of the present invention is more excellent in crosslinkability.

The definitions and examples of the arylene group represented by Ar ² and Ar ⁴ are the same as the definitions and examples of the arylene group represented by Ar ^X1 and Ar ^X3 in formula (X) described later.

The definitions and examples of the divalent heterocyclic group represented by Ar ² and Ar ⁴ are the same as the definitions and examples of the divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 in formula (X) described later. is there.

The groups represented by Ar ² , Ar ³ and Ar ⁴ may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, Examples thereof include a halogen atom, a monovalent heterocyclic group, and a cyano group.

Alkylene group represented by K ^A, a cycloalkylene group, an arylene group, a divalent definitions and examples of the heterocyclic group, respectively, the alkylene group represented by L ^A, a cycloalkylene group, an arylene group, a divalent heterocyclic The definition and examples of the ring group are the same.

K ^A, since the synthesis of the polymer compound of the present invention is easy, it is preferable that a phenylene group or a methylene group.

Q ² is preferably a group represented by the formula (1), a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group because the polymer compound of the present invention can be easily synthesized. The group represented by 1) is more preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a group represented by the formula (1), a hydrogen atom or an alkyl group. It may have a substituent. However, at least one Q ² is a group represented by the formula (1).

  The content of the structural unit represented by the formula (2 ′) is preferably 2 to 90 with respect to the total content of the structural units contained in the polymer compound since the stability of the polymer compound of the present invention is excellent. It is mol%, More preferably, it is 2-70 mol%, More preferably, it is 3-50 mol%.

  Examples of the structural unit represented by the formula (2 ′) include structural units represented by the formula (2′-1) to the formula (2′-12), preferably the formula (2′-2). To a structural unit represented by the formula (2′-9), and more preferably a structural unit represented by the formula (2′-7) to the formula (2′-9).

［式中、Ｑ^２は前記と同じ意味を表す。］

[Wherein Q ² represents the same meaning as described above. ]

  As for the structural unit represented by the formula (2 ′), only one type of structural unit may be contained, or two or more types may be contained in the polymer compound.

[Other structural units]
Since the polymer compound of the present invention has excellent hole transport properties, it is preferable that the polymer compound further contains a structural unit represented by the following formula (X).

［式中、
ａ^X1およびａ^X2は、それぞれ独立に、０以上の整数を表す。
Ａｒ^X1およびＡｒ^X3は、それぞれ独立に、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^X2およびＡｒ^X4は、それぞれ独立に、アリーレン基、２価の複素環基、または、少なくとも１種のアリーレン基と少なくとも１種の２価の複素環基とが直接結合した２価の基を表し、これらの基は置換基を有していてもよい。
Ｒ^X1、Ｒ^X2およびＲ^X3は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。］

[Where:
a ^X1 and a ^X2 each independently represent an integer of 0 or more.
Ar ^X1 and Ar ^X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
Ar ^X2 and Ar ^X4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other. And these groups may have a substituent.
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. ]

a ^X1 is preferably 2 or less, more preferably 1, because the luminance life of the light-emitting device using the polymer compound of the present invention is excellent.

a ^X2 is preferably 2 or less, more preferably 0, because the luminance lifetime of the light-emitting device using the polymer compound of the present invention is excellent.

R ^X1 , R ^X2 and R ^X3 are preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups have a substituent. Also good.

The arylene group represented by Ar ^X1 and Ar ^X3 is more preferably a group represented by the formula (A-1) or the formula (A-9), more preferably a formula (A-1). These groups may have a substituent.

The divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 is more preferably represented by formula (AA-1), formula (AA-2), or formula (AA-7) to formula (AA-26). These groups may have a substituent.

Ar ^X1 and Ar ^X3 are preferably an arylene group which may have a substituent.

More preferably, the arylene group represented by Ar ^X2 and Ar ^X4 is represented by formula (A-1), formula (A-6), formula (A-7), formula (A-9) to formula (A-11). Or it is group represented by a formula (A-19), and these groups may have a substituent.

The more preferable range of the divalent heterocyclic group represented by Ar ^X2 and Ar ^X4 is the same as the more preferable range of the divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 .

More preferable range of the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group represented by Ar ^X2 and Ar ^X4 and the at least one divalent heterocyclic group are directly bonded to each other Further preferred ranges are the same as the more preferred ranges and further preferred ranges of the arylene group and divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 , respectively.

Examples of the divalent group in which at least one arylene group represented by Ar ^X2 and Ar ^X4 and at least one divalent heterocyclic group are directly bonded include groups represented by the following formulae: These may have a substituent.

［式中、Ｒ^XXは、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。］

[Wherein R ^XX represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. ]

R ^XX is preferably an alkyl group, a cycloalkyl group, or an aryl group, and these groups optionally have a substituent.

Ar ^X2 and Ar ^X4 are preferably an arylene group which may have a substituent.

The substituents that the groups represented by Ar ^{X1 to} Ar ^X4 and R ^{X1 to} R ^X3 may have are preferably an alkyl group, a cycloalkyl group, or an aryl group, and these groups further have a substituent. You may do it.

  The structural unit represented by the formula (X) is preferably a structural unit represented by the formulas (X-1) to (X-7), more preferably the formula (X-3) to (X-7). ), More preferably structural units represented by formulas (X-3) to (X-6).

［式中、Ｒ^X4およびＲ^X5は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、ハロゲン原子、１価の複素環基またはシアノ基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^X4は、同一でも異なっていてもよい。複数存在するＲ^X5は、同一でも異なっていてもよく、隣接するＲ^X5同士は互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。］

[Wherein, R ^X4 and R ^X5 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group or cyano. Represents a group, and these groups may have a substituent. A plurality of R ^X4 may be the same or different. A plurality of R ^X5 may be the same or different, and adjacent R ^X5 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

  Since the structural unit represented by the formula (X) is excellent in hole transportability, it is preferably 0.1 to 90 mol%, more preferably based on the total amount of structural units contained in the polymer compound. It is 1-70 mol%, More preferably, it is 5-50 mol%.

  Examples of the structural unit represented by formula (X) include structural units represented by formulas (X1-1) to (X1-19), preferably formulas (X1-6) to (X1-14). ).

  In the polymer compound of the present invention, the structural unit represented by the formula (X) may be included alone or in combination of two or more.

  The polymer compound of the present invention preferably further contains a structural unit represented by the formula (Y) because the luminance life of a light emitting device using the polymer compound of the present invention is excellent.

  Since the polymer compound of the present invention is more excellent in luminous efficiency of a light emitting device using the polymer compound of the present invention, the structural unit represented by the formula (X) and the structural unit represented by the formula (Y) It is preferable to contain.

［式中、Ａｒ^Y1は、アリーレン基、２価の複素環基、または、少なくとも１種のアリーレン基と少なくとも１種の２価の複素環基とが直接結合した２価の基を表し、これらの基は置換基を有していてもよい。］

[In the formula, Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, and these This group may have a substituent. ]

The arylene group represented by Ar ^Y1 is more preferably a formula (A-1), a formula (A-6), a formula (A-7), a formula (A-9) to a formula (A-11), a formula (A A-13) or a group represented by formula (A-19), more preferably in formula (A-1), formula (A-7), formula (A-9) or formula (A-19). And these groups may have a substituent.

More preferably, the divalent heterocyclic group represented by Ar ^Y1 is represented by the formula (AA-4), formula (AA-10), formula (AA-13), formula (AA-15), formula (AA-18) ) Or a group represented by formula (AA-20), more preferably represented by formula (AA-4), formula (AA-10), formula (AA-18) or formula (AA-20) These groups may have a substituent.

More preferable range of the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group represented by Ar ^Y1 and at least one divalent heterocyclic group are directly bonded, and further preferable. The ranges are the same as the more preferable ranges and further preferable ranges of the above-mentioned arylene group and divalent heterocyclic group represented by Ar ^Y1 .

As the divalent group in which at least one arylene group represented by Ar ^Y1 and at least one divalent heterocyclic group are directly bonded, at least represented by Ar ^X2 and Ar ^X4 in the formula (X) Examples thereof include the same divalent groups in which one kind of arylene group and at least one kind of divalent heterocyclic group are directly bonded.

The substituent that the group represented by Ar ^Y1 may have is preferably an alkyl group, a cycloalkyl group, or an aryl group, and these groups may further have a substituent.

  Examples of the structural unit represented by the formula (Y) include structural units represented by the formulas (Y-1) to (Y-7), and brightness of a light-emitting element using the polymer compound of the present invention. From the viewpoint of lifetime, it is preferably a structural unit represented by the formula (Y-1) or (Y-2), and from the viewpoint of electron transport properties, preferably the formula (Y-3) or (Y-4) From the viewpoint of hole transportability, the structural units are preferably represented by the formulas (Y-5) to (Y-7).

［式中、Ｒ^Y1は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Y1は、同一でも異なっていてもよく、隣接するＲ^Y1同士は互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。］

[Wherein R ^Y1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. . A plurality of R ^Y1 may be the same or different, and adjacent R ^Y1 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

R ^Y1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and these groups optionally have a substituent.

  The structural unit represented by the formula (Y-1) is preferably a structural unit represented by the formula (Y-1 ′).

［式中、Ｒ^Y11は、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Y1は、同一でも異なっていてもよい。］

[Wherein, R ^Y11 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of R ^Y1 may be the same or different. ]

R ^Y11 is preferably an alkyl group, a cycloalkyl group, or an aryl group, more preferably an alkyl group or a cycloalkyl group, and these groups optionally have a substituent.

［式中、Ｒ^Y1は前記と同じ意味を表す。Ｘ^Y1は、−Ｃ(Ｒ^Y2)₂−、−Ｃ(Ｒ^Y2)＝Ｃ(Ｒ^Y2)−または−Ｃ(Ｒ^Y2)₂−Ｃ(Ｒ^Y2)₂−で表される基を表す。Ｒ^Y2は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^Y2は、同一でも異なっていてもよく、Ｒ^Y2同士は互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。］

[Wherein, R ^Y1 represents the same meaning as described above. X ^{Y1 _{is, -C (R Y2) 2 -}} , - represents a group represented by ^{- C (R Y2) = C} (R Y2) - or _{^{-C (R Y2) 2 -C (}} R Y2) 2. R ^Y2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ^Y2 may be the same or different, and R ^Y2 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

R ^Y2 is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups have a substituent. May be.

In X ^Y1 , the combination of two R ^{Y2 in} the group represented by —C (R ^Y2 ) ₂ — is preferably an alkyl group or a cycloalkyl group, both are aryl groups, and both are monovalent complex. A cyclic group, or one is an alkyl group or a cycloalkyl group and the other is an aryl group or a monovalent heterocyclic group, more preferably one is an alkyl group or a cycloalkyl group and the other is an aryl group. May have a substituent. Two R ^{Y2 s} may be bonded to each other to form a ring together with the atoms to which they are bonded, and when R ^Y2 forms a ring, the group represented by —C (R ^Y2 ) ₂ — Is preferably a group represented by formulas (Y-A1) to (Y-A5), more preferably a group represented by formula (Y-A4), and these groups have a substituent. It may be.

In X ^Y1 , the combination of two R ^{Y2 in} the group represented by —C (R ^Y2 ) ═C (R ^Y2 ) — is preferably both an alkyl group or a cycloalkyl group, or one of which is an alkyl group Alternatively, a cycloalkyl group and the other is an aryl group, and these groups may have a substituent.

In X ^Y1 , four R ^Y2 in the group represented by —C (R ^Y2 ) ₂ —C (R ^Y2 ) ₂ — are preferably an alkyl group or a cycloalkyl group which may have a substituent. It is. A plurality of R ^Y2 may be bonded to each other to form a ring together with the atoms to which each is bonded. When R ^Y2 forms a ring, —C (R ^Y2 ) ₂ —C (R ^Y2 ) ₂ — The group represented is preferably a group represented by formulas (Y-B1) to (Y-B5), more preferably a group represented by formula (Y-B3), and these groups are substituted. It may have a group.

［式中、Ｒ^Y2は前記と同じ意味を表す。］

[Wherein, R ^Y2 represents the same meaning as described above. ]

  The structural unit represented by the formula (Y-2) is preferably a structural unit represented by the formula (Y-2 ′).

［式中、Ｒ^Y1およびＸ^Y1は前記と同じ意味を表す。］

[Wherein, R ^Y1 and X ^Y1 represent the same meaning as described above. ]

［式中、Ｒ^Y1は前記と同じ意味を表す。Ｒ^Y3は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。］

[Wherein, R ^Y1 represents the same meaning as described above. R ^Y3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. ]

R ^Y3 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups have a substituent. May be.

［式中、Ｒ^Y1は前記を同じ意味を表す。Ｒ^Y4は、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。］

[Wherein, R ^Y1 represents the same meaning as described above. R ^Y4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. ]

R ^Y4 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups have a substituent. May be.

  Examples of the structural unit represented by the formula (Y) include structural units represented by the formulas (Y-11) to (Y-55).

The structural unit represented by the formula (Y), in which Ar ^Y1 is an arylene group, is excellent in the luminance life of the light-emitting element using the polymer compound of the present invention, and therefore is a component included in the polymer compound. Preferably it is 0.5-80 mol% with respect to the total amount of a unit, More preferably, it is 30-60 mol%.

A structural unit represented by formula (Y), wherein Ar ^Y1 is a divalent heterocyclic group, or at least one arylene group and at least one divalent heterocyclic group directly bonded to each other. The structural unit which is a group is preferably 0.5 to 30 mol% with respect to the total amount of the structural units contained in the polymer compound because the charge transport property of the light emitting device using the polymer compound of the present invention is excellent. Yes, more preferably 3 to 40 mol%.

  One type of structural unit represented by the formula (Y) may be contained in the polymer compound, or two or more types may be contained.

  Since the polymer compound of the present invention is excellent in stability, it further comprises at least one structural unit selected from the group consisting of a structural unit represented by formula (3) and a structural unit represented by formula (3 ′). It is preferable to include.

  [Structural Unit Represented by Formula (3)]

［式中、
ｎＣは０〜５の整数を表し、ｐは１または２の整数を表す。
Ａｒ^５は、芳香族炭化水素基または複素環基を表し、これらの基は置換基を有していてもよい。
Ｌ^Ｃは、アルキレン基、シクロアルキレン基、アリーレン基、２価の複素環基、−ＮＲ’’’−で表される基、酸素原子または硫黄原子を表し、これらの基は置換基を有していてもよい。Ｒ’’’は、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。Ｌ^Ｃが複数存在する場合、それらは同一でも異なっていてもよい。
Ｑ^３は、架橋基Ａ群から選ばれる架橋基を表す。Ｑ^３が複数存在する場合、それらは同一でも異なっていてもよい。］

[Where:
nC represents an integer of 0 to 5, and p represents an integer of 1 or 2.
Ar ⁵ represents an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent.
L ^C represents an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, a group represented by —NR ′ ″ —, an oxygen atom or a sulfur atom, and these groups have a substituent. It may be. R ′ ″ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. When a plurality of ^LC are present, they may be the same or different.
Q ³ represents a crosslinking group selected from the crosslinking group A group. When a plurality of Q ³ are present, they may be the same or different. ]

  nC is preferably 0 or 1, more preferably 0, because the crosslinkability of the polymer compound of the present invention is more excellent.

  p is preferably 1 or 2 and more preferably 2 because the crosslinkability of the polymer compound of the present invention is more excellent.

Ar ⁵ is preferably an aromatic hydrocarbon group which may have a substituent since the crosslinkability of the polymer compound of the present invention is more excellent.

The number of carbon atoms of the aromatic hydrocarbon group represented by Ar ⁵ is usually 6 to 60, preferably 6 to 30 and more preferably 6 to 18 without including the number of carbon atoms of the substituent. is there.
The arylene group part excluding p substituents of the aromatic hydrocarbon group represented by Ar ⁵ is preferably a group represented by the formula (A-1) to the formula (A-20), More preferably, a group represented by formula (A-1), formula (A-2), formula (A-6) to formula (A-10), formula (A-19) or formula (A-20) And more preferably a group represented by formula (A-1), formula (A-2), formula (A-7), formula (A-9) or formula (A-19), This group may have a substituent.

The number of carbon atoms of the heterocyclic group represented by Ar ⁵ is usually 6 to 60, preferably 6 to 30 and more preferably 6 to 18 without including the number of carbon atoms of the substituent.
The divalent heterocyclic group part excluding p substituents of the heterocyclic group represented by Ar ⁵ is preferably a group represented by the formula (AA-1) to the formula (AA-34). is there.

The aromatic hydrocarbon group and heterocyclic group represented by Ar ⁵ may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and an aryloxy group. Group, halogen atom, monovalent heterocyclic group and cyano group.

The alkylene group represented by L ^C does not include the number of carbon atoms of the substituent, and is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3. The cycloalkylene group represented by L ^C is usually 3 to 10 without including the number of carbon atoms of the substituent.
The alkylene group and the cycloalkylene group may have a substituent, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group, and an octylene group.

The alkylene group and cycloalkylene group represented by L ^C may have a substituent. Examples of the substituent that the alkylene group and the cycloalkylene group may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a halogen atom, and a cyano group.

The arylene group represented by L ^C may have a substituent. Examples of the arylene group include o-phenylene, m-phenylene, and p-phenylene. Examples of the substituent that the aryl group may have include, for example, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a halogen atom, a cyano group, and a bridge. Examples thereof include a crosslinking group selected from the group A.

L ^C is preferably a phenylene group or an alkylene group because the production of the polymer compound of the present invention is facilitated, and these groups may have a substituent.

The bridging group represented by Q ^3, since the crosslinking of the polymer compound of the present invention is excellent, preferably of formula (XL-1), (XL -3), (XL-5) or (XL-7) And more preferably a crosslinking group represented by the formula (XL-1).

  The structural unit represented by the formula (3) is preferably 0.5 to 50 mol% based on the total amount of the structural units contained in the polymer compound because the stability of the polymer compound of the present invention is excellent. More preferably, it is 3-30 mol%, More preferably, it is 3-20 mol%.

[Where:
mC represents an integer of 0 to 5, m ″ represents an integer of 1 to 4, and m ′ represents 0 or 1. When a plurality of mCs are present, they may be the same or different.
Ar ⁷ represents an aromatic hydrocarbon group, a heterocyclic group, or a group in which at least one aromatic hydrocarbon ring and at least one heterocyclic ring are directly bonded, and these groups have a substituent. May be.
Ar ⁶ and Ar ⁸ each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
Ar ⁶ , Ar ⁷ and Ar ⁸ are each bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded, directly or via an oxygen atom or sulfur atom to form a ring. It may be.
K ^C represents an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, a group represented by —NR ″ ″ —, an oxygen atom or a sulfur atom, and these groups have a substituent. You may do it. R ″ ″ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. If K ^C there are a plurality, they may be the same or different.
Q ⁴ represents a bridging group selected from the bridging group A, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. However, at least one Q ⁴ is a crosslinking group selected from the crosslinking group A group. ]

  mC is preferably 0 or 1, and more preferably 0, because the crosslinkability of the polymer compound of the present invention is more excellent.

  m ″ is preferably 2 because it facilitates the synthesis of the polymer compound of the present invention.

  m ′ is preferably 0 because it facilitates the synthesis of the polymer compound of the present invention.

Ar ⁷ is preferably an aromatic hydrocarbon group since the light emitting efficiency of the light emitting device obtained using the polymer compound of the present invention is more excellent.

The definition and examples of the arylene group part excluding m ″ substituents of the aromatic hydrocarbon group represented by Ar ⁷ are the definitions and examples of the arylene group represented by Ar ^X2 in the above formula (X). Is the same.

The definition and examples of the divalent heterocyclic group part excluding m ″ substituents of the heterocyclic group represented by Ar ⁷ are the divalent complex represented by Ar ^X2 in the above formula (X). This is the same as the definition and examples of the ring group moiety.

The definition and examples of the divalent group excluding m ″ substituents of the group in which at least one aromatic hydrocarbon ring represented by Ar ⁷ and at least one heterocycle are directly bonded are as described above. This is the same as the definition and examples of a divalent group in which at least one arylene group represented by Ar ^X2 in formula (X) and at least one divalent heterocyclic group are directly bonded.

Ar ⁶ and Ar ⁸ are preferably an arylene group because the polymer compound of the present invention is more excellent in crosslinkability.

The definitions and examples of the arylene group represented by Ar ⁶ and Ar ⁸ are the same as the definitions and examples of the arylene group represented by Ar ^X1 and Ar ^X3 in the above formula (X).

The definitions and examples of the divalent heterocyclic group represented by Ar ⁶ and Ar ⁸ are the same as the definitions and examples of the divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 in the above formula (X). is there.

The groups represented by Ar ⁶ , Ar ⁷ and Ar ⁸ may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, Examples thereof include a halogen atom, a monovalent heterocyclic group, and a cyano group.

The definitions and examples of the alkylene group, cycloalkylene group, arylene group, and divalent heterocyclic group represented by K ^C are respectively the alkylene group, cycloalkylene group, arylene group, and divalent complex represented by L ^C. The definition and examples of the ring group are the same.

K ^C is preferably a phenylene group or a methylene group because it facilitates the synthesis of the polymer compound of the present invention.

The preferred range of cross-linking groups represented by Q ^4, and more preferably ranges and more preferable range is preferably a range of cross-linking group selected from the bridging group A group represented by Q ^3, similar to the preferred ranges and still more preferably in the range is there.

  The structural unit represented by the formula (3 ′) is 0.5 to 50 mol% with respect to the total amount of the structural units contained in the polymer compound because the stability of the polymer compound of the present invention is excellent. It is preferably 3 to 30 mol%, more preferably 3 to 20 mol%.

  Each of the structural unit represented by the formula (3) and the structural unit represented by the formula (3 ′) may be included in the polymer compound alone, or may be included in two or more types. Good.

  As a structural unit represented by Formula (3), the structural unit represented by Formula (3-1)-Formula (3-20) is mentioned, for example, As a structural unit represented by Formula (3 ') Examples include structural units represented by formula (3′-1) to formula (3′-9). Among these, since the crosslinkability of the polymer compound of the present invention is excellent, the formula (3-1) to the formula (3-7), the formula (3-11), the formula (3-12) or the formula ( 3-15) to structural units represented by formula (3-20), and more preferably, formula (3-1) to formula (3-4), formula (3-7), formula (3-11). ), A formula (3-12), a formula (3-15) or a formula (3-17), more preferably a formula (3-1) to a formula (3-4), a formula It is a structural unit represented by (3-11) or Formula (3-15).

  Examples of the polymer compound of the present invention include polymer compounds P-1 to P-10 shown in Table 3. Here, the “other structural unit” is other than the structural unit represented by the formula (2), the formula (2 ′), the formula (X), the formula (Y), the formula (3), and the formula (3 ′). This means a structural unit.

［表中、ｑ、ｒ、ｓ、ｔ、ｕ、ｖおよびｗは、各構成単位のモル比率を表す。ｑ＋ｒ＋ｓ＋ｔ＋ｕ＋ｖ＋ｗ＝100であり、かつ、70≦ｑ＋ｒ＋ｓ＋ｔ＋ｗ≦100である。］

[In the table, q, r, s, t, u, v, and w represent the molar ratio of each structural unit. q + r + s + t + u + v + w = 100 and 70 ≦ q + r + s + t + w ≦ 100. ]

  In the polymer compounds P-1 to P-10, the structural units represented by formula (2), formula (2 ′), formula (X), formula (Y), formula (3), and formula (3 ′) Examples and preferred ranges are as described above.

  The terminal group of the polymer compound of the present invention preferably has a polymerization active group as it is, because when the polymer compound is used for the production of a light emitting device, the light emission characteristics and the luminance life may be lowered. It is a stable group. The terminal group is preferably a group that is conjugated to the main chain, and includes a group that is bonded to an aryl group or a monovalent heterocyclic group via a carbon-carbon bond.

  The polymer compound of the present invention may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer, and may be in other embodiments, but a plurality of types of raw materials A copolymer obtained by copolymerizing monomers is preferred.

<Method for producing polymer compound>
Next, a method for producing the polymer compound of the present invention will be described.

  The polymer compound of the present invention includes, for example, a compound represented by the formula (2M) and / or a compound represented by (2′M), a compound represented by the formula (M-1) and / or the formula ( It can be produced by condensation polymerization of a compound represented by M-2) and another compound (for example, a compound represented by Formula (M-3) and / or Formula (M-3 ′)). it can. In the present specification, the compounds used for the production of the polymer compound of the present invention are sometimes collectively referred to as “raw material monomers”.

［式中、
Ａｒ^１、ｎ、Ｑ^１、ｍＡ、ｍ、ｃ、Ａｒ^２、Ａｒ^３、Ａｒ^４、Ｋ^Ａ、Ｑ²、ａ^Ｘ1、ａ^Ｘ2、Ａｒ^Ｘ１〜Ａｒ^Ｘ４、Ｒ^Ｘ１〜Ｒ^Ｘ３、Ａｒ^Ｙ１、ｎＣ、ｐ、Ａｒ^５、Ｌ^Ｃ、Ｑ^３、ｍＣ、ｍ’’、ｍ’、Ａｒ^６、Ａｒ^７、Ａｒ^８、Ｋ^ＣおよびＱ^４は、前記と同じ意味を表す。
Ｚ^１〜Ｚ^１０は、それぞれ独立に、置換基Ａ群から選ばれる基または置換基Ｂ群から選ばれる基を表す。］

[Where:
Ar ¹ , n, Q ¹ , mA, m, c, Ar ² , Ar ³ , Ar ⁴ , K ^A , Q ² , a ^{X 1} , a ^{X 2} , Ar ^{X 1} to Ar ^{X 4} , R ^{X 1 to} R ^{X 3} , Ar ^{Y 1} , nC, p, Ar ⁵ , L ^C , Q ³ , mC, m ″, m ′, Ar ⁶ , Ar ⁷ , Ar ⁸ , K ^C and Q ⁴ represent the same meaning as described above.
Z ^{1 to} Z ¹⁰ each independently represent a group selected from the substituent group A or a group selected from the substituent group B. ]

For example, when Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁷ and Z ⁸ are groups selected from the substituent group A, Z ⁵ , Z ⁶ , Z ⁹ , Z ¹⁰ , Z ¹¹ and Z ¹² are , A group selected from the substituent group B is selected.

For example, when Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁷ and Z ⁸ are groups selected from the substituent group B, Z ⁵ , Z ⁶ , Z ⁹ , Z ¹⁰ , Z ¹¹ and Z ¹² are , A group selected from the substituent group A is selected.

<Substituent group A>
Chlorine atom, bromine atom, iodine atom, —O—S (═O) ₂ R ^C1 (wherein R ^C1 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups have a substituent. A group represented by:

<Substituent group B>
-B in (OR ^C2) ₂ (wherein, R ^C2 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, these groups may have a substituent. There exist a plurality of R ^C2 is Groups which may be the same or different and may be linked to each other to form a ring structure together with the oxygen atoms to which they are bonded.
A group represented by —BF ₃ Q ′ (wherein Q ′ represents Li, Na, K, Rb or Cs);
-A group represented by MgY '(wherein Y' represents a chlorine atom, a bromine atom or an iodine atom);
A group represented by —ZnY ″ (wherein Y ″ represents a chlorine atom, a bromine atom or an iodine atom); and
-Sn (R ^C3) ₃ (wherein, R ^C3 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, these groups may have a substituent. More existing R ^C3 is The groups may be the same or different and may be linked to each other to form a ring structure together with the tin atoms to which they are bonded.

Examples of the group represented by —B (OR ^C2 ) ₂ include groups represented by the following formulae.

  The compound having a group selected from the substituent group A and the compound having a group selected from the substituent group B are subjected to condensation polymerization by a known coupling reaction, and the group selected from the substituent group A and the substituent group B Carbon atoms bonded to a group selected from are bonded to each other. Therefore, if a compound having two groups selected from Substituent Group A and a compound having two groups selected from Substituent Group B are subjected to a known coupling reaction, condensation of these compounds by condensation polymerization A polymer can be obtained.

  The condensation polymerization is usually performed in the presence of a catalyst, a base and a solvent, but may be performed in the presence of a phase transfer catalyst, if necessary.

  Examples of the catalyst include dichlorobis (triphenylphosphine) palladium, dichlorobis (tris-o-methoxyphenylphosphine) palladium, palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate and the like. Transition of nickel complexes such as palladium complexes of nickel, nickel [tetrakis (triphenylphosphine)], [1,3-bis (diphenylphosphino) propane] dichloronickel, [bis (1,4-cyclooctadiene)] nickel Metal complexes; these transition metal complexes may further include complexes having ligands such as triphenylphosphine, tri-o-tolylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, diphenylphosphinopropane, bipyridyl, etc. . A catalyst may be used individually by 1 type, or may use 2 or more types together.

  The amount of the catalyst used is usually 0.00001 to 3 molar equivalents as the amount of transition metal relative to the total number of moles of raw material monomers.

  Examples of the base and phase transfer catalyst include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, and tripotassium phosphate; organics such as tetrabutylammonium fluoride and tetrabutylammonium hydroxide. Examples of the base include phase transfer catalysts such as tetrabutylammonium chloride and tetrabutylammonium bromide. Each of the base and the phase transfer catalyst may be used alone or in combination of two or more.

  The usage-amount of a base and a phase transfer catalyst is 0.001-100 molar equivalent normally with respect to the total number of moles of a raw material monomer, respectively.

  Examples of the solvent include organic solvents such as toluene, xylene, mesitylene, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and water. A solvent may be used individually by 1 type, or may use 2 or more types together.

  The amount of the solvent used is usually 10 to 100,000 parts by weight with respect to a total of 100 parts by weight of the raw material monomers.

  The reaction temperature of the condensation polymerization is usually -100 to 200 ° C. The reaction time of the condensation polymerization is usually 1 hour or more.

  Post-treatment of the polymerization reaction is a known method, for example, a method of removing water-soluble impurities by liquid separation, adding the reaction solution after polymerization reaction to a lower alcohol such as methanol, filtering the deposited precipitate, and then drying. These methods are carried out alone or in combination. When the purity of the polymer compound is low, it can be purified by a usual method such as recrystallization, reprecipitation, continuous extraction with a Soxhlet extractor, column chromatography, or the like.

  [Compound represented by Formula (2M)]

  The compound of the present invention is a compound represented by the formula (2M), and can be suitably used in the production method of the polymer compound of the present invention.

Z ¹ and Z ² each independently represent a group selected from the above-mentioned substituent group A or substituent group B. Z ¹ and Z ² are preferably the same group because the production of the compound of the present invention is facilitated.

[Method for Producing Compound Represented by Formula (2M)]

  The compound represented by the formula (2M) can be produced, for example, by the method described in the following scheme 1.

In Scheme 1,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , L ^A , nA, Ar ¹ and n represent the same meaning as described above.
Z ^D1 represents an alkali metal atom or a group represented by -M ¹⁰ Z ^1H . M ¹⁰ represents a magnesium atom or a zinc atom, and Z ^1H represents a halogen atom.
Z ^E1 represents a group selected from the substituent group A.
Z ^1a and Z ^2a each independently represent a hydrogen atom or a group selected from the substituent group A.

^Examples of the alkali metal atom represented by Z ^D1 include a lithium atom, a sodium atom, and a potassium atom.

Examples of the halogen atom represented by Z ^E1 include a chlorine atom, a bromine atom, and an iodine atom.

  In Scheme 1, first, a compound represented by the formula (2M-1) and a compound represented by the formula (2M-2) are reacted with each other by a nucleophilic substitution reaction to obtain a compound represented by the formula (2M). Can be synthesized.

The compound represented by the formula (2M) in which Z ^1a and Z ^2a are hydrogen atoms can convert a hydrogen atom into a group selected from the substituent group A by a reaction such as bromination reaction.

The compound represented by the formula (2M) in which Z ^1a and Z ^2a are groups selected from the substituent group A is bispinacolatodiboron or 2-alkoxy-4,4,5,5-tetramethyl-1, A group selected from the substituent group A can be converted to a group selected from the substituent group B by a known reaction such as boronic esterification using 3,2-dioxaborolane.

  [Compound represented by Formula (2'M)]

  The compound of the present invention is a compound represented by the formula (2'M), and can be suitably used in the production method of the polymer compound of the present invention.

Z ³ and Z ⁴ each independently represent a group selected from the above-mentioned substituent group A or substituent group B. Z ³ and Z ⁴ are preferably the same group because the production of the compound of the present invention is facilitated.

[Method for Producing Compound Represented by Formula (2′M)]

  The compound represented by the formula (2′M) can be produced, for example, by the method described in Scheme 2 below.

In Scheme 2,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , mA, m, c, Ar ² , Ar ³ , Ar ⁴ , K ^A , Q ² and Z ^D1 represent the same meaning as described above.
Z ^E2 represents a group selected from the substituent group A.
Z ^1a and Z ^2a each independently represent a hydrogen atom or a group selected from the substituent group A.

The halogen atom represented by Z ^E2, a chlorine atom, a bromine atom or an iodine atom.

  In Scheme 2, a compound represented by the formula (2M-3) and a compound represented by the formula (2M-2) are first subjected to a nucleophilic substitution reaction to represent the compound represented by the formula (2′M). Compounds can be synthesized.

The compound represented by the formula (2′M) in which Z ^3a and Z ^4a are hydrogen atoms can convert a hydrogen atom into a group selected from the substituent group A by a reaction such as bromination reaction.

A compound represented by the formula (2′M) in which Z ^3a and Z ^4a are groups selected from the substituent group A is bispinacolatodiboron or 2-alkoxy-4,4,5,5-tetramethyl- By a known reaction such as boronic esterification using 1,3,2-dioxaborolane, a group selected from the substituent group A can be converted into a group selected from the substituent group B.

<Composition>
The composition of the present invention comprises at least one material selected from the group consisting of a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material, an antioxidant, and a solvent, Containing molecular compounds.

  The composition containing the polymer compound of the present invention and a solvent (hereinafter sometimes referred to as “ink”) is suitable for manufacturing a light-emitting element using a printing method such as an inkjet printing method or a nozzle printing method.

  The viscosity of the ink may be adjusted according to the type of printing method, but when applying a printing method such as an inkjet printing method to a printing method that passes through a discharge device, in order to prevent clogging and flight bending at the time of discharge. It is preferably 1 to 20 mPa · s at 25 ° C.

  The solvent contained in the ink is preferably a solvent that can dissolve or uniformly disperse the solid content in the ink. Examples of the solvent include chlorine solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene; ether solvents such as tetrahydrofuran, dioxane, anisole and 4-methylanisole; toluene, Aromatic hydrocarbon solvents such as xylene, mesitylene, ethylbenzene, n-hexylbenzene, cyclohexylbenzene; cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n- Aliphatic hydrocarbon solvents such as decane, n-dodecane, and bicyclohexyl; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and acetophenone; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate, and phenyl acetate Solvents: ethylene glycol, rubber Polyhydric alcohol solvents such as serine and 1,2-hexanediol; alcohol solvents such as isopropyl alcohol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; N-methyl-2-pyrrolidone, N, N-dimethylformamide and the like And amide solvents. A solvent may be used individually by 1 type, or may use 2 or more types together.

  In the ink, the amount of the solvent is usually 1000 to 100000 parts by weight, preferably 2000 to 20000 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention.

[Hole transport material]
The hole transport material is classified into a low molecular compound and a high molecular compound, and a high molecular compound is preferable, and a high molecular compound having a crosslinking group is more preferable.

  Examples of the polymer compound include polyvinyl carbazole and derivatives thereof; polyarylene having an aromatic amine structure in the side chain or main chain and derivatives thereof. The polymer compound may be a compound to which an electron accepting site is bonded. Examples of the electron accepting site include fullerene, tetrafluorotetracyanoquinodimethane, tetracyanoethylene, trinitrofluorenone, and fullerene is preferable.

  In the composition of the present invention, the compounding amount of the hole transport material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention.

  A hole transport material may be used individually by 1 type, or may use 2 or more types together.

[Electron transport materials]
Electron transport materials are classified into low molecular compounds and high molecular compounds. The electron transport material may have a crosslinking group.

  Examples of the low molecular weight compound include a metal complex having 8-hydroxyquinoline as a ligand, oxadiazole, anthraquinodimethane, benzoquinone, naphthoquinone, anthraquinone, tetracyanoanthraquinodimethane, fluorenone, diphenyldicyanoethylene, and , Diphenoquinone, and derivatives thereof.

  Examples of the polymer compound include polyphenylene, polyfluorene, and derivatives thereof. The polymer compound may be doped with a metal.

  In the composition of the present invention, the compounding amount of the electron transport material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention.

  An electron transport material may be used individually by 1 type, or may use 2 or more types together.

[Hole injection material and electron injection material]
The hole injection material and the electron injection material are each classified into a low molecular compound and a high molecular compound. The hole injection material and the electron injection material may have a crosslinking group.

  Examples of the low molecular weight compound include metal phthalocyanines such as copper phthalocyanine; carbon; metal oxides such as molybdenum and tungsten; and metal fluorides such as lithium fluoride, sodium fluoride, cesium fluoride, and potassium fluoride.

  Examples of the polymer compound include polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polythienylene vinylene, polyquinoline, and polyquinoxaline, and derivatives thereof; polymers containing an aromatic amine structure in the main chain or side chain, etc. The conductive polymer is mentioned.

  In the composition of the present invention, the compounding amounts of the hole injection material and the electron injection material are each usually 1 to 400 parts by weight, preferably 5 to 150 parts, per 100 parts by weight of the polymer compound of the present invention. Parts by weight.

  Each of the hole injection material and the electron injection material may be used alone or in combination of two or more.

[Ion dope]
When the hole injection material or the electron injection material includes a conductive polymer, the electrical conductivity of the conductive polymer is preferably 1 × 10 ⁻⁵ S / cm to 1 × 10 ³ S / cm. In order to make the electric conductivity of the conductive polymer within such a range, the conductive polymer can be doped with an appropriate amount of ions.

  The type of ions to be doped is an anion for a hole injection material and a cation for an electron injection material. Examples of the anion include polystyrene sulfonate ion, alkylbenzene sulfonate ion, and camphor sulfonate ion. Examples of the cation include lithium ion, sodium ion, potassium ion, and tetrabutylammonium ion.

  Only one kind or two or more kinds of ions may be doped.

[Luminescent material]
Luminescent materials are classified into low molecular compounds and high molecular compounds. The light emitting material may have a crosslinking group.

  Examples of the low molecular weight compound include naphthalene and derivatives thereof, anthracene and derivatives thereof, perylene and derivatives thereof, and triplet light-emitting complexes having iridium, platinum, or europium as a central metal.

  Examples of the polymer compound include a phenylene group, a naphthalenediyl group, a fluorenediyl group, a phenanthrene diyl group, a dihydrophenanthrene diyl group, a group represented by the formula (X), a carbazole diyl group, a phenoxazine diyl group, and a phenothiazine diyl. And polymer compounds containing a group, an anthracenediyl group, a pyrenediyl group, and the like.

  The light emitting material may include a low molecular compound and a high molecular compound, and preferably includes a triplet light emitting complex and a high molecular compound.

  As the triplet light-emitting complex, iridium complexes such as metal complexes represented by the formulas Ir-1 to Ir-5 are preferable.

［式中、
Ｒ^D1〜Ｒ^D8、Ｒ^D11〜Ｒ^D20、Ｒ^D21〜Ｒ^D26およびＲ^D31〜Ｒ^D37は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、１価の複素環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い。Ｒ^D1〜Ｒ^D8、Ｒ^D11〜Ｒ^D20、Ｒ^D21〜Ｒ^D26およびＲ^D31〜Ｒ^D37が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
−Ａ^D1---Ａ^D2−は、アニオン性の２座配位子を表し、Ａ^D1およびＡ^D2は、それぞれ独立に、イリジウム原子と結合する炭素原子、酸素原子または窒素原子を表し、これらの原子は環を構成する原子であってもよい。−Ａ^D1---Ａ^D2−が複数存在する場合、それらは同一でも異なっていてもよい。
ｎ_D1は、１、２または３を表し、ｎ_D2は、１または２を表す。］

[Where:
R ^{D1 to} R ^D8 , R ^{D11 to} R ^D20 , R ^{D21 to} R ^D26 and R ^{D31 to} R ^D37 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryl It represents an oxy group, a monovalent heterocyclic group or a halogen atom, and these groups optionally have a substituent. When there are a plurality of R ^{D1 to} R ^D8 , R ^{D11 to} R ^D20 , R ^{D21 to} R ^D26 and R ^{D31 to} R ^D37 , they may be the same or different.
-A ^D1 --- A ^D2 -represents an anionic bidentate ligand, and A ^D1 and A ^D2 each independently represent a carbon atom, an oxygen atom or a nitrogen atom bonded to an iridium atom, The atom may be an atom constituting a ring. When a plurality of -A ^D1 --- A ^D2 -are present, they may be the same or different.
n _D1 represents 1, 2 or 3, and n _D2 represents 1 or 2. ]

In the triplet light emitting complex represented by the formula Ir-1, at least one of R ^{D1 to} R ^D8 is preferably a group represented by the formula (DA).

［式中、
ｍ^DA1、ｍ^DA2およびｍ^DA3は、それぞれ独立に、０以上の整数を表す。
Ｇ^DAは、窒素原子、芳香族炭化水素基または複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^DA1、Ａｒ^DA2およびＡｒ^DA3は、それぞれ独立に、アリーレン基または２価の複素環基を表し、これらの基は置換基を有していてもよい。Ａｒ^DA1、Ａｒ^DA2およびＡｒ^DA3が複数ある場合、それらはそれぞれ同一でも異なっていてもよい。
Ｔ^DAは、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数あるＴ^DAは、同一でも異なっていてもよい。］

[Where:
m ^DA1 , m ^DA2 and m ^DA3 each independently represent an integer of 0 or more.
^GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent.
Ar ^DA1 , Ar ^DA2 and Ar ^DA3 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. When there are a plurality of Ar ^DA1 , Ar ^DA2 and Ar ^DA3 , they may be the same or different.
^TDA represents an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. The plurality of ^TDAs may be the same or different. ]

m ^DA1 , m ^DA2 and m ^DA3 are usually an integer of 10 or less, preferably an integer of 5 or less, more preferably 0 or 1. m ^DA1 , m ^DA2 and m ^DA3 are preferably the same integer.

G ^DA1 is preferably a group represented by the formulas (GDA-11) to (GDA-15), and these groups may have a substituent.

［式中、
＊、＊＊および＊＊＊は、各々、Ａｒ^DA1、Ａｒ^DA2、Ａｒ^DA3との結合を表す。
Ｒ^DAは、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基または１価の複素環基を表し、これらの基は更に置換基を有していてもよい。Ｒ^DAが複数ある場合、それらは同一でも異なっていてもよい。］

[Where:
*, **, and *** each represent a bond with Ar ^DA1 , Ar ^DA2 , and Ar ^DA3 .
R ^DA represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may further have a substituent. When there are a plurality of ^RDA , they may be the same or different. ]

R ^DA is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, more preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and these groups have a substituent. May be.

Ar ^DA1 , Ar ^DA2 and Ar ^DA3 are preferably groups represented by the formulas (ArDA-1) to (ArDA-3).

［式中、
Ｒ^DAは前記と同じ意味を表す。
Ｒ^DBは、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。Ｒ^DBが複数ある場合、それらは同一でも異なっていてもよい。］

[Where:
R ^DA represents the same meaning as described above.
R ^DB represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. When there are a plurality of ^RDBs , they may be the same or different. ]

T ^DA is preferably a group represented by the formula (TDA-1) ~ (TDA -3).

［式中、Ｒ^DAおよびＲ^DBは前記と同じ意味を表す。］

[Wherein, R ^DA and R ^DB represent the same meaning as described above. ]

In Formula Ir-2, preferably at least one of R ^{D11 to} R ^D20 is a group represented by Formula (DA).

In the formula Ir-3, preferably at least one of R ^{D1 to} R ^D8 and R ^{D11 to} R ^D20 is a group represented by the formula (DA).

In the formula Ir-4, preferably at least one of R ^{21 to} R ^D26 is a group represented by the formula (DA).

In formula Ir-5, preferably at least one of R ^{D31 to} R ^D37 is a group represented by formula (DA).

  The group represented by the formula (D-A) is preferably a group represented by the formulas (D-A1) to (D-A3).

［式中、
Ｒ^p1、Ｒ^p2およびＲ^p3は、それぞれ独立に、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基またはハロゲン原子を表す。Ｒ^p1およびＲ^p2が複数ある場合、それらはそれぞれ同一であっても異なっていてもよい。
ｎｐ１は、０〜５の整数を表し、ｎｐ２は０〜３の整数を表し、ｎｐ３は０または１を表す。複数あるｎｐ１は、同一でも異なっていてもよい。］

[Where:
R ^p1 , R ^p2 and R ^p3 each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom. When there are a plurality of R ^p1 and R ^p2 , they may be the same or different.
np1 represents an integer of 0 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. A plurality of np1 may be the same or different. ]

  np1 is preferably 0 or 1, more preferably 1. np2 is preferably 0 or 1, more preferably 0. np3 is preferably 0.

R ^p1 , R ^p2 and R ^p3 are preferably an alkyl group or a cycloalkyl group.

Examples of the anionic bidentate ligand represented by -A ^D1 --- A ^D2- include a ligand represented by the following formula.

［式中、＊は、Ｉｒと結合する部位を表す。］

[In formula, * represents the site | part couple | bonded with Ir. ]

  The metal complex represented by the formula Ir-1 is preferably a metal complex represented by the formulas Ir-11 to Ir-13. The metal complex represented by the formula Ir-2 is preferably a metal complex represented by the formula Ir-21. The metal complex represented by the formula Ir-3 is preferably a metal complex represented by the formula Ir-31 to Ir-33. The metal complex represented by the formula Ir-4 is preferably an iridium complex represented by the formula Ir-41 to Ir-43. The metal complex represented by the formula Ir-5 is preferably an iridium complex represented by the formula Ir-51 to Ir-53.

［式中、Dは、式(D-A)で表される基を表す。複数存在するDは、同一でも異なっていてもよい。ｎ_D2は、１または２を表す。Ｒ^ＤＣは、水素原子、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^ＤＣは、同一でも異なっていてもよい。Ｒ^ＤＤは、アルキル基、シクロアルキル基、アリール基または１価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するＲ^ＤＤは、同一でも異なっていてもよい。］

[Wherein, D represents a group represented by the formula (DA). A plurality of D may be the same or different. n _D2 represents 1 or 2. R ^DC represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of R ^DCs may be the same or different. R ^DD represents an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. A plurality of R ^DD may be the same or different. ]

  Examples of the triplet luminescent complex include the metal complexes shown below.

  In the composition of the present invention, the content of the light emitting material is usually 0.1 to 400 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention.

[Antioxidant]
The antioxidant may be any compound that is soluble in the same solvent as the polymer compound of the present invention and does not inhibit light emission and charge transport. Examples thereof include phenol-based antioxidants and phosphorus-based antioxidants.

  In the composition of the present invention, the blending amount of the antioxidant is usually 0.001 to 10 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention.

  Antioxidants may be used alone or in combination of two or more.

<Membrane>
The membrane contains the polymer compound of the present invention.

  The membrane includes an insolubilized membrane obtained by insolubilizing the polymer compound of the present invention in a solvent by crosslinking. The insolubilized film is a film obtained by crosslinking the polymer compound of the present invention by an external stimulus such as heating or light irradiation. Since the insolubilized film is substantially insoluble in a solvent, the insolubilized film can be suitably used for stacking light emitting elements.

  The heating temperature for crosslinking the film is usually 25 to 300 ° C., and the light emission efficiency becomes good. Therefore, the heating temperature is preferably 50 to 250 ° C., more preferably 150 to 200 ° C.

  Types of light used for light irradiation for crosslinking the film are, for example, ultraviolet light, near ultraviolet light, and visible light.

  The film is suitable as a hole transport layer or a hole injection layer in the light emitting device.

  The film is made of ink, for example, 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 printing, offset printing, ink jet printing, capillary coating, and nozzle coating.

  The thickness of the film is usually 1 nm to 10 μm.

<Light emitting element>
The light-emitting element of the present invention is a light-emitting element such as organic electroluminescence obtained using the polymer compound of the present invention. The light-emitting element includes, for example, a light-emitting element containing the polymer compound of the present invention, There is a light-emitting element in which a high molecular compound is cross-linked in a molecule, between molecules, or both.
As a structure of the light emitting element of this invention, it has an electrode which consists of an anode and a cathode, and a layer obtained using the polymer compound of this invention provided between this electrode, for example.

[Layer structure]
The layer obtained using the polymer compound of the present invention is usually one or more of a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer and an electron injection layer, preferably a hole. It is a transport layer. Each of these layers includes a light emitting material, a hole transport material, a hole injection material, an electron transport material, and an electron injection material. Each of these layers is the same as the above-described film production, in which a light-emitting material, a hole transport material, a hole injection material, an electron transport material, and an electron injection material are dissolved in the above-described solvent and ink is prepared and used. It can be formed using a method.

The light emitting element has a light emitting layer between an anode and a cathode. The light-emitting element of the present invention preferably has at least one of a hole injection layer and a hole transport layer between the anode and the light-emitting layer from the viewpoint of hole injection and hole transport. From the viewpoint of injection property and electron transport property, it is preferable to have at least one of an electron injection layer and an electron transport layer between the cathode and the light emitting layer.
As a material for the hole transport layer, the electron transport layer, the light emitting layer, the hole injection layer, and the electron injection layer, in addition to the polymer compound of the present invention, the above-described hole transport material, electron transport material, and light emission, respectively. Examples include materials, hole injection materials, and electron injection materials.

  The material of the hole transport layer, the material of the electron transport layer, and the material of the light emitting layer are used when forming the hole transport layer, the electron transport layer, and the layer adjacent to the light emitting layer, respectively, in the production of the light emitting device. When dissolved in a solvent, it is preferable that the material has a crosslinking group in order to avoid dissolution of the material in the solvent. After forming each layer using a material having a crosslinking group, the layer can be insolubilized by crosslinking the crosslinking group.

  In the light emitting device of the present invention, as a method for forming each layer such as a light emitting layer, a hole transport layer, an electron transport layer, a hole injection layer, and an electron injection layer, when using a low molecular compound, for example, vacuum deposition from powder For example, a method using a film formation from a solution or a molten state may be used.

  What is necessary is just to adjust the order of the layer to laminate | stack, the number, and thickness in consideration of luminous efficiency and element lifetime.

[Substrate / Electrode]
The substrate in the light-emitting element may be any substrate that can form electrodes and does not change chemically when the organic layer is formed. For example, the substrate is made of a material such as glass, plastic, or silicon. In the case of an opaque substrate, the electrode farthest from the substrate is preferably transparent or translucent.

  Examples of the material for the anode include conductive metal oxides and translucent metals, preferably indium oxide, zinc oxide, tin oxide; indium tin oxide (ITO), indium zinc oxide, etc. A conductive compound of silver, palladium and copper (APC); NESA, gold, platinum, silver and copper.

Examples of the material of the cathode include metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, zinc, indium; two or more kinds of alloys thereof; Alloys of one or more species with one or more of silver, copper, manganese, titanium, cobalt, nickel, tungsten, tin; and graphite and graphite intercalation compounds. Examples of the alloy include a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum alloy, an indium-silver alloy, a lithium-aluminum alloy, a lithium-magnesium alloy, a lithium-indium alloy, and a calcium-aluminum alloy.
Each of the anode and the cathode may have a laminated structure of two or more layers.

[Usage]
In order to obtain planar light emission using the light emitting element, the planar anode and the cathode may be arranged so as to overlap each other. In order to obtain pattern-like light emission, a method in which a mask having a pattern-like window is provided on the surface of a planar light-emitting element, a layer that is desired to be a non-light-emitting portion is formed extremely thick and substantially non-light-emitting. There is a method, a method of forming an anode or a cathode, or both electrodes in a pattern. By forming a pattern by any of these methods and arranging several electrodes so that they can be turned on and off independently, a segment type display device capable of displaying numbers, characters, and the like can be obtained. In order to obtain a dot matrix display device, both the anode and the cathode may be formed in stripes and arranged orthogonally. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of polymer compounds having different emission colors, or a method using a color filter or a fluorescence conversion filter. The dot matrix display device can be driven passively, or can be driven active in combination with a TFT or the like. These display devices can be used for displays of computers, televisions, portable terminals and the like. The planar light emitting element can be suitably used as a planar light source for backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can also be used as a curved light source and a display device.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

  In the examples, the polystyrene-equivalent number average molecular weight (Mn) and polystyrene-equivalent weight average molecular weight (Mw) of the polymer compound are size exclusion chromatography (SEC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp). Determined by The SEC measurement conditions are as follows.

[Measurement condition]
The polymer compound to be measured was dissolved in THF at a concentration of about 0.05% by weight, and 10 μL was injected into SEC. THF was used as the mobile phase of SEC and flowed at a flow rate of 2.0 mL / min. As a column, PLgel MIXED-B (manufactured by Polymer Laboratories) was used. A UV-VIS detector (manufactured by Shimadzu Corporation, trade name: SPD-10Avp) was used as the detector.

Liquid chromatograph mass spectrometry (LC-MS) was performed by the following method.
The measurement sample was dissolved in chloroform or THF to a concentration of about 2 mg / mL, and about 1 μL was injected into LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD). The LC-MS mobile phase was used while changing the ratio of acetonitrile and THF, and was allowed to flow at a flow rate of 0.2 mL / min. As the column, 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) was used.

NMR measurement was performed by the following method.
Dissolve 5-10 mg of the sample in about 0.5 mL of deuterated chloroform (CDCl ₃ ), deuterated dimethyl sulfoxide (DMSO-d ₆ ), deuterated tetrahydrofuran (THF-d ₈ ) or methylene chloride (CD ₂ Cl ₂ ). And an NMR apparatus (trade name: MERCURY 300, manufactured by Varian, Inc.).

  High performance liquid chromatography (HPLC) area percentage values were used as indicators of compound purity. Unless otherwise specified, this value is a value at 254 nm by HPLC (manufactured by Shimadzu Corporation, trade name: LC-20A). At this time, the compound to be measured was dissolved in THF or chloroform so that the concentration was 0.01 to 0.2% by weight, and 1 to 10 μL was injected into HPLC depending on the concentration. As the mobile phase of HPLC, acetonitrile and THF were used and allowed to flow at a flow rate of 1 mL / min in a gradient analysis of acetonitrile / THF = 100/0 to 0/100 (volume ratio). As the column, Kaseisorb LC ODS 2000 (manufactured by Tokyo Chemical Industry Co., Ltd.) or an ODS column having equivalent performance was used. A photodiode array detector (manufactured by Shimadzu Corporation, trade name: SPD-M20A) was used as the detector.

  <Synthesis Example 1> Synthesis of Compound Mb3

  After replacing the gas in the flask equipped with a stirrer with nitrogen gas, compound Mb1 (185.0 g), compound Mb2 (121.1 g), CuI (3.2 g), dichloromethane (185 ml) and triethylamine (2.59 L) ) Was added and the temperature was raised to reflux temperature. Then, it stirred at reflux temperature for 0.5 hour and cooled to room temperature. Dichloromethane (1.85 L) was added thereto, followed by filtration with a filter packed with celite. A 10 wt% aqueous sodium hydrogen carbonate solution was added to the obtained filtrate, and then the aqueous layer was separated. The obtained organic layer was washed twice with water, washed with saturated NaCl solution, and then magnesium sulfate was added. The obtained mixture was filtered, and the obtained filtrate was concentrated under reduced pressure. The obtained residue was purified using a silica gel column (developing solvent: mixed solvent of chloroform and ethyl acetate) to obtain a crude product. The obtained crude product was dissolved in ethanol (1.4 L), and then activated carbon (5 g) was added and filtered. The obtained filtrate was concentrated under reduced pressure, and the obtained residue was recrystallized from hexane to obtain 99.0 g of Compound Mb3 as a white solid. The obtained compound Mb3 had an HPLC area percentage value (UV254 nm) of 99.5% or more. By repeating this operation, the required amount of Compound Mb3 was obtained.

¹ H-NMR (DMSO-d6, 300 MHz) δ (ppm): 1.52-1.55 (8H, m), 2.42 (4H, t), 3.38-3.44 (4H, m), 4.39-4.43 (2H, m), 7.31 (4H, s).

  <Synthesis Example 2> Synthesis of Compound Mb4

  After replacing the gas in the flask equipped with a stirrer with nitrogen gas, Compound Mb3 (110.0 g), ethanol (1.65 L) and palladium / carbon (Pd weight 10%) (11.0 g) were added, and 30 The temperature was raised to ° C. Thereafter, the gas in the flask was replaced with hydrogen gas. Then, it stirred at 30 degreeC for 3 hours, supplying hydrogen gas in a flask. Thereafter, the gas in the flask was replaced with nitrogen gas. The obtained mixture was filtered, and the obtained filtrate was concentrated under reduced pressure. The obtained residue was purified using a silica gel column (developing solvent: mixed solvent of chloroform and ethyl acetate) to obtain a crude product. The obtained crude product was recrystallized with hexane to obtain 93.4 g of Compound Mb4 as a white solid. The obtained compound Mb4 had an HPLC area percentage value (UV254 nm) of 98.3%.

¹ H-NMR (CDCl ₃ , 300 MHz) δ (ppm): 1.30-1.40 (8H, m), 1.55-1.65 (8H, m), 2.58 (4H, t), 3.64 (4H, t), 7.09 (4H , s).

¹³ C-NMR (CDCl ₃ , 75 MHz) δ (ppm): 25.53, 28.99, 31.39, 32.62, 35.37, 62.90, 128.18, 139.85.

  <Synthesis Example 3> Synthesis of Compound Mb5

  After replacing the gas in the flask equipped with a stirrer with nitrogen gas, Compound Mb4 (61.0 g), pyridine (0.9 g) and toluene (732 ml) were added, and the temperature was raised to 60 ° C. The thionyl chloride (91.4g) was dripped there over 1.5 hours, Then, it stirred at 60 degreeC for 5 hours. The resulting mixture was cooled to room temperature and concentrated under reduced pressure. The obtained residue was purified using a silica gel column (developing solvent: mixed solvent of hexane and ethyl acetate) to obtain 64.3 g of Compound Mb5 as a colorless oil. The compound Mb5 obtained had an HPLC area percentage value (UV254 nm) of 97.2%.

¹ H-NMR (CDCl ₃ , 300 MHz) δ (ppm): 1.35-1.40 (4H, m), 1.41-1.50 (4H, m), 1.60-1.68 (4H, m), 1.75-1.82 (4H, m) , 2.60 (4H, t), 3.55 (4H, t), 7.11 (4H, s).

  <Synthesis Example 4> Synthesis of Compound Mb6

  After replacing the gas in the flask equipped with a stirrer with nitrogen gas, Compound Mb5 (42.0 g), iron powder (1.7 g), iodine (0.3 g) and dichloromethane (800 ml) were added. Thereafter, the entire flask was shielded from light and cooled to 0 to 5 ° C. A mixture of bromine (44.7 g) and dichloromethane (200 ml) was added dropwise thereto over 1 hour, and the mixture was stirred overnight at 0 to 5 ° C. The obtained mixture was added to water (1.2 L) cooled to 0 to 5 ° C., and then the organic layer was separated. The obtained organic layer was washed with a 10% by weight aqueous sodium thiosulfate solution, and further washed with a saturated aqueous sodium chloride solution and water in this order. Sodium sulfate was added to the obtained organic layer, followed by filtration, and the resulting filtrate was concentrated under reduced pressure. The resulting residue was purified using a silica gel column (developing solvent: hexane) to obtain a crude product. The obtained crude product was recrystallized from hexane to obtain 47.0 g of Compound Mb6 as a white solid. The compound Mb6 obtained had an HPLC area percentage value (UV254 nm) of 98.3%.

¹ H-NMR (CDCl ₃ , 300 MHz) δ (ppm): 1.38-1.45 (4H, m), 1.47-1.55 (4H, m), 1.57-1.67 (4H, m), 1.77-1.84 (4H, m) , 2.66 (4H, t), 3.55 (4H, t), 7.36 (2H, s).

  <Synthesis Example 5> Synthesis of Compound Mb7

  After replacing the gas in the flask equipped with a stirrer with nitrogen gas, sodium iodide (152.1 g) and acetone (600 ml) were added, and the mixture was stirred at room temperature for 0.5 hour. Mb6 (40.0 g) was added thereto, and then the temperature was raised to the reflux temperature and stirred at the reflux temperature for 24 hours. Then, it cooled to room temperature and the obtained liquid mixture was added to water (1.2L). The precipitated solid was filtered off and washed with water to obtain a crude product. The obtained crude product was recrystallized with a mixed solution of toluene and methanol to obtain 46.0 g of Compound Mb7 as a white solid. The obtained compound Mb7 had an HPLC area percentage value (UV254 nm) of 99.4%. By repeating this operation, the required amount of Compound Mb7 was obtained.

¹ H-NMR (CDCl ₃ , 300 MHz) δ (ppm): 1.35-1.50 (8H, m), 1.57-1.65 (4H, m), 1.80-1.89 (4H, m), 2.65 (4H, t), 3.20 (4H, t), 7.36 (2H, s).

  Synthesis Example 6 Synthesis of Compound Mb8

  After replacing the gas in the flask equipped with a stirrer with nitrogen gas, 1,2,3,4,5-pentamethylcyclopentadiene (24.41 g) and tetrahydrofuran (330 mL) were added, and the flask was dried ice / methanol. Cooled in the bath. Thereto, n-butyllithium (1.6 M, 100 mL) was added, and the flask was stirred for 0.5 hour while being cooled in a dry ice / methanol bath. Compound Mb7 (22.08 g) and tetrahydrofuran (200 mL) were added thereto, and the mixture was stirred for 5 hours while cooling the flask with a dry ice / methanol bath. Methanol (100 mL) was added thereto, and then the temperature was raised to room temperature. Water and heptane were added thereto, and then the organic layer and the aqueous layer were separated. The obtained organic layer was washed with an aqueous sodium chloride solution and then with water. Sodium sulfate was added to the obtained organic layer, followed by filtration, and the resulting filtrate was concentrated under reduced pressure. The obtained crude product was washed twice with methanol to obtain 17.0 g of Compound Mb8 as a white solid. The obtained compound Mb8 had an HPLC area percentage value (UV254 nm) of 97.1%.

¹ H-NMR (CD ₂ Cl ₂ , 300 MHz) δ (ppm): 0.50-0.66 (4H, m), 0.85 (6H, s), 1.12-1.32 (8H, m), 1.34-1.43 (4H, m) , 1.44-1.57 (4H, m), 1.66 (12H, s), 1.76 (12H, s), 2.60 (4H, t, d = 7.8Hz), 7.35 (2H, s).

  Synthesis Example 7 Synthesis of Compounds MM10 to MM13

Compound MM10 was synthesized according to the synthesis method described in JP-A-2008-106241.
Compound MM11 was synthesized according to the synthesis method described in International Publication No. 2012/086669.
Compound MM12 was synthesized according to the synthesis method described in International Publication No. 2005/049546.
Compound MM13 was synthesized according to the synthesis method described in JP 2010-215886 A.

  <Example 1> Synthesis of polymer compound 1

(Step 1) After making the inside of the reaction vessel an inert gas atmosphere, Compound MM11 (1.1 g), Compound MM12 (920 mg), Compound MM13 (58 mg), Compound Mb8 (84 mg), Dibutylhydroxytoluene (11 mg), Dichlorobis (Tris-o-methoxyphenylphosphine) palladium (1.1 mg) and toluene (50 mL) were added and heated to 105 ° C.
(Step 2) A 20 wt% tetraethylammonium hydroxide aqueous solution (8.0 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 5 hours.
(Step 3) After the reaction, phenylboronic acid (16 mg), 20 wt% tetraethylammonium hydroxide aqueous solution (8.0 mL) and dichlorobis (tris-o-methoxyphenylphosphine) palladium (1.1 mg) were added thereto, Refluxed for 15 hours.
(Step 4) After the reaction, an aqueous sodium diethyldithiacarbamate solution was added thereto and stirred at 80 ° C. for 2 hours. After cooling, the reaction solution was washed twice with water, twice with a 3% by weight aqueous acetic acid solution and twice with water, and when the resulting solution was added dropwise to methanol, precipitation occurred. The 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 1.3 g of polymer compound 1. The Mn of the polymer compound 1 was 3.7 × 10 ⁴ and the Mw was 2.0 × 10 ⁵ .

  The theoretical value obtained from the amount of the raw material used for polymer compound 1 is that the structural unit derived from compound MM11, the structural unit derived from compound MM12, the structural unit derived from compound MM13, and the compound Mb8 The derived structural unit is a copolymer composed of a molar ratio of 50: 40: 5: 5.

<Comparative Example 1> Synthesis of polymer compound 2 (Step 1) in the synthesis of polymer compound 1 was made as follows: “After the reaction vessel was filled with an inert gas atmosphere, compound MM11 (8.4 g), compound MM12 (6. 9 g), compound MM10 (500 mg), compound MM13 (430 mg), dichlorobis (tris-o-methoxyphenylphosphine) palladium (5.0 mg) and toluene (220 mL) were added and heated to 105 ° C. ”. Produced 11 g of polymer compound 2 in the same manner as in the synthesis of polymer compound 1. The Mn of the polymer compound 2 was 6.4 × 10 ⁴ and the Mw was 3.1 × 10 ⁵ .

  The theoretical value obtained from the amount of charged raw material for polymer compound 2 is that the structural unit derived from compound MM11, the structural unit derived from compound MM12, the structural unit derived from compound MM10, and the compound MM13 The derived structural unit is a copolymer composed of a molar ratio of 50: 40: 5: 5.

<Evaluation Example 1 of Remaining Film Ratio>
Polymer compound 1 was dissolved in xylene to prepare a 0.7 wt% xylene solution. A film having a thickness of 20 nm was formed on a glass substrate by spin coating using this xylene solution, and then heated on a hot plate at 160 ° C. for 60 minutes in a nitrogen gas atmosphere. Then, the measurement sample 1-1 was produced by cooling to room temperature.

Next, the light transmittance of the measurement sample 1-1 was measured, and the minimum transmittance (T ₁ ) of the measurement sample 1-1 was obtained. T _{1 of} measurement sample 1-1 was 0.727. For the measurement, a light transmittance measuring device (manufactured by Varian, Inc., trade name: Cary 5E UV / visible spectrophotometer) was used, and the wavelength sweep during the light transmittance measurement was 300 to 600 nm.

  Next, the measurement sample 1-1 was immersed in xylene, stirred for 60 minutes, and then taken out from xylene. Then, the measurement sample 1-2 was produced by installing in a spin coater, rotating at 1000 rpm for 10 seconds, and drying.

Next, similarly to the measurement sample 1-1, the light transmittance of the measurement sample 1-2 was measured, and the minimum transmittance (T ₂ ) of the measurement sample 1-2 was obtained. T _{2 of} measurement sample 1-2 was 0.834.

  It was 56.9% when the remaining film rate of the film | membrane using the high molecular compound 1 was calculated using the following formula.

Remaining film ratio (%) = (log _e T ₂ / log _e T ₁ ) × 100

<Evaluation comparative example 1 of remaining film ratio>
Evaluation of Residual Film Ratio A measurement sample 2-1 before immersion in xylene was prepared in the same manner as in Evaluation Example 1 of residual film ratio, except that polymer compound 2 was used instead of polymer compound 1 in Example 1. The minimum transmittance (T ₁ ) of the measurement sample 2-1 was obtained. T _{1 of the} measurement sample 2-1 was 0.692. Next, measurement sample 2-2 after xylene immersion was prepared, and the minimum transmittance (T ₂ ) of measurement sample 2-2 was obtained. T _{2 of} measurement sample 2-2 was 0.856. And when the remaining film rate of the film | membrane using the high molecular compound 2 was calculated using the said formula, it was 42.2%.

  From these results, since the remaining film ratio of the film using the polymer compound 1 is superior to the remaining film ratio of the film using the polymer compound 2, the crosslinkability of the polymer compound 1 is It turns out that it is superior to crosslinkability.

Claims (13)

The high molecular compound containing the structural unit which has group represented by following formula (1).

[Where:
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group or monovalent heterocyclic group These groups may have a substituent. R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.
nA represents an integer of 0 to 5.
L ^A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, the group represented by -NR'-, an oxygen atom or a sulfur atom, these groups have a substituent Also good. R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. When a plurality of ^LA are present, they may be the same or different. ] The polymer compound according to claim 1, wherein the structural unit having a group represented by the formula (1) is a structural unit represented by the following formula (2) or formula (2 ′).

[Where:
Ar ¹ represents an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent.
n represents an integer of 1 to 4.
Q ¹ represents a group represented by the formula (1). When a plurality of Q ¹ are present, they may be the same or different. ]

[Where:
mA represents an integer of 0 to 5, m represents an integer of 1 to 4, and c represents 0 or 1. When a plurality of mA are present, they may be the same or different.
Ar ³ represents an aromatic hydrocarbon group, a heterocyclic group, or a group in which at least one aromatic hydrocarbon ring and at least one heterocyclic ring are directly bonded, and these groups have a substituent. It may be.
Ar ² and Ar ⁴ each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
Ar ² , Ar ^3, and Ar ⁴ are each bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded, directly or via an oxygen atom or sulfur atom, to form a ring. It may be.
K ^A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, -NR '' -, a group represented by an oxygen atom or a sulfur atom, these groups have a substituent May be. R ″ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. When a plurality of K ^A are present, they may be the same or different.
Q ² represents a group represented by the formula (1), a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. . However, at least one Q ² is a group represented by the formula (1). ] Each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or The polymer compound according to claim 1, which is an aryl group which may have a substituent. The polymer compound according to claim 3, wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently an alkyl group which may have a substituent. Ar ¹ may have a benzene ring which may have a substituent, a fluorene ring which may have a substituent, a naphthalene ring which may have a substituent, or a substituent. The phenanthrene ring or a dihydrophenanthrene ring which may have a substituent, is a group obtained by removing (2 + n) hydrogen atoms directly bonded to carbon atoms constituting the ring. The polymer compound according to one item. The polymer compound according to claim 5, wherein Ar ¹ is a group obtained by removing (2 + n) hydrogen atoms directly bonded to carbon atoms constituting the ring from an optionally substituted benzene ring. . Furthermore, the high molecular compound as described in any one of Claims 1-6 containing the structural unit represented by following formula (X).

[Where:
a ¹ and a ² each independently represents an integer of 0 or more.
Ar ^X1 and Ar ^X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
Ar ^X2 and Ar ^X4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other. And these groups may have a substituent.
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. ] Furthermore, the high molecular compound as described in any one of Claims 1-7 containing the structural unit represented by a following formula (Y).

[In the formula, Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, and these This group may have a substituent. ] The structural unit represented by the formula (Y) is a structural unit represented by the following formula (Y-1) or a structural unit represented by the following formula (Y-2). Molecular compound.

[Wherein R ^Y1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. . A plurality of R ^Y1 may be the same or different, and adjacent R ^Y1 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

[Wherein, R ^Y1 represents the same meaning as described above. X ^{Y1 _{is, -C (R Y2) 2 -}} , - represents a group represented by ^{- C (R Y2) = C} (R Y2) - or _{^{C (R Y2) 2 -C (}} R Y2) 2. R ^Y2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of R ^Y2 may be the same or different, and R ^Y2 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]   The content of the structural unit represented by the formula (2) is 2 to 90 mol% with respect to the total content of the structural units included in the polymer compound. The high molecular compound as described in. A compound represented by the following formula (2M) or (2′M).

[Where:
Ar ¹ represents an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent.
n represents an integer of 1 to 4.
Q ¹ represents a group represented by the following formula (1). When a plurality of Q ¹ are present, they may be the same or different.
Z ¹ and Z ² each independently represent a group selected from the following substituent group A or a group selected from substituent group B. ]

[Where:
mA represents an integer of 0 to 5, m represents an integer of 1 to 4, and c represents 0 or 1. When a plurality of mA are present, they may be the same or different.
Ar ³ represents an aromatic hydrocarbon group, a heterocyclic group, or a group in which at least one aromatic hydrocarbon ring and at least one heterocyclic ring are directly bonded, and these groups have a substituent. It may be.
Ar ² and Ar ⁴ each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
Ar ² , Ar ^3, and Ar ⁴ are each bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded, directly or via an oxygen atom or sulfur atom, to form a ring. It may be.
K ^A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, -NR '' -, a group represented by an oxygen atom or a sulfur atom, these groups have a substituent May be. R ″ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. When a plurality of K ^A are present, they may be the same or different.
Q ² represents a group represented by the following formula (1), a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. . However, at least one Q ² is a group represented by the following formula (1).
Z ³ and Z ⁴ each independently represent a group selected from the following substituent group A or substituent group B. ]

[Where:
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group or monovalent heterocyclic group These groups may have a substituent. R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.
L ^A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, the group represented by -NR'-, an oxygen atom or a sulfur atom, these groups have a substituent Also good. R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. When a plurality of ^LA are present, they may be the same or different.
nA represents an integer of 0 to 5. ]

<Substituent group A>
Chlorine atom, bromine atom, iodine atom, —O—S (═O) ₂ R ^C1 (wherein R ^C1 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups have a substituent. A group represented by:
<Substituent group B>
-B in (OR ^C2) ₂ (wherein, R ^C2 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, these groups may have a substituent. There exist a plurality of R ^C2 is Groups which may be the same or different and may be linked to each other to form a ring structure together with the oxygen atoms to which they are bonded.
A group represented by —BF ₃ Q ′ (wherein Q ′ represents Li, Na, K, Rb or Cs);
-A group represented by MgY '(wherein Y' represents a chlorine atom, a bromine atom or an iodine atom);
A group represented by —ZnY ″ (wherein Y ″ represents a chlorine atom, a bromine atom or an iodine atom); and
-Sn (R ^C3) ₃ (wherein, R ^C3 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, these groups may have a substituent. More existing R ^C3 is The groups may be the same or different and may be linked to each other to form a ring structure together with the tin atoms to which they are bonded. The polymer compound according to any one of claims 1 to 10,
A composition comprising a hole transport material, a hole injection material, an electron transport material, an electron injection material, a light emitting material, an antioxidant, and at least one material selected from the group consisting of a solvent.   The light emitting element obtained using the high molecular compound as described in any one of Claims 1-10.