JP7354557B2 - Polymer compounds and light emitting devices using them - Google Patents

Description

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

As a polymer compound used in a light emitting device such as an organic electroluminescent device, for example, a polymer compound containing a repeating unit represented by the following formula (Patent Document 1) is known.

Special Publication No. 2013-538438

However, light emitting devices manufactured using the above polymer compounds do not necessarily have a sufficient brightness life.

Therefore, an object of the present invention is to provide a polymer compound useful for manufacturing a light emitting element with excellent luminance life.

The present invention provides the following [1] to [13].
[1]
A polymer compound having a structural unit consisting of a group obtained by removing one or more hydrogen atoms from a compound represented by formula (1a) or formula (1b).

［式中、
環Ａ及び環Ｂは、それぞれ独立に、脂肪族炭化水素環、芳香族炭化水素環又は複素環を表し、これらの環は置換基を有していてもよい。前記置換基が複数存在する場合、それらが結合して環を形成していてもよい。
Ｒ¹及びＲ²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、アリール基又は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。２つあるＲ²は、同一でも異なっていてもよい。
Ｌは、単結合、アルキレン基、シクロアルキレン基、アリーレン基又は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。
Ｒ'は、アルキル基、シクロアルキル基、アリール基又は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。
Ｑは、単結合、酸素原子又は硫黄原子を表す。
波線は、二重結合に結合するＲ¹及び環Ｂが、二重結合に対して同じ側であっても、反対側であってもよいことを表す。］
［２］
前記式（１ａ）又は前記式（１ｂ）で表される化合物から水素原子を１個以上取り除いた基が、前記Ｒ'から２個の水素原子を取り除いた基である、［１］に記載の高分子化合物。
［３］
前記式（１ａ）で表される化合物から水素原子を１個以上取り除いた基からなる構成単位を有する、［１］又は［２］に記載の高分子化合物。
［４］
環Ａ及び環Ｂがベンゼン環である、［１］～［３］のいずれかに記載の高分子化合物。
［５］
Ｒ¹が水素原子であり、Ｌ及びＱが単結合である、［１］～［４］のいずれかに記載の高分子化合物。
［６］
Ｒ'がアリール基である、［１］～［５］のいずれかに記載の高分子化合物。
［７］
更に、式（Ｘ）で表される構成単位を含む、［１］～［６］のいずれかに記載の高分子化合物。

[In the formula,
Ring A and ring B each independently represent an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, or a heterocycle, and these rings may have a substituent. When a plurality of the substituents are present, they may be combined to form a ring.
R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. Two R ² 's may be the same or different.
L represents a single bond, an alkylene group, a cycloalkylene group, an arylene group, or a divalent heterocyclic group, and these groups may have a substituent.
R' represents an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent.
Q represents a single bond, an oxygen atom or a sulfur atom.
The wavy line indicates that R ¹ and ring B bonded to the double bond may be on the same side or on opposite sides with respect to the double bond. ]
[2]
The group according to [1], wherein the group obtained by removing one or more hydrogen atoms from the compound represented by the formula (1a) or the formula (1b) is a group obtained by removing two hydrogen atoms from the R'. High molecular compound.
[3]
The polymer compound according to [1] or [2], which has a structural unit consisting of a group obtained by removing one or more hydrogen atoms from the compound represented by the formula (1a).
[4]
The polymer compound according to any one of [1] to [3], wherein ring A and ring B are benzene rings.
[5]
The polymer compound according to any one of [1] to [4], wherein R ¹ is a hydrogen atom, and L and Q are single bonds.
[6]
The polymer compound according to any one of [1] to [5], wherein R' is an aryl group.
[7]
The polymer compound according to any one of [1] to [6], further comprising a structural unit represented by formula (X).

［式中、
ａ¹及びａ²は、それぞれ独立に、０以上２以下の整数を表す。
Ａｒ^X1及びＡｒ^X3は、それぞれ独立に、アリーレン基又は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及びＡｒ^X4は、それぞれ独立に、アリーレン基、２価の複素環基、又は、アリーレン基と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。Ａｒ^X2又はＡｒ^X4が複数存在する場合、それらは各々同一でも異なっていてもよい。
Ｒ^X1、Ｒ^X2及び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、アリール基又は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^X2又はＲ^X3が複数存在する場合、それらは各々同一でも異なっていてもよい。］
［８］
更に、前記式（１ａ）又は前記式（１ｂ）で表される化合物から水素原子を１個取り除いた基からなる構成単位とは異なる、式（Ｙ）で表される構成単位を含む、［１］～［７］のいずれかに記載の高分子化合物。

[In the formula,
a ¹ and a ² each independently represent an integer of 0 or more and 2 or less.
Ar ^X1 and Ar ^X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent.
Ar ^X2 and Ar ^X4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded; It may have. When a plurality of Ar ^X2 or Ar ^X4 exist, they may be the same or different.
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 may have a substituent. When a plurality of R ^X2 or R ^X3 are present, they may be the same or different. ]
[8]
[1 ] to [7]. The polymer compound according to any one of [7].

［式中、Ａｒ^Y1は、アリーレン基、２価の複素環基、又は、アリーレン基と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。］
［９］
前記式（Ｙ）で表される構成単位が、式（Ｙ－１）又は式（Ｙ－２）で表される構成単位である、［８］に記載の高分子化合物。

[In the formula, Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded, and these groups have a substituent. You can leave it there. ]
[9]
The polymer compound according to [8], wherein the structural unit represented by the formula (Y) is a structural unit represented by the formula (Y-1) or the formula (Y-2).

［式中、
Ｘ^Y1は、－Ｃ(Ｒ^Y2)₂－、－Ｃ(Ｒ^Y2)＝Ｃ(Ｒ^Y2)－又は－Ｃ(Ｒ^Y2)₂－Ｃ(Ｒ^Y2)₂－で表される基を表す。複数存在するＲ^Y2は、同一でも異なっていてもよい。
Ｒ^Y1、Ｒ^Y2及びＲ^Y4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、アリール基又は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^Y11及びＲ^Y2は、各々、同一でも異なっていてもよく、隣接する炭素原子に結合するＲ^Y1同士、隣接する炭素原子に結合するＲ^Y2同士、又は、同一の炭素原子に結合する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。］
［１０］
前記式（１ａ）又は式（１ｂ）で表される化合物から水素原子を１個以上取り除いた基からなる構成単位の含有量が、高分子化合物に含まれる全構成単位の含有量に対して、0.01～30モル％である、［１］～［９］のいずれかに記載の高分子化合物。
［１１］
前記式（１ａ）又は前記式（１ｂ）で表される化合物における１個以上の水素原子が、ハロゲン原子、－Ｂ（ＯＨ）₂で表される基又はホウ酸エステル残基で置換された化合物。
［１２］
［１］～［１０］のいずれかに記載の高分子化合物と、
正孔輸送材料、正孔注入材料、電子輸送材料、電子注入材料、発光材料、酸化防止剤及び溶媒からなる群より選ばれる少なくとも１種の材料とを含有する組成物。
［１３］
［１］～［１０］のいずれかに記載の高分子化合物を含有する発光素子。

[In the formula,
X ^Y1 represents a group represented by -C(R ^Y2 ) ₂ -, -C(R ^Y2 )=C(R ^Y2 )-, or -C(R ^Y2 ) ₂ -C(R ^Y2 ) ₂ -. A plurality of R ^Y2s may be the same or different.
R ^Y1 , R ^Y2 and R ^Y4 each independently represent 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 have no substituents. may have. A plurality of R ^Y11 and R ^Y2 may be the same or different, and each R ^Y1 is bonded to an adjacent carbon atom, R Y2 is bonded to an adjacent carbon atom, or R ^Y2 is bonded to the same carbon atom. R ^Y2 may be bonded to each other to form a ring with the carbon atoms to which they are bonded. ]
[10]
The content of the structural unit consisting of a group obtained by removing one or more hydrogen atoms from the compound represented by formula (1a) or formula (1b) is relative to the content of all structural units contained in the polymer compound, The polymer compound according to any one of [1] to [9], which has a content of 0.01 to 30 mol%.
[11]
A compound in which one or more hydrogen atoms in the compound represented by the above formula (1a) or the above formula (1b) is substituted with a halogen atom, a group represented by -B(OH) ₂ or a boric acid ester residue .
[12]
The polymer compound according to any one of [1] to [10],
A composition containing 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 luminescent material, an antioxidant, and a solvent.
[13]
A light-emitting device containing the polymer compound according to any one of [1] to [10].

According to the present invention, it is possible to provide a polymer compound useful for manufacturing a light emitting element with excellent luminance life. Further, according to the present invention, a composition and a light emitting device containing 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 herein 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 a metal complex, a solid line representing a bond with the central metal means a covalent bond or a coordinate bond.

The term "polymer compound" means a polymer having a molecular weight distribution and a number average molecular weight in terms of polystyrene of 1×10 ³ to 1×10 ⁸ .

"Low molecular compound" means a compound that has no molecular weight distribution and has a molecular weight of 1×10 ⁴ or less.

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

"Aliphatic hydrocarbon ring" represents cycloalkane, cycloalkene, and cycloalkyne, and may be a single ring or may be composed of multiple rings. The number of carbon atoms forming the aliphatic hydrocarbon ring, not including the number of carbon atoms of substituents, is usually 3 to 22, preferably 6 to 14, and more preferably 6, 10 or 14.

"Aromatic hydrocarbon ring" represents a hydrocarbon exhibiting aromaticity, and may be a single ring or may be composed of a plurality of rings. The number of carbon atoms forming the aromatic hydrocarbon ring, not including the number of carbon atoms of substituents, is usually 3 to 22, preferably 6 to 14, and more preferably 6, 10 or 14.
The aromatic hydrocarbon ring may have a substituent, for example, a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, an indene ring, a phenanthrene ring, a pyrene ring, a tetracene ring, and a hydrogen atom in these groups. However, examples thereof include groups substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, and the like.

"Heterocycle" refers to a cyclic compound in which at least one carbon atom forming the ring is replaced with an element other than a carbon atom, and may be a single ring or may be composed of multiple rings. , is preferably an aromatic heterocycle. The number of carbon atoms forming the heterocycle is usually 2 to 21, and preferably 5 to 13, not including the number of carbon atoms of substituents.

The "alkyl group" may be either straight chain or branched. The number of carbon atoms in the straight chain alkyl group, not including the number of carbon atoms in substituents, is usually 1 to 50, preferably 3 to 30, and more preferably 4 to 20. The number of carbon atoms in the branched alkyl group, not including the number of carbon atoms in substituents, is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20.
The alkyl group may have a substituent, for example, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-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 groups in which the hydrogen atoms in these groups are substituted with cycloalkyl groups, alkoxy groups, cycloalkoxy groups, aryl groups, fluorine atoms, etc. (e.g., trifluoromethyl groups, pentafluoroethyl groups, perfluorobutyl groups) , perfluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, 3-(4-methylphenyl)propyl group, 3-(3,5-di-hexylphenyl)propyl group, 6-ethyloxyhexyl group) can be mentioned.
The number of carbon atoms in the "cycloalkyl group", not including the number of carbon atoms in substituents, is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20.
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 number of carbon atoms in the aryl group, not including the number of carbon atoms in substituents, is usually 6 to 60, preferably 6 to 20, more preferably 6 to 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 However, examples thereof include groups substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, and the like.

The "alkoxy group" may be either linear or branched. The number of carbon atoms in the straight chain alkoxy group, not including the number of carbon atoms in substituents, is usually 1 to 40, preferably 4 to 10. The number of carbon atoms in the branched alkoxy group, not including the number of carbon atoms in substituents, is usually 3 to 40, preferably 4 to 10.
The alkoxy group may have a substituent, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a tert-butyloxy group, a pentyloxy group, a hexyloxy group, Heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, and the hydrogen atoms in these groups are cycloalkyl group, alkoxy group, Examples include groups substituted with a cycloalkoxy group, an aryl group, and a fluorine atom.
The number of carbon atoms in the "cycloalkoxy group", not including the number of carbon atoms in substituents, is usually 3 to 40, preferably 4 to 10.
The cycloalkoxy group may have a substituent, such as a cyclohexyloxy group.

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

A "p-valent heterocyclic group" (p represents an integer of 1 or more) refers to a heterocyclic compound in which p hydrogen atoms are directly bonded to carbon atoms or heteroatoms constituting the ring. means the remaining atomic group excluding the hydrogen atom. Among p-valent heterocyclic groups, it is an atomic group remaining after removing p hydrogen atoms from the hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring from an aromatic heterocyclic compound. A "p-valent aromatic heterocyclic group" is preferred.
"Aromatic heterocyclic compounds" include complex compounds such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole, etc. Compounds in which the ring itself is aromatic, and heterocycles such as phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, benzopyran, etc., have an aromatic ring condensed to the heterocycle even if the ring itself does not exhibit aromaticity. means a compound.

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

A "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. The substituent that the amino group has is preferably an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group.
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 either straight chain or branched. The number of carbon atoms in the straight chain alkenyl group, not including the number of carbon atoms in substituents, is usually 2 to 30, preferably 3 to 20. The number of carbon atoms in the branched alkenyl group, not including the number of carbon atoms in substituents, is usually 3 to 30, preferably 4 to 20.
The number of carbon atoms in the "cycloalkenyl group", not including the number of carbon atoms in substituents, is usually 3 to 30, preferably 4 to 20.
The alkenyl group and cycloalkenyl group may have a substituent, for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4- Examples include pentenyl group, 1-hexenyl group, 5-hexenyl group, 7-octenyl group, and groups in which these groups have a substituent.

The "alkynyl group" may be either straight chain or branched. The number of carbon atoms in the alkynyl group, excluding carbon atoms of substituents, is usually 2 to 20, preferably 3 to 20. The number of carbon atoms in the branched alkynyl group, excluding carbon atoms of substituents, is usually 4 to 30, preferably 4 to 20.
The number of carbon atoms in the "cycloalkynyl group", excluding carbon atoms of substituents, is usually 4 to 30, preferably 4 to 20.
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 thereof include a pentynyl group, a 1-hexynyl group, a 5-hexynyl group, and groups in which these groups have a substituent.

"Arylene group" means an atomic group remaining after removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from an aromatic hydrocarbon. The number of carbon atoms in the arylene group, not including the number of carbon atoms in substituents, is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18.
The arylene group may have a substituent, for example, a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a dihydrophenanthenediyl group, a naphthacenediyl group, a fluorenediyl group, a pyrenediyl group, a perylene diyl group, Examples include chrysendiyl groups and groups in which these groups have substituents, and groups represented by formulas (A-1) to (A-20) are preferred. The arylene group includes a group in which a plurality of these groups are bonded.

［式中、Ｒ及び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、アリール基又は１価の複素環基を表す。複数存在するＲ及び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。］

[In the formula, R and R ^a each independently represent 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 with the atoms to which they are bonded. ]

The number of carbon atoms in the divalent heterocyclic group, not including the number of carbon atoms in substituents, is usually 2 to 60, preferably 3 to 20, and more preferably 4 to 15.
The divalent heterocyclic group may have a substituent, for example, pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, phenoxazine, phenothiazine, acridine, Dihydroacridine, furan, thiophene, azole, diazole, triazole, divalent groups in which two hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring are removed, and preferred are are groups represented by formulas (AA-1) to (AA-34). The divalent heterocyclic group includes a group in which a plurality of these groups are bonded.

［式中、Ｒ及びＲ^aは、前記と同じ意味を表す。］

[In the formula, R and R ^a have the same meanings as above. ]

A "crosslinking group" is a group that can generate new bonds by being subjected to heating, ultraviolet irradiation, near ultraviolet irradiation, visible light irradiation, infrared ray irradiation, radical reaction, etc., and preferably the following: These are crosslinking groups represented by formulas (XL-1) to (XL-17) of group A of crosslinking groups.
(Bridging group A group)

［式中、Ｒ^XLは、メチレン基、酸素原子又は硫黄原子を表し、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。これらの架橋性基は置換基を有していてもよい。］

[In the formula, 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 's exist, they may be the same or different; when a plurality of n ^XL 's exist, they may be the same or different. * represents the bonding position. These crosslinkable groups may have a substituent. ]

"Substituent" refers to 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 bridging group.

<High molecular compound>
The polymer compound of the present invention has a structural unit consisting of a group obtained by removing one or more hydrogen atoms from the compound represented by the above formula (1a) or the above formula (1b).
The number average molecular weight of the polymer compound of the present invention in terms of polystyrene is preferably 5×10 ³ to 2.5×10 ⁵ , more preferably 1.5×10 ⁴ to 1×10 ⁵ .
The weight average molecular weight of the polymer compound of the present invention in terms of polystyrene is preferably 1×10 ⁴ to 5×10 ⁵ , more preferably 3×10 ⁴ to 2×10 ⁵ , even more preferably 3×10 ⁴ to 1×10 ⁵ .

[Structural unit consisting of a group obtained by removing one or more hydrogen atoms from the compound represented by formula (1a) or formula (1b)]
A structural unit consisting of a group obtained by removing one or more hydrogen atoms from a compound represented by formula (1a) or formula (1b) (hereinafter simply referred to as "constituent unit (1a)" or "constituent unit (1b)", respectively) ) is preferably a structural unit consisting of a group obtained by removing one or more hydrogen atoms from the compound represented by formula (1a), since the luminance life of the light-emitting element of the present invention is more excellent; Preferably, it is a structural unit consisting of a group obtained by removing 1 to 2 hydrogen atoms from the compound represented by formula (1a), and more preferably a group obtained by removing 2 hydrogen atoms from the compound represented by formula (1a). It is a constituent unit consisting of.

A group obtained by removing one or more hydrogen atoms from the compound represented by formula (1a) or formula (1b) is preferable from ring A, ring B, or R' because the luminance life of the light emitting device of the present invention is better. A group from which one or more hydrogen atoms have been removed, more preferably a group from which one or more hydrogen atoms have been removed from R', even more preferably a group from which one or two hydrogen atoms have been removed from R', especially Preferably, it is a group obtained by removing two hydrogen atoms from R'.

Ring A and ring B are preferably aromatic hydrocarbon rings or heterocycles, and more preferably aromatic hydrocarbon rings, since the luminance life of the light emitting device of the present invention is more excellent.

The aromatic hydrocarbon ring represented by ring A is preferably a phenanthrene ring, benzonaphthalene ring, benzene ring or naphthalene ring, more preferably a benzene ring or It is a naphthalene ring, more preferably a benzene ring, and these groups may have a substituent.

The substituent that the aromatic hydrocarbon ring represented by ring A may have is preferably an aryl group, an alkyl group, or a cycloalkyl group, since the luminance life of the light emitting element of the present invention is more excellent. More preferred is an alkyl group.

The aromatic hydrocarbon ring represented by ring B is preferably a benzene ring, a naphthalene ring, an anthracene ring, or a fluorene ring, more preferably a benzene ring or a naphthalene ring, since the luminance life of the light emitting device of the present invention is more excellent. A ring, more preferably a benzene ring, which may have a substituent.

The substituent that the aromatic hydrocarbon ring represented by ring B may have is preferably an aryl group, an alkyl group, or a cycloalkyl group, since the luminance life of the light emitting element of the present invention is more excellent. More preferred is an alkyl group. When a plurality of substituents (especially alkyl groups) are present, they may be combined to form a ring.

R ¹ is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an aryl group, and still more preferably a hydrogen atom, since the luminance life of the light emitting element of the present invention is more excellent. The group may have a substituent.

^R2 is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and still more preferably a hydrogen atom, since the luminance life of the light emitting element of the present invention is more excellent. The group may have a substituent.

L is preferably a single bond, an alkylene group, or an arylene group, more preferably a single bond or an arylene group, and even more preferably a single bond, since the luminance life of the light emitting element of the present invention is more excellent. The group may have a substituent.

The substituent that the aryl group represented by L may have is preferably an aryl group, an alkyl group, or a cycloalkyl group, since the luminance life of the light emitting device of the present invention is more excellent.

R' is preferably an aryl group or a monovalent heterocyclic group, more preferably an aryl group, since the luminance life of the light emitting element of the present invention is more excellent, and these groups have a substituent. Good too.

The aryl group represented by R' is preferably a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9 since the luminance life of the light emitting element of the present invention is more excellent. - anthracenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group or 4-phenylphenyl group, more preferably phenyl group, 1-naphthyl group, A 2-naphthyl group or a 2-fluorenyl group, more preferably a phenyl group, and these groups may have a substituent.

The substituent that the aryl group represented by R' may have is preferably an aryl group, an alkyl group, or a cycloalkyl group, since the luminance life of the light emitting element of the present invention is more excellent.

Q is preferably a single bond because the luminance life of the light emitting element of the present invention is more excellent.

In structural unit (1a) and structural unit (1b), geometric isomers may occur, for example, when LQR' and R ¹ are different from each other. The polymer compound may have only structural units having the same geometric isomer as the structural unit (1a) and the structural unit (1b), or may have multiple structural units having mutually different geometric isomers. You can leave it there. Geometric isomers include, for example, cis/trans isomers and E/Z isomers.

In the polymer compound of the present invention, the total amount of the structural unit (1a) and the structural unit (1b) is smaller than the total amount of all the structural units contained in the polymer compound, since the luminance life of the light emitting element of the present invention is better. In contrast, it is preferably 0.01 to 30 mol%, more preferably 0.1 to 15 mol%, even more preferably 0.5 to 5 mol%, particularly preferably 0.7 to 2. It is 5 mol%.

Examples of the structural unit (1a) include structural units represented by formulas (1a-1) to (1a-14) in the table below. In addition, * in the table represents the bond position, and J represents the bond of the constituent unit (i.e., the bond of the constituent unit consisting of a group obtained by removing one or more hydrogen atoms from the compound represented by formula (1a)). represent.

Examples of the structural unit (1b) include structural units represented by formulas (1b-1) to (1b-14) in the table below. Note that * in the table represents the bond position, and J represents the bond of the constituent unit (i.e., the bond of the constituent unit consisting of a group obtained by removing one or more hydrogen atoms from the compound represented by formula (1b)). represent.

The structural unit (1a) and the structural unit (1b) may each contain one type or two or more types in the polymer compound of the present invention.

[Other constituent 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 formula (X).

a ¹ is preferably 0 or 1, more preferably 1, since the luminance life of the light emitting element of the present invention is better.

a ² is preferably 0 or 1, more preferably 0, since the luminance life of the light emitting element of the present invention is better.

R ^X1 to 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 may have a substituent.

^The arylene group represented by Ar ^X1 and Ar 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 arylene groups which may have substituents.

The arylene group represented by Ar ^X2 and ^Ar or a group represented by formula (A-19), and these groups may have a substituent.

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

More preferable ranges of the arylene group and the divalent heterocyclic group in the divalent groups represented by Ar ^X2 and ^Ar The more preferred range is the same as the more preferred range of the arylene group and divalent heterocyclic group represented by Ar ^X1 and Ar ^X3 .

Examples ^of divalent groups in which an arylene group and a divalent heterocyclic group represented by Ar ^X2 and Ar You can leave it there.

［式中、Ｒ^XXは、水素原子、アルキル基、シクロアルキル基、アリール基又は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。］

[In the formula, R ^XX 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. ]

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

Ar ^X2 and Ar ^X4 are preferably arylene groups which may have substituents.

The substituents that ^the groups represented by Ar ^X1 to Ar ^X4 and R ^X1 to R You may do so.

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

［式中、Ｒ^X4及び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価の複素環基又はシアノ基を表し、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、隣接する炭素原子に結合する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。］

[In the formula, R ^X4 and ^R represents a group, and these groups may have a substituent. A plurality of R ^X4 's may be the same or different. A plurality of R ^X5s may be the same or different, and R ^X5s bonded to adjacent carbon atoms may be bonded to each other to form a ring with the carbon atoms to which they are bonded. ]

Since the structural unit represented by formula (X) has excellent hole transport properties, it is preferably 0.1 to 50 mol% with respect to the total amount of structural units contained in the polymer compound of the present invention, More preferably 0.5 to 30 mol%, still more preferably 1 to 10 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, only one type of structural unit represented by formula (X) may be included, or two or more types may be included.

Since the polymer compound of the present invention has a better brightness life than the light emitting device of the present invention, the polymer compound of the present invention further has a structural unit consisting of a group obtained by removing one hydrogen atom from the compound represented by formula (1a) or formula (1b). It is preferable to include a structural unit represented by formula (Y) different from .

The polymer compound of the present invention preferably further contains a structural unit represented by the formula (X) and a structural unit represented by the formula (Y), since the light emitting device of the present invention has excellent luminous efficiency.

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-13) or formula (A-19), more preferably formula (A-1), formula (A-7), formula (A-9) or formula (A-19). These groups may have a substituent.

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

In the divalent group in which the arylene group and the divalent heterocyclic group are directly bonded, represented by ^Ar The more preferred range is the same as the more preferred range of the arylene group and divalent heterocyclic group represented by ^Y1 .

Examples of divalent groups in which an arylene group represented by Ar ^Y1 and a divalent heterocyclic group are directly bonded include an arylene group and a divalent heterocyclic group represented by Ar ^X2 and Ar ^X4 in formula (X). Examples include the same divalent groups as 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 formula (Y) include structural units represented by formulas (Y-1) to (Y-7), and since the luminance life of the light emitting element of the present invention is excellent, Preferably it is a structural unit represented by formula (Y-1) or formula (Y-2).

［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、アリール基又は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、隣接する炭素原子に結合する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。
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、アリール基又は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。］

[In the formula,
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 may have a substituent. A plurality of R ^Y1s may be the same or different, and R ^Y1s bonded to adjacent carbon atoms may be bonded to each other to form a ring with the carbon atoms to which they are bonded.
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 may have a substituent. ]

R ^Y1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, more preferably a hydrogen atom, and these groups may 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, and more preferably a group represented by the below-mentioned formula (DA). , these groups may 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)－又は－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、アリール基又は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。］

[In the formula,
R ^Y1 represents the same meaning as above.
X ^Y1 represents a group represented by -C(R ^Y2 ) ₂ -, -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 ^Y2s may be the same or different, and R ^Y2s may be bonded to each other to form a ring with the carbon atoms to which they are 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. It's okay.

In X ^Y1 , the combination of two R ^Y2s in the group represented by -C(R ^Y2 ) ₂ - is preferably such that both are alkyl groups or cycloalkyl groups, both are aryl groups, and both are monovalent hetero 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 both are an alkyl group, or both are an aryl group, and these groups are substituted. It may have a group. Two R ^Y2s may be bonded to each other to form a ring with the atoms to which they are bonded, and when R ^Y2 forms a ring, as a group represented by -C(R ^Y2 ) ₂ - is preferably a group represented by formula (Y-A1) to formula (Y-A5), more preferably a group represented by formula (Y-A4), and these groups have a substituent. You may do so.

In X ^Y1 , the combination of two R ^Y2s in the group represented by -C(R ^Y2 )=C(R ^Y2 )- is preferably such that both are an alkyl group or a cycloalkyl group, or one is an alkyl group. Alternatively, one is a cycloalkyl group and the other is an aryl group, and these groups may have a substituent.

In X ^Y1 , four R ^Y2s 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 with each bonding atom, and when R ^Y2 forms a ring, -C(R ^Y2 ) ₂ -C(R ^Y2 ) ₂ - The group represented is preferably a group represented by formula (Y-B1) to formula (Y-B5), more preferably a group represented by formula (Y-B3), and these groups are It may have a substituent.

［式中、Ｒ^Y2は前記と同じ意味を表す。］

[In the formula, R ^Y2 represents the same meaning as 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、アリール基又は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。］

[In the formula,
R ^Y1 represents the same meaning as 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. It's okay.

［式中、Ｒ^Y1は前記と同じ意味を表す。］

[In the formula, R ^Y1 represents the same meaning as above. ]

The structural unit represented by formula (Y-5) is preferably a structural unit represented by formula (Y-5').

［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、アリール基又は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^Y11は、同一でも異なっていてもよい。］

[In the formula, 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 may have a substituent. A plurality of R ^Y11 's 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 may have a substituent.

［式中、Ｒ^Y1及びＲ^Y4は前記を同じ意味を表す。］

[In the formula, R ^Y1 and R ^Y4 represent the same meanings as above. ]

Examples of the structural unit represented by formula (Y) include structural units represented by formulas (Y-11) to (Y-56).

The structural unit represented by formula (Y) in which Ar ^Y1 is an arylene group has a better brightness life of the light-emitting element of the present invention, and therefore, the structural unit contained in the polymer compound of the present invention is It is preferably 30 to 98 mol%, more preferably 50 to 95 mol%, based on the total amount.

A structural unit represented by formula (Y) in which Ar ^Y1 is a divalent heterocyclic group or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded, Since the light emitting device of the present invention has excellent charge transport properties, the amount is preferably 0.5 to 30 mol%, more preferably 1.5 to 15 mol%, based on the total amount of structural units contained in the polymer compound. It is.

The polymer compound may contain only one type of structural unit represented by formula (Y), or may contain two or more types of structural units.

Examples of the polymer compounds of the present invention include polymer compounds Poly-1 to Poly-4 shown in Table 5. Here, "other structural units" means structural units other than structural unit (1a), structural unit (1b), structural unit represented by formula (X) or formula (Y).

［表中、ｐ、ｑ、ｒ及びｓは、各構成単位のモル比率を表す。ｐ＋ｑ＋ｒ＋ｓ＝100であり、かつ、70≦ｐ＋ｑ＋ｒ≦100である。］

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

Examples and preferred ranges of the structural unit (1a), the structural unit (1b), the structural unit represented by the formula (X), or the formula (Y) in the polymer compounds Poly-1 to Poly-4 are as described above. be.

The terminal group of the polymer compound of the present invention is preferable because if the polymerization active group remains as it is, the luminescence characteristics and brightness life may deteriorate when the polymer compound is used for producing a light emitting device. 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 a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, or may have other embodiments, but it may be made of multiple types of raw materials. A copolymer formed by copolymerizing monomers is preferable.

<Production method of polymer compound>
Next, the method for producing the polymer compound of the present invention will be explained.

The polymer compound of the present invention may be produced by any method, but for example, one or more hydrogen atoms in the compound represented by the formula (1a) or the formula (1b) (especially R' It can be produced using a compound in which two hydrogen atoms in the represented group are replaced with a halogen atom, a group represented by -B(OH) ₂ or a boric acid ester residue. Here, to explain one example, the polymer compound of the present invention includes, for example, a compound represented by formula (M-1) and/or a compound represented by formula (M-2), and a compound represented by formula (M-2). It can be produced by condensation polymerization of the compound represented by 3) and/or the compound represented by formula (M-4). Further, other polymer compounds of the present invention can be produced in the same manner. In this specification, the compounds used for producing the polymer compound of the present invention may be collectively referred to as "raw material monomers."
Here, each of the compounds represented by formulas (M-1) to (M-4) may be used alone or in combination of two or more.

［式中、
環Ａ、環Ｂ、Ｒ¹、Ｒ²、Ｌ、Ｑ、波線、ａ¹、ａ²、Ａｒ^X1～Ａｒ^X4、Ｒ^X1～Ｒ^X3及びＡｒ^Y1は、前記と同じ意味を表す。
Ｒ''は、アルキル基、シクロアルキル基、アリール基又は１価の複素環基を表し、これらの基は置換基として、Ｚ^C1とＺ^C2、又は、Ｚ^C3とＺ^C4を有する。
Ｚ^C1～Ｚ^C8は、それぞれ独立に、置換基Ａ群及び置換基Ｂ群からなる群から選ばれる基を表す。］

[In the formula,
Ring A, ring B, R ¹ , R ² , L, Q, the wavy line, a ¹ , a ² , Ar ^X1 to Ar ^X4 , R ^X1 to R ^X3 and Ar ^Y1 have the same meanings as above.
R'' represents an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups have Z ^C1 and Z ^C2 or Z ^C3 and Z ^C4 as substituents.
Z ^C1 to Z ^C8 each independently represent a group selected from the group consisting of substituent group A and substituent group B. ]

The preferred range of R'' is the same as the preferred range of R'.

For example, when Z ^C1 , Z ^C2 , Z ^C3 and Z ^C4 are groups selected from substituent group A, Z ^C5 , Z ^C6 , Z ^C7 and Z ^C8 are groups selected from substituent group B. .

For example, when Z ^C1 , Z ^C2 , Z ^C3 and Z ^C4 are groups selected from substituent group B, Z ^C5 , Z ^C6 , Z ^C7 and Z ^C8 are groups selected from substituent group A .

<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. ).

<Substituent group B>
Boric acid ester residue (i.e. -B(OR ^C2 ) ₂ (wherein R ^C2 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, even if these groups have a substituent) A group represented by ); a plurality of R ^C2 may be the same or different, and may be linked to each other to form a ring structure with the oxygen atom to which each is 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 (In the formula, R ^C3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and these groups may have a substituent. A plurality of 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 formula.

A compound having a group selected from substituent group A and a compound having a group selected from substituent group B are condensed together by a known coupling reaction to form a group selected from substituent group A and a substituent group B. Carbon atoms that are bonded to groups 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, the condensation of these compounds will occur through condensation polymerization. Polymers can be obtained.

Condensation polymerization is usually carried out in the presence of a catalyst, a base, and a solvent, but may be carried out in the presence of a phase transfer catalyst if necessary.

Examples of the catalyst include bis(triphenylphosphine)palladium(II) dichloride, bis(tris-o-methoxyphenylphosphine)palladium(II) dichloride, tetrakis(triphenylphosphine)palladium(0), and tris(dibenzylideneacetone). ) Dipalladium(0), palladium complexes such as palladium acetate, tetrakis(triphenylphosphine)nickel(0), [1,3-bis(diphenylphosphino)propane)nickel(II) dichloride, bis(1,4- Transition metal complexes such as nickel complexes such as cyclooctadiene)nickel(0); these transition metal complexes can further be used to form triphenylphosphine, tri(o-tolyl)phosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, Examples include complexes having ligands such as 1,3-bis(diphenylphosphino)propane and bipyridyl. The catalysts may be used alone or in combination of two or more.

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

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

The amounts of the base and phase transfer catalyst used are usually 0.001 to 100 molar equivalents, respectively, based on the total number of moles of the raw material monomers.

Examples of the solvent include organic solvents such as toluene, xylene, mesitylene, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, N,N-dimethylacetamide, and N,N-dimethylformamide, and water. The solvents may be used alone or in combination of two or more.

The amount of solvent used is usually 10 to 100,000 parts by mass based on a total of 100 parts by mass of raw material monomers.

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

Post-treatment of the polymerization reaction can be carried out by known methods, such as removing water-soluble impurities by liquid separation, adding the reaction solution after the polymerization reaction to a lower alcohol such as methanol, filtering the precipitate, and then drying. Use these methods alone or in combination. If the purity of the polymer compound is low, it can be purified by conventional methods such as crystallization, reprecipitation, continuous extraction using a Soxhlet extractor, and column chromatography.

The compound represented by formula (M-1) can be prepared, for example, by reacting the compound represented by formula (M-1-a) with a base and then reacting the reaction solution with trialkylsilane chloride. , a step of producing a compound represented by formula (M-1-b) (first step), and a step of reacting the compound represented by formula (M-1-b) with a base, and then reacting with the reaction solution. It can be produced by a step (second step) of producing a compound represented by formula (M-1) by reacting it with a compound represented by formula (M-1-c). Note that the compound represented by formula (M-2) can also be produced in the same manner. Here, the compounds represented by formulas (M-1-a) to (M-1-c), bases, and trialkyl chloride may be used alone or in combination of two or more. good.

［式中、
環Ａ、環Ｂ、Ｒ¹、Ｒ²、Ｌ、Ｑ、Ｒ''、Ｚ^C1及びＺ^C2は、前記と同じ意味を表す。
Ｒ^Siは、置換基を有していてもよいアルキル基を表し、３つあるＲ^Siは、同一でも異なっていてもよい。］

[In the formula,
Ring A, ring B, R ¹ , R ² , L, Q, R'', Z ^C1 and Z ^C2 have the same meanings as above.
R ^Si represents an alkyl group which may have a substituent, and the three R ^Sis may be the same or different. ]

It is preferable that the three R ^Sis be the same because raw materials are easily available. Further, the alkyl group represented by R ^Si is preferably a butyl group, a propyl group, an ethyl group, or a methyl group, since the yield of the compound represented by formula (M-1) is excellent.

The first step and the second step are usually performed in a solvent. Examples of the solvent include ether solvents such as diethyl ether, tetrahydrofuran, dioxane, cyclopentyl methyl ether, and diglyme; and hydrocarbon solvents such as hexane, decalin, toluene, xylene, and mesitylene.

In the first step, the amount of the base and trialkylsilane chloride used is usually 0.1 to 10 molar equivalents, respectively, based on the number of moles of the compound represented by formula (M-1-a).

In the second step, the amount of the base and the compound represented by formula (M-1-c) to be used is usually 0 to the number of moles of the compound represented by formula (M-1-b). .1 to 10 molar equivalents.

The reaction time of the first step and the second step is usually 0.5 to 50 hours each, and the reaction temperature is usually between the melting point and boiling point of the solvent present in the reaction system.

Examples of the base that can be used in the first and second steps include n-butyllithium, sec-butyllithium, tert-butyllithium, sodium hydride, lithium diisopropylamide, diisobutylaluminum hydride, tert-butoxypotassium, etc. Can be mentioned.

The trialkylsilane chloride and the compound represented by formula (M-1-a) in the first step and the compound represented by formula (M-1-c) in the second step are prepared using commercially available reagents. Alternatively, a separately synthesized product may be used.

<Composition>
The composition of the present invention includes the polymer compound of the present invention and at least one member selected from the group consisting of a hole transport material, a hole injection material, an electron transport material, an electron injection material, a luminescent material, an antioxidant, and a solvent. Contains the following materials. Here, these materials are different from the polymer compound of the present invention.

The composition containing the polymer compound and solvent of the present invention (hereinafter sometimes referred to as "ink") is suitable for producing light emitting elements using printing methods such as inkjet printing and nozzle printing.

The viscosity of the ink can be adjusted depending on the type of printing method, but when applied to printing methods such as inkjet printing in which the solution passes through a discharge device, it is necessary to adjust the viscosity of the ink to prevent clogging and deflection during discharge. , 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 solvents include chlorinated 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; and esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate, and phenyl acetate. Solvents: Polyhydric alcohol solvents such as ethylene glycol, glycerin, 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 other amide solvents. The solvents may be used alone or in combination of two or more.

In the ink, the amount of the solvent blended is usually 1,000 to 100,000 parts by mass, preferably 2,000 to 20,000 parts by mass, per 100 parts by mass of the polymer compound of the present invention.

[Hole transport material]
Hole transport materials are classified into low molecular weight compounds and high molecular weight compounds, with high molecular weight compounds being preferred, and high molecular weight compounds having a crosslinking group being more preferred.

Examples of the polymer compound include polyvinylcarbazole 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, and trinitrofluorenone, with fullerene being preferred.

In the composition of the present invention, the amount of the hole transporting material is generally 1 to 400 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of the polymer compound of the present invention. The hole transport materials may be used alone or in combination of two or more.

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

Examples of low-molecular compounds include metal complexes 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 metal.

In the composition of the present invention, the amount of the electron transporting material blended is usually 1 to 400 parts by mass, preferably 5 to 150 parts by mass, per 100 parts by mass of the polymer compound of the present invention. The electron transport materials may be used alone or in combination of two or more.

[Hole injection material and electron injection material]
Hole-injecting materials and electron-injecting materials are classified into low-molecular compounds and high-molecular compounds, respectively. The hole injection material and the electron injection material may have a crosslinking group.

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

In the composition of the present invention, the amount of the hole-injecting material and the electron-injecting material is usually 1 to 400 parts by mass, preferably 5 to 150 parts by mass, relative to 100 parts by mass of the polymer compound of the present invention. Part by mass. 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 electron injection material contains 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 keep the electrical conductivity of the conductive polymer within this range, the conductive polymer can be doped with an appropriate amount of ions.

The type of ion to be doped is an anion if it is a hole injection material, and a cation if it is 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. The number of ions to be doped may be one type or two or more types.

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

Examples of the low-molecular compound include naphthalene and its derivatives, anthracene and its derivatives, perylene and its derivatives, and triplet luminescent complexes having iridium, platinum, or europium as the central metal.

Examples of the polymer compound include a phenylene group, a naphthalenediyl group, a fluorenediyl group, a phenanthrenediyl group, a dihydrophenanthrenediyl group, a group represented by formula (X), a carbazolediyl group, a phenoxazinediyl group, and a phenothiazinediyl group. Examples include polymeric compounds containing anthracenediyl group, anthracenediyl group, pyrenediyl group, and the like.

The luminescent material may include a low-molecular compound and a high-molecular compound, preferably a triplet luminescent complex and a high-molecular compound.

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

［式中、
Ｒ^D1～Ｒ^D8、Ｒ^D11～Ｒ^D20、Ｒ^D21～Ｒ^D26及び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価の複素環基又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及び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及び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、酸素原子又は窒素原子を表し、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又は３を表し、ｎ_D2は、１又は２を表す。］

[In the formula,
R ^D1 to R ^D8 , R ^D11 to R ^D20 , R ^D21 to R ^D26 and R ^D31 to R ^D37 each independently represent 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 may have a substituent. When a plurality of R ^D1 to R ^D8 , R ^D11 to R ^D20 , R ^D21 to R ^D26 and R ^D31 to R ^D37 are present, 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, oxygen atom, or nitrogen atom bonded to an iridium atom; The atoms may be atoms constituting a ring. When a plurality of -A ^D1 ---A ^D2 - exist, they may be the same or different.
n _D1 represents 1, 2 or 3, and n _D2 represents 1 or 2. ]

In the metal complex represented by formula Ir-1, at least one of R ^D1 to R ^D8 is preferably a group represented by formula (DA).
In the metal complex represented by formula Ir-2, at least one of R ^D11 to R ^D20 is preferably a group represented by formula (DA).
In the metal complex represented by formula Ir-3, at least one of R ^D1 to R ^D8 and R ^D11 to R ^D20 is preferably a group represented by formula (DA).
In the metal complex represented by formula Ir-4, at least one of R ²¹ to R ^D26 is preferably a group represented by formula (DA).
In the metal complex represented by formula Ir-5, at least one of R ^D31 to R ^D37 is preferably a group represented by formula (DA).

［式中、
ｍ^DA1～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、芳香族炭化水素基又は複素環基を表し、これらの基は置換基を有していてもよい。
Ａｒ^DA1～Ａｒ^DA3は、それぞれ独立に、アリーレン基又は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^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、アリール基又は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。］

[In the formula,
m ^DA1 to m ^DA3 each independently represent an integer of 0 or more.
G ^DA represents a nitrogen atom, an aromatic hydrocarbon group, or a heterocyclic group, and these groups may have a substituent.
Ar ^DA1 to Ar ^DA3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When there are multiple Ar ^DA1 to Ar ^DA3 , they may be the same or different.
T ^DA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of ^TDAs may be the same or different. ]

m ^DA1 to m ^DA3 are usually integers of 10 or less, preferably 5 or less, and more preferably 0 or 1. It is preferable that m ^DA1 to m ^DA3 are the same integer.

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

［式中、
＊、＊＊及び＊＊＊は、各々、Ａｒ^DA1、Ａｒ^DA2及び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、アリール基又は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。］

[In the formula,
*, ** and *** represent bonds with Ar ^DA1 , Ar ^DA2 and Ar ^DA3 , respectively.
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 multiple R ^DAs , they may be the same or different. ]

^RDA 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. It's okay.

Ar ^DA1 to Ar ^DA3 are preferably groups represented by 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、アリール基又は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。］

[In the formula,
R ^DA represents the same meaning as 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. If there are multiple R ^DBs , they may be the same or different. ]

T ^DA is preferably a group represented by formulas (TDA-1) to (TDA-3).

［式中、Ｒ^DA及びＲ^DBは前記と同じ意味を表す。］

[In the formula, R ^DA and R ^DB represent the same meanings as above. ]

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

［式中、
Ｒ^p1～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又はハロゲン原子を表す。Ｒ^p1及び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又は１を表す。複数あるｎｐ１は、同一でも異なっていてもよい。］

[In the formula,
R ^p1 to R ^p3 each independently represent 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 from 0 to 5, np2 represents an integer from 0 to 3, and np3 represents 0 or 1. A plurality of np1s may be the same or different. ]

np1 is preferably an integer of 0 to 3, more preferably an integer of 1 to 3, and still more preferably 1. np2 is preferably 0 or 1, more preferably 0. np3 is preferably 0.

R ^p1 to 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 the formula, * represents a site that binds to Ir. ]

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

［式中、
ｎ_D2は、１又は２を表す。
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。
Ｒ^DCは、水素原子、アルキル基、シクロアルキル基、アリール基又は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、アリール基又は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。］

[In the formula,
n _D2 represents 1 or 2.
D represents a group represented by formula (DA). A plurality of D's may be the same or different.
R ^DC 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. 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 may have a substituent. A plurality of R ^DDs may be the same or different. ]

Examples of triplet luminescent complexes include metal complexes represented by the following formula.

In the composition of the present invention, the content of the luminescent material is usually 0.1 to 400 parts by mass based on 100 parts by mass of the polymer compound of the present invention. The luminescent materials may be used alone or in combination of two or more.

[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 luminescence and charge transport, and examples thereof include phenolic antioxidants and phosphorus antioxidants.

In the composition of the present invention, the amount of antioxidant added is usually 0.001 to 10 parts by mass per 100 parts by mass of the polymer compound of the present invention. The antioxidants may be used alone or in combination of two or more.

<Light emitting element>
The light emitting device of the present invention is a light emitting device containing the polymer compound of the present invention.
The light emitting device of the present invention has, for example, an electrode consisting of an anode and a cathode, and a layer containing the polymer compound of the present invention provided between the electrodes.

[Layer structure]
The layer containing 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, and is preferably a light emitting layer. These layers each contain a luminescent material, a hole transport material, a hole injection material, an electron transport material, and an electron injection material.

A light emitting element has a light emitting layer between an anode and a cathode. From the viewpoint of hole injection and hole transport properties, the light emitting device of the present invention preferably has at least one layer of a hole injection layer and a hole transport layer between the anode and the light emitting layer, and From the viewpoint of injection properties and electron transport properties, it is preferable to have at least one layer of an electron injection layer and an electron transport layer between the cathode and the light emitting layer.
Materials for the hole transport layer, electron transport layer, light emitting layer, hole injection layer, and electron injection layer include the above-mentioned hole transport materials, electron transport materials, and light emitting materials, in addition to the polymer compound of the present invention. materials, hole-injecting materials, and electron-injecting materials.

The material for the hole transport layer, the material for the electron transport layer, and the material for 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 producing the light emitting device. When the material is dissolved in a solvent, it is preferable that the material has a crosslinking group in order to prevent the material from dissolving in the solvent. After each layer is formed using a material having a crosslinking group, the layer can be made insolubilized by crosslinking the crosslinking group.

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

The order, number, and thickness of the layers to be laminated may be adjusted in consideration of luminous efficiency and device life.

[Substrate/electrode]
The substrate in the light emitting element may be any substrate as long as it is capable of forming an electrode and is not chemically changed during the formation of an organic layer, and is, for example, a substrate made of a material such as glass, plastic, or silicon. In the case of an opaque substrate, it is preferred that the electrode furthest from the substrate be 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. conductive compounds; silver-palladium-copper composite (APC); NESA, gold, platinum, silver, and copper.

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

[Application]
Using the light emitting element of the present invention, for example, planar or patterned light emission can be obtained. Examples of display devices using patterned light emission include segment type and dot matrix type display devices. The light-emitting element of the present invention can be used, for example, as a display device for displays of computers, televisions, mobile terminals, etc., and can also be used for lighting.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

In the examples, the number average molecular weight (Mn) in terms of polystyrene and the weight average molecular weight (Mw) in terms of polystyrene of the polymer compound were determined by the following size exclusion chromatography (SEC) using tetrahydrofuran as the mobile phase. . In addition, each measurement condition of SEC is as follows.

The polymer compound to be measured was dissolved in tetrahydrofuran at a concentration of about 0.05% by mass, and 10 μL was injected into the SEC. The mobile phase was run at a flow rate of 1.0 mL/min. PLgel MIXED-B (manufactured by Polymer Laboratories) was used as a column. A UV-VIS detector (manufactured by Tosoh, trade name: UV-8320GPC) was used as a detector.

LC-MS was measured by the following method.
The measurement sample was dissolved in chloroform or tetrahydrofuran to a concentration of about 2 mg/mL, and about 1 μL was injected into an LC-MS (manufactured by Agilent, trade name: 1100LCMSD). The mobile phase for LC-MS was acetonitrile and tetrahydrofuran in varying ratios and flowed at a flow rate of 0.2 mL/min. The column used was L-column 2 ODS (3 μm) (manufactured by Japan Chemical Evaluation and Research Institute, inner diameter: 2.1 mm, length: 100 mm, particle size 3 μm).

TLC-MS was measured by the following method.
The measurement sample is dissolved in a solvent such as toluene, tetrahydrofuran, or chloroform at an arbitrary concentration, applied on a DART TLC plate (manufactured by Techno Applications, trade name: YSK5-100), and then subjected to TLC-MS (JEOL Ltd.). The measurement was performed using a commercially available product manufactured by JMS-T100TD (The AccuTOF TLC). The helium gas temperature during the measurement was adjusted within the range of 200 to 400°C.

NMR was measured by the following method.
5 to 10 mg of the measurement sample is mixed with about 0.5 mL of deuterated chloroform (CDCl ₃ ), deuterated tetrahydrofuran, deuterated dimethyl sulfoxide, deuterated acetone, deuterated N,N-dimethylformamide, deuterated toluene, deuterated methanol, deuterated ethanol, deuterated 2-propanol. Alternatively, it was dissolved in methylene dichloride and measured using an NMR device (manufactured by Agilent, trade name: INOVA300 or MERCURY 400VX).

High performance liquid chromatography (HPLC) area percentage values were used as an indicator of compound purity. Unless otherwise specified, this value is a value at UV=254 nm using HPLC (manufactured by Shimadzu Corporation, trade name: LC-20A). At this time, the compound to be measured was dissolved in tetrahydrofuran or chloroform to a concentration of 0.01 to 0.2% by mass, and 1 to 10 μL was injected into HPLC depending on the concentration. For the mobile phase of HPLC, the ratio of acetonitrile/tetrahydrofuran was varied from 100/0 to 0/100 (volume ratio), and the mixture was flowed at a flow rate of 1.0 mL/min. The column used was Kaseisorb LC ODS 2000 (manufactured by Tokyo Kasei Kogyo) or an ODS column having equivalent performance. A photodiode array detector (manufactured by Shimadzu Corporation, trade name: SPD-M20A) was used as a detector.

<Example 1> Synthesis of compound M1

(Synthesis of compound M1b)
After replacing the gas in a 30 mL two-necked flask equipped with a stirrer with argon gas, compound M1a (1.0 g) and cyclopentyl methyl ether (ultra-dehydrated product, 10 mL) were added, and the mixture was cooled to 0°C while stirring. . Thereafter, a hexane solution of n-butyllithium (1.6 mol/L, 3.1 mL) was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 0 to 5°C. The mixture was stirred for 1 hour to obtain slurry A. Thereafter, slurry A was heated to room temperature.
Separately, after replacing the gas in a 50 mL three-necked flask equipped with a stir bar with argon gas, chlorotrimethylsilane (0.70 mL) and cyclopentyl methyl ether (super dehydrated product, 5.0 mL) were added and stirred. The mixture was cooled to 5 to 10° C. to obtain a reaction mixture.
Thereafter, slurry A was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 5 to 10°C, and the resulting reaction mixture was heated to room temperature and further stirred for 2 hours. Thereafter, ion-exchanged water (5.0 mL) was added thereto, and the obtained organic layer was washed with ion-exchanged water. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and the obtained organic layer was washed with ion-exchanged water. The resulting filtrate was concentrated under reduced pressure to obtain an oily substance. The obtained oil was crystallized using n-heptane to obtain compound M1b (0.46 g) as a white solid. The HPLC area percentage value of compound M1b was greater than 99.5%.

LC-MS (ESI negative): m/z = 287 [MH] ^-
1 H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 8.01-7.97 (m, 2H), 7.91-7.88 (m, 2H), 7.81 (d, 1H), 7.58 (d, 1H), 7.49 (dt, 1H), 7.43 (dt, 1H), 7.36 (dt, 1H), 7.29 (dt, 1H) , 4.50 (s, 1H), -0.22 (s, 9H).

(Synthesis of compound M1)
After replacing the gas in a 50 mL four-necked flask equipped with a stirring bar with argon gas, compound M1b (0.46 g) and cyclopentyl methyl ether (ultra-dehydrated product, 9.2 mL) were added, and the mixture was heated to 0°C with stirring. Cooled to . Thereafter, a hexane solution of n-butyllithium (1.6 mol/L, 0.94 mL) was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 0 to 5°C. The mixture was stirred for 30 minutes. Thereafter, a solution of compound M1c (0.43 g) in cyclopentyl methyl ether (2.3 mL) was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 0 to 10°C. The mixture was warmed to room temperature and stirred for an additional 3 hours. Thereafter, toluene (10 mL) and ion exchange water (5.0 mL) were added thereto, and the obtained organic layer was washed with ion exchange water, and the obtained organic layer was dried over anhydrous magnesium sulfate. , and the obtained filtrate was concentrated under reduced pressure to obtain a solid. Toluene was added to the obtained solid, which was filtered using silica gel, and the obtained filtrate was concentrated under reduced pressure. The obtained concentrate was crystallized using a mixed solvent of toluene and acetonitrile to obtain compound M1 (0.53 g) as an orange solid. The HPLC area percentage value of compound M1 was greater than 99.5%. ¹ H-NMR revealed that compound M1 was a mixture of E/Z isomers.

LC-MS (APPI positive): m/z = 460 [M] ^+
1 H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 8.53 (d, 1H), 8.17 (s, 1H), 7.93-7.67 (m, 6H ), 7.60-7.55 (m, 1H), 7.47-7.43 (m, 1H), 7.37-7.29 (m, 2H), 7.23-7.15 (m , 1H), 7.08-7.01 (m, 1H).

<Example 2> Synthesis of compound M2

(Synthesis of compound M2b)
After replacing the gas in a 30 mL two-necked flask equipped with a stirrer with argon gas, compound M2a (1.2 g) and cyclopentyl methyl ether (super dehydrated product, 12 mL) were added, and the mixture was cooled to 0°C while stirring. . Thereafter, a hexane solution (1.6 mol/L, 3.7 mL) of n-butyllithium was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 0 to 5°C. The mixture was stirred for 1 hour to obtain slurry B. Thereafter, slurry B was heated to room temperature.
Separately, after replacing the gas in a 50 mL three-necked flask equipped with a stir bar with argon gas, chlorotrimethylsilane (0.84 mL) and cyclopentyl methyl ether (super dehydrated product, 6.0 mL) were added and stirred. The mixture was cooled to 5 to 10° C. to obtain a reaction mixture.
Thereafter, slurry B was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 5 to 10°C, and the resulting reaction mixture was heated to room temperature and further stirred for 3 hours. Thereafter, toluene (6.0 mL) and ion-exchanged water (6.0 mL) were added thereto, and the obtained organic layer was washed with ion-exchanged water, and the obtained organic layer was dried over anhydrous magnesium sulfate. After that, the resulting filtrate was concentrated under reduced pressure to obtain a solid. The obtained solid was crystallized using a mixed solvent of toluene and acetonitrile to obtain compound M2b (1.2 g) as a very thin pink-white solid. The HPLC area percentage value of compound M2b was greater than 99.5%.

¹ H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 8.27 (s, 1H), 7.99-7.84 (m, 4H), 7.53-7.50 (m, 1H), 7.45-7.41 (m, 2H), 7.39-7.31 (m, 2H), 4.01 (s, 1H), -0.06 (s, 9H) ．．

(Synthesis of compound M2)
After replacing the gas in a 100 mL four-necked flask equipped with a stirrer with argon gas, compound M2b (1.0 g) and cyclopentyl methyl ether (super dehydrated product, 25 mL) were added, and the mixture was cooled to 0°C while stirring. did. Thereafter, a hexane solution of n-butyllithium (1.6 mol/L, 2.1 mL) was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 0 to 5°C. The mixture was stirred for 30 minutes. Thereafter, a solution of compound M1c (0.93 g) in cyclopentyl methyl ether (5.0 mL) was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 0 to 10°C. The mixture was warmed to room temperature and stirred for an additional 3 hours. Thereafter, toluene (15 mL) and ion-exchanged water (10 mL) were added thereto, and the obtained organic layer was washed with ion-exchanged water. The obtained organic layer was dried over anhydrous magnesium sulfate, and then filtered. The resulting filtrate was concentrated under reduced pressure. Toluene was added to the obtained solid, which was filtered using silica gel, and the obtained filtrate was concentrated under reduced pressure. The obtained concentrate was crystallized using a mixed solvent of toluene and acetonitrile, and then purified by reverse phase chromatography (filling material: Wakogel 15C18) using a mixed solvent of methanol and acetonitrile. By distilling off under reduced pressure, compound M2 (0.30 g) was obtained as a yellow solid. The HPLC area percentage value of compound M2 was greater than 99.5%. ¹ H-NMR revealed that compound M2 was a mixture of E/Z isomers.

LC-MS (ESI positive): m/z = 461 [M+H] ^+
1 H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 8.18-8.10 (m, 1H), 8.09-7.98 (m, 1H), 7.91 -7.84 (m, 3H), 7.79-7.70 (m, 3H), 7.64-7.60 (m, 1H), 7.50-7.13 (m, 5H).

<Synthesis Example 1> Synthesis of compound M3

(Synthesis of compound M3b)
After replacing the gas in a 500 mL four-neck flask equipped with a stirrer with argon gas, compound M3a (24 g), compound B0 (32 g), [1,1'-bis(diphenylphosphino)ferrocene] palladium ( II) Dichloride dichloromethane adduct (6.5 g), potassium acetate (25 g) and cyclopentyl methyl ether (super dehydrated product, 165 mL) were added, and the mixture was stirred at 106° C. for 22 hours. After the resulting reaction mixture was cooled to room temperature, toluene (165 mL) was added, filtered using Celite and silica gel, the filter cake was washed with toluene (170 mL), and the resulting solution was concentrated under reduced pressure. N-heptane, toluene and activated carbon were added to the obtained concentrate, and the mixture was stirred at room temperature for 1 hour. The obtained mixture was filtered using Celite and silica gel, and the obtained filtrate was concentrated under reduced pressure to obtain an oily substance. The obtained oil was purified by silica gel column chromatography using a mixed solvent of hexane and toluene, and then the solvent was distilled off under reduced pressure to obtain compound M3b (15 g) as a green-white solid. The GC area percentage value of compound M3b was 98.0%.

¹ H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 8.06 (d, 1H), 7.76-7.73 (m, 2H), 7.42 (dt, 1H) ), 7.36 (dt, 1H), 7.28 (d, 1H), 2.58 (s, 3H), 1.44 (s, 12H).

(Synthesis of compound M3c)
After replacing the gas in a 300 mL four-necked flask equipped with a stirrer with argon gas, compound M3b (6.0 g), 1-bromo-2-chlorobenzene (4.5 g), toluene (60 mL), 2- Dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.38g), tris(dibenzylideneacetone)dipalladium(0) 0.75-dibenzylideneacetone adduct (0.24g) and 20% by mass tetraethyl hydroxide An aqueous ammonium solution (49 g) was added, and the mixture was stirred at 83° C. for 14 hours. After the obtained reaction mixture was cooled to room temperature, it was washed with ion-exchanged water, and the obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure. N-heptane, toluene and activated carbon were added to the obtained concentrate, and the mixture was stirred at room temperature for 30 minutes. The resulting mixture was filtered using Celite and silica gel, and the resulting filtrate was concentrated under reduced pressure to obtain compound M3c (5.7 g) as an amber oil. The GC area percentage value of compound M3c was 96.0%.

¹ H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 7.84 (d, 1H), 7.81 (d, 1H), 7.58-7.55 (m, 1H ), 7.44-7.38 (m, 4H), 7.32 (dt, 1H), 7.25-7.22 (m, 1H), 7.19 (d, 1H), 2.17 ( s, 3H).

(Synthesis of compound M3d)
After replacing the gas in a 200 mL four-necked flask equipped with a stirrer with argon gas, compound M3c (4.9 g), 1-methyl-2-pyrrolidone (super dehydrated product, 58 mL), anhydrous potassium carbonate (fine Powder, 2.9 g), palladium(II) acetate (0.11 g) and 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (0.42 g) were added, and the mixture was stirred at 143° C. for 15 hours. Toluene (58 mL) was added to the resulting reaction mixture, which was filtered using Celite and silica gel, and the filtered mass was washed with toluene (120 mL). The obtained solution was washed with ion-exchanged water, the obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure. Toluene and activated carbon were added to the obtained concentrate, and the mixture was stirred at room temperature for 1 hour. The resulting mixture was filtered using Celite and silica gel, and the resulting filtrate was concentrated under reduced pressure. The obtained concentrate was crystallized using a mixed solvent of toluene and ethanol to obtain compound M3d (1.2 g) as an off-white solid. The HPLC area percentage value of compound M3d was greater than 99.5%.

¹ H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 8.75 (d, 1H), 8.38 (d, 1H), 7.96 (d, 1H), 7. 82 (d, 1H), 7.71-7.63 (m, 3H), 7.54-7.46 (m, 2H), 7.32 (t, 1H), 4.02 (s, 2H) ．．

(Synthesis of compound M3e)
After replacing the gas in a 50 mL four-necked flask equipped with a stirring bar with argon gas, compound M3d (1.1 g) and cyclopentyl methyl ether (ultra-dehydrated product, 11 mL) were added, and the mixture was cooled to 0°C while stirring. did. Thereafter, a hexane solution (1.6 mol/L, 3.6 mL) of n-butyllithium was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 5 to 10°C. The mixture was warmed to room temperature and stirred for an additional hour. Thereafter, chlorotrimethylsilane (0.78 mL) and cyclopentyl methyl ether (super dehydrated product, 5.6 mL) were added dropwise thereto at room temperature while stirring, and the resulting reaction mixture was further stirred at room temperature for 1 hour. . Thereafter, toluene (11 mL) and ion-exchanged water (11 mL) were added thereto, and the obtained organic layer was washed with ion-exchanged water. The obtained organic layer was dried over anhydrous magnesium sulfate, and then filtered. The resulting filtrate was concentrated under reduced pressure. N-heptane, toluene and activated carbon were added to the obtained concentrate, and the mixture was stirred at room temperature for 30 minutes. The resulting mixture was filtered using Celite and silica gel, and the resulting filtrate was concentrated under reduced pressure. The obtained solid was crystallized using ethanol to obtain compound M3e (0.94 g) as a very thin pink-white solid. The HPLC area percentage value of compound M3e was 97.8%.

¹ H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 8.80 (d, 1H), 8.45 (d, 1H), 7.96 (d, 1H), 7. 80 (d, 1H), 7.69-7.61 (m, 3H), 7.50 (dt, 1H), 7.45 (t, 1H), 7.33 (dt, 1H), 4.08 (s, 1H), -0.09 (s, 9H).

(Synthesis of compound M3)
After replacing the gas in a 100 mL four-necked flask equipped with a stirring bar with argon gas, compound M3e (0.72 g) and cyclopentyl methyl ether (ultra-dehydrated product, 22 mL) were added, and the mixture was cooled to 0°C while stirring. did. Thereafter, a hexane solution (1.6 mol/L, 1.7 mL) of n-butyllithium was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 0 to 5°C. The mixture was stirred for 30 minutes. Thereafter, a solution of compound M1c (0.69 g) in cyclopentyl methyl ether (3.6 mL) was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 0 to 10°C. The mixture was warmed to room temperature and stirred for an additional 2 hours. Thereafter, toluene (22 mL) and ion-exchanged water (10 mL) were added thereto, and the obtained organic layer was washed with ion-exchanged water. The obtained organic layer was dried over anhydrous magnesium sulfate, and then filtered. The resulting filtrate was concentrated under reduced pressure. The obtained concentrate was purified by GPC (gel permeation chromatography) (JAIGEL-2HH-40 and JAIGEL-2.5HH-40, manufactured by Japan Analytical Industry Co., Ltd.) and using a mixed solvent of toluene and acetonitrile. Compound M3 (0.3 g) was obtained as an orange solid by sequentially performing crystallization. The HPLC area percentage value of compound M3 was greater than 99.5%. ¹ H-NMR revealed that compound M3 was a mixture of E/Z isomers.

LC-MS (ESI positive): m/z = 461 [M+H] ^+
1 H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 8.69 (t, 1H), 8.30-8.27 (m, 1H), 7.94 (d, 1H) ), 7.90-7.81 (m, 2H), 7.74-7.69 (m, 3H), 7.66-7.59 (m, 2H), 7.57-7.11 (m , 4H).

<Synthesis Example 2> Synthesis of compound M4

(Synthesis of compound M4b)
After replacing the gas in a 1 L four-necked flask equipped with a stirrer with argon gas, compound M4a (26 g) and dichloromethane (230 mL) were added, and the mixture was cooled to 0 to 5° C. with stirring. Thereafter, triethylamine (30 mL) was added thereto while keeping the internal temperature at 0-10°C, then trifluoromethanesulfonic anhydride (32 mL) was added dropwise while keeping the internal temperature at 0-10°C, and the mixture was allowed to cool to room temperature. The temperature was raised and the mixture was further stirred for 3 hours. Thereafter, toluene (230 mL) was added thereto, filtered using silica gel, the filter cake was washed with toluene (260 mL), and the resulting solution was concentrated under reduced pressure. The obtained concentrate was dissolved in toluene, washed with ion-exchanged water, the obtained organic layer was dried over anhydrous magnesium sulfate, and filtered. The obtained filtrate was concentrated under reduced pressure to remove the oily substance. Obtained. The obtained oil was purified by silica gel column chromatography using a mixed solvent of hexane and toluene, and then the solvent was distilled off under reduced pressure to obtain compound M4b (34 g) as a pale yellow oil. The HPLC area percentage value of compound M4b was 98.7%.

¹ H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 8.31 (d, 1H), 7.93 (d, 1H), 7.88 (d, 1H), 7. 71 (dt, 1H), 7.64 (dt, 1H), 7.44 (d, 1H).

(Synthesis of compound M4c)
After replacing the gas in a 500 mL four-neck flask equipped with a stirrer with argon gas, compound M4b (11.2 g), (3,5,5,8,8-pentamethyl-5,6,7,8 -Tetrahydronaphthalen-2-yl)boronic acid (9.5g), lithium bromide (3.1g), bis(triphenylphosphine)palladium(II) dichloride (0.63g), 1,2-dimethoxyethane (90mL) ), and a 15% by mass aqueous sodium carbonate solution (66 g) were added, and the mixture was stirred at 80° C. for 4 hours. The obtained reaction mixture was cooled to room temperature, toluene (134 mL) and ion-exchanged water were added thereto, and then the obtained organic layer was washed with ion-exchanged water. The washed organic layer was dried over anhydrous magnesium sulfate, filtered using silica gel, the filter cake was washed with toluene, and the obtained filtrate was concentrated under reduced pressure. Toluene and silica gel were added to the obtained concentrate, and the mixture was stirred at room temperature for 30 minutes. The resulting mixture was filtered, and the resulting filtrate was concentrated under reduced pressure to obtain compound M4c (13.6 g) as a pale yellow candy. The HPLC area percentage value of compound M4c was 96.3%.

¹ H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 8.35 (d, 1H), 7.90 (d, 1H), 7.80 (d, 1H), 7. 63 (t, 1H), 7.56 (t, 1H), 7.33 (d, 1H), 7.23 (s, 1H), 7.14 (s, 1H), 2.07 (s, 3H) ), 1.72 (s, 4H), 1.35 (s, 3H), 1.31 (s, 3H), 1.26 (s, 3H), 1.25 (s, 3H).

(Synthesis of compound M4d)
After replacing the gas in a 300 mL four-necked flask equipped with a stirrer with argon gas, compound M4c (13.0 g), 1-methyl-2-pyrrolidone (super dehydrated product, 104 mL), anhydrous potassium carbonate (fine Powder, 14.9 g), palladium(II) acetate (0.40 g) and 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (1.53 g) were added, and the mixture was stirred at 153° C. for 4 hours. Toluene (156 mL) was added to the resulting reaction mixture, which was filtered using Celite and silica gel, and the filtered mass was washed with toluene (78 mL). The obtained solution was washed with ion-exchanged water, the obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and the obtained filtrate was concentrated under reduced pressure. Toluene and silica gel were added to the obtained concentrate, and the mixture was stirred at room temperature for 30 minutes. The resulting mixture was filtered, and the resulting filtrate was concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography using a mixed solvent of hexane and toluene, and then crystallized using a mixed solvent of toluene, acetonitrile, and ethanol to obtain compound M4d (6.1 g). was obtained as a white solid. The HPLC area percentage value of compound M4d was 99.0%.

¹ H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 7.99 (d, 1H), 7.91-7.83 (m, 3H), 7.75 (s, 1H) ), 7.57 (s, 1H), 7.51 (dt, 1H), 7.42 (dt, 1H), 4.11 (s, 2H), 1.73 (s, 4H), 1.37 (s, 6H), 1.34 (s, 6H).

(Synthesis of compound M4e)
After replacing the gas in a 300 mL four-necked flask equipped with a stirring bar with argon gas, compound M4d (4.00 g) and cyclopentyl methyl ether (ultra-dehydrated product, 48 mL) were added, and the mixture was cooled to 0°C while stirring. did. Thereafter, a hexane solution of n-butyllithium (1.55 mol/L, 8.1 mL) was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 0 to 5°C, and the resulting reaction mixture was stirred at 0-5°C for 30 minutes. Thereafter, the resulting reaction mixture was heated to room temperature and further stirred for 2 hours. Thereafter, chlorotrimethylsilane (3.9 mL) was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 0 to 5°C, and the resulting reaction mixture was stirred at 0 to 5°C for 2 hours. . Thereafter, ion-exchanged water (40 mL) was added thereto, and the obtained organic layer was washed with ion-exchanged water. The washed organic layer was dried over anhydrous magnesium sulfate, filtered, and the resulting filtrate was concentrated under reduced pressure. The obtained concentrate was crystallized using acetonitrile to obtain compound M4e (4.57 g) as a very thin pink-white solid. The HPLC area percentage value of compound M4e was 98.4%. By repeating the above operation, a total of 5.7 g of M4e was obtained.

¹ H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 7.98-7.94 (m, 2H), 7.88 (d, 1H), 7.80 (s, 1H) ), 7.78(d, 1H),
7.49 (s, 1H), 7.46 (dt, 1H), 7.40 (dt, 1H), 4.38 (s, 1H), 1.74 (s, 4H), 1.38-1 .37 (m, 9H), 1.32 (s, 3H), -0.22 (s, 9H).

(Synthesis of compound M4)
After replacing the gas in a 500 mL four-necked flask equipped with a stirring bar with argon gas, compound M4e (5.50 g) and cyclopentyl methyl ether (ultra-dehydrated product, 165 mL) were added, and the mixture was cooled to 0°C while stirring. did. Thereafter, a hexane solution of n-butyllithium (1.55 mol/L, 9.1 mL) was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 0 to 5°C. Stir for 30 minutes. Thereafter, the resulting reaction mixture was heated to room temperature and further stirred for 2 hours. Then, a solution of compound M1c (3.75 g) in cyclopentyl methyl ether (24 mL) was added dropwise thereto while stirring while maintaining the temperature of the reaction mixture at 0 to 5°C, and the mixture was stirred at 0 to 5°C for 1 hour. did. Thereafter, toluene (110 mL) and ion-exchanged water were added thereto, and the obtained organic layer was washed with ion-exchanged water. The obtained organic layer was dried over anhydrous magnesium sulfate, and then filtered. The resulting filtrate was concentrated under reduced pressure. Toluene and n-heptane were added to the obtained concentrate, which was filtered using silica gel, the filter cake was washed with a mixed solvent of toluene and n-heptane, and the obtained filtrate was concentrated under reduced pressure. The obtained concentrate was repeatedly purified by crystallization using a mixed solvent of toluene and acetonitrile to obtain compound M4 (6.4 g) as an orange solid. The HPLC area percentage value of compound M4 was greater than 99.5%. ¹ H-NMR revealed that compound M4 was a mixture of E/Z isomers.

LC-MS (ESI positive): m/z = 571 [M+H] ^+
1 H-NMR (CD ₂ Cl ₂ -d ₂ , 400 MHz): δ (ppm) = 8.53-8.08 (m, 1H), 7.91-7.41 (m, 9H), 7.31 -7.02 (m, 2H), 1.73-1.61 (m, 4H), 1.36 (s, 6H), 1.32 (s, 3H), 1.07 (s, 3H).

<Synthesis Example 3> Synthesis of Compounds M11 to M20 Compound M11 was synthesized according to the method described in JP-A-2011-174062.
Compound M12 was synthesized according to the method described in WO 2002/045184.
Compound M13 was synthesized according to the method described in JP-A-2012-144722.
Compound M14 was synthesized according to the method described in JP-A-2004-143419.
Compound M15 was synthesized according to the method described in JP-A-2010-031259.
Compound M16 was synthesized according to the method described in Japanese Patent Publication No. 2013-538438.
Compound M17 was synthesized according to the method described in International Publication No. 2015/163241.
Compound M18 was synthesized according to the method described in JP-A-2011-174062.
Compound M19 was synthesized according to the method described in WO 2005/049546.
Compound M20 was synthesized according to the method described in JP-A-2008-106241.

<Synthesis Example 4> Synthesis of polymer compound P-1 Polymer compound P-1 was synthesized using compounds M11 to M15 according to the method described in JP-A-2012-144722. The Mn of the polymer compound P-1 was 8.5×10 ⁴ and the Mw was 2.3×10 ⁵ .

The polymer compound P-1 has a structural unit derived from the compound M11, a structural unit derived from the compound M13, a structural unit derived from the compound M12, and a compound A random copolymer (having terminal blocks and non-terminal blocks) consisting of a structural unit derived from M14 and a structural unit derived from compound M15 in a molar ratio of 50:32:10:3:5. It is a copolymer with phenyl groups as end groups.

<Example 3> Synthesis of polymer compound P-2
(Step 1) After creating an inert gas atmosphere in the reaction container, compound M11 (2.105 g), compound M13 (1.204 g), compound M12 (0.329 g), compound M14 (0.133 g), compound M15 (0.351 g), Compound M1 (0.028 g), dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.7 mg) and toluene (60 mL) were added, and the mixture was heated to 80°C.
(Step 2) Then, a 10% by mass aqueous tetraethylammonium hydroxide solution (42 mL) was added dropwise thereto, and the mixture was refluxed for 3.5 hours.
(Step 3) Thereafter, phenylboronic acid (295 mg) and dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.7 mg) were added thereto, and the mixture was refluxed for 6 hours.
(Step 4) After the obtained reaction mixture was cooled, it was sequentially washed once with ion-exchanged water, once with a 10% by mass aqueous hydrochloric acid solution, once with 3% by mass aqueous ammonia, and once with ion-exchanged water. Anhydrous magnesium sulfate was added to the obtained organic layer and stirred, and the obtained mixture was purified by passing the solution through an alumina column and a silica gel column in that order. When the obtained solution was added dropwise to methanol and stirred, a precipitate was generated. The obtained precipitate was collected by filtration and dried to obtain 1.85 g of polymer compound P-2. The Mn of polymer compound P-2 was 3.2×10 ⁴ and the Mw was 7.1×10 ⁴ .

The polymer compound P-2 is composed of a structural unit derived from compound M11, a structural unit derived from compound M13, a structural unit derived from compound M12, and a structural unit derived from compound M12, according to the theoretical value determined from the amount of raw materials. A random compound consisting of a structural unit derived from M14, a structural unit derived from compound M15, and a structural unit derived from compound M1 in a molar ratio of 50:31:10:3:5:1. It is a polymer (copolymer without terminal blocks and non-terminal blocks) and has phenyl groups as terminal groups.

<Comparative example 1> Synthesis of polymer compound P-3 (Step 1) in Example 3 was changed to "After creating an inert gas atmosphere in the reaction vessel, compound M11 (2.139 g), compound M13 (1.204 g) ), Compound M12 (0.329g), Compound M14 (0.133g), Compound M15 (0.351g), Compound M16 (0.029g), Dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.7mg) and toluene (60 mL), and heated to 80°C.'' In the same manner as in Example 3, 2.25 g of polymer compound P-3 was obtained. The Mn of polymer compound P-3 was 2.9×10 ⁴ and the Mw was 6.7×10 ⁴ .

The polymer compound P-3 is composed of a structural unit derived from compound M11, a structural unit derived from compound M13, a structural unit derived from compound M12, and a structural unit derived from compound M12, according to the theoretical value determined from the amount of raw materials. A random compound consisting of a structural unit derived from M14, a structural unit derived from compound M15, and a structural unit derived from compound M16 in a molar ratio of 50:31:10:3:5:1. It is a polymer (copolymer without terminal blocks and non-terminal blocks) and has phenyl groups as terminal groups.

<Comparative Example 2> Synthesis of polymer compound P-4 (Step 1) in Example 3 was changed to "After creating an inert gas atmosphere in the reaction vessel, compound M11 (2.167 g), compound M13 (1.216 g) ), Compound M12 (0.332g), Compound M14 (0.135g), Compound M15 (0.355g), Compound M17 (0.025g), Dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.7mg) and toluene (60 mL), and heated to 80°C.'' In the same manner as in Example 3, 0.38 g of polymer compound P-4 was obtained. The Mn of polymer compound P-4 was 3.2×10 ⁴ and the Mw was 7.4×10 ⁴ .

The polymer compound P-4 is composed of a structural unit derived from compound M11, a structural unit derived from compound M13, a structural unit derived from compound M12, and a structural unit derived from compound M12, according to the theoretical value determined from the amount of raw materials to be charged. A random compound consisting of a structural unit derived from M14, a structural unit derived from compound M15, and a structural unit derived from compound M17 in a molar ratio of 50:31:10:3:5:1. It is a polymer (copolymer without terminal blocks and non-terminal blocks) and has phenyl groups as terminal groups.

<Comparative Example 3> Synthesis of polymer compound P-5 (Step 1) in Example 3 was changed to "After creating an inert gas atmosphere in the reaction vessel, compound M11 (2.185 g), compound M13 (1.266 g) ), Compound M12 (0.335g), Compound M14 (0.136g), Compound M15 (0.358g), Compound M3 (0.028g), Dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.7mg) and toluene (60 mL), and heated to 80°C.'' In the same manner as in Example 3, 0.93 g of polymer compound P-5 was obtained. The Mn of polymer compound P-5 was 3.4×10 ⁴ and the Mw was 7.4×10 ⁴ .

The polymer compound P-5 is composed of a structural unit derived from compound M11, a structural unit derived from compound M13, a structural unit derived from compound M12, and a structural unit derived from compound M12, according to the theoretical value determined from the amount of raw materials charged. A random compound consisting of a structural unit derived from M14, a structural unit derived from compound M15, and a structural unit derived from compound M3 in a molar ratio of 50:31:10:3:5:1. It is a polymer (copolymer without terminal blocks and non-terminal blocks) and has phenyl groups as terminal groups.

<Example 4> Synthesis of polymer compound P-6 (Step 1) in Example 3 was changed to ``After creating an inert gas atmosphere in the reaction vessel, compound M11 (2.105 g), compound M13 (1.204 g) ), Compound M12 (0.329g), Compound M14 (0.133g), Compound M15 (0.351g), Compound M2 (0.028g), Dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.7mg) and toluene (60 mL), and heated to 80° C.'' In the same manner as in Example 3, 1.75 g of polymer compound P-6 was obtained. The Mn of polymer compound P-6 was 2.9×10 ⁴ and the Mw was 6.6×10 ⁴ .

Polymer compound P-6 is composed of a structural unit derived from compound M11, a structural unit derived from compound M13, a structural unit derived from compound M12, and a structural unit derived from compound M12, according to the theoretical value determined from the amount of raw materials. A random compound consisting of a structural unit derived from M14, a structural unit derived from compound M15, and a structural unit derived from compound M2 in a molar ratio of 50:31:10:3:5:1. It is a polymer (copolymer without terminal blocks and non-terminal blocks) and has phenyl groups as terminal groups.

<Example 5> Synthesis of polymer compound P-7 (Step 1) in Example 3 was changed to ``After creating an inert gas atmosphere in the reaction vessel, compound M11 (2.105 g), compound M12 (0.329 g) ), Compound M13 (1.204g), Compound M14 (0.133g), Compound M15 (0.351g), Compound M4 (0.034g), Dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.7mg) and toluene (60 mL), and heated to 80°C.'' In the same manner as in Example 3, 1.91 g of polymer compound P-7 was obtained. The Mn of polymer compound P-7 was 3.0×10 ⁴ and the Mw was 7.0×10 ⁴ .

Polymer compound P-7 has a structural unit derived from compound M11, a structural unit derived from compound M12, a structural unit derived from compound M13, and a compound A random compound consisting of a structural unit derived from M14, a structural unit derived from compound M15, and a structural unit derived from compound M4 in a molar ratio of 50:31:10:3:5:1. It is a polymer (copolymer without terminal blocks and non-terminal blocks) and has phenyl groups as terminal groups.

<Synthesis Example 5> Synthesis of polymer compound HTL-1 Polymer compound HTL-1 was synthesized using compound M18, compound M12, compound M19, and compound M20 according to the method described in JP-A-2012-144722. . The Mn of the polymer compound HTL-1 was 7.8×10 ⁴ and the Mw was 2.6×10 ⁵ .
The polymer compound HTL-1 is composed of a structural unit derived from compound M18, a structural unit derived from compound M12, a structural unit derived from compound M19, and a structural unit derived from compound M19, according to the theoretical value determined from the amount of raw materials. It is a random copolymer composed of structural units derived from M20 in a molar ratio of 50:12.5:30:7.5, and has a phenyl group as a terminal group.

<Example D1> Production and evaluation of light emitting element D1 (formation of anode and hole injection layer)
An anode was formed by attaching an ITO film with a thickness of 45 nm to a glass substrate by sputtering. A polythiophene sulfonic acid-based hole injection agent AQ-1200 (manufactured by Plectronics) was formed on the anode to a thickness of 50 nm by spin coating, and heated at 170°C on a hot plate in an air atmosphere. A hole injection layer was formed by heating for 15 minutes.

(Formation of hole transport layer)
Polymer compound HTL-1 was dissolved in xylene at a concentration of 0.6% by mass. Using the obtained xylene solution, a film with a thickness of 20 nm was formed by spin coating on the hole injection layer, and positive polarization was performed by heating it on a hot plate at 180°C for 60 minutes in a nitrogen gas atmosphere. A pore transport layer was formed.

(Formation of light emitting layer)
Polymer compound P-1 and polymer compound P-2 (polymer compound P-1/polymer compound P-2 = 50% by mass/50% by mass) were dissolved in xylene at a concentration of 1.2% by mass. Using the obtained xylene solution, a film with a thickness of 60 nm was formed by spin coating on the hole transport layer, and the film was heated at 150°C for 10 minutes on a hot plate in a nitrogen gas atmosphere to emit light. formed a layer.

(Formation of cathode)
After reducing the pressure of the substrate on which the light-emitting layer was formed to 1×10 ^-4 Pa or less in a vapor deposition machine, about 4 nm of sodium fluoride was placed on the light-emitting layer as a cathode, and then on the sodium fluoride layer, Approximately 80 nm of aluminum was deposited. After vapor deposition, the light emitting element D1 was produced by sealing using a glass substrate.

(Evaluation of light emitting device)
EL light emission was observed by applying a voltage to the light emitting element D1. Constant current driving was performed at an initial brightness of 3000 cd/m ² , and the time until the brightness reached 75% of the initial brightness (hereinafter referred to as "LT75") was measured. The results are shown in Table 6.

<Comparative Examples CD1 to CD4> Production and evaluation of light emitting devices CD1 to CD4 Example D1 except that in (formation of the light emitting layer) of Example D1, the material and composition ratio of the light emitting layer were as shown in Table 6. In the same manner as above, light emitting devices CD1 to CD4 were manufactured. When a voltage was applied to each of the light emitting elements CD1 to CD4, EL light emission was observed. The light emitting elements CD1 to CD4 were driven at a constant current with an initial luminance of 3000 cd/m ² and LT75 was measured. The results are shown in Table 6.

<Example D2, Comparative Examples CD5 to CD6> Production and evaluation of light emitting elements D2 and CD5 to CD6 In Example D1 (formation of light emitting layer), the materials and composition ratios of the light emitting layer were as shown in Table 7. Except for this, light emitting devices D2 and CD5 to CD6 were produced in the same manner as in Example D1. When a voltage was applied to each of the light emitting elements D2 and CD5 to CD6, EL light emission was observed. The light emitting elements D2, CD5 to CD6 were driven with a constant current at an initial brightness of 6000 cd/m ² , and the time until the brightness reached 50% of the initial brightness (hereinafter referred to as "LT50") was measured. The results are shown in Table 7.

From the comparison between the light emitting element D1 and the light emitting elements CD1 to CD4, and the comparison between the light emitting element D2 and the light emitting elements CD5 to 6, the luminance life of the light emitting element manufactured using the polymer compound of the present invention is excellent. I understand that.

<Example D3, Comparative Examples CD7 to CD9> Production and evaluation of light emitting elements D3 and CD7 to CD9 In Example D1 (formation of light emitting layer), the materials and composition ratios of the light emitting layer were as shown in Table 8. Except for this, light emitting devices D3 and CD7 to CD9 were produced in the same manner as in Example D1. When a voltage was applied to each of the light emitting elements D3 and CD7 to CD9, EL light emission was observed. The light emitting elements D3 and CD7 to CD9 were driven with a constant current at an initial brightness of 2000 cd/m ² , and the time until the brightness reached 80% of the initial brightness (hereinafter referred to as "LT80") was measured. The results are shown in Table 8.

A comparison of light emitting element D3 and light emitting elements CD7 to CD9 reveals that the light emitting elements manufactured using the polymer compound of the present invention have excellent brightness life.

Claims (11)

A polymer compound having a structural unit consisting of a group obtained by removing two hydrogen atoms from R' in a compound represented by formula (1a) or formula (1b).

[In the formula,
Ring A and ring B each independently represent an aromatic hydrocarbon ring, and this ring may have a substituent. When a plurality of the substituents are present, they may be combined to form a ring.
R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. Two R ² 's may be the same or different.
L represents a single bond.
R' represents an aryl group, and this group may have a substituent.
Q represents a single bond.
The wavy line indicates that R ¹ and ring B bonded to the double bond may be on the same side or on opposite sides with respect to the double bond. ] 2. The polymer compound according to claim 1 , which has a structural unit consisting of a group obtained by removing two hydrogen atoms from R' in the compound represented by the formula (1a). The polymer compound according to claim 1 or 2 , wherein ring A and ring B are benzene rings. The polymer compound according to any one of claims 1 to 3 , wherein R ¹ is a hydrogen atom. The polymer compound according to any one of claims 1 to 4 , further comprising a structural unit represented by formula (X).

[In the formula,
a ¹ and a ² each independently represent an integer of 0 or more and 2 or less.
Ar ^X1 and Ar ^X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent.
Ar ^X2 and Ar ^X4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded; It may have. When a plurality of Ar ^X2 or Ar ^X4 exist, they may be the same or different.
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 may have a substituent. When a plurality of R ^X2 or R ^X3 are present, they may be the same or different. ] Furthermore, it contains a structural unit represented by formula (Y) that is different from the structural unit consisting of a group obtained by removing two hydrogen atoms from R' in the compound represented by formula (1a) or formula (1b). , the polymer compound according to any one of claims 1 to 5 .

[In the formula, Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are directly bonded, and these groups have a substituent. You can leave it there. ] The polymer compound according to claim 6 , wherein the structural unit represented by formula (Y) is a structural unit represented by formula (Y-1) or formula (Y-2).

[In the formula,
X ^Y1 represents a group represented by -C(R ^Y2 ) ₂ -, -C(R ^Y2 )=C(R ^Y2 )-, or -C(R ^Y2 ) ₂ -C(R ^Y2 ) ₂ -. A plurality of R ^Y2s may be the same or different.
R ^Y1 , R ^Y2 and R ^Y4 each independently represent 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 have no substituents. may have. A plurality of R ^Y1s and R ^Y2s may be the same or different, and R ^{Y1s are bonded to adjacent carbon atoms, R Y2s} are bonded to adjacent carbon atoms, or R ^Y2s are bonded to the same carbon atom. R ^Y2 may be bonded to each other to form a ring with the carbon atoms to which they are bonded. ] The content of the structural unit consisting of a group obtained by removing two hydrogen atoms from R' in the compound represented by formula (1a) or formula (1b) is relative to the content of all structural units contained in the polymer compound. The polymer compound according to any one of claims 1 to 7 , wherein the amount thereof is 0.01 to 30 mol%. A compound in which two hydrogen atoms in R' of the compound represented by formula (1a) or formula (1b) are substituted with a halogen atom, a group represented by -B(OH) ₂ or a borate ester residue .

[In the formula,
Ring A and ring B each independently represent an aromatic hydrocarbon ring, and this ring may have a substituent.
R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. Two R ² 's may be the same or different.
L represents a single bond.
R' represents an aryl group, and this group may have a substituent.
Q represents a single bond.
The wavy line indicates that R ¹ and ring B bonded to the double bond may be on the same side or on opposite sides with respect to the double bond. ] The polymer compound according to any one of claims 1 to 8 ,
A composition containing 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 luminescent material, an antioxidant, and a solvent. A light emitting device comprising the polymer compound according to any one of claims 1 to 8 .