JP2016196610A - Polymeric compound and light-emitting element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymeric compound useful for the manufacture of a light-emitting element excellent in a luminance lifetime.SOLUTION: The polymeric compound contains, as a structural unit, a triarylamine moiety in which two or more groups or atoms connecting two arylene groups are present. The group or atom connecting the two arylene groups is a group represented by -NR'- (where R' is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group), an oxygen atom or a sulfur atom.SELECTED DRAWING: None

Description

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

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

  As a material used for a light emitting layer of a light emitting element, Non-Patent Document 1 proposes a polymer compound including a fluorene structural unit 1 represented by the following formula and an arylamine structural unit 1 represented by the following formula. . Patent Document 1 proposes a polymer compound including a fluorene structural unit 1 represented by the following formula and an arylamine structural unit 2 represented by the following formula.

Journal of the American Chemical Society, 2005, 127, 3172-3183 International Publication Number WO2010 / 001982A1

  However, a light-emitting element manufactured using a polymer compound including the arylamine structural unit 1 and the arylamine structural unit 2 does not necessarily have a sufficient luminance life.

  Then, this invention aims at providing the high molecular compound useful for manufacture of the light emitting element which is excellent in a brightness | luminance half life by introduce | transducing the new structural unit of arylamine different from the arylamine structural unit 1. . Another object of the present invention is to provide a compound useful for producing the polymer compound. Another object of the present invention is to provide a composition containing the polymer compound and a light-emitting device obtained using the polymer compound.

  The present invention provides a polymer compound containing a structural unit represented by the following formula (1), (2) or (3).

[Where:
E ¹ , E ² and E ³ represent a group represented by —NR′—, an oxygen atom or a sulfur atom. The plurality of E ¹ , E ² and E ³ may be the same or different.
R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent.
Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b , Ar ^2c , Ar ^3a , Ar ^3b and Ar ^3c each independently represent an aromatic hydrocarbon group or a heterocyclic group, and these groups are substituents You may have. A plurality of Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b , Ar ^2c , Ar ^3a , Ar ^3b and Ar ^3c may be the same or different.
R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
3A, 3B and 3C each represent an integer of 0 to 3. ]

  The present invention secondly provides a compound represented by the following formula (1M) or (2M).

[Where:
E ¹ and E ² represent a group represented by —NR′—, an oxygen atom, or a sulfur atom. The plurality of E ¹ and E ² may be the same or different.
Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b and Ar ^2c each independently represent an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent. A plurality of Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b and Ar ^2c may be the same or different.
R ¹ and R ² 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.
3A and 3B each represent an integer of 0 to 3.
Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a group selected from the following substituent group A or a group selected from substituent group B. ]

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

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

  Thirdly, the present invention provides a composition containing the polymer compound and a solvent.

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

  ADVANTAGE OF THE INVENTION According to this invention, the high molecular compound useful for manufacture of the light emitting element which is excellent in a luminance lifetime can be provided. Moreover, according to this invention, the compound useful for manufacture of this high molecular compound can be provided. Furthermore, according to the present invention, a composition containing the polymer compound and a light emitting device obtained using the polymer compound can be provided.

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

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

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

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

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

The “polymer compound” means a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1 × 10 ³ or more, preferably 1 × 10 ⁴ or more. The upper limit of the number average molecular weight of the polymer compound is not particularly limited, but is generally about 1 × 10 ⁸ .

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

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

  The “alkyl group” may be linear or branched. The carbon atom number of a linear alkyl group is 1-50 normally without including the carbon atom number of a substituent, Preferably it is 3-30, More preferably, it is 4-20. The number of carbon atoms of the branched alkyl group is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20, not including the number of carbon atoms of the substituent.

  The alkyl group may have a substituent, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isoamyl group, 2-ethylbutyl group, Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, 3-propylheptyl group, decyl group, 3,7-dimethyloctyl group, 2-ethyloctyl group, 2-hexyldecyl group, dodecyl group, and these Examples include groups in which the hydrogen atom in the group is substituted with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, etc., for example, a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorobutyl group, Fluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, 3- (4-methylphenyl) propyl group, 3- (3,5-di-hexyl group Ruphenyl) propyl group and 6-ethyloxyhexyl group.

  The number of carbon atoms of the “cycloalkyl group” is usually 3 to 50, preferably 3 to 30 and more preferably 4 to 20 without including the number of carbon atoms of the substituent.

  The cycloalkyl group may have a substituent, and examples thereof include a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.

  “Aryl group” means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The carbon atom number of an aryl group is 6-60 normally without including the carbon atom number of a substituent, Preferably it is 6-20, More preferably, it is 6-10.

  The aryl group may have a substituent, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2 -Pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and hydrogen atoms in these groups Are groups substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, or the like.

  The “alkoxy group” may be linear or branched. The number of carbon atoms of a linear alkoxy group is 1-40 normally without including the carbon number of a substituent, Preferably it is 4-10. The number of carbon atoms of the branched alkoxy group is usually 3 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent.

  The alkoxy group may have a substituent, for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, tert-butyloxy group, pentyloxy group, hexyloxy group, Heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, and the hydrogen atom in these groups is a cycloalkyl group, an alkoxy group, And a group substituted with a cycloalkoxy group, an aryl group, a fluorine atom, or the like.

  The number of carbon atoms of the “cycloalkoxy group” is usually 3 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent.

  The cycloalkoxy group may have a substituent, and examples thereof include a cyclohexyloxy group.

  The number of carbon atoms of the “aryloxy group” is usually 6 to 60, preferably 7 to 48, not including the number of carbon atoms of the substituent.

  The aryloxy group may have a substituent, for example, a phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, 1- Examples include a pyrenyloxy group and a group in which a hydrogen atom in these groups is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom, or the like.

  “P-valent heterocyclic group” (p represents an integer of 1 or more) is a p-group of hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from a heterocyclic compound. This means the remaining atomic group excluding the hydrogen atom. Among the p-valent heterocyclic groups, this is an atomic group obtained by removing p hydrogen atoms from an aromatic heterocyclic compound directly bonded to carbon atoms or heteroatoms constituting the ring. A “p-valent aromatic heterocyclic group” is preferable.

  `` Aromatic heterocyclic compounds '' are oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole, etc. A compound in which the ring itself exhibits aromaticity and a heterocyclic ring such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, and benzopyran itself does not exhibit aromaticity, but the aromatic ring is condensed to the heterocyclic ring. Means a compound.

  The number of carbon atoms of the monovalent heterocyclic group is usually 2 to 60, preferably 4 to 20, not including the number of carbon atoms of the substituent.

  The monovalent heterocyclic group may have a substituent, for example, thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidinyl group, quinolinyl group, isoquinolinyl group, pyrimidinyl group, triazinyl group, and these And a group in which the hydrogen atom in the group is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or the like.

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

  The “amino group” may have a substituent, and a substituted amino group is preferable. As a substituent which an amino group has, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group is preferable.

  Examples of the substituted amino group include a dialkylamino group, a dicycloalkylamino group, and a diarylamino group.

  Examples of the amino group include dimethylamino group, diethylamino group, diphenylamino group, bis (4-methylphenyl) amino group, bis (4-tert-butylphenyl) amino group, bis (3,5-di-tert- Butylphenyl) amino group.

  The “alkenyl group” may be linear or branched. The number of carbon atoms of a linear alkenyl group is 2-30 normally without including the carbon atom number of a substituent, Preferably it is 3-20. The number of carbon atoms of the branched alkenyl group is usually 3 to 30, and preferably 4 to 20, not including the number of carbon atoms of the substituent.

  The number of carbon atoms of the “cycloalkenyl group” is usually 3 to 30, preferably 4 to 20, not including the number of carbon atoms of the substituent.

  The alkenyl group and the cycloalkenyl group may have a substituent, for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, Examples include a pentenyl group, a 1-hexynyl group, a 5-hexynyl group, a 7-octenyl group, and groups in which these groups have a substituent.

  The “alkynyl group” may be linear or branched. The carbon atom number of an alkynyl group is 2-20 normally without including the carbon atom of a substituent, Preferably it is 3-20. The number of carbon atoms of the branched alkynyl group is usually 4 to 30, preferably 4 to 20, not including the carbon atom of the substituent.

  The number of carbon atoms of the “cycloalkynyl group” is usually 4 to 30, preferably 4 to 20, not including the carbon atom of the substituent.

  The alkynyl group and cycloalkynyl group may have a substituent, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4- Examples include a pentynyl group, 1-hexenyl group, 5-hexynyl group, and groups in which these groups have a substituent.

  The “arylene group” means an atomic group remaining after removing two hydrogen atoms directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The carbon atom number of an arylene group is 6-60 normally without including the carbon atom number of a substituent, Preferably it is 6-30, More preferably, it is 6-18.

  The arylene group may have a substituent, for example, phenylene group, naphthalenediyl group, anthracenediyl group, phenanthrene diyl group, dihydrophenanthenediyl group, naphthacene diyl group, fluorenediyl group, pyrenediyl group, perylene diyl group, Examples include chrysenediyl groups and groups in which these groups have substituents, and groups represented by formula (A-1) to formula (A-20) are preferable. The arylene group includes a group in which a plurality of these groups are bonded.

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

  The carbon atom number of a bivalent heterocyclic group is 2-60 normally without including the carbon atom number of a substituent, Preferably it is 3-20, More preferably, it is 4-15.

  The divalent heterocyclic group may have a substituent, for example, pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilol, phenoxazine, phenothiazine, acridine, Divalent acridine, furan, thiophene, azole, diazole, and triazole include divalent groups obtained by removing two hydrogen atoms from hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring, and preferably Is a group represented by formula (AA-1) to formula (AA-34). The divalent heterocyclic group includes a group in which a plurality of these groups are bonded.

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

  The “crosslinking group” is a group capable of generating a new bond by being subjected to heat treatment, ultraviolet irradiation treatment, radical reaction, and the like, and preferably has formulas (B-1) to (B-17) It is group represented by either. These groups may have a substituent.

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

<Polymer compound>
The polymer compound of the present invention is a polymer compound containing a structural unit represented by the following formula (1), (2) or (3). In a preferred embodiment, the polymer compound of the present invention is a polymer compound containing a structural unit represented by the following formula (1) or (2).

  [Structural unit represented by the following formula (1), (2) or (3)]

E ¹ , E ² and E ³ represent a group represented by —NR′—, an oxygen atom or a sulfur atom. The plurality of E1, E2 and E3 may be the same or different. Among these, since the luminance half life of the light emitting element using the polymer compound of the present invention is more excellent, an oxygen atom is preferable.

  The presence of two or more groups or atoms E linking two arylene groups Ar effectively suppresses the decomposition of the triarylamine moiety. As a result, a light emitting device using the polymer compound of the present invention is It is considered that the luminance life is excellent.

  R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. Among these, since the luminance half life of the light emitting device using the polymer compound of the present invention is more excellent, an aryl group or a monovalent heterocyclic group is preferable, and these groups may have a substituent. . Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group, and a cyano group.

Further, among the polymer compounds containing the structural unit represented by the formula (1), (2) or (3), the polymer is represented by the following formula (1-1), (2-1) or (3-1). A polymer compound containing the structural unit is preferably used.

  [Structural Unit Represented by Formula (1-1), (2-1) or (3-1) below]

Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b , Ar ^2c , Ar ^3a , Ar ^3b and Ar ^3c each independently represent an aromatic hydrocarbon group or a heterocyclic group, and these groups are substituents You may have. A plurality of Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b , Ar ^2c , Ar ^3a , Ar ^3b and Ar ^3c may be the same or different. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group, and a cyano group.

Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b , Ar ^2c , Ar ^3a , Ar ^3b and Ar ^3c are preferable because the luminance half-life of the light-emitting element using the polymer compound of the present invention is superior. An aromatic hydrocarbon group, more preferably a benzene ring which may have a substituent, a fluorene which may have a substituent, a naphthalene ring which may have a substituent, and a substituent. It is a group obtained by removing a hydrogen atom directly bonded to a carbon atom constituting the ring from an optionally substituted phenanthrene ring or an optionally substituted dihydrophenanthrene ring, and more preferably a substituent. A group obtained by removing a hydrogen atom directly bonded to a carbon atom constituting a ring from a benzene ring optionally having a fluorene and a fluorene optionally having a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group, and a cyano group.

When Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b , Ar ^2c , Ar ^3a , Ar ^3b and Ar ^3c are heterocyclic groups, oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, Carbon atoms constituting the ring from the rings of furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole, dibenzothiophene, dibenzofuran, phenoxazine, phenothiazine, dibenzoborol, dibenzosilol and benzopyran A group in which a hydrogen atom directly bonded to is removed. These rings may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group, and A cyano group is mentioned.

Furthermore, among the polymer compounds containing the structural unit represented by the formula (1-1), (2-1) or (3-1), the following formulas (1-2), (2-2) or ( The polymer compound containing the structural unit represented by 3-2) is preferable.

  [Structural unit represented by the following formula (1-2), (2-2) or (3-2)]

3A, 3B and 3C each represent an integer of 0 to 3. 3A, 3B and 3C are preferably 0 or 1 because they are simple in synthesis.

R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group, and a cyano group. R ¹ , R ² and R ³ are preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, more preferably an alkyl group, since the luminance half life of the light emitting device using the polymer compound of the present invention is excellent. Group, a cycloalkyl group or an aryl group, more preferably an aryl group.

Among the aryl groups, R ¹ , R ² and R ³ are monovalent groups represented by the following formula (0) because the luminance half-life of the light emitting device using the polymer compound of the present invention is excellent. Particularly preferred.

[Wherein Ar ⁰ is a hydrogen atom, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, alkenyl group, arylalkenyl group, alkynyl group, arylalkynyl group, halogen atom, acyl group, acyloxy group, amide group It represents a substituent represented by a monovalent heterocyclic group, heterocyclic oxy group, carboxyl group, nitro group or cyano group. However, a plurality of Ar ⁰ may be the same as or different from each other, and at least two of Ar ⁰ are aryl groups. These groups may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group, and a cyano group. * Represents a bond with an adjacent carbon atom. ]

Among the monovalent groups represented by the formula (0), R ¹ , R ² and R ³ are excellent in the luminance half life of the light emitting device using the polymer compound of the present invention. Is particularly preferred.

[Wherein, R ⁴ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group, and a cyano group.
a represents an integer of 0 to 3.
A plurality of R ⁴ and a may be the same or different.
* Represents a bond with an adjacent carbon atom. ]

a is preferably 1 or 2 because it is simple in synthesis.

R ⁴ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, more preferably an alkyl group, a cycloalkyl group, or an aryl group because the luminance lifetime of the light-emitting device using the polymer compound of the present invention is excellent. Group, more preferably an aryl group. These groups may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group, and a cyano group.

Among the monovalent groups represented by the above formula (0-1), R ¹ , R ² and R ³ are excellent in luminance half life of the light emitting device using the polymer compound of the present invention. -2) is particularly preferable.

[Wherein R ⁵ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group, and a cyano group.
b represents an integer of 0 to 3.
The plurality of R ⁵ and b may be the same or different.
* Represents a bond with an adjacent carbon atom. ]

b is preferably 1 or 2 because it is simple in synthesis.

R ⁵ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, more preferably an alkyl group, a cycloalkyl group, or an aryl group because the luminance lifetime of the light-emitting device using the polymer compound of the present invention is excellent. A group, more preferably an alkyl group or a cycloalkyl group. These groups may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group, and a cyano group.

Among alkyl groups, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isoamyl group, 2-ethylbutyl group, hexyl group, heptyl group, octyl group, 2- Ethylhexyl group, 3-propylheptyl group, decyl group, 3,7-dimethyloctyl group, 2-ethyloctyl group, 2-hexyldecyl group or dodecyl group are preferable, methyl group, ethyl group, propyl group, isopropyl group, butyl Group, isobutyl group, tert-butyl group, pentyl group, isoamyl group, 2-ethylbutyl group, hexyl group, heptyl group, octyl group or 2-ethylhexyl group are more preferable, methyl group, ethyl group, propyl group, isopropyl group, A butyl group, isobutyl group, and tert-butyl group are particularly preferred.

  The total content of the structural units represented by the formula (1), (2) or (3) is excellent in the stability of the polymer compound of the present invention. Is preferably 0.1 to 50 mol%, more preferably 0.1 to 50 mol%, and still more preferably 0.1 to 20 mol%.

  In consideration of the solubility of the polymer compound in the organic solvent, the total content of the structural units represented by the formula (1), (2), or (3) is included in the polymer compound. It is 0.1-15 mol% with respect to the total content of a unit, Preferably it is 0.1-10 mol%, More preferably, it is 0.1-5 mol%. When the total content of the structural units represented by the formula (1), (2) or (3) exceeds 15 mol% with respect to the total content of the structural units contained in the polymer compound, Solubility in solvents may be reduced.

The polymer compound of the present invention has a number average molecular weight of 1 × 10 ⁴ to 2 × 10 ⁵ , preferably 1.5 × 10 ⁴ to 1 × 10 ⁵ , more preferably 2 × 10 ^{4 to} 5 × 10 ⁵ . . When the number average molecular weight of the polymer compound of the present invention exceeds 2 × 10 ⁵ , the solubility of the polymer compound in an organic solvent may be lowered.

Examples of the structural unit represented by the formula (1), (2) or (3) include structural units represented by the formula (1-a) to the formula (1-aa) shown in Table 1. , Formula (1-a), Formula (1-c), Formula (1-d), Formula (1-j), Formula (1-l), Formula (1-m), Formula (1-s), The structural unit represented by the formula (1-u) and the formula (1-v) is preferable, and the formula (1-c), the formula (1-d), the formula (1-l), the formula (1-m), The structural unit represented by Formula (1-u) or Formula (1-v) is more preferable, and the structural unit represented by Formula (1-d), Formula (1-m), or Formula (1-v) is more preferable. Particularly preferred. These may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group, and a cyano group.

When the polymer compound of the present invention is a polymer compound containing a structural unit represented by the formula (1), only one kind of the structural unit represented by the formula (1) is contained in the polymer compound. It may be included and two or more kinds may be included.
When the polymer compound of the present invention is a polymer compound containing a structural unit represented by formula (2), only one type of structural unit represented by formula (2) is contained in the polymer compound. It may be included and two or more kinds may be included.
When the polymer compound of the present invention is a polymer compound containing a structural unit represented by the formula (3), only one kind of the structural unit represented by the formula (3) is contained in the polymer compound. It may be included and two or more kinds may be included.

[Other structural units]
Since the polymer compound of the present invention is excellent in stability of the polymer compound, it is further represented by a structural unit represented by the formula (Y) (a structural unit represented by the formula (1), represented by the formula (2). And the structural unit represented by the formula (3) are preferably included.

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

  Since the polymer compound of the present invention is more excellent in luminous efficiency of a light emitting device using the polymer compound of the present invention, the structural unit represented by the formula (1), the structural unit represented by the formula (2), and the formula The two bonds in at least one type of structural unit selected from the group consisting of the structural unit represented by (3) are polymer compounds that are respectively bonded to the structural unit represented by the formula (Y). preferable.

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

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

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

Examples of the divalent group in which at least one arylene group represented by Ar ^Y1 and at least one divalent heterocyclic group are directly bonded include groups represented by the following formulas, Qi may have a substituent.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of the structural unit represented by the formula (Y) include structural units represented by the formulas (Y-11) to (Y-60).

The structural unit represented by the formula (Y), in which Ar ^Y1 is an arylene group, is included in the polymer compound because the light-emitting element using the polymer compound of the present invention has better luminous efficiency. Preferably it is 0.5-80 mol% with respect to the total content of a structural unit, More preferably, it is 30-60 mol%.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The divalent group in which at least one arylene group represented by Ar ^X2 and Ar ^X4 and at least one divalent heterocyclic group are directly bonded to each other is at least represented by Ar ^Y1 in the formula (Y) Examples thereof include the same divalent group in which one kind of arylene group and at least one kind of divalent heterocyclic group are directly bonded.

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

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

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

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

  Since the structural unit represented by the formula (X) is excellent in hole transportability, it is preferably 0.1 to 50 mol%, more preferably 1 to 50 mol%, based on the total amount of structural units contained in the polymer compound. It is 30 mol%, More preferably, it is 2-20 mol%.

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

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

  Examples of the polymer compound of the present invention include polymer compounds P-1 to P-12 shown in Table 1. Here, the “other structural unit” means a structural unit other than the structural units represented by Formula (1), Formula (2), Formula (3), Formula (X), and Formula (Y).

[In the table, p, q, r, s, t, and u represent the molar ratio of each structural unit. p + q + r + s + t + u = 100 and 70 ≦ p + q + r + s + t ≦ 100. The other structural unit means a structural unit other than the structural units represented by Formula (1), Formula (2), Formula (3), Formula (X), and Formula (Y). ]

  Examples and preferred ranges of the structural units represented by the formula (1), formula (2), formula (3), formula (X) and formula (Y) in the polymer compounds P-1 to P-12 are described above. It is as follows.

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

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

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

The polymer compound of the present invention is, for example,
At least one compound selected from a compound represented by formula (1M) and a compound represented by formula (2M);
Condensation with another compound (for example, at least one compound selected from the group consisting of a compound represented by formula (1Mc), a compound represented by formula (2Mc), and a compound represented by formula (3Mc)) It can be produced by polymerization. In the present specification, the compounds used for the production of the polymer compound of the present invention are sometimes collectively referred to as “raw material monomers”.

[Where:
E ¹ and E ² represent a group represented by —NR′—, an oxygen atom, or a sulfur atom. The plurality of E ¹ and E ² may be the same or different.
Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b and Ar ^2c each independently represent an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent. A plurality of Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b and Ar ^2c may be the same or different.
R ¹ and R ² 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.
3A and 3B each represent an integer of 0 to 3.
In the formula, Ar ^Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded. The group may have a substituent.
a ^X1 and a ^X2 each independently represent an integer of 0 or more.
Ar ^X1 and Ar ^X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
Ar ^X2 and Ar ^X4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other. And these groups may have a substituent.
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
Z ^{1 to} Z ¹⁰ each independently represent a group selected from the group consisting of the substituent group A and the substituent group B. ]

For example, when Z ^{1 to} Z ⁴ and Z ^{7 to} Z ¹⁰ are groups selected from the substituent group A, Z ⁵ and Z ⁶ select groups selected from the substituent group B.

For example, when Z ^{1 to} Z ⁴ and Z ^{7 to} Z ¹⁰ are groups selected from the substituent group B, Z ⁵ and Z ⁶ select groups selected from the 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. A group represented by:

<Substituent group B>
-B in (OR ^C2) ₂ (wherein, R ^C2 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, these groups may have a substituent. There exist a plurality of R ^C2 is Groups which may be the same or different and may be bonded to each other to form a ring together 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 (wherein, R ^C3 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, these groups may have a substituent. More existing R ^C3 is The groups may be the same or different, and may be bonded to each other to form a ring together with the tin atoms to which they are bonded.

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

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

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

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

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

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

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

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

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

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

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

<Compound>
Next, the compound of the present invention will be described.

  The compound of the present invention is a compound represented by the formula (1M) or (2M), and is useful as a raw material monomer for the polymer compound of the present invention.

[Where:
E ¹ , E ² , Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b , Ar ^2c , R ¹ , R ² , 3A, 3B, Z ¹ , Z ² , Z ³ and Z ⁴ have the same meaning as above. Represents. ]

  When the compound represented by the formula (1M) and the compound represented by the formula (2M) are used for the production of the polymer compound of the present invention, the luminous efficiency of the light emitting device using the polymer compound of the present invention is high. Since it is more excellent, it is preferable that they are a compound represented by Formula (1M-1) and a compound represented by Formula (2M-1), respectively. The compound represented by the formula (1M-2) is preferably a compound represented by the formula (2M-2).

[Where:
Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b , Ar ^2c , R ¹ , R ² , 3A, 3B, Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]

[Where:
R ¹ , R ² , 3A, 3B, Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]

<Method for producing compound>
Next, the manufacturing method of the compound of this invention is demonstrated.

  The compound represented by the formula (1M-2), which is a compound of the present invention, can be produced, for example, by the method described in the following scheme.

[Where:
Z ^a represents a group selected from the substituent group A.
Z ^b represents a group selected from the substituent group B.
Z ^c and ^{Z d} represents a group selected from the substituent group A.
R ¹ represents the same meaning as described above. ]

  In the above scheme, first, a compound represented by the formula (1M-2-st0) (hereinafter referred to as “compound (1M-2-st0)”) is represented by the formula (1M-2 -St1) (hereinafter referred to as "compound (1M-2-st1)") is obtained.

In the above scheme, then, the compound (1M-2-st1), By using a known reaction, the compound of the formula was introduced ^{Z a (1M-2-st2} ) ( hereinafter "compounds (1M -2-st2) ") is obtained.

  In the above scheme, the compound (1M-2-st2) is then reacted with an acid to dealkylate the compound represented by the formula (1M-2-st3) (hereinafter referred to as “compound (1M-2-st3)”. st3) ") is obtained.

  Next, in the above scheme, the compound (1M-2-st3) is converted to a compound represented by the formula (1M-2-st4) (hereinafter, “compound (1M-2-st4)” by using a known reaction. ") Is obtained.

  Next, in the above scheme, a compound represented by the formula (1M-2-st5) (hereinafter, “compound (1M-2-st5)” is obtained by a coupling reaction between the compound (1M-2-st4) and a predetermined compound. ) ") Is obtained. Examples of the coupling reaction used include Suzuki coupling, Kumada-Tamao coupling, Negishi coupling, and Stille coupling.

Next, in the above scheme, the compound (1M-2-st5) is represented by the formula (1M-2) by using a known reaction (hereinafter referred to as “compound (1M-2)”). Is obtained. Z ^c and Z ^d directly bonded to the carbon atom of the compound (1M-2) can be converted into a group selected from the substituent group B using a known reaction.

  The compound represented by the formula (2M-2) which is the compound of the present invention can be produced, for example, by the method described in the following scheme.

[Where:
Z ^e represents a group selected from the substituent group A.
Z ^f represents a group selected from the substituent group B.
Z ^g and Z ^h represent a group selected from the substituent group A.
R ² represents the same meaning as described above. ]

  In the above scheme, first, a compound represented by the formula (2M-2-st1) (hereinafter, “compound (2M-2-st1)” is obtained by a coupling reaction between the compound (2M-2-st0) and a predetermined compound. ") Is obtained. Examples of the coupling reaction used include Suzuki coupling, Kumada-Tamao coupling, Negishi coupling, and Stille coupling.

  Next, in the above scheme, the compound (2M-2-st1) is converted into a compound represented by the formula (2M-2-st2) (hereinafter, “compound (2M-2-st2)” by using a known reaction. ") Is obtained.

Next, in the above scheme, the compound (2M-2-st2) is converted into a compound represented by the formula (2M-2-st3) (hereinafter referred to as “compound (2M-2-st3)” by using a known reaction. ") Is obtained. Z ^g and Z ^h directly bonded to the carbon atom of the compound (2M-2-st3) can be converted into a group selected from the substituent group B using a known reaction.

  Next, in the above scheme, the compound (2M-2-st3) is reacted with an acid to dealkylate the compound represented by the formula (2M-2-st4) (hereinafter referred to as “compound (2M-2-st4)”. st4) ") is obtained.

  Next, in the above scheme, the compound (2M-2-st4) is represented by the formula (2M-2) by using a known reaction (hereinafter referred to as “compound (2M-2)”). Is obtained.

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

  The polymer compound of the present invention is used as a hole transport material, a hole injection material, an electron transport material, an electron injection material, or a light emitting material for producing a light emitting device. In a preferred embodiment, the polymer compound of the present invention is used as a light emitting material for producing a light emitting device. Depending on the respective uses of the polymer compound of the present invention, the composition of the present invention may contain functional materials or additives other than the polymer compound of the present invention.

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

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

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

[Hole transport material]
When the polymer compound of the present invention is used as a hole transport material, the composition of the present invention may contain a hole transport material other than the polymer compound of the present invention. The hole transport material is classified into a low molecular compound and a high molecular compound, and a high molecular compound is preferable, and a high molecular compound having a crosslinking group is more preferable.

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

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

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

[Electron transport materials]
When the polymer compound of the present invention is used as an electron transport material, the composition of the present invention may contain an electron transport material other than the polymer compound of the present invention. Electron transport materials are classified into low molecular compounds and high molecular compounds. The electron transport material may have a crosslinking group.

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

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

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

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

[Hole injection material and electron injection material]
When the polymer compound of the present invention is used as a hole injection material or an electron injection material, the composition of the present invention may contain a hole injection material or an electron injection material other than the polymer compound of the present invention. . The hole injection material and the electron injection material are each classified into a low molecular compound and a high molecular compound. The hole injection material and the electron injection material may have a crosslinking group.

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

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

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

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

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

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

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

[Luminescent material]
When the polymer compound of the present invention is used as a light emitting material, the composition of the present invention may contain a light emitting material other than the polymer compound of the present invention. Luminescent materials are classified into low molecular compounds and high molecular compounds. The light emitting material may have a crosslinking group.

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

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

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

  As the triplet light-emitting complex, an iridium complex such as a metal complex represented by the formulas Ir-1 to Ir-3 is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The metal complex represented by the formula Ir-1 is preferably a metal complex represented by the formulas Ir-11 to Ir-13. The metal complex represented by the formula Ir-2 is preferably a metal complex represented by the formula Ir-21. The metal complex represented by the formula Ir-3 is preferably a metal complex represented by the formula Ir-31 to Ir-33.

[Wherein, D represents a group represented by the formula (DA). n _D2 represents 1 or 2. ]

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

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

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

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

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

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

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

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

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

  The film is suitable as a light emitting layer in a light emitting element.

  The film is made of an ink, for example, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method. , Flexographic printing, offset printing, ink jet printing, capillary coating, and nozzle coating.

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

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

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

  The light emitting element has a light emitting layer between an anode and a cathode. The light-emitting element of the present invention preferably has at least one of a hole injection layer and a hole transport layer between the anode and the light-emitting layer from the viewpoint of hole injection and hole transport. From the viewpoint of injection property and electron transport property, it is preferable to have at least one of an electron injection layer and an electron transport layer between the cathode and the light emitting layer.

  As a material for the hole transport layer, the electron transport layer, the light emitting layer, the hole injection layer, and the electron injection layer, in addition to the polymer compound of the present invention, the above-described hole transport material, electron transport material, and light emission, respectively. Examples include materials, hole injection materials, and electron injection materials.

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

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

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

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

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

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

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

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

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

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

Liquid chromatograph mass spectrometry (LC-MS) was performed by the following method.
The measurement sample was dissolved in chloroform or THF to a concentration of about 2 mg / mL, and about 1 μL was injected into LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD). The LC-MS mobile phase was used while changing the ratio of acetonitrile and THF, and was allowed to flow at a flow rate of 0.2 mL / min. The column used was L-column 2 ODS (3 μm) (manufactured by Chemicals Evaluation and Research Institute, inner diameter: 2.1 mm, length: 100 mm, particle size 3 μm).

NMR measurement was performed by the following method.
5 to 10 mg of a measurement sample was dissolved in about 0.5 mL of deuterated chloroform (CDCl ₃ ), deuterated tetrahydrofuran (THF-d ₈ ), or methylene chloride (CD ₂ Cl ₂ ), and an NMR apparatus (Varian, Inc. The product name was measured using a product name: MERCURY 300).

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

  <Synthesis Example 1> Synthesis of Compound 1-2

化合物１−１ 化合物１−２

Compound 1-1 Compound 1-2

  After making the inside of the reaction vessel equipped with a stirrer a nitrogen gas atmosphere, compound 1-1 (15.8 g), orthoiodoanisole (63.2 g), Cu powder (24.9 g), potassium carbonate (67.8 g) And orthodichlorobenzene (160 mL) were added, heated to 180 ° C., and stirred for 100 hours. After cooling the obtained reaction liquid to room temperature, toluene (480 mL) was added, it heated at 60 degreeC, and it filtered with the filter which pre-coated celite. The obtained filtrate was concentrated, and the obtained residue was purified by recrystallization from toluene / methanol to obtain 25.4 g of compound 1-2 as a white solid.

  Compound 1-2 was used as a raw material for compound 1-3 as a compound having the above structure.

  <Synthesis Example 2> Synthesis of Compound 1-3

  After making the inside of the reaction vessel equipped with a stirrer a nitrogen gas atmosphere, compound 1-2 (25.2 g), chloroform (1.0 L) and N-bromosuccinimide (13.1 g) were added and cooled to −10 ° C. And stirred for 4 hours. A 10% aqueous sodium sulfite solution (18.6 g) was added to the obtained reaction solution, the temperature was raised to room temperature, water and toluene were added, and the mixture was stirred at room temperature. Thereafter, the aqueous layer was separated and the organic layer was washed. The obtained organic layer was concentrated to obtain a crude product. The obtained residue was purified by recrystallization from toluene / isopropyl alcohol to obtain 23.6 g of compound 1-3 as a white solid.

  Compound 1-3 was used as a raw material for compound 1-4 as a compound having the above structure.

  <Synthesis Example 3> Synthesis of Compound 1-4

化合物１−３ 化合物１−４

Compound 1-3 Compound 1-4

  After making the inside of the reaction vessel equipped with a stirrer a nitrogen gas atmosphere, the reaction vessel was cooled to −78 ° C., Compound 1-3 (10.0 g), dichloromethane (400 mL) and 1M tribromoborane dichloromethane solution (60 mL) were added, Stir for 1 hour. Then, it heated up to room temperature and stirred for further 4 hours. After adding water to the obtained reaction solution, the aqueous layer was separated and the organic layer was washed. After filtering the obtained organic layer, the filtrate was concentrated to obtain a product. The same operation was performed once again to obtain 12.0 g of compound 1-4 as a light purple oil.

  Compound 1-4 was used as a raw material for compound 1-5 as a compound having the above structure.

  <Synthesis Example 4> Synthesis of Compound 1-5

化合物１−４ 化合物１−５

Compound 1-4 Compound 1-5

  After making the inside of the reaction vessel equipped with a stirrer a nitrogen gas atmosphere, Compound 1-4 (10.0 g), N, N′-dimethylformamide (300 mL) and potassium carbonate (10.5 g) were added, and the temperature was increased to 100 ° C. After heating, the mixture was stirred for 5 hours. Then, it cooled to room temperature and further stirred for 1 hour. Water and toluene were added, the aqueous layer was separated, and the organic layer was washed. Magnesium sulfate was added to the obtained organic layer, followed by filtration and concentration to obtain 8.24 g of compound 1-5 as a white solid.

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 6.47-6.53 (2H), 6.73-6.79 (1H), 6.88-7.28 (7H).

  <Synthesis Example 5> Synthesis of Compound 1-6

化合物１−５ 化合物１−６

Compound 1-5 Compound 1-6

After making the inside of the reaction vessel a nitrogen gas atmosphere, Compound 1-5 (5.88 g), Tris (dibenzylideneacetone) dipalladium (0) (76.4 mg), Compound (A) (14.9 g), 2- Dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (144 mg), 13 wt% tetraethylammonium hydroxide aqueous solution (40 g) and toluene (180 mL) were added, and the mixture was stirred at 90 ° C. for 1 hour. After cooling the obtained reaction liquid to room temperature, hexane was added and the obtained organic layer was washed with ion-exchanged water and dried over anhydrous magnesium sulfate. The obtained mixture was filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a solid. The obtained solid was purified by a silica gel column using toluene / hexane as a developing solvent to obtain 16.3 g of compound 1-6 as a pale yellow solid.

LC-MS (APCI, positive): [M + H] ⁺ 1031
¹ H-NMR (THF-d ₈ , 300 MHz): δ (ppm) = 1.43 (36H), 6.61 (2H), 6.80-8.20 (33H).

  Example 1 Synthesis of Compound 1-7

化合物１−６ 化合物１−７

Compound 1-6 Compound 1-7

After making the inside of reaction container nitrogen atmosphere, compound 1-6 (8.24g), trimethylbenzylammonium tribromide (18.7g), and chloroform (330mL) were added, and it stirred at room temperature for 200 hours. A 10% aqueous sodium sulfite solution (18.6 g) was added to the resulting reaction solution, water and hexane were added, the aqueous layer was separated, and the organic layer was washed. The obtained organic layer was concentrated to obtain a crude product. The same operation was repeated once more. The obtained residue was repulp washed with acetonitrile to obtain 7.40 g of Compound 1-7 as a pale yellow solid.

LC-MS (APCI, positive): [M + H] ⁺ 1186
¹ H-NMR (THF-d ₈ , 300 MHz): δ (ppm) = 1.41 (36H), 6.82 (2H), 7.16-7.24 (2H), 7.38-7.64 (12H), 7.69-7.78 (8H), 7.90 (2H, m), 8.02 (4H), 8.07 (2H) 8.15 (1H).

  <Synthesis Example 6> Synthesis of Compound 2-2

化合物２−１ 化合物２−２

Compound 2-1 Compound 2-2

The reaction vessel was filled with a nitrogen gas atmosphere, then compound 2-1 (4.00 g), tris (dibenzylideneacetone) dipalladium (0) (129 mg), compound (A) (16.7 g), 2-dicyclohexylphos Fino-2 ′, 6′-dimethoxybiphenyl (199 mg), 13 wt% tetraethylammonium hydroxide aqueous solution (42 g) and toluene (160 mL) were added, and the mixture was stirred at 90 ° C. for 6 hours. After cooling the obtained reaction liquid to room temperature, hexane was added and the obtained organic layer was washed with ion-exchanged water and dried over anhydrous magnesium sulfate. The obtained mixture was filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a solid. The obtained solid was purified by a silica gel column using toluene / hexane as a developing solvent. Then, the obtained solid was dissolved in toluene / heptane, stirred in the presence of activated carbon, and filtered through a filter pre-coated with celite. The obtained filtrate was concentrated, and the obtained residue was purified by recrystallization using toluene / isopropyl alcohol to obtain 12.0 g of compound 2-2 as a solid.

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 1.41 (36H), 3.81 (2H), 7.22 (2H), 7.52 to 7.85 (24H), 7. 92 (1H).

  <Synthesis Example 7> Synthesis of Compound 2-3

  After making the inside of the reaction vessel equipped with a stirrer a nitrogen gas atmosphere, compound 2-2 (11.0 g), orthoiodoanisole (29.1 g), Cu powder (7.89 g), potassium carbonate (8.58 g) And orthodichlorobenzene (55 mL) were added, and the mixture was heated to 180 ° C. and stirred for 9 hours. After cooling the obtained reaction liquid to room temperature, monochlorobenzene was added and it filtered with the filter which pre-coated silica gel. The obtained filtrate was concentrated and repulp washed with monochlorobenzene / acetonitrile. The obtained residue was purified by recrystallization from monochlorobenzene to obtain 11.8 g of compound 2-3 as a white solid.

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 1.38 (36H), 3.63 (6H), 6.85-7.09 (8H), 7.21 (2H), 7. 49-7.85 (24H), 7.95 (1H).
LC-MS (APCI, positive): [M + H] ⁺ 1099

  <Synthesis Example 8> Synthesis of Compound 2-4

化合物２−３ 化合物２−４

Compound 2-3 Compound 2-4

  The reaction vessel equipped with a stirrer was placed in a nitrogen gas atmosphere, cooled to 0 ° C., compound 2-3 (12.0 g), chloroform (600 mL) and N-bromosuccinimide (3.89 g) were added, For 12 hours. A 10% aqueous sodium sulfite solution (6.88 g) was added to the resulting reaction solution, water was added, the aqueous layer was separated, and the organic layer was washed. The obtained organic layer was concentrated to obtain a crude product. The obtained residue was taken out by recrystallization using toluene / acetonitrile / ethyl acetate to obtain 11.8 g of compound 2-4 as a white solid.

LC-MS (APCI, positive): [M + H] ⁺ 1254

  <Synthesis Example 9> Synthesis of Compound 2-5

化合物２−４ 化合物２−５

Compound 2-4 Compound 2-5

  The reaction vessel equipped with a stirrer was filled with a nitrogen gas atmosphere, cooled to −20 ° C., compound 2-4 (11.8 g), dichloromethane (140 mL) and 1M tribromoborane dichloromethane solution (24 mL) were added, Stir for 0.5 hour. Then, it heated up to room temperature and further stirred for 7 hours. Water / chloroform was added to the resulting reaction solution, the aqueous layer was separated, the organic layer was washed, and dried over anhydrous magnesium sulfate. The obtained mixture was filtered, and the obtained filtrate was concentrated under reduced pressure to obtain a solid. The obtained solid was purified by a silica gel column using toluene / hexane as a developing solvent to obtain 11.8 g of compound 2-5 as a white solid.

  Compound 2-5 was not further purified, and was used as a raw material for compound 2-6 as a compound having the above structure.

  Example 2 Synthesis of Compound 2-6

化合物２−５ 化合物２−６

Compound 2-5 Compound 2-6

  After making the inside of the reaction vessel equipped with a stirrer a nitrogen gas atmosphere, compound 2-5 (11.8 g), N, N′-dimethylformamide (200 mL) and potassium carbonate (4.25 g) were added, and the temperature was increased to 100 ° C. After heating, the mixture was stirred for 1.5 hours. Then, it cooled to room temperature, water and toluene were added, the water layer was isolate | separated, and the organic layer was wash | cleaned. Magnesium sulfate was added to the obtained organic layer, followed by filtration and concentration to obtain a crude product. The obtained residue was purified by recrystallization using toluene / isopropyl alcohol to obtain 9.00 g of compound 2-6 as a pale yellow solid.

LC-MS (APCI, positive): [M + H] ⁺ 1186
¹ H-NMR (THF-d ₈ , 300 MHz): δ (ppm) = 1.41 (36H), 7.10 to 7.26 (6H), 7.31 to 7.40 (2H), 7.55 (8H), 7.74 (8H), 7.90 (2H), 7.99-8.06 (6H), 8.15 (1H).

  <Example 3> Synthesis of polymer compound 1

Compound M1 was synthesized according to the method described in JP2011-174061A.
Compound M2 was synthesized according to the method described in JP 2006-257094 A.

(Step 1) After making the inside of the reaction vessel an inert gas atmosphere, Compound M1 (1.4 g), Compound M2 (1.0 g), Compound 1-7 (0.24 g), dichlorobis (tris-o-methoxyphenyl) Phosphine) palladium (1.8 mg) and toluene (40 mL) were added and heated to 105 ° C.

(Step 2) Then, a 10 wt% tetraethylammonium hydroxide aqueous solution (31 mL) was added dropwise thereto and refluxed for 4 hours.

(Step 3) Thereafter, phenylboronic acid (98 mg) and dichlorobis (tris-o-methoxyphenylphosphine) palladium (1.8 mg) were added thereto and refluxed for 17 hours.

(Step 4) After cooling, the reaction solution was washed twice with a 10 wt% aqueous hydrochloric acid solution, twice with a 3 wt% aqueous ammonia solution and twice with water, and the resulting solution was added dropwise to methanol. The obtained precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.5 g of polymer compound 1. The Mn of the polymer compound 1 was 3.4 × 10 ⁴ and the Mw was 8.9 × 10 ⁴ .

  The theoretical value obtained from the amount of the raw material used for the polymer compound 1 includes a structural unit derived from the compound M1, a structural unit derived from the compound M2, and a structural unit derived from the compound 1-7. It is a copolymer composed of a molar ratio of 50: 45: 5.

  <Example 4> Synthesis of polymer compound 2

(Step 1) After making the inside of the reaction vessel an inert gas atmosphere, Compound M1 (1.4 g), Compound M2 (1.0 g), Compound 2-6 (0.25 g), dichlorobis (tris-o-methoxyphenyl) Phosphine) palladium (1.8 mg) and toluene (40 mL) were added and heated to 105 ° C.

(Step 2) Then, a 10 wt% tetraethylammonium hydroxide aqueous solution (31 mL) was added dropwise thereto and refluxed for 3 hours.

(Step 3) Thereafter, phenylboronic acid (98 mg) and dichlorobis (tris-o-methoxyphenylphosphine) palladium (1.8 mg) were added thereto and refluxed for 19 hours.

(Step 4) After cooling, the reaction solution was washed twice with a 10 wt% aqueous hydrochloric acid solution, twice with a 3 wt% aqueous ammonia solution and twice with water, and the resulting solution was added dropwise to methanol. The obtained precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.3 g of polymer compound 2. The Mn of the polymer compound 2 was 3.0 × 10 ⁴ and the Mw was 7.9 × 10 ⁴ .

  The theoretical value obtained from the amount of the raw material used for polymer compound 2 is that the structural unit derived from compound M1, the structural unit derived from compound M2, and the structural unit derived from compound 2-7 are: It is a copolymer composed of a molar ratio of 50: 45: 5.

  <Comparative example 1> Synthesis of polymer compound 3

(Step 1) After making the inside of the reaction vessel an inert gas atmosphere, Compound M1 (1.4 g), Compound M2 (1.0 g), Compound M3 (0.092 g), dichlorobis (tris-o-methoxyphenylphosphine) Palladium (1.8 mg) and toluene (37 mL) were added and heated to 105 ° C.

(Step 2) Thereafter, a 10 wt% tetraethylammonium hydroxide aqueous solution (31 mL) was added dropwise thereto and refluxed for 2 hours.

(Step 3) Thereafter, phenylboronic acid (98 mg) and dichlorobis (tris-o-methoxyphenylphosphine) palladium (1.8 mg) were added thereto and refluxed for 20 hours.

(Step 4) After cooling, the reaction solution was washed twice with a 10 wt% aqueous hydrochloric acid solution, twice with a 3 wt% aqueous ammonia solution and twice with water, and the resulting solution was added dropwise to methanol. The obtained precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.3 g of polymer compound 3. The Mn of the polymer compound 3 was 3.9 × 10 ⁴ and the Mw was 1.0 × 10 ⁵ .

  The theoretical value obtained from the amount of the raw material used for the polymer compound 3 is 50: a structural unit derived from the compound M1, a structural unit derived from the compound M2, and a structural unit derived from the compound M3. It is a copolymer composed of a 45: 5 molar ratio.

  Comparative Example 2 Synthesis of polymer compound 4

(Step 1) After making the inside of the reaction vessel an inert gas atmosphere, Compound M1 (1.5 g), Compound M2 (1.0 g), Compound M4 (0.095 g), Tris-o-methoxyphenylphosphine (5. 6 mg), palladium acetate (0.9 mg) and toluene (37 mL) were added and heated to 95 ° C.

(Step 2) Thereafter, a 20 wt% tetraethylammonium hydroxide aqueous solution (6.8 mL) was dropped therein and refluxed for 3.5 hours.

(Step 3) Thereafter, 4-tert-butyl-phenylboronic acid (180 mg), tris-o-methoxyphenylphosphine (5.6 mg) and palladium acetate (0.9 mg) were added thereto, and the mixture was refluxed for 1.7 hours. I let you.

(Step 4) After cooling, the reaction solution was washed twice with a 2N aqueous hydrochloric acid solution twice, twice with a 10 wt% aqueous sodium acetate solution and twice with water, and the resulting solution was added dropwise to methanol. The obtained precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.6 g of polymer compound 4. The Mn of the polymer compound 4 was 5.9 × 10 ⁴ and the Mw was 1.4 × 10 ⁵ .

  The theoretical value obtained from the amount of the raw material used for the polymer compound 4 is 50: a structural unit derived from the compound M1, a structural unit derived from the compound M2, and a structural unit derived from the compound M4. It is a copolymer composed of a 45: 5 molar ratio.

  Comparative Example 3 Synthesis of Polymer Compound 5

(Step 1) After making the inside of the reaction vessel an inert gas atmosphere, Compound M1 (2.9 g), Compound M2 (2.0 g), Compound M5 (0.44 g), dichlorobis (triphenylphosphine) palladium (2. 8 mg) and toluene (44 mL) were added and heated to 45 ° C.

(Step 2) Thereafter, a 20 wt% tetraethylammonium hydroxide aqueous solution (13.5 mL) was dropped therein and refluxed for 11 hours.

(Step 3) Thereafter, phenylboronic acid (680 mg) and dichlorobis (triphenylphosphine) palladium (2.8 mg) were added thereto and refluxed for 4 hours.

(Step 4) After cooling, the reaction solution was washed twice with water, twice with a 3 wt% aqueous acetic acid solution and twice with water, and the resulting solution was added dropwise to methanol. The obtained precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 3.0 g of polymer compound 5. The Mn of the polymer compound 5 was 9.9 × 10 ⁴ , and the Mw was 2.7 × 10 ⁵ .

  The theoretical value obtained from the amount of the raw material used for the polymer compound 5 is 50: a structural unit derived from the compound M1, a structural unit derived from the compound M2, and a structural unit derived from the compound M5. It is a copolymer composed of a 45: 5 molar ratio.

  <Synthesis Example 10> Synthesis of Polymer Compound 6

Compound mm1 was synthesized according to the method described in JP2011-174062.
Compound mm2 was synthesized according to the method described in JP-T-2007-512249.
Compound mm3 was synthesized according to the method described in JP-A-2008-106241.

  (Step 1) in the synthesis of the polymer compound 1 is “after the inside of the reaction vessel is set to an inert gas atmosphere, the compound mm1 (2.70727 g), the compound M2 (0.2459 g), the compound mm2 (1.6509 g), Compound mm3 (0.2409 g), dichlorobis (triphenylphosphine) palladium (2.1 mg) and toluene (62 ml) were mixed and heated to 105 ° C. ”

(Step 2) in the synthesis of the polymer compound 1 was “After that, 20 wt% tetraethylammonium hydroxide aqueous solution (10 mL) was dropped therein and refluxed for 4.5 hours”.
The (step 3) in the synthesis of the polymer compound 1 is “after that, phenylboronic acid (36.6 mg) and dichlorobis (triphenylphosphine) palladium (2.1 mg) were added thereto and refluxed for 14”. Except that, 3.12 g of the polymer compound 6 was obtained in the same manner as the synthesis of the polymer compound 1. The Mn of the polymer compound 6 was 7.8 × 10 ⁴ , and the Mw was 2.6 × 10 ⁵ .

  The polymer compound 6 has a theoretical value determined from the amount of raw materials charged, a structural unit derived from the compound mm1, a structural unit derived from the compound M2, a structural unit derived from the compound mm2, and a compound mm3. The derived structural unit is a copolymer composed of a molar ratio of 50: 12.5: 30: 7.5.

<Example D1> Production and Evaluation of Light-Emitting Element D1 An anode was formed by attaching an ITO film with a thickness of 45 nm to a glass substrate by a sputtering method. A polythiophene / sulfonic acid-based hole injecting agent (trade name: AQ-1200, manufactured by Spectronics Co., Ltd.) was formed on the anode in a thickness of 35 nm by a spin coating method. A hole injection layer was formed by heating at 170 ° C. for 15 minutes.

  Polymer compound 5 was dissolved in xylene at a concentration of 0.7% by weight to prepare a xylene solution. Using this xylene solution, a film having a thickness of 20 nm was formed on the hole injection layer by spin coating, and heated on a hot plate at 180 ° C. for 60 minutes in a nitrogen gas atmosphere to thereby form a hole transport layer. Formed.

  Polymer compound 1 was dissolved in xylene at a concentration of 1.2% by weight to prepare a xylene solution. Using this xylene solution, a film having a thickness of 60 nm was formed on the hole transport layer by spin coating, and a light emitting layer was formed by heating at 150 ° C. for 10 minutes in a nitrogen gas atmosphere.

The substrate on which the light emitting layer is formed is placed in a vapor deposition machine, and the pressure is reduced to 1.0 × 10 ⁻⁴ Pa or less. Then, about 4 nm of sodium fluoride is formed on the light emitting layer as a cathode, and then aluminum is formed thereon. About 80 nm was deposited. Then, the light emitting element D1 was produced by sealing using a glass substrate.

As a result of applying a forward voltage to the light-emitting element D1 and measuring the luminance half-life, it was 64 hours. Here, the luminance half life, the luminance of 5000 cd / ^{m 2,} which means the time until reduced to 2500 cd / ^{m 2.}

<Example D2> Production and Evaluation of Light-Emitting Element D2 A light-emitting element D2 was produced in the same manner as in Example D1, except that the polymer compound 2 was used instead of the polymer compound 1 in Example D1.

As a result of applying a forward voltage to the light emitting element D2 and measuring the luminance half life, it was 68 hours. Here, the luminance half life, the luminance of 5000 cd / ^{m 2,} which means the time until reduced to 2500 cd / ^{m 2.}

<Comparative Example CD1> Production and Evaluation of Light-Emitting Element CD1 A light-emitting element CD1 was produced in the same manner as in Example D1, except that polymer compound 3 was used instead of polymer compound 1 in Example D1.

As a result of applying a forward voltage to the light emitting device CD1 and measuring the luminance half life, it was 2 hours. Here, the luminance half life, the luminance of 5000 cd / ^{m 2,} which means the time until reduced to 2500 cd / ^{m 2.}

<Comparative Example CD2> Production and Evaluation of Light-Emitting Element CD2 A light-emitting element CD2 was produced in the same manner as in Example D1, except that polymer compound 4 was used instead of polymer compound 1 in Example D1.

As a result of applying a forward voltage to the light emitting device CD2 and measuring the luminance half life, it was 9 hours. Here, the luminance half life, the luminance of 5000 cd / ^{m 2,} which means the time until reduced to 2500 cd / ^{m 2.}

<Comparative Example CD3> Production and Evaluation of Light-Emitting Element CD3 A light-emitting element CD3 was produced in the same manner as in Example D1, except that polymer compound 5 was used instead of polymer compound 1 in Example D1.

As a result of applying a forward voltage to the light emitting device CD3 and measuring the luminance half life, it was 0.1 hour. Here, the luminance half life, the luminance of 5000 cd / ^{m 2,} which means the time until reduced to 2500 cd / ^{m 2.}

  Comparison of the light-emitting element D1 and the light-emitting element D2 with the light-emitting element CD1, the light-emitting element CD2, and the light-emitting element CD3 shows that the light-emitting element manufactured using the polymer compound of the present invention has excellent luminance half-life. It was done.

Claims (9)

The high molecular compound containing the structural unit represented by following formula (1), (2) or (3).

[Where:
E ¹ , E ² and E ³ represent a group represented by —NR′—, an oxygen atom or a sulfur atom. The plurality of E ¹ , E ² and E ³ may be the same or different.
R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent.
Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b , Ar ^2c , Ar ^3a , Ar ^3b and Ar ^3c each independently represent an aromatic hydrocarbon group or a heterocyclic group, and these groups are substituents You may have. A plurality of Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b , Ar ^2c , Ar ^3a , Ar ^3b and Ar ^3c may be the same or different.
R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
3A, 3B and 3C each represent an integer of 0 to 3. ] E ¹ , E ² or E ^{3 in the} formula (1), (2) or (3) is an oxygen atom and is represented by the following formula (1-1), (2-1) or (3-1), respectively. The polymer compound according to claim 1, comprising a structural unit.

The polymer compound according to claim ¹ , wherein Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b , Ar ^2c , Ar ^3a , Ar ^3b, and Ar ^3c are benzene rings. Furthermore, the high molecular compound as described in any one of Claims 1-3 containing the structural unit represented by Formula (Y).

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

[Where:
E ¹ and E ² represent a group represented by —NR′—, an oxygen atom, or a sulfur atom. The plurality of E ¹ and E ² may be the same or different.
Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b and Ar ^2c each independently represent an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent. A plurality of Ar ^1a , Ar ^1b , Ar ^1c , Ar ^2a , Ar ^2b and Ar ^2c may be the same or different.
R ¹ and R ² 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.
3A and 3B each represent an integer of 0 to 3.
Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a group selected from the following substituent group A or a group selected from substituent group B. ]
<Substituent group A>
Chlorine atom, bromine atom, iodine atom, —O—S (═O) ₂ R ^C1 (wherein R ^C1 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups have a substituent. A group represented by:
<Substituent group B>
-B in (OR ^C2) ₂ (wherein, R ^C2 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, these groups may have a substituent. There exist a plurality of R ^C2 is Groups which may be the same or different and may be linked to each other to form a ring structure together with the oxygen atoms to which they are bonded.
A group represented by —BF ₃ Q ′ (wherein Q ′ represents Li, Na, K, Rb or Cs);
-A group represented by MgY '(wherein Y' represents a chlorine atom, a bromine atom or an iodine atom);
A group represented by —ZnY ″ (wherein Y ″ represents a chlorine atom, a bromine atom or an iodine atom); and
-Sn (R ^C3) ₃ (wherein, R ^C3 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, these groups may have a substituent. More existing R ^C3 is The groups may be the same or different and may be linked to each other to form a ring structure together with the tin atoms to which they are bonded.   A hole transport material, a hole injection material, an electron transport material, an electron injection material, or a light emitting material for producing a light emitting device having an electrode composed of an anode and a cathode and an organic layer provided between the electrodes. The high molecular compound as described in any one of 1-4.   The polymer compound according to any one of claims 1 to 4, which is a light-emitting material for producing a light-emitting element having an electrode composed of an anode and a cathode and an organic layer provided between the electrodes.   A composition comprising the polymer compound according to claim 6 or 7 and a solvent.   The light emitting element which has the electrode which consists of an anode and a cathode obtained using the polymer compound as described in any one of Claims 1-4, and the organic layer provided between this electrode.