JP2019019326A - Conjugated polymer compound, and use therefor - Google Patents

Abstract

To provide a conjugated polymer compound excellent in the life and luminous efficiency of an organic EL element, and an organic EL element containing the same.SOLUTION: The present invention provides an arylamine polymer with at least one terminal having a structure represented by general formula (3) [where c is 1 or 2, d is 0 or 1, the total of d and c is 2. Aris a C6-20 monocyclic, bonded, or condensed aromatic hydrocarbon group, or a C4-20 monocyclic, bonded, or condensed hetero aromatic heat crosslinking group, a C1-18 alkyl group, or a C1-18 alkoxy group. X independently represent a carbazole group optionally substituted with an aromatic group (phenyl group) or a 9-phenylcarbazole group].SELECTED DRAWING: None

Description

  The present invention relates to a conjugated polymer compound and use thereof.

  An organic EL (electroluminescence) element usually has a structure in which a plurality of organic thin films are sandwiched between a pair of electrodes, and has recently been used in various applications such as portable displays and lighting fixtures. Low molecular weight compounds are the current mainstream materials used for the organic thin film layer, but the production cost is high because vacuum deposition is generally used to form the organic thin film layer of the low molecular weight compound. There was a problem. For this reason, there is a demand for the development of high-molecular materials that can be applied and formed at low manufacturing costs.

  As polymer coating materials, for example, poly (p-phenylene vinylene), polyalkylthiophene (see, for example, Patent Document 1), and polyfluorene-based conductive π-conjugated polymers are known.

  Further, PEDOT-PSS, conjugated polymer compounds, and the like have been proposed as hole injection (transport) materials. As conjugated polymer compounds, non-conjugated polymers having an arylamino group in the side chain (for example, see Patent Documents 2 to 6) and conjugated polymers having an arylamine structure in the main chain have been reported (for example, Patent Documents 7 to 6). 8).

  Regarding hole transfer, which is an important factor in terms of efficiency and lifetime of organic EL devices, hole transfer of non-conjugated conjugated polymer compounds proceeds via hopping transport between molecules, whereas in conjugated polymer compounds, Advantageously, holes can move along the main chain structure in addition to via hopping transport between molecules. Therefore, the conjugated polymer compound is particularly preferable in terms of efficiency.

  Furthermore, it is generally said that the device lifetime is improved by protecting the polymer terminal (for example, halogen atom, secondary amino group, boronic acid residue, etc.) with a phenyl group, and the terminal is a phenyl group or diphenylamino. Examples protected by a group are described in Patent Documents 9 and 10, for example.

JP-A-3-230787 JP-A-8-54833 JP-A-8-259935 Japanese Patent Laid-Open No. 11-35687 JP-A-11-292828 Japanese Patent Laid-Open No. 13-98023 JP 2004-292882 A JP-T-2001-527102 Japanese Patent No. 495896 Japanese Patent No. 4032180

  The present invention has been made in view of the above background art. The object is to provide a polymer material having further high characteristics since it has not yet exceeded the performance of an organic EL element made of a low molecular material. That is, the present invention relates to a novel conjugated polymer compound that is superior in durability and luminous efficiency to conventional materials.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a conjugated polymer compound having a specific structure at the terminal is excellent in durability and luminous efficiency of the organic electroluminescence device. The invention has been completed.

  That is, the present invention provides an arylamine polymer (hereinafter, appropriately referred to as “arylamine polymer (3)”) having at least one terminal having a structure represented by the following general formula (3), and uses thereof And an organic EL device using the arylamine polymer (3).

[Wherein, c represents 1 or 2, d represents 0 or 1, and the sum of d and c is 2.
Ar ⁵ represents a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms, or a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms {these groups are , Each independently a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms (the groups are each independently a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and One or more substituents selected from the group consisting of an alkoxy group having 1 to 18 carbon atoms may be present), a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms (this Each group may independently have one or more substituents selected from the group consisting of a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. , A thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. It may have one or more substituents}, represents a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms.
X represents each independently the group represented by the following general formula (2) or general formula (2) ′.

{Where,
A ring and B ring are each independently a monocyclic, connected or condensed aromatic hydrocarbon ring having 6 to 16 carbon atoms, or a monocyclic, connected or condensed heterocycle having 4 to 16 carbon atoms. Represents an aromatic ring.
Ar ³ is each independently a monocyclic, linked, or condensed bivalent aromatic hydrocarbon group having 6 to 36 carbon atoms, or a monovalent, linked, or condensed bivalent group having 4 to 36 carbon atoms. Heteroaromatic group (These groups are each independently one or more substituents selected from the group consisting of a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. Which may have).
Ar ⁴ is each independently a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms, or a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms. (These groups are each independently a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms, a monocyclic, linked or condensed heteroaromatic group having 4 to 20 carbon atoms. 1 or more substituents selected from the group consisting of a group, a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms), a thermal crosslinking group, carbon An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is represented.
Each Ar ⁶ is independently a monocyclic, linked, or condensed divalent aromatic hydrocarbon group having 6 to 36 carbon atoms, or a monovalent, linked, or condensed divalent group having 4 to 36 carbon atoms. Heteroaromatic group (These groups are each independently one or more substituents selected from the group consisting of a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. Which may have).
a represents an integer of 0 to 3 each independently.
b represents 0 or 1. }]

  The arylamine polymer (3) of the present invention has an excited triplet level equal to or higher than that of a conventionally known polymer compound, and also has high stability in an excited state. Moreover, the stability with respect to electric charge is also excellent. For this reason, the organic EL element using the arylamine polymer (3) of the present invention is expected to have excellent luminous efficiency and lifetime. Therefore, the arylamine polymer (3) of the present invention has an effect of providing a phosphorescent or fluorescent organic EL element having a high luminance and a long lifetime.

  Moreover, since the arylamine polymer (3) of the present invention is excellent in selective solubility in a specific solvent, it is suitable for a coating process using a good solvent. Further, even if the light emitting layer is overcoated by a coating process using a poor solvent, the conjugated polymer compound layer is not eroded. Therefore, the arylamine polymer (3) of the present invention has an effect that a material necessary for a continuous coating film forming process of an organic EL element can be provided.

  Moreover, since the arylamine polymer (3) of the present invention has excellent electrical durability and solubility, it is not limited to an organic EL element, but an electrophotographic photosensitive member, a photoelectric conversion element, an organic solar cell, and an organic TFT element. The effect that it can be used effectively is also produced.

  The present invention is described in detail below.

  The arylamine polymer (3) of the present invention is an arylamine polymer characterized in that at least one terminal has a structure represented by the general formula (3).

  In the general formula (3), c represents 1 or 2, d represents 0 or 1, and the sum of d and c is 2. It is preferable that both c and d are 1.

In General Formula (3), Ar ⁵ represents a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms, or a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms. Group, each of which is independently a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms (the groups are each independently a thermal crosslinking group, carbon number 1 1 to 18 substituents selected from the group consisting of alkyl groups having 18 to 18 carbon atoms and alkoxy groups having 1 to 18 carbon atoms), monocyclic, linked, or condensed rings having 4 to 20 carbon atoms. A heteroaromatic group (in which each group independently represents one or more substituents selected from the group consisting of a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. Which may have), a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. May have one or more substituents selected from the group consisting of}, a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms.

  The monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a biphenylyl group, a terphenyl group, a naphthalenyl group, and a phenylnaphthyl group. Group, naphthylphenyl group, anthracenyl group, pyrenyl group, phenanthrenyl group, perylenyl group, triphenylenyl group, and the like.

  The monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms is not particularly limited, and examples thereof include a furanyl group, a benzofuranyl group, a dibenzofuranyl group, a thienyl group, and a benzothienyl. Group, dibenzothienyl group, pyridylenyl group, pyrimidinyl group, pyrazinyl group, quinolinyl group, isoquinolinyl group, carbazolyl group, pyridyl-phenyl group, phenyl-pyridyl group, pyridyl-biphenylyl group, pyrimidyl-phenyl group, phenyl-pyrimidyl group, etc. Is mentioned.

  Although it does not specifically limit as said heat-crosslinking group, For example, group represented by either of the following general formula (K1)-(K17) is mentioned.

  The alkyl group having 1 to 18 carbon atoms can be paraphrased as a methyl group, an ethyl group, or a chain or branched alkyl group having 3 to 18 carbon atoms, and is not particularly limited. Group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, i-butyl group, n-hexyl group, cyclohexyl group, cyclohexadienyl group, octyl group , A trifluoromethyl group, a benzyl group, or a phenethyl group. Of these, a methyl group, an ethyl group, or an n-butyl group is preferable.

  The alkoxy group having 1 to 18 carbon atoms can be paraphrased as a methoxy group, an ethoxy group, or a chain or branched alkoxy group having 3 to 18 carbon atoms, and is not particularly limited. Group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, i-butoxy group, n-hexyloxy group, cyclohexyloxy group, cyclohexadienyloxy group Octyloxy group, tetrahydrofuranyloxy group, trifluoromethoxy group, benzyloxy group, or phenethyloxy group. Of these, a methoxy group, an ethoxy group, or an n-butoxy group is preferable.

Ar ⁵ is independently a phenyl group, a biphenyl group, a fluorenyl group, a carbazolyl group, a dibenzofuranyl group, or a dibenzothiophenyl group {theses in terms of excellent hole transport properties of the arylamine polymer (3). Is a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms (the groups are each independently an alkyl group having 1 to 18 carbon atoms, and One or more substituents selected from the group consisting of alkoxy groups), or a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms (the groups are independent of each other). And optionally having one or more substituents selected from the group consisting of an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms), an alkyl group having 1 to 18 carbon atoms. Or an alco having 1 to 18 carbon atoms It may be substituted with a xyl group. Are preferably each independently a phenyl group, a biphenyl group, a fluorenyl group, or a carbazolyl group (these groups are each independently a phenyl group, an alkyl group having 1 to 18 carbon atoms, and a carbon number). It may have one or more substituents selected from the group consisting of 1 to 18 alkoxy groups), each independently a phenyl group, biphenyl group, fluorenyl group, 9,9- Dimethylfluorenyl group, 9,9-diethylfluorenyl group, 9,9-dibutylfluorenyl group, 9,9-diphenylfluorenyl group, 9-phenylcarbazolyl group, 9- (methylphenyl) A carbazolyl group, a 9- (ethylphenyl) carbazolyl group, a 9- (butylphenyl) carbazolyl group, or a 9- (9,9-dimethylfluorenyl) carbazolyl group. It is preferable.

  X represents each independently the group represented by the general formula (2) or the general formula (2) ′.

  In the group represented by the general formula (2) or the general formula (2) ′, the A ring and the B ring are each independently a monocyclic, linked, or condensed aromatic hydrocarbon having 6 to 16 carbon atoms. Represents a ring, or a monocyclic, linked, or condensed heteroaromatic ring having 4 to 16 carbon atoms.

  Although it does not specifically limit as said C6-C16 monocyclic, a connection, or a condensed aromatic hydrocarbon ring, For example, a phenyl ring, a naphthalene ring, an anthracene ring, or a fluorene ring is mentioned. .

  The monocyclic, linked, or condensed heteroaromatic ring having 4 to 16 carbon atoms is not particularly limited, and examples thereof include a pyridine ring, a carbazolyl ring, a thiophene ring, and a benzothiophene ring. .

  About A ring and B ring, it is preferable that they are each independently a monocyclic, linked, or condensed aromatic hydrocarbon ring having 6 to 10 carbon atoms in terms of excellent durability of the polymer. Independently, a phenyl ring or a naphthalene ring is more preferable.

In the group represented by the general formula (2) or the general formula (2) ′, each Ar ³ is independently a monocyclic, linked, or condensed divalent aromatic hydrocarbon group having 6 to 36 carbon atoms. Or a monocyclic, linked, or condensed divalent heteroaromatic group having 4 to 36 carbon atoms (these groups are each independently a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and a carbon number) Which may have one or more substituents selected from the group consisting of 1 to 18 alkoxy groups).

  The monocyclic, linked or condensed divalent aromatic hydrocarbon group having 6 to 36 carbon atoms is not particularly limited, and examples thereof include benzenediyl group, biphenyldiyl group, terphenyldiyl group, A triphenylenediyl group, a fluorenediyl group, a phenanthrene diyl group, a naphthalenediyl group, an anthracene diyl group, a pyrenediyl group, or the like can be given.

  The divalent heteroaromatic group having 4 to 36 carbon atoms, which is a monocyclic, linked or condensed ring, is not particularly limited, and examples thereof include a flangyl group, a benzofurandyl group, a dibenzofurandyl group, and a thiophenediyl group. Group, benzothiophenediyl group, dibenzothiophenediyl group, pyridinediyl group, pyrimidinediyl group, pyrazinediyl group, quinolinediyl group, isoquinolinediyl group, carbazolediyl group, biscarbazolediyl group, or benzenediyl-carbazolediyl-benzenediyl group Is mentioned.

In Ar ^3, thermal crosslinking group, for definitions and preferred ranges of the alkyl group, and alkoxy group having 1 to 18 carbon atoms having 1 to 18 carbon atoms, the same definition and preferred ranges indicated in Ar ^5.

As for Ar ³ , each is independently a phenylene group or a divalent heteroaromatic group having 4 to 5 carbon atoms in terms of excellent durability of the polymer (these groups are each independently a thermal crosslinking group, It may preferably have one or more substituents selected from the group consisting of an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms. A group, a pyridylene group, a pyrazylene group, a pyrimidylene group, a furandiyl group, or a thiophenediyl group (these groups are each independently composed of an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms). It may preferably have one or more substituents selected from the group), and more preferably is a phenylene group that may have an alkyl group having 1 to 18 carbon atoms.

  In addition, the divalent heteroaromatic group having 4 to 5 carbon atoms is not particularly limited, and examples thereof include a pyridylene group, a pyrazylene group, a pyrimidylene group, a furandiyl group, and a thiophenediyl group. Can do.

In the group represented by the general formula (2) or the general formula (2) ′, each Ar ⁴ independently represents a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms, or A monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms (these groups are each independently a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms) 1 selected from the group consisting of a monocyclic, linked or fused heteroaromatic group having 4 to 20 carbon atoms, a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. Or a substituent having at least one species), a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms.

  The monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a biphenylyl group, a terphenyl group, a naphthalenyl group, and a phenylnaphthyl group. Group, naphthylphenyl group, anthracenyl group, pyrenyl group, phenanthrenyl group, perylenyl group, triphenylenyl group, and the like.

  The monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms is not particularly limited, and examples thereof include a furanyl group, a benzofuranyl group, a dibenzofuranyl group, a thienyl group, and a benzothienyl. Group, dibenzothienyl group, pyridylenyl group, pyrimidinyl group, pyrazinyl group, quinolinyl group, isoquinolinyl group, carbazolyl group, pyridyl-phenyl group, phenyl-pyridyl group, pyridyl-biphenylyl group, pyrimidyl-phenyl group, phenyl-pyrimidyl group, etc. Is mentioned.

The definitions and preferred ranges of the thermal crosslinking group, the alkyl group having 1 to 18 carbon atoms, and the alkoxy group having 1 to 18 carbon atoms are the same as the definitions and preferred ranges shown for Ar ⁵ .

With respect to Ar ⁴ , a phenyl group, a biphenyl group, a carbazolyl group, or a phenyl-carbazolyl group (these groups are each independently an alkyl group having 1 to 18 carbon atoms, and It is preferably an alkyl group having 1 to 6 carbon atoms which may have one or more substituents selected from the group consisting of an alkoxy group having 1 to 18 carbon atoms, and a phenyl group (the group is , May have an alkyl group having 1 to 18 carbon atoms), a biphenyl group (the group may have an alkyl group having 1 to 18 carbon atoms), a methyl group, or an ethyl group. It is more preferable.

In the group represented by the general formula (2) or the general formula (2) ′, each Ar ⁶ is independently a monocyclic, linked, or condensed divalent aromatic hydrocarbon group having 6 to 36 carbon atoms. Or a monocyclic, linked, or condensed divalent heteroaromatic group having 4 to 36 carbon atoms (these groups are each independently a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and a carbon number) Which may have one or more substituents selected from the group consisting of 1 to 18 alkoxy groups).

Monocyclic 6 to 36 carbon atoms in the Ar ^6, linked, or fused divalent aromatic hydrocarbon group, a monocyclic, linked, or fused divalent heteroaromatic group having 4 to 36 carbon atoms, heat The definitions and preferred ranges of the bridging group, the alkyl group having 1 to 18 carbon atoms, and the alkoxy group having 1 to 18 carbon atoms are the same as the definitions and preferred ranges shown for Ar ⁵ .

As for Ar ⁶ , in terms of excellent durability of the polymer, a phenylene group (the groups are each independently a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms). Or a divalent heteroaromatic group having 4 to 5 carbon atoms (the groups are each independently a thermal crosslinking group, carbon number 1). It may preferably have one or more substituents selected from the group consisting of an alkyl group having 18 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms, and an alkyl group having 1 to 18 carbon atoms. It is more preferable that it is a phenylene group which may have.

  In addition, the divalent heteroaromatic group having 4 to 5 carbon atoms is not particularly limited, and examples thereof include a pyridylene group, a pyrazylene group, a pyrimidylene group, a furandiyl group, and a thiophenediyl group. Can do.

  In the group represented by the general formula (2) or the general formula (2) ', each a independently represents an integer of 0 to 3. a is preferably 0, 1, or 2, and more preferably 0 or 1.

  In the group represented by the general formula (2) or the general formula (2) ′, b represents 0 or 1. b is preferably 0.

  Further, the groups represented by the general formula (2) or (2) ′ are the following (B1) to (B10) in that the durability of the polymer is excellent.

(In the formula, Ar ⁴ , Ar ³ , and a have the same meanings as those in the general formula (2) or (2) ′, and the preferred ranges are also the same).
Or any one of the groups represented by the above (B1) to (B6) (in these groups, Ar ³ and a are represented by the general formula (2) or (2) It is synonymous with ', and the same applies to the preferred range. Ar ⁴ each independently represents an alkyl group having 1 to 6 carbon atoms.

  The arylamine polymer (3) of the present invention is preferably an arylamine polymer characterized by having at least a repeating structure represented by the following general formula (1) from the viewpoint of excellent hole transport properties.

[Where:
Ar ¹ is a monocyclic, linked, or condensed divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a monovalent, linked, or condensed divalent heteroaromatic group having 4 to 30 carbon atoms { These groups are each independently a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms (the groups are each independently a phenanthryl group, dibenzofuranyl group, dibenzothienyl group). 1 or more substituents selected from the group consisting of a group, a thermal cross-linking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms), and 4 to 20 carbon atoms. A monocyclic, linked, or condensed heteroaromatic group (the groups are each independently selected from the group consisting of a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms). One or more selected substituents may be selected), a thermal cross-linking group, a carbon number of 1 to 18 Which may have one or more substituents selected from the group consisting of an alkyl group and an alkoxy group having 1 to 18 carbon atoms}.
Ar ² is a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms, or a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms {these groups are , Each independently a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms (the groups are each independently a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and One or more substituents selected from the group consisting of an alkoxy group having 1 to 18 carbon atoms may be present), a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms (this Each group may independently have one or more substituents selected from the group consisting of a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. , A thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. It may have one or more substituents}, represents a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. ]
The monocyclic, linked or condensed divalent aromatic hydrocarbon group having 6 to 20 carbon atoms in Ar ¹ is not particularly limited, and examples thereof include a benzenediyl group, a biphenyldiyl group, and a terphenyldiyl group. , Triphenylenediyl group, fluorenediyl group, phenanthrene diyl group, naphthalenediyl group, anthracene diyl group, or pyrenediyl group.

The monovalent, linked, or condensed divalent heteroaromatic group having 4 to 30 carbon atoms in Ar ¹ is not particularly limited, and examples thereof include a flangyl group, a benzofurandyl group, a dibenzofurandyl group, and thiophene. A diyl group, a benzothiophene diyl group, a dibenzothiophene diyl group, a pyridine diyl group, a pyrimidine diyl group, a pyrazine diyl group, a quinoline diyl group, an isoquinoline diyl group, a carbazole diyl group, or a biscarbazole diyl group.

In Ar ¹ , a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms, a monocyclic, linked or condensed heteroaromatic group having 4 to 20 carbon atoms, a thermal crosslinking group, carbon The definitions and preferred ranges of the alkyl group having 1 to 18 carbon atoms and the alkoxy group having 1 to 18 carbon atoms are the same as the definitions and preferred ranges shown for Ar ³ and Ar ⁵ .

Regarding Ar ¹ , each of the following (A1) to (A14) is independently from the viewpoint that the durability of the polymer is excellent.

(In the formula, d represents 0 or 1. These groups are each independently one or more selected from the group consisting of an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms. May have a substituent of
Is preferably a group represented by any one of the above (A3) to (A6) or any one of the groups represented by (A8) to (A14) (these groups are each independently More preferably, it may have one or more substituents selected from the group consisting of an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms, and (A3) above, Groups represented by (A4), (A6), (A8), (A10), or (A14) (these groups may each independently have an alkyl group having 1 to 18 carbon atoms). It is more preferable.

Ar ² monocyclic, connected or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms, monocyclic, connected or condensed heteroaromatic group having 4 to 20 carbon atoms, thermal crosslinking group, carbon The definition and preferred range of the alkyl group having 1 to 18 and the alkoxy group having 1 to 18 carbon atoms are the same as the definition and preferred range shown for Ar ⁵ .

Ar ² is independently a phenyl group, a biphenyl group, a fluorenyl group, a carbazolyl group, a dibenzofuranyl group, or a dibenzothiophenyl group in terms of excellent hole transport properties of the arylamine polymer (3) {these Is a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms (the groups are each independently an alkyl group having 1 to 18 carbon atoms, and One or more substituents selected from the group consisting of alkoxy groups), or a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms (the groups are independent of each other). And optionally having one or more substituents selected from the group consisting of an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms), an alkyl group having 1 to 18 carbon atoms. Or an alco having 1 to 18 carbon atoms Which may be substituted with a xy group}, each independently a phenyl group, a biphenyl group, a fluorenyl group, or a carbazolyl group (these groups are each independently a phenyl group, a carbon number of 1 Preferably have one or more substituents selected from the group consisting of an alkyl group having 18 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms, and each independently represents a phenyl group or biphenyl. Group, fluorenyl group, 9,9-dimethylfluorenyl group, 9,9-diethylfluorenyl group, 9,9-dibutylfluorenyl group, 9,9-diphenylfluorenyl group, 9-phenylcarbazolyl Group, 9- (methylphenyl) carbazolyl group, 9- (ethylphenyl) carbazolyl group, 9- (butylphenyl) carbazolyl group, or 9- (9,9-dimethylful) Reniru) is preferably a carbazolyl group.

  That is, the arylamine polymer (3) is preferably one represented by the following general formula (4-1) or (4-2).

(In the formula, each n independently represents an integer of 3 or more.
About A ring, B ring, Ar < ³ >, Ar < ⁴ >, and a, it is synonymous with the definition shown in General formula (3), General formula (2), and General formula (2) '.
About Ar < ¹ > and Ar < ² >, it is synonymous with the definition shown in General formula (1).
Ar ¹ and Ar ² may have different structures for each appearance. )
The arylamine polymer (3) is preferably one represented by the following general formula (5-1), (5-2), (5-3), or (5-4).

(Where
Formula (5-1) and Formula (5-3) represent a random copolymer or an alternating copolymer, and Formula (5-2) and Formula (5-4) represent a block copolymer. .
f, each independently represents an integer of 1 to 10;
n independently represents an integer of 3 or more.
About A ring, B ring, Ar < ³ >, Ar < ⁴ >, and a, it is synonymous with the definition shown in General formula (3), General formula (2), and General formula (2) '.
About Ar < ¹ > and Ar < ² >, it is synonymous with the definition shown in General formula (1). )
Although it will not specifically limit as a compound represented by the above-mentioned general formula (1) if it corresponds to the above-mentioned definition, The following general formula (C1)-(C188) is mentioned (In formula, R is Each independently represents a bridging group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms).

  The compound represented by the general formula (2) or (2) ′ is not particularly limited as long as it falls under the above definition, but includes the following general formulas (D1) to (D69) (wherein , R each independently represents a bridging group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms).

  The arylamine polymer (3) of the present invention is not particularly limited as long as it falls within the above definition, but is preferably represented by any of the following compounds (E1) to (E884) ( Table 1 to Table 26). (C1) to (C188) and (D1) to (D69) shown in Tables 1 to 26 are as described above.

  In addition, about the said arylamine polymer (3), the following arylamine polymer is shown, About the following (a)-(d) and the further structural unit, alternating copolymerization, random copolymerization, block polymerization Any of these polymerizations may be carried out, or a combination thereof may be carried out.

(Terminal Structure)-(a) w- (b) x- (c) y- (d) z- (Terminal Structure)
w, x, y, and z represent the number of repetitions or the monomer abundance ratio.

  Next, the manufacturing method of the arylamine polymer (3) of this invention is demonstrated.

  The arylamine polymer (3) of the present invention is not particularly limited, but a palladium catalyst and a base are used for an arylamine polymer having an amino group having an active hydrogen or a detachable substituent such as a halogen element at the terminal. In the presence of an aromatic halogen compound represented by the following general formula (5) and / or (5) ′, or an aromatic amine compound represented by the following general formula (6) and / or (6) ′, or It is obtained by reacting both and introducing a terminal group.

(In the formula, A ring, B ring, Ar ³ , Ar ⁴ , Ar ⁶ and a have the same definition as in the above general formulas (2) and (2) ′. X represents a chlorine atom, a bromine atom, or iodine. Represents an atom.)

(In the formula, A ring, B ring, Ar ³ , Ar ⁴ , Ar ⁶ and a have the same definition as in the above general formulas (2) and (2) ′, and Ar ² is the same as in the above general formula (1). Definition.)
The reaction is performed by simultaneously using the aromatic halogen compound represented by the general formula (5) or (5) ′ and the aromatic amine compound represented by the general formula (6) or (6) ′. However, it is preferable to carry out the steps separately from the viewpoint of reaction efficiency. When performing the reaction separately, either the reaction using the aromatic halogen compound or the reaction using the aromatic amine compound may be performed first.

  In addition, an amine compound represented by the following general formula (7) in the presence of a palladium catalyst and a base for an arylamine polymer having a detachable substituent such as an amino group or a halogen element having an active hydrogen at the terminal Is substituted with an amino group for a detachable substituent such as a halogen element at the terminal of the arylamine polymer, and then the aromatic halogen compound represented by the general formula (5) or (5) ′ is reacted. You may let them.

(In the formula, Ar ² has the same definition as in the general formula (1).)
The above reaction may be performed in one pot following the polymerization reaction, or may be performed separately in the presence of a palladium catalyst and a base after once isolating the polymerization reaction product. Further, a reaction using an aromatic halogen compound represented by the general formula (5) or (5) ′, a reaction using an aromatic amine compound represented by the general formula (6) or (6) ′, and the general formula After reacting (7), the reaction of reacting the aromatic halogen compound represented by the general formula (5) or (5) ′ can be carried out continuously in one pot, or after one reaction, It is also possible to isolate the product and perform the other reaction in a separate batch.

  All of the above reactions are carried out in the presence of a palladium catalyst and a base, and the reaction conditions are not particularly limited, but any of the following can be used. The palladium catalyst usually comprises a palladium compound and a ligand.

  Although it does not specifically limit as a palladium compound which is a structural component of a palladium catalyst, For example, tetravalent palladium compounds [Specifically, sodium hexachloro palladium (IV) acid tetrahydrate, hexachloro palladium (IV Potassium diacid), divalent palladium compounds (for example, palladium chloride (II), palladium bromide (II), palladium acetate (II), palladium (II) acetylacetonate, dichlorobis (benzonitrile) palladium (II ), Dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium (II) trifluoroa Tate etc.], and zero-valent palladium compounds [specifically, tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (triphenylphosphine) palladium (0) etc.].

  The ligand that is a constituent component of the palladium catalyst is not particularly limited, but may be any ligand that can coordinate to palladium, such as trialkylphosphines, arylphosphines, carbene-based ligands, and the like. Is mentioned.

  Although it does not specifically limit as trialkyl phosphine, For example, a triethyl phosphine, a tricyclohexyl phosphine, a triisopropyl phosphine, a tri-n-butyl phosphine, a triisobutyl phosphine, a tri-sec-butyl phosphine, a tri-tert- And butylphosphine. Of these, tri-tert-butylphosphine is preferably used because of its particularly high reaction activity as a catalyst.

  The aryl phosphines are not particularly limited, and examples thereof include triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, and 2,2′-bis. (Diphenylphosphino) -1,1′-binaphthyl (BINAP), trimesitylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinoferrocene and the like.

  Examples of the carbene-based ligand include 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene hydrochloride.

  The amount of the ligand used in the palladium catalyst is not particularly limited, but it may be used usually in the range of 0.01 to 10000 times mol of 1 mol of palladium atom in the palladium compound, and expensive trialkyl. Since phosphines, arylphosphines, and carbene-based ligands are used, the range of 0.1 to 10 moles per mole of palladium atom in the palladium compound is preferable.

  The amount of palladium catalyst used is not particularly limited, but in terms of palladium atom relative to 1 mol of the aromatic halogen compound represented by the general formula (5) or (5) ′ and the main chain polymer halogen atom. In general, the range is preferably 0.0000001 to 0.20 moles. Of these, from the viewpoint of catalytic activity and the use of expensive palladium compounds, it is usually more preferably in the range of 0.00001 to 0.10 times mole.

  The addition method of the palladium catalyst is not particularly limited, but a palladium compound, a ligand, and other components may be added individually to the reaction system, or these catalyst components are mixed in advance to form a palladium complex. You may add what was prepared in the form of.

  Although it does not specifically limit as a base used for reaction, For example, inorganic metal bases, such as hydroxide of alkali metal (specifically sodium, potassium, etc.), carbonate, an alkoxide, or tertiary amine etc. An organic base is mentioned. Of these, preferred are alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide, and the like. It can be added as it is to the system, or it can be prepared in situ by subjecting an alkali metal, alkali metal hydride or alkali metal hydroxide and alcohol to the reaction system. More preferred is a method in which an alkali metal tertiary alkoxide such as lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide or the like is added to the reaction system as it is.

  The amount of the base used is not particularly limited, but is usually in the range of 1 to 1000 times mol with respect to 1 mol of the halogen atom of the aromatic halogen compound represented by the general formula (5) or (5) ′. Preferably, it is selected from the range of 1 to 20 times mol, the range of 1 to 100000 times mol, preferably the range of 1 to 1000 times mol for 1 mol of the halogen atom of the main chain polymer.

  It is preferable to carry out the reaction usually in the presence of an inert solvent. The solvent used is not particularly limited as long as it does not significantly inhibit this reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane. A solvent, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphotriamide, etc. can be mentioned. Of these, aromatic hydrocarbon solvents such as benzene, toluene and xylene are preferred.

  The reactions are preferably carried out under normal pressure and an inert gas atmosphere such as nitrogen or argon, but can be carried out even under pressurized conditions.

  The reaction temperature is not particularly limited as long as the reaction proceeds at an economically acceptable rate, but is usually 20 to 300 ° C, preferably 50 to 200 ° C, more preferably 100 to 150 ° C. It is a range.

  The reaction time is not particularly limited because it is not constant depending on the conjugated polymer compound to be produced, palladium catalyst, reaction temperature, etc. In many cases, it may be selected from the range of several minutes to 72 hours. Preferably it is less than 24 hours.

  The arylamine polymer (3) produced by the reaction is preferably separated and purified from unreacted low molecular weight compounds by reprecipitation or the like. Further, it is preferable to perform an adsorption treatment with silica gel, activated alumina, zeolite or the like in order to remove impurities such as a palladium catalyst.

  The arylamine polymer (3) of the present invention is not particularly limited. For example, the arylamine polymer (3) is used as a conductive polymer material in electronic devices such as field effect transistors, optical functional devices, dye-sensitized solar cells, and organic EL devices. can do.

  In particular, it is extremely useful as a hole transport material, a light emitting material and a buffer material of an organic EL device.

  If the organic EL element of this invention is equipped with the organic layer containing the arylamine polymer (3) of this invention, element structure will not be specifically limited.

  Since the arylamine polymer (3) of the present invention is excellent in solubility, for example, a spin coating method, a casting method, a dipping method, a bar coating method, using a solution, a mixed solution or a melt of these materials, The element can be easily produced by a conventionally known coating method such as a roll coating method. It can also be easily produced by an inkjet method, a Langmuir Blodget method, or the like.

  The basic structure of the organic EL device capable of obtaining the effects of the present invention is not particularly limited. For example, the substrate, the anode, the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and It is preferable to include a cathode.

  The anode and cathode of the organic EL element are connected to a power source through an electrical conductor. The organic EL element operates by applying a potential between the anode and the cathode.

  Holes are injected into the organic EL element from the anode, and electrons are injected into the organic EL element at the cathode.

  The organic EL element is typically placed on a substrate, and the anode or cathode can be in contact with the substrate. The electrode in contact with the substrate is called the lower electrode for convenience. Generally, the lower electrode is an anode, but the organic EL element of the present invention is not limited to such a form.

  The substrate may be light transmissive or opaque depending on the intended emission direction. The light transmission characteristics can be confirmed by electroluminescence emission through the substrate. Generally, transparent glass or plastic is used as the substrate in such a case. The substrate may be a composite structure including multiple material layers.

  When the electroluminescent emission is confirmed through the anode, the anode is formed by passing or substantially passing through the emission.

  The general transparent anode (anode) material used in the present invention is not particularly limited, and examples thereof include indium-tin oxide (ITO), indium-zinc oxide (IZO), and tin oxide. . Other metal oxides such as aluminum or indium doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide can also be used. In addition to these oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, or metal sulfides such as zinc sulfide can be used as the anode.

  The anode can be modified with plasma deposited fluorocarbon. If electroluminescence emission is confirmed only through the cathode, the transmission properties of the anode are not critical and any conductive material that is transparent, opaque or reflective can be used. Examples of conductors for this application include gold, iridium, molybdenum, palladium, platinum and the like.

  A hole injection layer can be provided between the anode and the hole transport layer. The hole injection material serves to improve the subsequent film-forming properties of the organic layer and to facilitate injection of holes into the hole transport layer.

  Examples of materials suitable for use in the hole injection layer include polythiophene derivatives, polyaniline derivatives, polypyrrole derivatives, preferably examples of materials suitable for use in the hole injection layer, preferably Examples include polythiophene derivatives.

  The conjugated polymer compound of the present application is preferably used for the hole transport layer of the organic EL device. In addition to the conjugated polymer compound of the present application, the hole transport layer may contain one or more hole transport compounds such as an aromatic tertiary amine. An aromatic tertiary amine means a compound containing one or more trivalent nitrogen atoms, and these trivalent nitrogen atoms are bonded only to carbon atoms, and one of these carbon atoms One or more form an aromatic ring. Specifically, aromatic tertiary amines include arylamines, monoarylamines, diarylamines, triarylamines, or polymeric arylamines. More specifically, for example, poly (N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline, NPD (N, N′-bis (naphthalen-1-yl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine), α- NPD (N, N′-di (1-naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine), TPBi (1,3,5-tris (1-phenyl-) 1H-benzimidazol-2-yl) benzene), or TPD (N, N′-bis (3-methylphenyl) -N, N′-diphenyl-1,1′-biphenyl-4,4 - diamine), and the like.

  Dipyrazino [2,3-f: 2 ′, 3′-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile as a charge generation layer between the hole injection layer and the hole transport layer A layer containing (HAT-CN) may be provided.

  The light emitting layer of the organic EL element contains a phosphorescent material or a fluorescent material, and emits light as a result of recombination of electron / hole pairs in this region.

  The emissive layer may consist of a single material that includes both small molecules and polymers, but more commonly consists of a host material doped with a guest compound, where the emission occurs primarily from the dopant, Can have a color.

  Examples of the host material for the light emitting layer include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, or an anthranyl group. For example, DPVBi (4,4′-bis (2,2-diphenylvinyl) -1,1′-biphenyl), BCzVBi (4,4′-bis (9-ethyl-3-carbazovinylene) 1,1′-biphenyl ), TBADN (2-tert-butyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4′-bis (carbazole-9) -Yl) biphenyl), CDBP (4,4′-bis (carbazol-9-yl) -2,2′-dimethylbiphenyl), 9,10-bis (biphenyl) anthracene and the like.

  The host material in the light emitting layer may be an electron transport material as defined below, a hole transport material as defined above, another material that supports hole / electron recombination (support), or a combination of these materials. Good.

  Examples of fluorescent dopants include anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compound, thiopyran compound, polymethine compound, pyrylium or thiapyrylium compound, fluorene derivative, perifuranthene derivative, indenoperylene derivative, Examples thereof include bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, and carbostyryl compounds.

  As an example of the phosphorescent dopant, an organometallic complex of a transition metal such as iridium, platinum, palladium, or osmium can be given.

Examples of dopants include Alq ₃ (tris (8-hydroxyquinoline) aluminum), DPAVBi (4,4′-bis [4- (di-para-tolylamino) styryl] biphenyl), perylene, Ir (PPy) ₃ (tris (2-Phenylpyridine) iridium (III), FlrPic (bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium (III)) and the like can be mentioned.

  Examples of the electron transporting material include alkali metal complexes, alkaline earth metal complexes, and earth metal complexes. Examples of the alkali metal complex, alkaline earth metal complex, or earth metal complex include 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinato) zinc, and bis (8-hydroxyquinolinate). Copper, bis (8-hydroxyquinolinato) manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, Bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolate) gallium, bis (2-methyl-8-quinolinate) 1-naphthyl Trat aluminum, bis (2-methyl-8-quinolinato) -2-naphthoquinone Trad gallium, and the like.

  A hole blocking layer may be provided between the light emitting layer and the electron transport layer for the purpose of improving carrier balance. Desirable compounds for the hole element layer are BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2 -Methyl-8-quinolinolato) -4- (phenylphenolato) aluminum) or bis (10-hydroxybenzo [h] quinolinato) beryllium).

  In the organic EL device of the present invention, an electron injection layer may be provided for the purpose of improving electron injection properties and improving device characteristics (for example, light emission efficiency, constant voltage driving, or high durability).

Preferred compounds for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, etc. Is mentioned. In addition, the above-described metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO ₂ , AlO, SiN, SiON, AlON, Various oxides such as GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, and C, and inorganic compounds such as nitride and oxynitride can also be used.

If light emission is confirmed only through the anode, the cathode used in the present invention can be formed from any conductive material. Desirable cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium , Lithium / aluminum mixtures, rare earth metals and the like.

  Examples of the present invention are shown below, but the present invention is not construed as being limited to these Examples.

  Polymer molecular weight: THF-based GPC (HLC-8220 (manufactured by Tosoh Corporation), column connected with TSKgel-SuperH3000, TSKgel-SuperH2000, TSKgel-SuperH1000 (both manufactured by Tosoh Corporation)), and molecular weight measurement of the synthesized polymer. Went. The molecular weight is shown in terms of standard polystyrene.

  Glass transition temperature: Measured using DSC200F3 (manufactured by Netch).

  HOMO level: Measured using an atmospheric photoelectron spectrometer measuring apparatus AC-3 (manufactured by Riken Keiki Co., Ltd.).

  LUMO level: The energy gap (Eg) was calculated from the absorption edge of the UV-vis absorption spectrum and subtracted from HOMO.

  Elemental analysis: Analysis was performed using a fully automatic elemental analyzer 2400II (manufactured by PerkinElmer).

  Phosphorescence spectrum measurement: Measured using a fluorimeter F-2500 (manufactured by Hitachi).

Example 1 Synthesis of Arylamine Polymer (HTP-1)-One Pot Synthesis
A 50 mL three-necked round bottom flask equipped with a condenser and a thermometer was charged with 1.50 g (3.69 mmol) of 4,4′-diiodobiphenyl and 0.55 g of 4-butylaniline at room temperature under a nitrogen atmosphere (3 .69 mmol), sodium-tert-butoxide 1.42 g (14.76 mmol) and o-xylene 13.3 g. To this mixed solution, 16.9 mg (0.0185 mmol) of tris (dibenzylideneacetone) dipalladium (0) prepared in advance in a nitrogen atmosphere and 15.0 mg (0.074 mmol) of tri-tert-butylphosphine o-xylene (59.9 mg) solution was added. Next, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 3 hours while heating and stirring at 120 ° C.

  Subsequently, 0.24 g (0.74 mmol) of 3-bromo-9-phenylcarbazole was added, and the reaction was further performed at 120 ° C. for 3 hours. Subsequently, 0.58 g (1.48 mmol) of 3- (4-butylphenyl) amino-9-phenylcarbazole was added, and the reaction was further performed at 120 ° C. for 3 hours.

  After completion of the reaction, the reaction mixture allowed to cool to about 80 ° C. was slowly added into a stirred solution of 90% aqueous acetone (200 mL) to precipitate a solid. The solid was collected by filtration, washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain 0.99 g of a pale yellow solid.

  Further, the polymer was dissolved in chlorobenzene and passed through an alumina and silica gel column. The eluted chlorobenzene solution containing the polymer was collected and poured into acetone to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 80 ° C. to obtain 0.78 g (yield 71%) of an arylamine polymer (HTP-1).

  The obtained arylamine polymer (HTP-1) had a weight average molecular weight of 42,000 and a number average molecule of 16,000 (dispersity of 2.6) in terms of polystyrene.

  The HOMO level was 5.35 eV, and the LUMO level was 2.41 eV. The glass transition temperature was 192 ° C.

  In a sample tube for UV-Vis spectrum measurement, 1 mg of arylamine polymer (HTP-1) and 1 mL of 2-methyltetrahydrofuran were mixed well to prepare a uniform solution. The solution was degassed by bubbling with nitrogen gas for 10 minutes, and then the sample tube was sealed and the phosphorescence spectrum was measured. The excited triplet level of the arylamine polymer (HTP-1) calculated from the phosphorescence spectrum was 2.34 eV.

Example 2 Synthesis of Arylamine Polymer (HTP-1) -2 Step Synthesis 4,4'-Diiodobiphenyl 1 in a 50 mL three-necked round bottom flask equipped with a condenser and a thermometer at room temperature under a nitrogen atmosphere .50 g (3.69 mmol), 4-butylaniline 0.55 g (3.69 mmol), sodium tert-butoxide 1.42 g (14.76 mmol) and o-xylene 13.3 g were charged. To this mixed solution, 16.9 mg (0.0185 mmol) of tris (dibenzylideneacetone) dipalladium (0) prepared in advance in a nitrogen atmosphere and 15.0 mg (0.074 mmol) of tri-tert-butylphosphine o-xylene (59.9 mg) solution was added. Next, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 3 hours while heating and stirring at 120 ° C.

  Subsequently, 0.11 g (0.74 mmol) of 4-butylaniline was added, and the reaction was further performed at 120 ° C. for 3 hours. After completion of the reaction, the reaction mixture allowed to cool to about 80 ° C. was slowly added into a stirred solution of 90% aqueous acetone (200 mL) to precipitate a solid. The solid was collected by filtration, washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain 0.97 g of a pale yellow solid 1.

  In a 50 mL three-necked round bottom flask equipped with a condenser and a thermometer, 0.97 g of the above pale yellow solid, 0.24 g (0.74 mmol) of 3-bromo-9-phenylcarbazole, at room temperature under a nitrogen atmosphere, Sodium-tert-butoxide (1.42 g, 14.76 mmol) and o-xylene (19.4 g) were charged. To this mixed solution, 16.9 mg (0.0185 mmol) of tris (dibenzylideneacetone) dipalladium (0) prepared in advance in a nitrogen atmosphere and 15.0 mg (0.074 mmol) of tri-tert-butylphosphine o-xylene (59.9 mg) solution was added. Next, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 3 hours while heating and stirring at 120 ° C. After completion of the reaction, the reaction mixture allowed to cool to about 80 ° C. was slowly added into a stirred solution of 90% aqueous acetone (200 mL) to precipitate a solid. The solid was collected by filtration, washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain 0.92 g of pale yellow solid 2.

  Further, the polymer was dissolved in chlorobenzene and passed through an alumina and silica gel column. The eluted chlorobenzene solution containing the polymer was collected and poured into acetone to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 80 ° C. to obtain 0.69 g (yield 63%) of an arylamine polymer (HTP-1).

  The obtained arylamine polymer (HTP-1) had a weight average molecular weight of 44,000 and a number average molecule of 20,000 (dispersity of 2.2) in terms of polystyrene.

  In the FT-IR measurement, the peak accompanying NH stretching observed at 3401 cm −1 in the light yellow solid 1 was not detected from the light yellow solid 2. The N—H group at the end of the polymer disappeared, suggesting that the 9-phenylcarbazol-3-yl group substituted the substituent on N.

Example 3 Synthesis of Arylamine Polymer (HTP-2) In a 50 mL three-necked round bottom flask equipped with a condenser and a thermometer, N, N′-bis (4-butylphenyl) benzidine was added at room temperature under a nitrogen atmosphere. 1.00 g (2.22 mmol), 2,7-dibromo-9,9-dimethylfluorene 0.78 g (2.22 mmol), sodium tert-butoxide 0.85 g (8.88 mmol) and o-xylene 18.9 g Was charged. To this mixed solution, 10.2 mg (0.0111 mmol) of tris (dibenzylideneacetone) dipalladium (0) prepared in advance in a nitrogen atmosphere and 9.0 mg (0.0444 mmol) of tri-tert-butylphosphine o-xylene (35.9 mg) solution was added. Next, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 3 hours while heating and stirring at 120 ° C.

  Next, 0.14 g (0.44 mmol) of 3-bromo-9-phenylcarbazole was added, and the reaction was further performed at 120 ° C. for 3 hours. Next, 0.34 g (0.88 mmol) of 3- (4-butylphenyl) amino-9-phenylcarbazole was added, and the reaction was further performed at 120 ° C. for 3 hours.

  After completion of the reaction, the reaction mixture allowed to cool to about 80 ° C. was slowly added into a stirred solution of 90% aqueous acetone (200 mL) to precipitate a solid. The solid was collected by filtration and washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain a pale yellow solid.

  Further, the polymer was dissolved in chlorobenzene and passed through an alumina and silica gel column. The eluted chlorobenzene solution containing the polymer was collected and poured into acetone to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 80 ° C. to obtain 0.92 g (yield 65%) of an arylamine polymer (HTP-2).

  The obtained arylamine polymer (HTP-2) had a weight average molecular weight of 98,000 and a number average molecule of 37,000 (dispersity of 2.6) in terms of polystyrene.

  The HOMO level was 5.23 eV, and the LUMO level was 2.35 eV. Moreover, the glass transition temperature was not detected by 300 degreeC.

  In a sample tube for UV-Vis spectrum measurement, 1 mg of arylamine polymer (HTP-2) and 1 mL of 2-methyltetrahydrofuran were mixed well to prepare a uniform solution. The solution was degassed by bubbling with nitrogen gas for 10 minutes, and then the sample tube was sealed and the phosphorescence spectrum was measured. The excited triplet level of the arylamine polymer (HTP-2) calculated from the phosphorescence spectrum was 2.33 eV.

Example 4 Synthesis of Arylamine Polymer (HTP-3) In Example 3, instead of 1.00 g (2.22 mmol) of N, N′-bis (4-butylphenyl) benzidine, N, N′-bis ( A mixture of 0.73 g (2.00 mmol) of 4-methylphenyl) benzidine and 0.086 g (0.22 mmol) of N, N′-bis (2,4-dimethylphenyl) benzidine was used, and 3- (4- Implementation was performed except that 0.31 g (0.88 mmol) of 3- (4-methylphenyl) amino-9-phenylcarbazole was used instead of 0.34 g (0.88 mmol) of butylphenyl) amino-9-phenylcarbazole. In the same manner as in Example 3, an arylamine polymer (HTP-3) was obtained in a yield of 72%.

The repeating structure represented in parentheses in the figure is a random polymer that appears randomly.
The ratio of n and m indicating the mole fraction of the repeating structure in the polymer is 0.91: 0.09.

  The obtained arylamine polymer (HTP-3) had a weight average molecular weight of 57,000 and a number average molecule of 22,000 (dispersity of 2.6) in terms of polystyrene.

  The HOMO level was 5.24 eV, and the LUMO level was 2.36 eV. Moreover, the glass transition temperature was 276 degreeC.

  The excited triplet level of the arylamine polymer (HTP-3) measured in the same manner as in Example 3 was 2.34 eV.

Example 5 Synthesis of arylamine polymer (HTP-4) In Example 3, instead of 1.00 g (2.22 mmol) of N, N′-bis (4-butylphenyl) benzidine, N, N′-bis ( Using a mixture of 0.73 g (2.00 mmol) 4-methylphenyl) benzidine and 0.086 g (0.22 mmol) N, N′-bis (2,4-dimethylphenyl) benzidine, 3-bromo-9 -Instead of 0.14 g (0.44 mmol) of phenylcarbazole 0.15 g (0.44 mmol) of 3-bromo-6-methyl-9-phenylcarbazole, 3- (4-methylphenyl) amino-9-phenylcarbazole 0 Instead of 34 g (0.88 mmol) 3- (4-methylphenyl) amino-6-methyl-9-phenylcarbazole Except for using .32g (0.88mmol) were performed in the same manner as in Example 3, was conducted to produce an arylamine polymer (HTP-4) in 68% yield.

  The obtained arylamine polymer (HTP-4) had a weight average molecular weight of 58,000 and a number average molecule of 21,000 (dispersity 2.8) in terms of polystyrene.

  The HOMO level was 5.23 eV, and the LUMO level was 2.35 eV. The glass transition temperature was 278 ° C.

  The excited triplet level of the arylamine polymer (HTP-4) measured in the same manner as in Example 3 was 2.34 eV.

Example 6 Synthesis of Arylamine Polymer (HTP-5) In Example 3, instead of 1.00 g (2.22 mmol) of N, N′-bis (4-butylphenyl) benzidine, N, N′-bis ( Using a mixture of 0.73 g (2.00 mmol) 4-methylphenyl) benzidine and 0.086 g (0.22 mmol) N, N′-bis (2,4-dimethylphenyl) benzidine, 3-bromo-9 -Instead of 0.14 g (0.44 mmol) of phenylcarbazole, 0.18 g (0.44 mmol) of 3-bromo-6,9-diphenylcarbazole, 0.34 g of 3- (4-methylphenyl) amino-9-phenylcarbazole Instead of (0.88 mmol) 3- (4-methylphenyl) amino-6,9-diphenylcarbazole 0.37 g ( .88Mmol) except for using were performed in the same manner as in Example 3, was conducted to produce an arylamine polymer (HTP-5) in 70% yield.

  The obtained arylamine polymer (HTP-5) had a weight average molecular weight of 56,000 and a number average molecule of 20,000 (dispersity of 2.8) in terms of polystyrene.

  The HOMO level was 5.25 eV, and the LUMO level was 2.37 eV. The glass transition temperature was 279 ° C.

  The excited triplet level of the arylamine polymer (HTP-5) measured in the same manner as in Example 3 was 2.33 eV.

Example 7 Synthesis of arylamine polymer (HTP-6) In Example 3, instead of 1.00 g (2.22 mmol) of N, N′-bis (4-butylphenyl) benzidine, N, N′-bis ( Using a mixture of 0.73 g (2.00 mmol) 4-methylphenyl) benzidine and 0.086 g (0.22 mmol) N, N′-bis (2,4-dimethylphenyl) benzidine, 3-bromo-9 -Instead of 0.14 g (0.44 mmol) of phenylcarbazole, 0.12 g (0.44 mmol) of 3-bromo-9-ethylcarbazole, 0.34 g (0 of 3- (4-methylphenyl) amino-9-phenylcarbazole) Instead of .88 mmol) 0.26 g (0.88 mmol) of 3- (4-methylphenyl) amino-9-ethylcarbazole Except using were performed in the same manner as in Example 3, arylamine polymer (HTP-6) was obtained in 66% yield.

  The obtained arylamine polymer (HTP-6) had a weight average molecular weight of 57,000 and a number average molecule of 21,000 (dispersity of 2.7) in terms of polystyrene.

  The HOMO level was 5.23 eV, and the LUMO level was 2.34 eV. The glass transition temperature was 266 ° C.

  The excited triplet level of the arylamine polymer (HTP-6) measured in the same manner as in Example 3 was 2.35 eV.

Example 8 Synthesis of Arylamine Polymer (HTP-7) In Example 3, instead of 1.00 g (2.22 mmol) of N, N′-bis (4-butylphenyl) benzidine, N, N′-bis ( Using a mixture of 0.73 g (2.00 mmol) 4-methylphenyl) benzidine and 0.086 g (0.22 mmol) N, N′-bis (2,4-dimethylphenyl) benzidine, 3-bromo-9 2-Phenylcarbazole instead of 0.14 g (0.44 mmol) 2-bromo-9-phenylcarbazole, 3- (4-methylphenyl) amino-9-phenylcarbazole instead of 0.34 g (0.88 mmol) 2 The same procedure as in Example 3 was carried out except that-(4-methylphenyl) amino-9-phenylcarbazole was used. Limer (HTP-7) was obtained with a yield of 74%.

  The obtained arylamine polymer (HTP-7) had a weight average molecular weight of 57,000 and a number average molecule of 23,000 (dispersity of 2.5) in terms of polystyrene.

  The HOMO level was 5.25 eV, and the LUMO level was 2.35 eV. The glass transition temperature was 266 ° C.

  The excited triplet level of the arylamine polymer (HTP-7) measured in the same manner as in Example 3 was 2.36 eV.

Example 9 Synthesis of Arylamine Polymer (HTP-8) 2,7-Dibromo-9,9-dimethylfluorene 1 was added to a 50 mL three-necked round bottom flask equipped with a condenser and a thermometer at room temperature under a nitrogen atmosphere. .30 g (3.69 mmol), 4-butylaniline 0.55 g (3.69 mmol), sodium tert-butoxide 1.42 g (14.76 mmol) and o-xylene 13.3 g were charged. To this mixed solution, 16.9 mg (0.0185 mmol) of tris (dibenzylideneacetone) dipalladium (0) prepared in advance in a nitrogen atmosphere and 15.0 mg (0.074 mmol) of tri-tert-butylphosphine o-xylene (59.9 mg) solution was added. Next, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 3 hours while heating and stirring at 120 ° C.

  Subsequently, 0.03 g (0.18 mmol) of 4-butylaniline was added, and the reaction was further performed at 120 ° C. for 2 hours. Thereafter, 0.35 g (1.08 mmol) of 3-bromo-9-phenylcarbazole was added, and the reaction was further performed at 120 ° C. for 2 hours. After completion of the reaction, the reaction mixture allowed to cool to about 80 ° C. was slowly added into a stirred solution of 90% aqueous acetone (200 mL) to precipitate a solid. The solid was collected by filtration, washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain 0.97 g of a pale yellow solid.

  The obtained polymer was dissolved in chlorobenzene and passed through an alumina and silica gel column. The eluted chlorobenzene solution containing the polymer was collected and poured into acetone to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 80 ° C. to obtain 0.74 g (yield 59%) of arylamine polymer (HTP-8).

  The obtained arylamine polymer (HTP-8) had a weight average molecular weight of 41,000 and a number average molecule of 17,000 (dispersity of 2.4) in terms of polystyrene.

  The HOMO level was 5.20 eV, and the LUMO level was 2.36 eV. The glass transition temperature was 221 ° C.

  The excited triplet level of the arylamine polymer (HTP-8) measured in the same manner as in Example 3 was 2.33 eV.

Example 10 Synthesis of Arylamine Polymer (HTP-9) In Example 9, instead of 0.55 g (3.69 mmol) of 4-butylaniline, N, N′-bis (2,4-dimethylphenyl) benzidine 1 .22 g (3.69 mmol) was used, and 0.02 g (0.18 mmol) of p-methylaniline instead of 0.03 g (0.18 mmol) of 4-butylaniline, 0.35 g of 3-bromo-9-phenylcarbazole The arylamine polymer (HTP-9) was recovered in the same manner as in Example 9 except that 0.43 g (1.08 mmol) of 3-bromo-6,9-diphenylcarbazole was used instead of (1.08 mmol). Obtained at a rate of 65%.

  The obtained arylamine polymer (HTP-9) had a weight average molecular weight of 36,000 and a number average molecule of 23,000 (dispersity of 2.2) in terms of polystyrene.

  The HOMO level was 5.22 eV, and the LUMO level was 2.32 eV. The glass transition temperature was 282 ° C.

  The excited triplet level of the arylamine polymer (HTP-9) measured in the same manner as in Example 3 was 2.33 eV.

Example 11 Synthesis of Arylamine Polymer (HTP-10) In Example 9, 4,4′-diiodobiphenyl 1 instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene Instead of 0.50 g (3.69 mmol) of 4-butylaniline, 0.60 g (3.69 mmol) of 4-butyl-2-methylaniline was used instead of 0.50 g (3.69 mmol) of 4-butylaniline. The arylamine polymer (HTP-10) was obtained in the same manner as in Example 9 except that 0.02 g (0.18 mmol) of 4-butyl-2-methylaniline was used instead of 03 g (0.18 mmol). Obtained at 60%.

  The obtained arylamine polymer (HTP-10) had a weight average molecular weight of 34,000 and a number average molecule of 21,000 (dispersity of 1.6) in terms of polystyrene.

  The HOMO level was 5.31 eV, and the LUMO level was 2.36 eV. The glass transition temperature was 202 ° C.

  The excited triplet level of the arylamine polymer (HTP-10) measured in the same manner as in Example 3 was 2.36 eV.

Example 12 Synthesis of Arylamine Polymer (HTP-11) In Example 9, instead of 0.55 g (3.69 mmol) of 4-butylaniline, N, N′-bis (4-butyl-2-methylphenyl) 1.76 g (3.69 mmol) of benzidine was used, and 0.02 g (0.18 mmol) of 4-butyl-2-methylaniline instead of 0.03 g (0.18 mmol) of 4-butylaniline, 3-bromo-9 -The same procedure as in Example 9 was repeated except that 0.43 g (1.08 mmol) of 3-bromo-6,9-diphenylcarbazole was used instead of 0.35 g (1.08 mmol) of phenylcarbazole. HTP-11) was obtained with a yield of 55%.

  The obtained arylamine polymer (HTP-11) had a weight average molecular weight of 46,000 and a number average molecule of 26,000 (dispersity of 1.8) in terms of polystyrene.

  The HOMO level was 5.23 eV, and the LUMO level was 2.33 eV. The glass transition temperature was 203 ° C.

  The excited triplet level of the arylamine polymer (HTP-11) measured in the same manner as in Example 3 was 2.34 eV.

Example 13 Synthesis of arylamine polymer (HTP-12) In Example 9, 2,7-dibromo-9,9 instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene -Instead of 1.82 g (3.69 mmol) of dihexylfluorene and 0.55 g (3.69 mmol) of 4-butylaniline, 1.66 g (3.69 mmol) of N, N′-bis (4-butylphenyl) benzidine was used. Except having used, it carried out similarly to Example 9 and obtained the arylamine polymer (HTP-12) by 50% of yield.

  The obtained arylamine polymer (HTP-12) had a weight average molecular weight of 200,000 and a number average molecule of 63,000 (dispersity of 3.1) in terms of polystyrene.

  The HOMO level was 5.34 eV and the LUMO level was 2.45 eV. The glass transition temperature was 143 ° C.

  The excited triplet level of the arylamine polymer (HTP-12) measured in the same manner as in Example 3 was 2.31 eV.

Example 14 Synthesis of Arylamine Polymer (HTP-13) In Example 9, 4,4′-diiodobiphenyl 1 instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene Instead of 0.55 g (3.69 mmol) of 4-butylaniline, 0.68 g (3.69 mmol) of 2-methyl-4-phenylaniline was used. Instead of 03 g (0.18 mmol) 2-methyl-4-phenylaniline 0.03 g (0.18 mmol), 3-bromo-9-phenylcarbazole instead of 0.35 g (1.08 mmol) 3-bromo-6 , 9-diphenylcarbazole was used in the same manner as in Example 9 except that 0.43 g (1.08 mmol) was used. Lumpur amine polymer (HTP-13) was obtained in 62% yield.

  The obtained arylamine polymer (HTP-13) had a weight average molecular weight of 18,000 and a number average molecule of 9,400 (dispersity 1.9) in terms of polystyrene.

  The HOMO level was 5.37 eV, and the LUMO level was 2.44 eV.

  The excited triplet level of the arylamine polymer (HTP-13) measured in the same manner as in Example 3 was 2.38 eV.

Example 15 Synthesis of arylamine polymer (HTP-14) In Example 9, 4,4′-diiodobiphenyl 1 instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene Instead of .50 g (3.69 mmol), 4-butylaniline 0.55 g (3.69 mmol), 1.08 g (3.69 mmol) of 2-amino-7-hexyl-9,9-dimethylfluorene was used, The same procedure as in Example 9 was performed except that 0.05 g (0.18 mmol) of 2-amino-7-hexyl-9,9-dimethylfluorene was used instead of 0.03 g (0.18 mmol) of 4-butylaniline. An arylamine polymer (HTP-14) was obtained in a yield of 58%.

  The obtained arylamine polymer (HTP-14) had a weight average molecular weight of 39,000 and a number average molecule of 25,000 (dispersity of 1.5) in terms of polystyrene.

  The HOMO level was 5.30 eV, and the LUMO level was 2.43 eV. The glass transition temperature was 178 ° C.

  The excited triplet level of the arylamine polymer (HTP-14) measured in the same manner as in Example 3 was 2.30 eV.

Example 16 Synthesis of Arylamine Polymer (HTP-15) In Example 9, 3,3′-dibromobiphenyl instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene. Instead of 15 g (3.69 mmol), 4-butylaniline 0.55 g (3.69 mmol), 1.66 g (3.69 mmol) of N, N′-bis (4-butylphenyl) benzidine was used. The same procedure as in Example 9 was carried out except that 0.43 g (1.08 mmol) of 3-bromo-6,9-diphenylcarbazole was used instead of 0.35 g (1.08 mmol) of bromo-9-phenylcarbazole. An amine polymer (HTP-15) was obtained with a yield of 52%.

  The obtained arylamine polymer (HTP-15) had a weight average molecular weight of 140,000 and a number average molecule of 59,000 (dispersion degree of 2.4) in terms of polystyrene.

  The HOMO level was 5.52 eV, and the LUMO level was 2.40 eV. The glass transition temperature was 156 ° C.

  The excited triplet level of the arylamine polymer (HTP-15) measured in the same manner as in Example 3 was 2.33 eV.

Example 17 Synthesis of arylamine polymer (HTP-16) In Example 9, instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, 4 ″, 5′-diiodo- 1,1 ′: 2 ′, 1 ″: 2 ″, 1 ′ ″-quaterphenyl 2.06 g (3.69 mmol), 4-butylaniline 0.55 g (3.69 mmol) instead of p-methyl Using 0.40 g (3.69 mmol) of aniline, 0.02 g (0.18 mmol) of p-methylaniline instead of 0.03 g (0.18 mmol) of 4-butylaniline, 3-bromo-9-phenylcarbazole 0 Example 9 with the exception that 0.43 g (1.08 mmol) of 3-bromo-6,9-diphenylcarbazole was used instead of .35 g (1.08 mmol). Performed as the arylamine polymer (HTP-16) was obtained in 50% yield.

  The obtained arylamine polymer (HTP-16) had a weight average molecular weight of 60,000 and a number average molecule of 24,000 (dispersity of 2.5) in terms of polystyrene.

  The HOMO level was 5.53 eV, and the LUMO level was 2.44 eV.

  The excited triplet level of the arylamine polymer (HTP-16) measured in the same manner as in Example 3 was 2.33 eV.

Example 18 Synthesis of Arylamine Polymer (HTP-17) In Example 9, 4,4 ″ -dibromo-1 instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene , 1 ′: 3 ′, 1 ″ -terphenyl, except that 1.43 g (3.69 mmol) was used, the arylamine polymer (HTP-17) was obtained in a yield of 62%. It was.

  The obtained arylamine polymer (HTP-17) had a weight average molecular weight of 130,000 and a number average molecule of 78,000 (dispersity of 1.7) in terms of polystyrene.

  The HOMO level was 5.69 eV, and the LUMO level was 2.50 eV.

  The excited triplet level of the arylamine polymer (HTP-17) measured in the same manner as in Example 3 was 2.52 eV.

Example 19 Synthesis of arylamine polymer (HTP-18) In Example 9, 3,3'-dibromobiphenyl instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene. Instead of 15 g (3.69 mmol), 4-butylaniline 0.55 g (3.69 mmol), p-methylaniline 0.40 g (3.69 mmol) was used, and 4-butylaniline 0.03 g (0.18 mmol) The arylamine polymer (HTP-18) was obtained in a yield of 45% in the same manner as in Example 9 except that 0.02 g (0.18 mmol) of p-methylaniline was used instead of.

  The obtained arylamine polymer (HTP-18) had a weight average molecular weight of 74,000 and a number average molecule of 34,000 (dispersity of 2.2) in terms of polystyrene.

  The HOMO level was 5.78 eV, and the LUMO level was 2.56 eV. The glass transition temperature was 165 ° C.

  The excited triplet level of the arylamine polymer (HTP-18) measured in the same manner as in Example 3 was 2.66 eV.

Example 20 Synthesis of Arylamine Polymer (HTP-19) In Example 9, 3,6-dibromo-9-phenyl instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene Instead of 1.48 g (3.69 mmol) of carbazole and 0.55 g (3.69 mmol) of 4-butylaniline, N, N′-bis (4-butylphenyl) -1,1 ′: 3 ′, 1 ″ -1.94 g (3.69 mmol) of terphenyl-4,4 "-diamine was used and 3-bromo-6,9- instead of 0.35 g (1.08 mmol) of 3-bromo-9-phenylcarbazole Except having used 0.43 g (1.08 mmol) of diphenylcarbazole, it carried out similarly to Example 9 and obtained the arylamine polymer (HTP-19) by 65% of yield.

  The obtained arylamine polymer (HTP-19) had a weight average molecular weight of 16,000 and a number average molecule of 11,000 (dispersity of 1.5) in terms of polystyrene.

  The HOMO level was 5.28 eV, and the LUMO level was 2.20 eV. The glass transition temperature was 224 ° C.

  The excited triplet level of the arylamine polymer (HTP-19) measured in the same manner as in Example 3 was 2.50 eV.

Example 21 Synthesis of Arylamine Polymer (HTP-20) In Example 9, instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, 4 ″, 5′-diiodo- 1,1 ′: 2 ′, 1 ″: 2 ″, 1 ′ ″-quaterphenyl 2.06 g (3.69 mmol), 4-butylaniline 0.55 g (3.69 mmol) instead of N, 1.34 g (3.69 mmol) of N′-bis (4-methylphenyl) benzidine was used and 0.02 g (0.18 mmol) of p-methylaniline instead of 0.03 g (0.18 mmol) of 4-butylaniline Instead of 0.35 g (1.08 mmol) of 3-bromo-9-phenylcarbazole, 0.43 g (1.08 mmol) of 3-bromo-6,9-diphenylcarbazole Was carried out in the same manner as in Example 9, except that the arylamine polymer (HTP-20) was obtained in a yield of 60%.

  The obtained arylamine polymer (HTP-20) had a weight average molecular weight of 51,000 and a number average molecule of 22,000 (dispersity of 2.3) in terms of polystyrene.

  The HOMO level was 5.42 eV and the LUMO level was 2.41 eV.

  The excited triplet level of the arylamine polymer (HTP-20) measured in the same manner as in Example 3 was 2.35 eV.

Example 22 Synthesis of Arylamine Polymer (HTP-21) In Example 9, 4,4′-diiodo-2, instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, Instead of 1.60 g (3.69 mmol) of 2′-dimethylbiphenyl and 0.55 g (3.69 mmol) of 4-butylaniline, 0.40 g (3.69 mmol) of p-methylaniline was used. 0.02 g (0.18 mmol) of p-methylaniline instead of 0.03 g (0.18 mmol), 3-bromo-6,9- instead of 0.35 g (1.08 mmol) of 3-bromo-9-phenylcarbazole Arylamine was prepared in the same manner as in Example 9 except that 0.43 g (1.08 mmol) of diphenylcarbazole was used. A polymer (HTP-21) was obtained with a yield of 50%.

  The obtained arylamine polymer (HTP-21) had a weight average molecular weight of 23,000 and a number average molecule of 17,000 (dispersity of 1.4) in terms of polystyrene.

  The HOMO level was 5.66 eV, and the LUMO level was 2.33 eV. The glass transition temperature was 230 ° C.

  The excited triplet level of the arylamine polymer (HTP-21) measured in the same manner as in Example 3 was 2.61 eV.

Example 23 Synthesis of arylamine polymer (HTP-22) In Example 9, 4,4 ″ -dibromo-1 instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene , 1 ′: 3 ′, 1 ″ -terphenyl 1.43 g (3.69 mmol), 4-butylaniline 0.55 g (3.69 mmol) instead of N, N′-bis (4-butylphenyl) 1.66 g (3.69 mmol) of benzidine was used, and instead of 0.35 g (1.08 mmol) of 3-bromo-9-phenylcarbazole, 0.43 g (1.08 mmol) of 3-bromo-6,9-diphenylcarbazole Was used in the same manner as in Example 9, except that the arylamine polymer (HTP-22) was obtained in a yield of 64%.

  The obtained arylamine polymer (HTP-22) had a weight average molecular weight of 120,000 and a number average molecule of 24,000 (dispersity of 5.0) in terms of polystyrene.

  The HOMO level was 5.48 eV and the LUMO level was 2.49 eV.

  The excited triplet level of the arylamine polymer (HTP-22) measured in the same manner as in Example 3 was 2.36 eV.

Example 24 Synthesis of arylamine polymer (HTP-23) In Example 9, 4,4'-dibromo-1, instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, 1 ′: N′N′-bis (4-methylphenyl) benzidine instead of 1.43 g (3.69 mmol) of 2 ′, 1 ″ -terphenyl and 0.55 g (3.69 mmol) of 4-butylaniline 1.34 g (3.69 mmol) was used, 0.04 g (0.18 mmol) of p-methylaniline instead of 0.03 g (0.18 mmol) of 4-butylaniline, 3-bromo-9-phenylcarbazole Except for using 0.43 g (1.08 mmol) of 3-bromo-6,9-diphenylcarbazole instead of 35 g (1.08 mmol), Performed in the same manner as Example 9, arylamine polymer (HTP-23) was obtained in 58% yield.

  The obtained arylamine polymer (HTP-23) had a weight average molecular weight of 59,000 and a number average molecule of 21,000 (dispersity 2.8) in terms of polystyrene.

  The HOMO level was 5.34 eV, and the LUMO level was 2.37 eV.

  The excited triplet level of the arylamine polymer (HTP-23) measured in the same manner as in Example 3 was 2.35 eV.

Example 25 Synthesis of arylamine polymer (HTP-24) In Example 9, 4,4'-dibromo-2, instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, Instead of 2.08 g (3.69 mmol) of 2′-di (2-naphthyl) biphenyl and 0.55 g (3.69 mmol) of 4-butylaniline, N, N′-bis (4-methylphenyl) benzidine 34 g (3.69 mmol) was used, and 0.02 g (0.18 mmol) of p-methylaniline instead of 0.03 g (0.18 mmol) of 4-butylaniline, 0.35 g of 3-bromo-9-phenylcarbazole ( Except that 0.43 g (1.08 mmol) of 3-bromo-6,9-diphenylcarbazole was used instead of 1.08 mmol) Were performed in the same manner as in Example 9, arylamine polymer (HTP-24) was obtained in 60% yield.

  The obtained arylamine polymer (HTP-24) had a weight average molecular weight of 50,000 and a number average molecule of 19,000 (dispersity of 2.6) in terms of polystyrene.

  The HOMO level was 5.41 eV, and the LUMO level was 2.44 eV.

  The excited triplet level of the arylamine polymer (HTP-24) measured in the same manner as in Example 3 was 2.32 eV.

Example 26 Synthesis of arylamine polymer (HTP-25) In Example 9, 4,4'-diiodobiphenyl 1 instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene .50 g (3.69 mmol), instead of 0.55 g (3.69 mmol) of 4-butylaniline, N, N′-bis (4-methylphenyl) -1,1 ′: 2 ′, 1 ″: 2 '', 1 '''-quaterphenyl-4'',5'-diamine 1.81 g (3.51 mmol) and N, N'-bis [3- (2-triphenylenyl) phenyl] benzidine 0.146 g (0 .18 mmol), and instead of 0.03 g (0.18 mmol) of 4-butylaniline, 0.02 g (0.18 mmol) of p-methylaniline, 3-bromo-9-pheny The arylamine polymer (HTP-) was prepared in the same manner as in Example 9 except that 0.43 g (1.08 mmol) of 3-bromo-6,9-diphenylcarbazole was used instead of 0.35 g (1.08 mmol) of carbazole. 25) was obtained in a yield of 56%.

  The obtained arylamine polymer (HTP-25) had a weight average molecular weight of 36,000 and a number average molecule of 24,000 (dispersity of 1.5) in terms of polystyrene.

  The HOMO level was 5.42 eV and the LUMO level was 2.41 eV.

  The excited triplet level of the arylamine polymer (HTP-25) measured in the same manner as in Example 3 was 2.31 eV.

Example 27 Synthesis of arylamine polymer (HTP-26) In Example 9, 4,4′-diiodobiphenyl 1 instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene .50 g (3.69 mmol), instead of 0.55 g (3.69 mmol) of 4-butylaniline, N, N′-bis (4-methylphenyl) -1,1 ′: 2 ′, 1 ″: 2 ″, 1 ′ ″-Quaterphenyl-4 ″, 5′-diamine 1.81 g (3.51 mmol) and N, N′-bis (4-methylphenyl) -2- (2-dibenzofuranyl) A mixture with 0.098 g (0.18 mmol) of biphenyl-4,4′-diamine was used, and 0.02 g (0.18 mm) of p-methylaniline instead of 0.03 g (0.18 mmol) of 4-butylaniline. ol), and Example 9 with the exception that 0.43 g (1.08 mmol) of 3-bromo-6,9-diphenylcarbazole was used instead of 0.35 g (1.08 mmol) of 3-bromo-9-phenylcarbazole. In the same manner, an arylamine polymer (HTP-26) was obtained with a yield of 48%.

  The obtained arylamine polymer (HTP-26) had a weight average molecular weight of 48,000 and a number average molecule of 21,000 (dispersion degree 2.3) in terms of polystyrene.

  The HOMO level was 5.42 eV and the LUMO level was 2.41 eV.

  The excited triplet level of the arylamine polymer (HTP-26) measured in the same manner as in Example 3 was 2.34 eV.

Example 28 Synthesis of arylamine polymer (HTP-27) In Example 9, 4,4 ″ -dibromo-1 instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene , 1 ′: 4 ′, 1 ″ -terphenyl, except that 1.43 g (3.69 mmol) was used, the arylamine polymer (HTP-27) was obtained in a yield of 64%. It was.

  The obtained arylamine polymer (HTP-27) had a weight average molecular weight of 19,000 and a number average molecule of 12,000 (dispersity of 1.6) in terms of polystyrene.

  The HOMO level was 5.35 eV, and the LUMO level was 2.29 eV. The glass transition temperature was 219 ° C.

  The excited triplet level of the arylamine polymer (HTP-27) measured in the same manner as in Example 3 was 2.27 eV.

Example 29 Synthesis of arylamine polymer (HTP-28) In Example 9, 4,4′-diiodobiphenyl 1 instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene .50 g (3.69 mmol), 4-butylaniline instead of 0.55 g (3.69 mmol), 4-butylaniline 0.28 g (1.85 mmol) and 4-fluoroaniline 0.21 g (1.85 mmol) The arylamine polymer (HTP-28) was obtained in a yield of 55% in the same manner as in Example 9 except that the mixture was used.

  The obtained arylamine polymer (HTP-28) had a weight average molecular weight of 19,000 and a number average molecule of 11,000 (dispersity 1.8) in terms of polystyrene.

  The HOMO level was 5.51 eV, and the LUMO level was 2.59 eV. The glass transition temperature was 219 ° C.

  The excited triplet level of the arylamine polymer (HTP-28) measured in the same manner as in Example 3 was 2.32 eV.

Example 30 Synthesis of arylamine polymer (HTP-29) In Example 9, instead of 0.55 g (3.69 mmol) of 4-butylaniline, 1.24 g of N, N′-bis (4-fluorophenyl) benzidine (3.32 mmol) and N, N′-bis (4-fluoro-2-methylphenyl) benzidine 0.148 g (0.369 mmol) was used, and 4-butylaniline 0.03 g (0.18 mmol) was used. The arylamine polymer (HTP-29) was obtained in a yield of 52% in the same manner as in Example 9 except that 0.02 g (0.18 mmol) of 4-fluoroaniline was used instead of.

  The obtained arylamine polymer (HTP-29) had a weight average molecular weight of 87,000 and a number average molecule of 42,000 (dispersity of 2.1) in terms of polystyrene.

  The HOMO level was 5.55 eV, and the LUMO level was 2.61 eV. The glass transition temperature was 228 ° C.

  The excited triplet level of the arylamine polymer (HTP-29) measured in the same manner as in Example 3 was 2.33 eV.

Example 31 Synthesis of Arylamine Polymer (HTP-30) In Example 9, 3,6-dibromo-9-phenyl instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene 1.76 g (3.69 mmol) of N, N′-bis (4-butyl-2-methylphenyl) benzidine instead of 1.48 g (3.69 mmol) of carbazole and 0.55 g (3.69 mmol) of 4-butylaniline ) Was used in the same manner as in Example 9 to obtain an arylamine polymer (HTP-30) in a yield of 59%.

  The obtained arylamine polymer (HTP-30) had a weight average molecular weight of 56,000 and a number average molecule of 26,000 (dispersity of 2.2) in terms of polystyrene.

  The HOMO level was 5.17 eV and the LUMO level was 2.18 eV. The glass transition temperature was 242 ° C.

  The excited triplet level of the arylamine polymer (HTP-30) measured in the same manner as in Example 3 was 2.37 eV.

Example 32 Synthesis of arylamine polymer (HTP-31) In Example 9, 2,7-dibromo-9-phenyl instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene 1.76 g (3.69 mmol) of N, N′-bis (4-butyl-2-methylphenyl) benzidine instead of 1.48 g (3.69 mmol) of carbazole and 0.55 g (3.69 mmol) of 4-butylaniline ) Was used in the same manner as in Example 9 to obtain an arylamine polymer (HTP-31) in a yield of 56%.

  The obtained arylamine polymer (HTP-31) had a weight average molecular weight of 66,000 and a number average molecule of 33,000 (dispersity 2.0) in terms of polystyrene.

  The HOMO level was 5.20 eV, and the LUMO level was 2.33 eV. The glass transition temperature was 212 ° C.

  The excited triplet level of the arylamine polymer (HTP-31) measured in the same manner as in Example 3 was 2.35 eV.

Example 33 Synthesis of arylamine polymer (HTP-32) In Example 9, instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, 6,6′-dibromo-9, Instead of 2.37 g (3.69 mmol) of 9′-diphenyl-3,3′-biscarbazole and 0.55 g (3.69 mmol) of 4-butylaniline, N, N′-bis (4-butylphenyl) benzidine Except having used 1.66 g (3.69 mmol), it carried out like Example 9 and obtained the arylamine polymer (HTP-32) with the yield of 60%.

  The obtained arylamine polymer (HTP-32) had a weight average molecular weight of 38,000 and a number average molecule of 16,000 (dispersion degree 2.3) in terms of polystyrene.

  The HOMO level was 5.26 eV and the LUMO level was 2.31 eV.

  The excited triplet level of the arylamine polymer (HTP-32) measured in the same manner as in Example 3 was 2.37 eV.

Example 34 Synthesis of arylamine polymer (HTP-33) In Example 9, instead of 1,30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, 3,6-dibromo-9- [ Instead of 2.13 g (3.69 mmol) 3- (9-phenanthryl) phenyl] carbazole, 0.55 g (3.69 mmol) 4-butylaniline, N, N′-bis (2,4-dimethylphenyl) benzidine Example 9 except that 1.76 g (3.69 mmol) was used and 0.02 g (0.18 mmol) of 2,4-dimethylaniline was used instead of 0.03 g (0.18 mmol) of 4-butylaniline The arylamine polymer (HTP-33) was obtained in a yield of 45%.

  The obtained arylamine polymer (HTP-33) had a weight average molecular weight of 59,000 and a number average molecule of 19,000 (dispersity of 3.1) in terms of polystyrene.

  The HOMO level was 5.06 eV, and the LUMO level was 2.08 eV.

  The excited triplet level of the arylamine polymer (HTP-33) measured in the same manner as in Example 3 was 2.41 eV.

Example 35 Synthesis of arylamine polymer (HTP-34) In Example 9, instead of 1,30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, 3,6-dibromo-9- [ Instead of 2.09 g (3.69 mmol) of 3- (4-dibenzofuranyl) phenyl] carbazole and 0.55 g (3.69 mmol) of 4-butylaniline, N, N′-bis (2,4-dimethylphenyl) ) Implementation, except that 1.76 g (3.69 mmol) of benzidine was used and 0.02 g (0.18 mmol) of 2,4-dimethylaniline was used instead of 0.03 g (0.18 mmol) of 4-butylaniline In the same manner as in Example 9, an arylamine polymer (HTP-34) was obtained in a yield of 48%.

  The obtained arylamine polymer (HTP-34) had a weight average molecular weight of 14,000 and a number average molecule of 6,000 (dispersion degree 2.3) in terms of polystyrene.

  The HOMO level was 5.16 eV and the LUMO level was 2.19 eV. The glass transition temperature was 267 ° C.

  The excited triplet level of the arylamine polymer (HTP-34) measured in the same manner as in Example 3 was 2.40 eV.

Example 36 Synthesis of Arylamine Polymer (HTP-35) In Example 9, instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, 3,6-dibromo-9- [ Instead of 2.15 g (3.69 mmol) of 3- (2-dibenzothiophenyl) phenyl] carbazole and 0.55 g (3.69 mmol) of 4-butylaniline, N, N′-bis (2,4-dimethylphenyl) ) Implementation, except that 1.76 g (3.69 mmol) of benzidine was used and 0.02 g (0.18 mmol) of 2,4-dimethylaniline was used instead of 0.03 g (0.18 mmol) of 4-butylaniline In the same manner as in Example 9, an arylamine polymer (HTP-35) was obtained in a yield of 42%.

  The obtained arylamine polymer (HTP-35) had a weight average molecular weight of 14,000 and a number average molecule of 7,000 (dispersity of 2.0) in terms of polystyrene.

  The HOMO level was 5.20 eV, and the LUMO level was 2.24 eV. The glass transition temperature was 264 ° C.

  The excited triplet level of the arylamine polymer (HTP-35) measured in the same manner as in Example 3 was 2.39 eV.

Example 37 Synthesis of Arylamine Polymer (HTP-36) In Example 9, instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, 2,7-dibromo-9- ( Instead of 1.87 g (3.69 mmol) of 2-dibenzothiophenyl) carbazole and 0.55 g (3.69 mmol) of 4-butylaniline 1.66 g (3 of N, N′-bis (4-butylphenyl) benzidine .69 mmol) and 0.43 g (1.08 mmol) of 3-bromo-6,9-diphenylcarbazole instead of 0.35 g (1.08 mmol) of 3-bromo-9-phenylcarbazole, In the same manner as in Example 9, an arylamine polymer (HTP-36) was obtained with a yield of 51%.

  The obtained arylamine polymer (HTP-36) had a weight average molecular weight of 120,000 and a number average molecule of 18,000 (dispersity of 6.6) in terms of polystyrene.

  The HOMO level was 5.27 eV and the LUMO level was 2.41 eV. The glass transition temperature was 218 ° C.

  The excited triplet level of the arylamine polymer (HTP-36) measured in the same manner as in Example 3 was 2.33 eV.

Example 38 Synthesis of Arylamine Polymer (HTP-37) In Example 9, instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, 2,7-dibromo-9- ( Instead of 1.81 g (3.69 mmol) of 3-dibenzofuranyl) carbazole and 0.55 g (3.69 mmol) of 4-butylaniline 1.66 g of N, N′-bis (4-butylphenyl) benzidine (3 .69 mmol) and 0.43 g (1.08 mmol) of 3-bromo-6,9-diphenylcarbazole instead of 0.35 g (1.08 mmol) of 3-bromo-9-phenylcarbazole, In the same manner as in Example 9, an arylamine polymer (HTP-37) was obtained with a yield of 55%.

  The obtained arylamine polymer (HTP-37) had a weight average molecular weight of 110,000 and a number average molecule of 54,000 (dispersity of 2.0) in terms of polystyrene.

  The HOMO level was 5.30 eV, and the LUMO level was 2.45 eV. The glass transition temperature was 227 ° C.

  The excited triplet level of the arylamine polymer (HTP-37) measured in the same manner as in Example 3 was 2.33 eV.

Example 39 Synthesis of arylamine polymer (HTP-38) In Example 9, 4,4 ''-dibromo-1 instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene , 1 ′: 4 ′, 1 ″ -terphenyl 1.43 g (3.69 mmol), 4-butylaniline 0.55 g (3.69 mmol) instead of N, N′-bis (4-butylphenyl) The arylamine polymer (HTP-38) was obtained in a yield of 64% in the same manner as in Example 9 except that 1.80 g (3.69 mmol) of fluorene-2,7-diamine was used.

  The obtained arylamine polymer (HTP-38) had a weight average molecular weight of 86,000 and a number average molecule of 49,000 (dispersity of 1.7) in terms of polystyrene.

  The HOMO level was 5.32 eV, and the LUMO level was 2.46 eV.

  The excited triplet level of the arylamine polymer (HTP-38) measured in the same manner as in Example 3 was 2.21 eV.

Example 40 Synthesis of arylamine polymer (HTP-39) In Example 9, instead of 0.55 g (3.69 mmol) of 4-butylaniline, N, N'-bis (9,9-dimethylfluorenyl- 2-yl) benzidine 1.76 g (3.69 mmol) was used and instead of 0.35 g (1.08 mmol) of 3-bromo-9-phenylcarbazole 0.43 g of 3-bromo-6,9-diphenylcarbazole ( 1.08 mmol) was used in the same manner as in Example 9, except that an arylamine polymer (HTP-39) was obtained in a yield of 55%.

  The obtained arylamine polymer (HTP-39) had a weight average molecular weight of 19,000 and a number average molecule of 12,000 (dispersity of 1.6) in terms of polystyrene.

  The HOMO level was 5.25 eV, and the LUMO level was 2.37 eV.

  The excited triplet level of the arylamine polymer (HTP-39) measured in the same manner as in Example 3 was 2.34 eV.

Example 41 Synthesis of arylamine polymer (HTP-40) In Example 9, instead of 0.55 g (3.69 mmol) of 4-butylaniline, N, N'-bis (4-methylphenyl) -1,1 ': 2', 1 '': 2 '', 1 '''-quaterphenyl-4'',5'-diamine 1.91 g (3.69 mmol) was used and 4-butylaniline 0.03 g (0 .18 mmol) instead of p-methylaniline 0.02 g (0.18 mmol), 3-bromo-9-phenylcarbazole instead of 0.35 g (1.08 mmol) 3-bromo-6,9-diphenylcarbazole Except having used 43 g (1.08 mmol), it carried out similarly to Example 9 and obtained the arylamine polymer (HTP-40) by 56% of the yield.

  The obtained arylamine polymer (HTP-40) had a weight average molecular weight of 36,000 and a number average molecule of 24,000 (dispersity of 1.5) in terms of polystyrene.

  The HOMO level was 5.40 eV and the LUMO level was 2.39 eV.

  The excited triplet level of the arylamine polymer (HTP-40) measured in the same manner as in Example 3 was 2.33 eV.

Example 42 Synthesis of arylamine polymer (HTP-41) In Example 9, instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, 1.42 g of 2,7-dibromotriphenylene (3.69 mmol), instead of 0.55 g (3.69 mmol) of 4-butylaniline, except that 1.66 g (3.69 mmol) of N, N′-bis (4-butylphenyl) benzidine was used In the same manner as in Example 9, an arylamine polymer (HTP-41) was obtained in a yield of 60%.

  The obtained arylamine polymer (HTP-41) had a weight average molecular weight of 15,000 and a number average molecule of 9,000 (dispersion degree 1.7) in terms of polystyrene.

  The HOMO level was 5.32 eV, and the LUMO level was 2.48 eV. The glass transition temperature was 228 ° C.

  The excited triplet level of the arylamine polymer (HTP-41) measured in the same manner as in Example 3 was 2.38 eV.

Example 43 Synthesis of arylamine polymer (HTP-42) In Example 9, instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, 1.24 g of 9,10-dibromoanthracene (3.69 mmol), instead of 0.55 g (3.69 mmol) of 4-butylaniline, except that 1.66 g (3.69 mmol) of N, N′-bis (4-butylphenyl) benzidine was used In the same manner as in Example 9, an arylamine polymer (HTP-42) was obtained in a yield of 40%.

  The obtained arylamine polymer (HTP-42) had a weight average molecular weight of 49,000 and a number average molecule of 26,000 (dispersity 1.9) in terms of polystyrene.

  The HOMO level was 5.42 eV, and the LUMO level was 3.09 eV.

Example 44 Synthesis of arylamine polymer (HTP-43) In Example 9, 4,4'-dibromobiphenyl instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene. A mixture of 92 g (2.95 mmol) and 2,12-dibromo-9,10-di (2-naphthyl) anthracene 0.412 g (0.74 mmol) was added to 0.55 g (3.69 mmol) of 4-butylaniline. Instead, 1.66 g (3.69 mmol) of N, N′-bis (4-butylphenyl) benzidine was used, and 3-bromo-9-phenylcarbazole instead of 0.35 g (1.08 mmol) 3-bromo The procedure of Example 9 was repeated except that 0.43 g (1.08 mmol) of -6,9-diphenylcarbazole was used. Min polymer (HTP-43) was obtained in 50% yield.

  The obtained arylamine polymer (HTP-43) had a weight average molecular weight of 42,000 and a number average molecule of 19,000 (dispersity of 2.2) in terms of polystyrene.

  The HOMO level was 5.31 eV and the LUMO level was 2.95 eV.

Example 45 Synthesis of arylamine polymer (HTP-44) In Example 9, instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene, 9,10-di (4-bromo) Instead of 1.80 g (3.69 mmol) of phenyl) anthracene and 0.55 g (3.69 mmol) of 4-butylaniline, 1.66 g (3.69 mmol) of N, N′-bis (4-butylphenyl) benzidine Except having used, it carried out similarly to Example 9 and obtained the arylamine polymer (HTP-44) by 43% of the yield.

  The obtained arylamine polymer (HTP-44) had a weight average molecular weight of 52,000 and a number average molecule of 24,000 (dispersity of 2.1) in terms of polystyrene.

  The HOMO level was 5.50 eV and the LUMO level was 2.78 eV.

Example 46 Synthesis of arylamine polymer (HTP-45) In Example 9, instead of 0.55 g (3.69 mmol) of 4-butylaniline, 1.24 g of N, N'-bis (4-butylphenyl) benzidine (2.77 mmol) and N, N′-bis [3- (2-triphenylene) phenyl] benzidine 0.726
g (0.92 mmol) was used and instead of 0.35 g (1.08 mmol) 3-bromo-9-phenylcarbazole 0.43 g (1.08 mmol) 3-bromo-6,9-diphenylcarbazole Was used in the same manner as in Example 9, except that the arylamine polymer (HTP-45) was obtained in a yield of 50%.

  The obtained arylamine polymer (HTP-45) had a weight average molecular weight of 36,000 and a number average molecule of 24,000 (dispersity of 1.5) in terms of polystyrene.

  The HOMO level was 5.33 eV and the LUMO level was 2.39 eV.

Example 47 Synthesis of arylamine polymer (HTP-46) In Example 9, 2,7-dibromo-9,9 instead of 1.30 g (3.69 mmol) of 2,7-dibromo-9,9-dimethylfluorene -Instead of 1.76 g (3.69 mmol) of diphenylfluorene and 0.55 g (3.69 mmol) of 4-butylaniline, 1.01 g (2.77 mmol) of N, N′-bis (4-methylphenyl) benzidine A mixture with 0.362 g (0.923 mmol) of N, N′-bis (2,4-dimethylphenyl) benzidine was used, and p-methylaniline 0 instead of 0.03 g (0.18 mmol) of 4-butylaniline Arylamine polymer (HTP-46) was prepared in the same manner as in Example 9 except that 0.02 g (0.18 mmol) was used. It was obtained in 52% yield.

  The obtained arylamine polymer (HTP-46) had a weight average molecular weight of 18,000 and a number average molecule of 11,000 (dispersity of 1.7) in terms of polystyrene.

  The HOMO level was 5.33 eV and the LUMO level was 2.39 eV. The glass transition temperature was 228 ° C.

  The excited triplet level of the arylamine polymer (HTP-46) measured in the same manner as in Example 3 was 2.37 eV.

  Comparative Example 1 Measurement of triplet level and glass transition temperature of conjugated polymer compound (REF-001)

  A phosphorescence spectrum was measured in the same manner as in Example 1 except that REF-001 was used in place of the arylamine polymer (HTP-001) in Example 1. The triplet calculated from the obtained phosphorescence spectrum was measured. The term level was 2.34 eV.

  The HOMO level was 5.34 eV and the LUMO level was 2.41 eV. The glass transition temperature was 170 ° C.

Example 48 (Production and Evaluation of Device)
The glass substrate on which the ITO transparent electrode (anode) having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Further, ultraviolet ozone cleaning was performed.

  On this substrate, a suspension of poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid (manufactured by Bayer, Baytron P CH8000) was applied by spin coating, and dried at 200 ° C. for 1 hour. As a result, a hole injection layer having a thickness of 80 nm was formed.

  Next, a 0.5 wt% chlorobenzene solution of the conjugated polymer compound (HTP-001) obtained in Example 1 was applied by spin coating, and dried at 160 ° C. for 3 hours. As a result, a 20 nm hole transport layer of a conjugated polymer compound (HTP-001) was formed.

Next, after installing in a vacuum evaporation apparatus, it exhausted with the vacuum pump until it became 5x10 <^-4> Pa or less. Subsequently, tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) as a phosphorescent dopant material and 4,4′-bis (N-carbazolyl) biphenyl (CBP) as a host material have a weight ratio of 1:11. Co-deposited at a deposition rate of 0.25 nm / second to obtain a 30 nm emission layer.

Next, BAlq (bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum) was deposited at a deposition rate of 0.3 nm / second to form a 5 nm exciton block layer, and then Alq ₃ (Tris). (8-quinolinolato) aluminum) was deposited at 0.3 nm / second to form a 45 nm electron transport layer. Subsequently, lithium fluoride was deposited as an electron injection layer to a thickness of 0.5 nm at a deposition rate of 0.01 nm / second, and aluminum was further deposited to a thickness of 100 nm at a deposition rate of 0.25 nm / second to form a cathode. In a nitrogen atmosphere, a sealing glass plate was bonded with a UV curable resin to obtain an organic EL element for evaluation.

A current of 20 mA / cm ² was applied to the device thus fabricated, and driving voltage and current efficiency were measured. Further, the luminance half life when the initial luminance was 2000 cd / m ² was examined. The evaluation results are shown in Table 1.

Example 49 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-002) synthesized in Example 3 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 50 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-003) synthesized in Example 4 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 51 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-004) synthesized in Example 5 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 52 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-005) synthesized in Example 6 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 53 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-006) synthesized in Example 7 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 54 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-007) synthesized in Example 8 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 55 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-008) synthesized in Example 9 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 56 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-012) synthesized in Example 13 was used instead of the arylamine polymer (HTP-001), and the emission characteristics and Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 57 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-013) synthesized in Example 14 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 58 (device fabrication and evaluation)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-014) synthesized in Example 15 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 59 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-015) synthesized in Example 16 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 60 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-016) synthesized in Example 17 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 61 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-017) synthesized in Example 18 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 62 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-018) synthesized in Example 19 was used instead of the arylamine polymer (HTP-001), and the emission characteristics and Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 63 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-019) synthesized in Example 20 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 64 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-020) synthesized in Example 21 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 65 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-021) synthesized in Example 22 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 66 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-022) synthesized in Example 23 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 67 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-023) synthesized in Example 24 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 68 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-024) synthesized in Example 25 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 69 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-025) synthesized in Example 26 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 70 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-026) synthesized in Example 27 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 71 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-027) synthesized in Example 28 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 72 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-028) synthesized in Example 29 was used instead of the arylamine polymer (HTP-001), and the emission characteristics and Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 73 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-029) synthesized in Example 30 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 74 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-030) synthesized in Example 31 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 75 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-031) synthesized in Example 32 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 76 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-032) synthesized in Example 33 was used instead of the arylamine polymer (HTP-001), and the emission characteristics and Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 77 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-033) synthesized in Example 34 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 78 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-034) synthesized in Example 35 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 79 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-035) synthesized in Example 36 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 80 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-036) synthesized in Example 37 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 81 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-037) synthesized in Example 38 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 82 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-038) synthesized in Example 39 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 83 (Element fabrication and evaluation)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-039) synthesized in Example 40 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 84 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-040) synthesized in Example 41 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 85 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-041) synthesized in Example 42 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 86 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-042) synthesized in Example 43 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 87 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-043) synthesized in Example 44 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 88 (Production and Evaluation of Device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-044) synthesized in Example 45 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 89 (Production and evaluation of device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-045) synthesized in Example 46 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Example 90 (Preparation and evaluation of device)
In Example 48, a device was prepared in the same manner as in Example 48 except that the arylamine polymer (HTP-046) synthesized in Example 47 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 1.

Comparative Example 2 (device fabrication and evaluation)
A device was fabricated in the same manner as in Example 9, except that the arylamine polymer (REF-001) in which the triplet level was measured in Comparative Example 1 was used instead of the arylamine polymer (HTP-001). The emission characteristics and luminance half-life were measured. The evaluation results are shown in Table 19. The measurement values of Examples 9 to 16 were normalized and displayed with the measurement value of Comparative Example 2 as 100.

  Therefore, the conjugated polymer compound of the present invention can provide a phosphorescent or fluorescent organic EL element having high luminance, low power consumption, and high durability.

  The arylamine polymer (3) of the present invention has an excited triplet level equivalent to or higher than that of a conventionally known polymer compound, and has high durability and high durability against electric charges.

  Therefore, if the arylamine polymer (3) of the present invention is used, it is possible to provide an organic EL device having excellent lifetime. Therefore, the conjugated polymer compound of the present invention can provide a phosphorescent or fluorescent organic EL device having high luminance and low power consumption.

Claims (12)

An arylamine polymer, wherein at least one terminal has a structure represented by the following general formula (3).

[Wherein, c represents 1 or 2, d represents 0 or 1, and the sum of d and c is 2.
Ar ⁵ represents a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms, or a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms {these groups are , Each independently a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms (the groups are each independently a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and One or more substituents selected from the group consisting of an alkoxy group having 1 to 18 carbon atoms may be present), a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms (this Each group may independently have one or more substituents selected from the group consisting of a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. , A thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. It may have one or more substituents}, represents a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms.
X represents each independently the group represented by the following general formula (2) or general formula (2) ′.

{Where,
A ring and B ring are each independently a monocyclic, connected or condensed aromatic hydrocarbon ring having 6 to 16 carbon atoms, or a monocyclic, connected or condensed heterocycle having 4 to 16 carbon atoms. Represents an aromatic ring.
Ar ³ is each independently a monocyclic, linked, or condensed bivalent aromatic hydrocarbon group having 6 to 36 carbon atoms, or a monovalent, linked, or condensed bivalent group having 4 to 36 carbon atoms. Heteroaromatic group (These groups are each independently one or more substituents selected from the group consisting of a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. Which may have).
Ar ⁴ is each independently a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms, or a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms. (These groups are each independently a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms, a monocyclic, linked or condensed heteroaromatic group having 4 to 20 carbon atoms. 1 or more substituents selected from the group consisting of a group, a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms), a thermal crosslinking group, carbon An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is represented.
Each Ar ⁶ is independently a monocyclic, linked, or condensed divalent aromatic hydrocarbon group having 6 to 36 carbon atoms, or a monovalent, linked, or condensed divalent group having 4 to 36 carbon atoms. Heteroaromatic group (These groups are each independently one or more substituents selected from the group consisting of a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. Which may have).
a represents an integer of 0 to 3 each independently.
b represents 0 or 1. }] The arylamine polymer according to claim 1, wherein the arylamine polymer has a repeating structure represented by at least the following general formula (1).

[Where:
Ar ¹ is a monocyclic, linked, or condensed divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a monovalent, linked, or condensed divalent heteroaromatic group having 4 to 30 carbon atoms { These groups are each independently a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms (the groups are each independently a phenanthryl group, dibenzofuranyl group, dibenzothienyl group). 1 or more substituents selected from the group consisting of a group, a thermal cross-linking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms), and 4 to 20 carbon atoms. A monocyclic, linked, or condensed heteroaromatic group (the groups are each independently selected from the group consisting of a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms). One or more selected substituents may be selected), a thermal cross-linking group, a carbon number of 1 to 18 Which may have one or more substituents selected from the group consisting of an alkyl group and an alkoxy group having 1 to 18 carbon atoms}.
Ar ² is a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms, or a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms {these groups are , Each independently a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 20 carbon atoms (the groups are each independently a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and One or more substituents selected from the group consisting of an alkoxy group having 1 to 18 carbon atoms may be present), a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms (this Each group may independently have one or more substituents selected from the group consisting of a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. , A thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. It may have one or more substituents}, represents a thermal crosslinking group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. ]   The arylamine according to claim 1 or 2, wherein the A ring and the B ring are each independently a monocyclic, linked, or condensed aromatic hydrocarbon ring having 6 to 10 carbon atoms. polymer. Ar ³ and Ar ⁶ are each independently a phenylene group, pyridylene group, pyrazylene group, pyrimidylene group, frangiyl group, or thiophenediyl group (these groups are each independently an alkyl group having 1 to 18 carbon atoms). And optionally having one or more substituents selected from the group consisting of alkoxy groups having 1 to 18 carbon atoms). The arylamine polymer described in 1.   The arylamine polymer according to any one of claims 1 to 4, wherein b is 0. 6. The group represented by the general formula (2) or (2) ′ is a group represented by any one of the following (B1) to (B10). The arylamine polymer according to item.

(In the formula, Ar ³ , Ar ⁴ , and a have the same meaning as in claim 1). Ar ² and Ar ⁵ are each independently a phenyl group, a fluorenyl group, a carbazolyl group, a dibenzofuranyl group, or a dibenzothiophenyl group (these groups are monocyclic, linked, or condensed having 6 to 20 carbon atoms). A ring aromatic hydrocarbon group (the groups each independently have one or more substituents selected from the group consisting of an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms); Or a monocyclic, linked, or condensed heteroaromatic group having 4 to 20 carbon atoms (the groups are each independently an alkyl group having 1 to 18 carbon atoms and 1 to 1 carbon atoms). Which may have one or more substituents selected from the group consisting of 18 alkoxy groups), an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. . The arylamine polymer according to any one of claims 1 to 6, wherein The arylamine polymer according to any one of claims 1 to 7, wherein Ar ¹ is a group represented by any one of the following (A1) to (A14).

(In the formula, d represents 0 or 1. These groups are each independently one or more selected from the group consisting of an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms. May have a substituent of The arylamine polymer according to any one of claims 1 to 8, wherein the arylamine polymer is represented by the following general formula (4-1) or (4-2).

(Where
n independently represents an integer of 3 or more.
The A ring, B ring, Ar ³ , Ar ⁴ , and a are as defined in claim 1.
Ar ¹ and Ar ² have the same meaning as in claim 2.
Ar ¹ and Ar ² may have different structures for each appearance. ) The arylamine polymer according to claim 1 or 2, represented by the following general formula (5-1), (5-2), (5-3), or (5-4): .

(Where
Formula (5-1) and Formula (5-3) represent a random copolymer or an alternating copolymer, and Formula (5-2) and Formula (5-4) represent a block copolymer. .
f, each independently represents an integer of 1 to 10; When e is 2 or more, Ar ¹ and Ar ² each have a different structure for each occurrence.
n independently represents an integer of 3 or more.
The A ring, B ring, Ar ³ , Ar ⁴ , and a are as defined in claim 1.
Ar ¹ and Ar ² have the same meaning as in claim 2. )   A charge transport material comprising the arylamine polymer according to any one of claims 1 to 10.   A hole transport material, a hole injection material, an electron block material, or a light-emitting host material, comprising the arylamine polymer according to any one of claims 1 to 10.