JP2017155208A - Arylamine polymer, and production method and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an arylamine polymer excellent in the life and luminous efficacy of an organic EL element; a production method thereof; and an organic EL element containing the same.SOLUTION: A triarylamine polymer has a backbone in which at least two repeating structures represented by the general formula (1) in the figure are connected.SELECTED DRAWING: None

Description

  The present invention relates to an arylamine polymer, a method for producing the same, and an application 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.

  Moreover, PEDOT-PSS, an arylamine polymer, etc. are proposed as a hole injection (transport) material. As the arylamine polymer, 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 8). reference).

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

  Furthermore, according to Patent Documents 7 to 8, it is reported that the device lifetime is improved by protecting the polymer terminal (for example, halogen atom, secondary amino group, etc.).

  On the other hand, in recent years, arylamine polymers having a thermally crosslinkable group and excellent laminate properties have been reported to improve laminate properties and film formability (for example, Patent Documents 9 to 10). Although these polymers can insolubilize the thin film by thermal polymerization after film formation on the substrate, unreacted cross-linking groups may be present in the film. Causing a decrease in performance is a problem (for example, Patent Document 11).

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 JP 2011-52229 A Japanese Patent No. 2011-149013 Japanese Patent No. 2011-204739

  The present invention has been made in view of the above background art. The purpose of the conjugated arylamine polymer with the polymer terminal protected has not yet exceeded the performance of an organic EL device made of a low molecular weight material. Is to provide.

  The present invention has been made in view of the above-described problems, and relates to a novel arylamine polymer that is superior in durability and luminous efficiency to conventional materials.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention are arylamine polymers having a metharyl substituent on the nitrogen atom on the main chain thereof, that is, the following general formula (1) It has been found that an arylamine polymer in which at least two of the represented structures are linked repeatedly is excellent in durability and luminous efficiency, and has completed the present invention.

  That is, the present invention relates to an arylamine polymer in which at least two or more structures represented by the following general formula (1) are linked repeatedly (hereinafter referred to as “arylamine polymer (1)” as appropriate), a production method and use thereof, The present invention also relates to an organic EL device using the arylamine polymer (1).

(Where
Ar ¹ is each independently a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a divalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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. May be).
Ar ² is each independently a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a monovalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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 an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydrogen atom.
a represents 0 or 1;
Me represents a methyl group. )

  The arylamine polymer (1) 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. For this reason, the organic EL element using the arylamine polymer (1) of the present invention is expected to be excellent in luminous efficiency and lifetime. Therefore, the arylamine polymer of the present invention can provide a phosphorescent or fluorescent organic EL element having high luminance and a long lifetime.

  Furthermore, the high molecular weight of the arylamine polymer of the present invention also contributes to high durability. Therefore, a long-life organic EL element can be provided.

  Further, since the arylamine polymer 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 arylamine polymer layer is not eroded. Therefore, the arylamine polymer of the present invention can provide a material necessary for a continuous coating film forming process of an organic EL element.

  Furthermore, the arylamine polymer of the present invention has high solubility in not only halogenated solvents but also non-halogenated solvents such as toluene and xylene. It is not desirable to use a halogen-based solvent in a large amount from the viewpoint of toxicity and environmental load, and the arylamine polymer of the present invention is excellent in the production process.

  The present invention is described in detail below.

  The arylamine polymer (1) of the present invention is one in which at least two structures represented by the above general formula (1) are repeatedly connected.

In the arylamine polymer (1) of the present invention, each Ar ¹ is independently a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a linked or condensed ring. A divalent heteroaromatic group having 4 to 36 carbon atoms (these groups are each independently 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 optionally having one or more substituents.

As described above, Ar ¹ may differ from each other for each appearance, but is preferably the same from the viewpoint of productivity and quality control.

  Although it does not specifically limit as a C6-C20 bivalent aromatic hydrocarbon group which may be connected or condensed, For example, a benzenediyl group, a biphenyldiyl group, a terphenyldiyl group, a triphenylene Examples thereof include a diyl group, a fluorenediyl group, a phenanthrene diyl group, a naphthalenediyl group, an anthracene diyl group, and a pyrenediyl group.

  The divalent heteroaromatic group having 4 to 36 carbon atoms which may be linked or condensed includes at least one heteroaromatic ring and is not particularly limited. Group, benzofuranyl group, dibenzofuranyl group, thiophenediyl group, benzothiophenediyl group, dibenzothiophenediyl group, pyridinediyl group, pyrimidinediyl group, pyrazinediyl group, quinolinediyl group, isoquinolinediyl group, carbazolediyl group, biscarbazolediyl group Or a benzenediyl-carbazolediyl-benzenediyl group and the like.

  The alkyl group having 1 to 18 carbon atoms can be rewritten as a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, and is not particularly limited, for example, methyl 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, trifluoro Examples include a methyl 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 rewritten as a linear, branched, or cyclic alkoxy group having 1 to 18 carbon atoms, and is not particularly limited, for example, methoxy 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.

In the arylamine polymer (1) of the present invention, each Ar ² is independently a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a linked or condensed ring. A monovalent heteroaromatic group having 4 to 36 carbon atoms (these substituents are each independently 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). 1 or more selected substituents), an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a hydrogen atom.

Ar ¹ is the following (A1) to (A14) in that the durability of the polymer is excellent.

(C represents 0 or 1; these groups are each independently 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. It may preferably have one or more kinds of substituents, and any of the groups represented by the above (A3) to (A6) or (A8) to (A14) (these groups) Each independently 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. Preferably, the groups represented by the above (A3), (A4), (A6), (A8), (A10), or (A14) (these groups each independently have a methyl group). It is more preferable.

Ar ² is each independently a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a monovalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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 an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydrogen atom.

  The monovalent 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, a phenylnaphthyl group, a naphthylphenyl group, and an anthracenyl group. , Pyrenyl group, phenanthrenyl group, perylenyl group, triphenylenyl group, and the like.

  The monovalent heteroaromatic group having 4 to 36 carbon atoms includes at least one heteroaromatic ring, and is not particularly limited. For example, a furanyl group, a benzofuranyl group, a dibenzofuranyl group, Thienyl group, 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, phenyl-carbazolyl group, carbazolyl-phenyl group, phenyl-carbazolyl-phenyl and the like.

Although it does not specifically limit as a C1-C18 alkyl group and a C1-C18 alkoxy group, The same substituent as the substituent shown by Ar < ¹ > can be illustrated.

Ar ² is independently a hydrogen atom, methyl group, butyl group, phenyl group, biphenyl 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-dimethylfluorenyl) carbazolyl group is preferable.

In Ar ¹ and Ar ² , the “alkyl group having 1 to 18 carbon atoms and alkoxy group having 1 to 18 carbon atoms” may be a carbon that may be linked or condensed in a range that does not impair the effects of the present invention. A plurality of them may be bonded to an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 4 to 36 carbon atoms which may be linked or condensed. Among these, the number of “alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms” is preferably in the range of 0 to 3, and the types of substituents may be the same or different. Good.

  In the arylamine polymer (1) of the present invention, a represents 0 or 1. A is preferably 0 in consideration of easiness of synthesis, but a is preferably 1 in consideration of hole transport / injection properties.

  In the arylamine polymer (1) of the present invention, Me represents a methyl group.

  Moreover, about the arylamine polymer (1), it is preferable that the terminal is a substituent represented by following General formula (2) from the point of the light emission characteristic as an organic EL element, and durability.

(Where
Ar ³ is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed or a monovalent heteroaromatic group having 4 to 36 carbon atoms which may be linked or condensed. (These substituents may 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) Represents. )
A monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, represented by Ar ³ , or a monovalent heteroaromatic group having 4 to 36 carbon atoms which may be linked or condensed The substituents of the group, the alkyl group having 1 to 18 carbon atoms, and the alkoxy group having 1 to 18 carbon atoms are synonymous with the substituents represented by Ar ¹ and Ar ² , respectively, and the same substituents are exemplified. be able to.

As for Ar ³ , each is independently a phenyl group or a biphenylyl group (these groups are each independently an alkyl group having 1 to 18 carbon atoms and a carbon number, in terms of excellent production efficiency of the arylamine polymer. 1 to 18 alkoxy groups) may be preferable, and each independently is more preferably a p-tolyl group, a phenyl group, or a biphenylyl group.

  That is, the arylamine polymer (1) is preferably an arylamine polymer represented by the following general formula (3).

(Where
Ar ¹ is each independently a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a divalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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. May be).
Ar ² is each independently a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a monovalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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 an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydrogen atom.
Ar ³ is each independently a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a monovalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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. May be).
a represents 0 or 1;
Me represents a methyl group. )
In general formula (3), Ar ¹ , Ar ² , Ar ³ and a each independently represent the same definition as in general formula (1), and Ar ³ is each independently the above general formula. It represents the same definition as (2). Moreover, about the preferable range of Ar < ¹ >, Ar < ² >, Ar < ³ > and a in General formula (3), it is the same as the above-mentioned respectively.

  The arylamine polymer (1) of the present invention is not particularly limited as long as it falls within the above definition, but the following general formulas (B1) to (B) are used in terms of physical properties such as luminous efficiency and lifetime of the organic EL device. B63) is preferable.

(In the general formulas (B1) to (B63), n represents an integer of 2 or more.)
Next, the manufacturing method of the arylamine polymer (1) of this invention is demonstrated.

  The arylamine polymer (1) of the present invention is not particularly limited, but is represented by an arylene halide compound represented by various general formulas (6) and a general formula (7) as shown by the following reaction formula. A biphenylenediamine compound can be synthesized by polymerizing in the presence of a catalyst comprising a trialkylphosphine and / or palladium compound and a base, and further an aryl halide represented by the following general formula (4): Or by reacting both the aryl halide represented by the general formula (4) and the diarylamine represented by the general formula (5).

(In Reaction Formula 1, Ar ¹ , Ar ² , and a each represent the same definition as in the general formula (1). X ² and X ³ each independently represent a chlorine atom, a bromine atom, or an iodine atom. Represent.
n represents an integer of 2 or more.
b represents 0 or 1; However, when b = 0, it is limited to the case where Ar ¹ is a 1,1′-biphenyl-4,4′-diyl group. )
The compound having the structure represented by the general formula (1) obtained by the reaction of the reaction formula 1 (hereinafter referred to as “polymerization step”) usually has a secondary amino group, a halogen group, or a secondary amino group at the end. Both are halogen groups.

  Further, in the presence of a palladium catalyst and a base, a compound having a structure represented by the general formula (1) obtained in the polymerization step and an aromatic halogen compound represented by the following general formula (4) or the following general formula (5) The terminal secondary protection of the terminal secondary amino group and / or the halogen group (hereinafter referred to as “protection step”) is carried out by reacting with the aromatic amine compound represented by

(In the formula, Ar ³ has the same definition as Ar ³ in the general formula (2). X ¹ represents a chlorine atom, a bromine atom, or an iodine atom.)

(In the formula, Ar ³ each independently has the same definition as Ar ³ in the general formula (2).)
As a product of the protection step, an arylamine polymer (1) whose reaction ends are protected, that is, an arylamine polymer represented by the following general formula (3) can be obtained.

(In the formula, Ar ¹ , Ar ² and a each independently represent the same definition as in the general formula (1). Ar ³ each independently represents the same definition as in the general formula (2). N represents an integer of 2 or more.)
The protection step may be carried out in one pot following the polymerization step, or once the arylamine polymer of the general formula (1), which is a product of the polymerization step, is isolated, separately, a palladium catalyst and a base It may be performed in the presence.

  In the protection step, it is possible to carry out the reaction using the aromatic halogen compound represented by the general formula (4) and the aromatic amine compound represented by the general formula (5) at the same time. In terms of reaction efficiency, the reaction with the aromatic halogen compound and the reaction with the aromatic amine compound are preferably performed separately. In the case of performing the reaction separately, either the reaction using an aromatic halogen compound or the reaction using an aromatic amine compound may be performed first.

  In the protection step, the reaction using the aromatic halogen compound and the reaction using the aromatic amine compound can be carried out continuously in one pot. After one reaction, the reaction product is isolated and separated in a separate batch. The other reaction can also be performed.

  The aromatic halogen compound represented by the general formula (4) is not particularly limited. For example, bromobenzenes which may have a substituent [specifically, bromobenzene, 2-bromotoluene] 3-bromotoluene, 4-bromotoluene, 2-bromo-m-xylene, 2-bromo-p-xylene, 3-bromo-o-xylene, 4-bromo-o-xylene, 4-bromo-m-xylene , 5-bromo-m-xylene, 1-bromo-2-ethylbenzene, 1-bromo-4-ethylbenzene, 1-bromo-4-propylbenzene, 1-bromo-4-n-butylbenzene, 1-bromo-4 -Tert-butylbenzene, 1-bromo-5- (trifluoromethoxy) benzene, 2-bromoanisole, 3-bromoanisole, 4-bromoanisole, 1- Lomonaphthalene, 2-bromonaphthalene, 2-bromobiphenyl, 3-bromobiphenyl, 4-bromobiphenyl, 9-bromoanthracene, 9-bromophenanthrene, N-methyl-3-bromocarbazole, N-ethyl-3- Bromocarbazole, N-propyl-3-bromocarbazole, N-butyl-3-bromocarbazole, 2-bromofluorene, 2-bromo-9,9-dimethylfluorene, 2-bromo-9,9-diethylfluorene, 2- Bromo-9,9-diisopropylfluorene, 2-bromo-9,9-di-n-butylfluorene, 2-bromo-9,9-di-tert-butylfluorene, 2-bromo-9,9-di-sec -Butylfluorene, 2-bromo-9,9-di-n-hexylfluorene, 2-bromo-9,9- -N-octylfluorene, 2-bromodibenzothiophene, 2-bromodibenzofuran, etc.], chlorobenzenes optionally having a substituent [specifically, chlorobenzene, 2-chlorotoluene, 3-chlorotoluene, 4-chloro Toluene, 2-chloro-m-xylene, 2-chloro-p-xylene, 3-chloro-o-xylene, 4-chloro-o-xylene, 4-chloro-m-xylene, 5-chloro-m-xylene, 1-chloro-2-ethylbenzene, 1-chloro-4-ethylbenzene, 1-chloro-4-propylbenzene, 1-chloro-4-n-butylbenzene, 1-chloro-4-tert-butylbenzene, 1-chloro -5- (trifluoromethoxy) benzene, 2-chloroanisole, 3-chloroanisole, 4-chloroanisole, Loronaphthalene, 2-chloronaphthalene, 2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 9-chloroanthracene, 9-chlorophenanthrene, N-methyl-3-chlorocarbazole, N-ethyl-3- Chlorocarbazole, N-propyl-3-chlorocarbazole, N-butyl-3-chlorocarbazole, 2-chlorofluorene, 2-chloro-9,9-dimethylfluorene, 2-chloro-9,9-diethylfluorene, 2- Chloro-9,9-diisopropylfluorene, 2-chloro-9,9-di-n-butylfluorene, 2-chloro-9,9-di-tert-butylfluorene, 2-chloro-9,9-di-sec -Butyl fluorene, 2-chloro-9,9-di-n-hexyl fluorene, 2-chloro-9,9-di n-octylfluorene, 2-chlorodibenzothiophene, 2-chlorodibenzofuran, etc.] and iodobenzenes which may have a substituent [specifically, iodobenzene, 2-iodotoluene, 3-iodotoluene, 4-iodotoluene, 2-iodo-m-xylene, 2-iodo-p-xylene, 3-iodo-o-xylene, 4-iodo-o-xylene, 4-iodo-m-xylene, 5-iodo-m -Xylene, 1-iodo-2-ethylbenzene, 1-iodo-4-ethylbenzene, 1-iodo-4-propylbenzene, 1-iodo-4-n-butylbenzene, 1-iodo-4-tert-butylbenzene, 1-iodo-5- (trifluoromethoxy) benzene, 2-iodoanisole, 3-iodoanisole, 4-iodoanisole, -Iodonaphthalene, 2-iodonaphthalene, 2-iodobiphenyl, 3-iodobiphenyl, 4-iodobiphenyl, 9-iodoanthracene, 9-iodophenanthrene, N-methyl-3-iodocarbazole, N-ethyl-3 -Iodocarbazole, N-propyl-3-iodocarbazole, N-butyl-3-iodocarbazole, 2-iodofluorene, 2-iodo-9,9-dimethylfluorene, 2-iodo-9,9-diethylfluorene, 2 -Iodo-9,9-diisopropylfluorene, 2-iodo-9,9-di-n-butylfluorene, 2-iodo-9,9-di-tert-butylfluorene, 2-iodo-9,9-di- sec-Butylfluorene, 2-iodo-9,9-di-n-hexylfluorene, 2-iodo-9,9 -Di-n-octylfluorene, 2-iododibenzothiophene, 2-iododibenzofuran, etc.].

  The aromatic amine compound represented by the general formula (5) is not particularly limited, and examples thereof include diphenylamine, bis (1,1′-biphenyl-4-yl) amine, di-p-tolylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, di (biphenyl-4-yl) amine and the like can be mentioned.

  The polymerization step and the protection step are both carried out in the presence of a palladium catalyst and a base, and the reaction conditions are not particularly limited, but the following may be used. it can. 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 the palladium catalyst used in the polymerization step is not particularly limited. For example, in the polymerization step of Reaction Formula 1, the amount is usually 0.0000001 to 0.20 in terms of palladium atom with respect to 1 mol of the halogen atom of the raw material. It is preferably in the range of a double mole. Of these, from the viewpoint of catalytic activity and the use of an expensive palladium compound, it is usually more preferably in the range of 0.00001 to 0.05 times mole.

  Although the usage-amount of the palladium catalyst in a protection process is not specifically limited, The halogen atom 1 of the aromatic halogen compound represented by General formula (6), or the polymer represented by General formula (1) It is preferably within a range of usually 0.0000001 to 0.20 times moles in terms of palladium atoms with respect to 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 method for adding the palladium catalyst in the polymerization step and the protection step is not particularly limited, but a palladium compound, a ligand, and other components may be added individually to the reaction system in the polymerization step or the protection step. The catalyst components may be added in advance and mixed in the form of a palladium complex.

  Although it does not specifically limit as a base used for a superposition | polymerization process and a protection process, For example, inorganic bases, such as a hydroxide of alkali metals (specifically sodium, potassium, etc.), carbonate, an alkoxide, or Organic bases such as tertiary amines can be 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 in the polymerization step is not particularly limited, but is not particularly limited. For example, in the reaction of arylene halide represented by Reaction Formula 1 with arylamine, the arylene raw material It is selected from the range of 1 to 1000 times moles per mole of halide halogen atoms. Among these, the range of 1 to 20 times mol is more preferable in consideration of the post-treatment operation after completion of the reaction.

  The amount of the base used in the protection step 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 (6), preferably The range is 1 to 20 times mol, or 1 to 100000 times mol, preferably 1 to 1000 times mol per mol of the halogen atom of the polymer having the structure represented by the general formula (1). It is.

  Both the polymerization step and the protection step are usually preferably carried out 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 polymerization step and the protection step are preferably carried out under normal pressure and in an inert gas atmosphere such as nitrogen or argon, but can be carried out even under pressurized conditions.

  The reaction temperature in the polymerization step and the protection step 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. Preferably it is the range of 100-150 degreeC.

  The reaction time in the polymerization step and the protection step is not particularly limited because it is not constant depending on the arylamine polymer to be produced, the palladium catalyst, the reaction temperature, etc. In many cases, the reaction time is from a range of several minutes to 72 hours. Just choose. Preferably it is less than 24 hours.

  The arylamine polymer (3) produced by the polymerization step and the protection step 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 (1) of the present invention 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. 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 (1) of this invention, element structure will not be specifically limited.

  Since the arylamine polymer (1) of the present invention is excellent in solubility, for example, using a solution, a mixed solution, or a melt of these materials, a spin coating method, a casting method, a dipping method, a bar coating method, 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 that can obtain the effects of the present invention includes a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and 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.

  For the hole transport layer of the organic EL device, the arylamine polymer of the present application is preferably used. In addition to the arylamine polymer of the present application, the hole transport layer may contain one or more hole transport compounds such as aromatic tertiary amines. 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, perifanthene 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-001) A 50 mL three-necked round bottom flask equipped with a condenser and a thermometer was charged with 1.50 g (3 of 4,4′-diiodobiphenyl at room temperature under a nitrogen atmosphere. .69 mmol), 0.45 g (3.69 mmol) of 2,4-dimethylaniline, 1.42 g (14.76 mmol) of sodium-tert-butoxide and 13.3 g of o-xylene. 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 16 hours with heating and stirring at 120 ° C.

  Subsequently, 0.23 g (1.48 mmol) of bromobenzene was added, and the reaction was further performed at 120 ° C. for 3 hours. Next, 0.50 g (2.96 mmol) of diphenylamine 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 0.91 g (yield 91%) of a pale yellow solid.

  The obtained arylamine polymer (HTP-001) had a weight average molecular weight of 35,000 and a number average molecule of 20,000 (dispersity of 1.5) in terms of polystyrene.

  The glass transition temperature was 283 ° C.

  The HOMO level was 5.30 eV, and the LUMO level was 2.36 eV.

  In a sample tube for UV-Vis spectrum measurement, 1 mg of arylamine polymer (HT-001) 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-001) calculated from the phosphorescence spectrum was 2.37 eV.

  The measurement results of elemental analysis are shown in Table 1.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 2 Synthesis of Arylamine Polymer (HTP-002) The same procedure as in Example 1 was performed except that 2-methyl-4-butylaniline was used instead of 2,4-dimethylaniline in Example 1. A yellow solid was obtained in 85% yield. The molar ratio of the monomers is 1: 1 as in Example 1.

  The obtained arylamine polymer (HTP-002) had a weight average molecular weight of 34,000 and a number average molecular weight of 21,000 (dispersity of 1.6) in terms of polystyrene.

  The glass transition temperature was 202 ° C.

  The HOMO level was 5.33 eV, and the LUMO level was 2.38 eV.

  The excited triplet level was 2.37 eV.

  The measurement results of elemental analysis are shown in Table 2.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 3 Synthesis of arylamine polymer (HTP-003) A light yellow solid was prepared in the same manner as in Example 1 except that 2,5-dimethylaniline was used instead of 2,4-dimethylaniline. Was obtained in 93% yield. The molar ratio of the monomers is 1: 1 as in Example 1.

  The obtained arylamine polymer (HTP-003) had a weight average molecular weight of 27,000 and a number average molecular weight of 16,000 (dispersity of 1.6) in terms of polystyrene.

  The glass transition temperature was 278 ° C.

  The HOMO level was 5.37 eV and the LUMO level was 2.40 eV.

The excited triplet level was 2.38 eV. Table 3 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 4 Synthesis of Arylamine Polymer (HT-004) In Example 1, N, N′-bis (2-methyl-4-butylphenyl) benzidine was used instead of 2,4-dimethylaniline. , 4′-Diiodobiphenyl was used in the same manner as in Example 1 except that 2,7-dibromo-9,9-dimethylfluorene was used, and a pale yellow solid was obtained with a yield of 88%. The molar ratio of the monomers is 1: 1 as in Example 1.

  The obtained arylamine polymer (HTP-004) had a weight average molecular weight of 46,000 and a number average molecular weight of 26,000 (dispersity of 1.8) in terms of polystyrene.

  The glass transition temperature was 203 ° C.

  The HOMO level was 5.23 eV, and the LUMO level was 2.33 eV.

  The excited triplet level was 2.34 eV.

  The measurement results of elemental analysis are shown in Table 4.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 5 Synthesis of Arylamine Polymer (HT-005) In Example 4, bromobiphenyl was used instead of bromobenzene, and bis (1,1′-biphenyl-4-yl) amine was used instead of diphenylamine. Otherwise, the same procedure as in Example 4 was carried out to obtain a pale yellow solid in 90% yield. The molar ratio of the monomers is 1: 1 as in Example 4.

  The obtained arylamine polymer (HTP-005) had a weight average molecular weight of 46,000 and a number average molecular weight of 26,000 (dispersity of 1.8) in terms of polystyrene.

  The glass transition temperature was 210 ° C.

  The HOMO level was 5.23 eV, and the LUMO level was 2.33 eV.

  The excited triplet level was 2.34 eV.

  The measurement results of elemental analysis are shown in Table 5.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 6 Synthesis of Arylamine Polymer (HT-006) In Example 4, instead of N, N′-bis (2-methyl-4-butyl) phenylbenzidine, N, N′-bis (2,4- Except that dimethylphenyl) benzidine was used, the same procedure as in Example 4 was performed to obtain a pale yellow solid with a yield of 90%. The molar ratio of the monomers is 1: 1 as in Example 4.

  The obtained arylamine polymer (HTP-006) had a weight average molecular weight of 73,000 and a number average molecular weight of 34,000 (dispersity of 2.2) in terms of polystyrene.

  The glass transition temperature was 281 ° C.

  The HOMO level was 5.23 eV, and the LUMO level was 2.33 eV.

  The excited triplet level was 2.33 eV.

  The measurement results of elemental analysis are shown in Table 6.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 7 Synthesis of arylamine polymer (HT-007) In Example 4, except that 2,7-dibromo-9-phenylcarbazole was used instead of 2,7-dibromo-9,9-dimethylfluorene, In the same manner as in Example 4, a pale yellow solid was obtained with a yield of 81%. The molar ratio of the monomers is 1: 1 as in Example 4.

  The obtained arylamine polymer (HTP-007) had a weight average molecular weight of 66,000 and a number average molecular weight of 33,000 (dispersity of 2.0) in terms of polystyrene.

  The glass transition temperature was 212 ° C.

  The HOMO level was 5.20 eV, and the LUMO level was 2.33 eV.

  The excited triplet level was 2.35 eV.

  Table 7 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 8 Synthesis of Arylamine Polymer (HTP-008) In Example 4, except that 3,6-dibromo-9-phenylcarbazole was used instead of 2,7-dibromo-9,9-dimethylfluorene, In the same manner as in Example 4, a pale yellow solid was obtained with a yield of 94%. The molar ratio of the monomers is 1: 1 as in Example 4.

  The obtained arylamine polymer (HTP-008) had a weight average molecular weight of 56,000 and a number average molecular weight of 26,000 (dispersity of 2.1) in terms of polystyrene.

  The glass transition temperature was 242 ° C.

  The HOMO level was 5.17 eV and the LUMO level was 2.18 eV.

  The excited triplet level was 2.37 eV.

  The measurement results of elemental analysis are shown in Table 8.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 9 Synthesis of arylamine polymer (HTP-009) In Example 4, 3,6-dibromo-9- (4-methylphenyl) carbazole was used instead of 2,7-dibromo-9,9-dimethylfluorene. The procedure was the same as in Example 4 except that it was used, and a pale yellow solid was obtained in 81% yield. The molar ratio of the monomers is 1: 1 as in Example 4.

  The obtained arylamine polymer (HTP-009) had a weight average molecular weight of 56,000 and a number average molecular weight of 26,000 (dispersity of 2.2) in terms of polystyrene.

  The glass transition temperature was 242 ° C.

  The HOMO level was 5.17 eV and the LUMO level was 2.18 eV.

  The excited triplet level was 2.39 eV.

  The measurement results of elemental analysis are shown in Table 9.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 10 Synthesis of Arylamine Polymer (HTP-010) In Example 4, instead of 2,7-dibromo-9,9-dimethylfluorene, 6,6′-dibromo-9,9′-diphenyl-3, A pale yellow solid was obtained in a yield of 75% in the same manner as in Example 4 except that 3′-bicarbazole was used. The molar ratio of the monomers is 1: 1 as in Example 4.

  The obtained arylamine polymer (HTP-010) had a weight average molecular weight of 36,000 and a number average molecular weight of 15,000 (dispersity of 2.4) in terms of polystyrene.

  The glass transition temperature was 205 ° C.

  The HOMO level was 5.29 eV, and the LUMO level was 2.33 eV.

  The excited triplet level was 2.39 eV.

  The measurement results of elemental analysis are shown in Table 10.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 11 Synthesis of Arylamine Polymer (HTP-011) In Example 6, except that 3,6-dibromo-9-phenylcarbazole was used instead of 2,7-dibromo-9,9-dimethylfluorene, In the same manner as in Example 6, a pale yellow solid was obtained in 88% yield. The molar ratio of the monomers is 1: 1 as in Example 6.

  The obtained arylamine polymer (HTP-011) had a weight average molecular weight of 39,000 and a number average molecular weight of 10,000 (dispersity 3.8) in terms of polystyrene.

  The glass transition temperature was 318 ° C.

  The HOMO level was 4.99 eV, and the LUMO level was 2.00 eV.

  The excited triplet level was 2.36 eV.

  The measurement results of elemental analysis are shown in Table 11.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 12 Synthesis of Arylamine Polymer (HTP-012) In Example 6, instead of 2,7-dibromo-9,9-dimethylfluorene, 3,6-dibromo-9- [3- (9-phenanthryl) The same procedure as in Example 6 was carried out except that phenyl] carbazole was used, and a pale yellow solid was obtained with a yield of 85%. The molar ratio of the monomers is 1: 1 as in Example 6.

  The obtained arylamine polymer (HTP-012) had a weight average molecular weight of 59,000 and a number average molecular weight of 6,000 (dispersity of 9.8) in terms of polystyrene.

  The glass transition temperature was 270 ° C.

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

  The excited triplet level was 2.41 eV.

  The results of elemental analysis are shown in Table 12.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 13 Synthesis of arylamine polymer (HTP-013) In Example 6, instead of 2,7-dibromo-9,9-dimethylfluorene, 9- [3- (4-dibenzofuranyl) phenyl] -3 The procedure was the same as in Example 6 except that 1,6-dibromocarbazole was used, and a pale yellow solid was obtained in a yield of 86%. The molar ratio of the monomers is 1: 1 as in Example 6.

  The obtained arylamine polymer (HTP-013) had a weight average molecular weight of 14,000 and a number average molecular weight of 6,000 (dispersity 2.3) in terms of polystyrene.

  The glass transition temperature was 263 ° C.

  The HOMO level was 5.16 eV and the LUMO level was 2.19 eV.

  The excited triplet level was 2.39 eV.

  The results of elemental analysis are shown in Table 13.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 14 Synthesis of Arylamine Polymer (HTP-014) In Example 6, instead of 2,7-dibromo-9,9-dimethylfluorene, 9- [3- (4-dibenzothienyl) phenyl] -3, A pale yellow solid was obtained in a yield of 85% in the same manner as in Example 6 except that 6-dibromocarbazole was used. The molar ratio of the monomers is 1: 1 as in Example 6.

  The obtained arylamine polymer (HTP-014) had a weight average molecular weight of 20,000 and a number average molecular weight of 8,800 (dispersion degree 2.3) in terms of polystyrene.

  The glass transition temperature was 267 ° C.

  The HOMO level was 5.14 eV and the LUMO level was 2.17 eV.

  The excited triplet level was 2.40 eV.

  The measurement results of elemental analysis are shown in Table 14.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 15 Synthesis of Arylamine Polymer (HTP-015) In Example 6, instead of 2,7-dibromo-9,9-dimethylfluorene, 9- [3- (2-dibenzofuranyl) phenyl] -3 The procedure was the same as in Example 6 except that 1,6-dibromocarbazole was used, and a pale yellow solid was obtained in a yield of 93%. The molar ratio of the monomers is 1: 1 as in Example 6.

  The obtained arylamine polymer (HTP-015) had a weight average molecular weight of 20,000 and a number average molecular weight of 9,800 (dispersion degree 2.0) in terms of polystyrene.

  The glass transition temperature was 262 ° C.

  The HOMO level was 5.19 eV, and the LUMO level was 2.21 eV.

  The excited triplet level was 2.39 eV.

  The measurement results of elemental analysis are shown in Table 15.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 16 Synthesis of Arylamine Polymer (HTP-016) In Example 6, instead of 2,7-dibromo-9,9-dimethylfluorene, 9- [3- (2-dibenzothienyl) phenyl] -3, The procedure was the same as Example 6 except that 6-dibromocarbazole was used, and a pale yellow solid was obtained with a yield of 96%. The molar ratio of the monomers is 1: 1 as in Example 6.

  The obtained arylamine polymer (HTP-016) had a weight average molecular weight of 14,000 and a number average molecular weight of 7,100 (dispersity of 1.5) in terms of polystyrene.

  The glass transition temperature was 264 ° C.

  The HOMO level was 5.20 eV, and the LUMO level was 2.24 eV.

  The excited triplet level was 2.39 eV.

  The measurement results of elemental analysis are shown in Table 16.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 17 Synthesis of Arylamine Polymer (HTP-017) Example 1 and Example 1 except that 4-amino-4′-butyl-3-methylbiphenyl was used instead of 2,4-dimethylaniline in Example 1. In the same manner, a pale yellow solid was obtained with a yield of 99%. The molar ratio of the monomers is 1: 1 as in Example 1.

  The obtained arylamine polymer (HTP-017) had a weight average molecular weight of 127,000 and a number average molecular weight of 61,000 (dispersion degree 3.6) in terms of polystyrene.

  The glass transition temperature was 223 ° C.

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

  The excited triplet level was 2.37 eV.

  The results of elemental analysis are shown in Table 17.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 18 Synthesis of Arylamine Polymer (HTP-018) The same procedure as in Example 1 was performed except that 3-amino-4-methylbiphenyl was used instead of 2,4-dimethylaniline in Example 1. A yellow solid was obtained in 92% yield. The molar ratio of the monomers is 1: 1 as in Example 1.

  The obtained arylamine polymer (HTP-018) had a weight average molecular weight of 27,000 and a number average molecular weight of 15,000 (dispersity 1.8) in terms of polystyrene.

  The glass transition temperature was 242 ° C.

  The HOMO level was 5.36 eV, and the LUMO level was 2.42 eV.

  The excited triplet level was 2.38 eV.

  The results of elemental analysis are shown in Table 18.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 19 Synthesis of Arylamine Polymer (HTP-019) In Example 1, NN′-bis (4-butyl-2-methylphenyl) -9- (2-dibenzothionyl) instead of 2,4-dimethylaniline A pale yellow solid was obtained with a yield of 95% in the same manner as in Example 1 except that carbazole-2,7-diamine was used. The molar ratio of the monomers is 1: 1 as in Example 1.

  The obtained arylamine polymer (HTP-019) had a weight average molecular weight of 123,000 and a number average molecular weight 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 excited triplet level was 2.33 eV.

  Table 19 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 20 Synthesis of Arylamine Polymer (HTP-020) In Example 1, NN′-bis (4-butyl-2-methylphenyl) -9- (3-dibenzofuranyl instead of 2,4-dimethylaniline ) A light yellow solid was obtained in a yield of 95% in the same manner as in Example 1 except that carbazole-2,7-diamine was used. The molar ratio of the monomers is 1: 1 as in Example 1.

  The obtained arylamine polymer (HTP-020) had a weight average molecular weight of 108,000 and a number average molecular weight of 54,000 (dispersity of 2.0) in terms of polystyrene.

  The glass transition temperature was 227 ° C.

  The HOMO level was 5.30 eV, and the LUMO level was 2.45 eV.

  The excited triplet level was 2.33 eV.

  Table 20 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 21 Synthesis of Arylamine Polymer (HTP-021) In Example 6, Example 2 was used except that 2,7-dibromotriphenylene was used instead of 2,7-dibromo-9,9-dimethylfluorene. In the same manner, a pale yellow solid was obtained with a yield of 96%. The molar ratio of the monomers is 1: 1 as in Example 6.

  The obtained arylamine polymer (HTP-021) had a weight average molecular weight of 19,000 and a number average molecular weight of 11,000 (dispersity of 1.7) in terms of polystyrene.

  The glass transition temperature was 310 ° C.

  The HOMO level was 5.28 eV, and the LUMO level was 2.41 eV.

  The excited triplet level was 2.39 eV.

  The results of elemental analysis are shown in Table 21.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 22 Synthesis of Arylamine Polymer (HT-022) In Example 4, instead of N, N′-bis (2-methyl-4-butyl) phenylbenzidine, N, N′-bis (2,4- The same procedure as in Example 4 was carried out except that dimethylphenyl) benzidine (benzidine A) and N, N′-bis (4-methylphenyl) benzidine (benzidine B) were used. Obtained. The molar ratio of the monomers is benzidine A: benzidine B: dihalogen = 1: 1: 1.

  The obtained arylamine polymer (HTP-022) had a weight average molecular weight of 52,000 and a number average molecular weight of 27,000 (dispersity of 1.9) in terms of polystyrene.

  The glass transition temperature was 272 ° C.

  The HOMO level was 5.20 eV, and the LUMO level was 2.32 eV.

  The excited triplet level was 2.33 eV.

  Table 22 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 23 Synthesis of Arylamine Polymer (HT-023) In Example 4, instead of N, N′-bis (2-methyl-4-butyl) phenylbenzidine, N, N′-bis (2,4- The same procedure as in Example 4 was conducted except that dimethylphenyl) benzidine (benzidine A) and N, N′-bis (4-methylphenyl) benzidine (benzidine B) were used. Obtained. The molar ratio of the monomers is benzidine A: benzidine B: dihalogen = 3 to 1: 4.

  The obtained arylamine polymer (HTP-023) had a weight average molecular weight of 27,000 and a number average molecular weight of 14,000 (dispersity of 3.2) in terms of polystyrene.

  The glass transition temperature was 270 ° C.

  The HOMO level was 5.21 eV, and the LUMO level was 2.33 eV.

  The excited triplet level was 2.34 eV.

  Table 23 shows the results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 24 Synthesis of Arylamine Polymer (HT-024) In Example 4, instead of N, N′-bis (2-methyl-4-butyl) phenylbenzidine, N, N′-bis (2,4- The same procedure as in Example 4 was carried out except that dimethylphenyl) benzidine (benzidine A) and N, N′-bis (4-methylphenyl) benzidine (benzidine B) were used. Obtained. The molar ratio of the monomers is benzidine A: benzidine B: dihalogen = 1: 3: 4.

  The obtained arylamine polymer (HTP-024) had a weight average molecular weight of 52,000 and a number average molecular weight of 25,000 (dispersity of 2.1) in terms of polystyrene.

  The glass transition temperature was 269 ° C.

  The HOMO level was 5.21 eV, and the LUMO level was 2.33 eV.

  The excited triplet level was 2.34 eV.

  Table 24 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 25 Synthesis of Arylamine Polymer (HT-025) In Example 4, instead of N, N′-bis (2-methyl-4-butyl) phenylbenzidine, N, N′-bis (2,4- The same procedure as in Example 4 was carried out except that dimethylphenyl) benzidine (benzidine A) and N, N′-bis (4-methylphenyl) benzidine (benzidine B) were used. Obtained. The molar ratio of the monomers is benzidine A: benzidine B: dihalogen = 1: 9: 10.

  The obtained arylamine polymer (HTP-022) had a weight average molecular weight of 47,000 and a number average molecular weight of 14,000 (dispersity of 3.4) in terms of polystyrene.

  The glass transition temperature was 274 ° C.

  The HOMO level was 5.27 eV, and the LUMO level was 2.40 eV.

  The excited triplet level was 2.34 eV.

  Table 25 shows the measurement results of elemental analysis.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Example 26 Synthesis of arylamine polymer (HT-026) In Example 21, in addition to N, N'-bis (2,4-dimethylphenyl) benzidine (benzidine A), N, N'-bis (4 -Butylphenyl) benzidine (benzidine B) was used in the same manner as in Example 21 to obtain a pale yellow solid with a yield of 90%. The molar ratio of the monomers is benzidine A: benzidine B: dihalogen = 1: 1: 1.

  The obtained arylamine polymer (HTP-026) had a weight average molecular weight of 14,000 and a number average molecular weight of 9,000 (dispersity 1.6) in terms of polystyrene.

  The glass transition temperature was 258 ° C.

  The HOMO level was 5.30 eV, and the LUMO level was 2.45 eV.

  The excited triplet level was 2.39 eV.

  The results of elemental analysis are shown in Table 26.

  The theoretical value was calculated based on the polymer structure obtained by reaction of all raw materials theoretically.

Comparative Example 1 Measurement of Triplet Level and Glass Transition Temperature of Arylamine Polymer (REF-001) Poly- (N, N′-bis (4-butylphenyl) in place of arylamine polymer (1) in Example 1 The phosphorescence spectrum was obtained by measuring the phosphorescence spectrum in the same manner as in Example 1 except that -N, N'-bis (phenyl) benzidine) (ADS254BE: manufactured by American Die Source) was used. The triplet level calculated from was 2.35 eV.

  The glass transition temperature was 170 ° C.

Example 27 (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 arylamine polymer (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 an arylamine polymer (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 27.

Example 28 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-002) synthesized in Example 2 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 27.

Example 29 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-003) 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 27.

Example 30 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-004) 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 27.

Example 31 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-005) 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 27.

Example 32 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-006) 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 27.

Example 33 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-007) 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 27.

Example 34 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-008) 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 27.

Example 35 (device fabrication and evaluation)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-009) 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 27.

Example 36 (Preparation and evaluation of device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-010) synthesized in Example 10 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 27.

Example 37 (Preparation and evaluation of device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-011) synthesized in Example 11 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 27.

Example 38 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-012) synthesized in Example 12 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 27.

Example 39 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-013) synthesized in Example 13 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 27.

Example 40 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-014) 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 27.

Example 41 (Preparation and evaluation of device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-015) 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 27.

Example 42 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-016) 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 27.

Example 43 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-017) 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 27.

Example 44 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-018) 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 27.

Example 45 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-019) synthesized in Example 19 was used instead of the arylamine polymer (HTP-001). Luminance half-life was measured. The evaluation results are shown in Table 27.

Example 46 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-020) 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 27.

Example 47 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-021) 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 27.

Example 48 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-022) 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 27.

Example 49 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-023) 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 27.

Example 50 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-024) 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 27.

Example 51 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-025) 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 27.

Example 52 (Production and Evaluation of Device)
In Example 27, a device was prepared in the same manner as in Example 27 except that the arylamine polymer (HTP-026) 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 27.

Comparative Example 2 (device fabrication and evaluation)
In Example 27, a device was fabricated in the same manner as in Example 27 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 27. The measurement values of Examples 27 to 52 were normalized and displayed with the measurement value of Comparative Example 2 being 100.

Therefore, the arylamine polymer of the present invention can provide a phosphorescent or fluorescent organic EL device having high luminance, low power consumption, and high durability.
Example 53 (Evaluation of solubility)
Prepare 1 wt% solution of HTP-001-026 and REF-001 at room temperature or 50 ° C-100 ° C, respectively, using chlorobenzene, xylene, and toluene as solvents. The presence or absence of was confirmed visually. The results are shown in Table 28.

  The arylamine polymer (1) 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.

  Therefore, if the arylamine polymer (1) of the present invention is used, it is possible to provide an organic EL device having excellent lifetime. Therefore, the arylamine polymer of the present invention can provide a phosphorescent or fluorescent organic EL device having high luminance and low power consumption.

Claims (12)

A triarylamine polymer having a skeleton in which at least two repeating structures represented by the following general formula (1) are linked.

(Where
Ar ¹ is each independently a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a divalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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. May be).
Ar ² is each independently a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a monovalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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 an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydrogen atom.
a represents 0 or 1;
Me represents a methyl group. ) 2. The arylamine polymer according to claim 1, wherein each terminal is independently an aromatic group represented by the following general formula (2).

(In the formula, Ar ³ is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed or a monovalent aromatic hydrocarbon group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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) It is also good) The triarylamine polymer according to claim 1 or 2, which is represented by the following general formula (3).

(Where
Ar ¹ is each independently a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a divalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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. May be).
Ar ² is each independently a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a monovalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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 an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydrogen atom.
Ar ³ is each independently a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a monovalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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. May be).
a represents 0 or 1;
Me represents a methyl group. ) Ar ¹ is the following (A1) to (A14) (c represents 0 or 1. These groups are each independently an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms. The arylamine polymer according to any one of claims 1 to 3, which may have one or more substituents selected from the group consisting of:

Ar ¹ is the following (A1) to (A11) (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) The arylamine polymer according to any one of claims 1 to 3, wherein the arylamine polymer may have any of the following substituents.

Ar ² each independently represents a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a phenanthrenyl group, a carbazolyl group, a dibenzothienyl group, or a dibenzofuryl group (these groups each independently have 1 to 18 carbon atoms) And may have one or more substituents selected from the group consisting of an alkoxy group having 1 to 18 carbon atoms), methyl group, ethyl group, butyl group, methoxy group, ethoxy group, butoxy The arylamine polymer according to any one of claims 1 to 5, wherein the arylamine polymer is a group or a hydrogen atom. Each of Ar ³ independently represents a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a triphenylyl group, a fluorenyl group, a phenanthrenyl group, a carbazolyl group, a biscarbazolyl group, a dibenzothienyl group, or a dibenzofuranyl group (these groups Are each independently 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. The arylamine polymer according to any one of claims 1 to 6. The following reaction formula

(Where
Ar ¹ is each independently a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a divalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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. May be).
Ar ² is each independently a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a monovalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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 an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a hydrogen atom.
Ar ³ is each independently a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or a monovalent group having 4 to 36 carbon atoms which may be linked or condensed. Heteroaromatic groups (these 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. May be).
a represents 0 or 1;
Me represents a methyl group.
X ² and X ³ each independently represent a chlorine atom, a bromine atom, or an iodine atom.
b represents 0 or 1, and when b = 0, Ar ¹ is a 1,1′-biphenyl-4,4′diyl group.
n represents an integer of 2 or more. )
A process for producing an arylamine polymer according to any one of claims 1 to 7, comprising an arylene halide compound represented by the general formula (6) and the general formula (7). And a biphenylenediamine compound represented by formula (I) is polymerized in the presence of a catalyst comprising a trialkylphosphine and / or palladium compound and a base. After the process according to claim 8, the following general formula (4)

(Where
Ar ³ is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed or a monovalent heteroaromatic group having 4 to 36 carbon atoms which may be linked or condensed. (These groups may 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). Represent.
X ¹ represents a chlorine atom, a bromine atom, or an iodine atom. )
An aryl halide represented by the following general formula (5)

(In the formula, each Ar ³ independently represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked or condensed, or 4 to 4 carbon atoms which may be linked or condensed). 36 monovalent heteroaromatic groups (these groups are each independently 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) May be included).)
Or a diarylamine represented by the general formula (5) and a diarylamine represented by the general formula (5) are reacted with each other. .   A charge transport material comprising the arylamine polymer according to any one of claims 1 to 7.   A hole transport material, a hole injection material, or a light-emitting host material comprising the arylamine polymer according to any one of claims 1 to 7.   An organic electroluminescent device comprising the arylamine polymer according to any one of claims 1 to 7.