WO2012086669A1

WO2012086669A1 - Organic light-emitting element and conjugated macromolecular compound

Info

Publication number: WO2012086669A1
Application number: PCT/JP2011/079595
Authority: WO
Inventors: 誠安立; 重也小林
Original assignee: 住友化学株式会社
Priority date: 2010-12-21
Filing date: 2011-12-21
Publication date: 2012-06-28
Also published as: TW201233771A; JP2012146968A

Abstract

The present invention provides an organic light-emitting element provided with a light-emitting layer. Said light-emitting layer contains either a compound having the structure represented by general formula (1) or a compound having a group derived from the structure represented by general formula (1). Furthermore, the skeleton of the structure represented by general formula (1) constitutes 0.01% to 20% of the total mass of organic compounds in the light-emitting layer. (In the formula, R^x represents either a hydrogen atom or a functional group selected from the group comprising: an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a silyl group, a halogen atom, an acyl group, an acyloxy group, a monovalent heterocyclic group, a monovalent heterocyclic thio group, an imine residue, an amide-compound residue, an acid-imide residue, a carboxyl group, a nitro group, and a cyano group. In functional groups containing a hydrogen atom, said hydrogen atom may be substituted by a substituent. The plurality of R^xs may be the same as or different from each other.)

Description

Organic light emitting device and conjugated polymer compound

The present invention relates to an organic light emitting device and a conjugated polymer compound.

In recent years, organic EL displays using organic electroluminescence (EL) elements (hereinafter referred to as organic light-emitting elements) have attracted attention as next-generation displays. The organic light emitting device includes organic layers such as a light emitting layer and a charge transport layer. The organic light emitting device may be made of a low molecular organic material or a high molecular organic material. When a polymer organic material is used as a main material, a uniform film can be easily formed when an application method such as ink jet or spin coating is used, which is advantageous for manufacturing a large organic EL display. Therefore, high molecular organic materials have been proposed so far (for example, Patent Documents 1 and 2).

JP 2008-56909 A WO99 / 54385 pamphlet

However, the conventional polymeric organic material cannot be said to have a sufficient luminance life when used in an organic light emitting device.

Therefore, an object of the present invention is to provide an organic light emitting device with an improved luminance life.

The present invention
With a light emitting layer,
The light emitting layer contains a compound having a structure represented by the following general formula (1) or a compound having a group derived from the structure represented by the following general formula (1), and
In the light-emitting layer, an organic light-emitting element (hereinafter referred to as “the skeleton having a structure represented by the general formula (1)” in the total amount of the organic compound contained in the light-emitting layer is 0.01% by mass to 20% by mass). , Sometimes referred to as “organic light-emitting element X”).

In general formula (1), R ^x represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a silyl group, a halogen atom, an acyl group, or an acyloxy group. A functional group selected from the group consisting of a monovalent heterocyclic group, a monovalent heterocyclic thio group, an imine residue, an amide compound residue, an acid imide residue, a carboxyl group, a nitro group and a cyano group, or hydrogen Indicates an atom. However, in the functional group having a hydrogen atom, the hydrogen atom may be substituted with a substituent. A plurality of R ^x may be the same or different.

The present invention also provides
A light emitting layer, and a charge transport layer adjacent to the light emitting layer,
The charge transport layer contains a compound having a structure represented by the following general formula (1) or a compound having a group derived from the structure represented by the following general formula (1), and
In the charge transport layer, the ratio of the skeleton having the structure represented by the general formula (1) to the total amount of the organic compound contained in the charge transport layer is 0.01% by mass to 50% by mass. (Hereinafter sometimes referred to as “organic light-emitting element Y”).

[Where:
R ^x is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group A functional group selected from the group consisting of a monovalent heterocyclic thio group, an imine residue, an amide compound residue, an acid imide residue, a carboxyl group, a nitro group and a cyano group, or a hydrogen atom.
However, in the functional group having a hydrogen atom, the hydrogen atom may be substituted with a substituent. A plurality of R ^x may be the same or different. ]

According to the present invention, when the organic light emitting device satisfies any of the above-described requirements, the luminance life of the organic light emitting device is improved.

The compound having a group derived from the structure represented by the general formula (1) is preferably a polymer compound, and more preferably a conjugated polymer compound. Moreover, it is preferable that the said conjugated polymer compound has as a repeating unit the group induced | guided | derived from the structure represented by the said General formula (1). Thereby, the electrical characteristics of the organic light emitting device are improved.

In the present invention, a group derived from a structure represented by the following general formula (1) and an optional additional group different from the above group are introduced by the above condensation polymerization. the number of moles of group and the optional additional groups derived from structures represented by 1), when the N ₁ and N _M, respectively, N ₁ and N _M satisfies the following formula (I), the conjugated system high A molecular compound (hereinafter sometimes referred to as “conjugated polymer compound Z”) is provided.
0.01 ≦ N ₁ × 100 / (N ₁ + N _M ) ≦ 20 (I)

Since the conjugated polymer compound of the present invention has a predetermined amount of groups derived from the structure represented by the general formula (1), the electrical characteristics of the organic light emitting device can be obtained by using it in the organic light emitting device. Can be further improved.

In the conjugated polymer compound, a group derived from the structure represented by the general formula (1) has the following formula (2), formula (3), formula (4), formula (5), formula (6). Or a group represented by formula (7). In the following formula, R ^x represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a silyl group, a halogen atom, an acyl group, an acyloxy group, or a monovalent group. A functional group selected from the group consisting of a heterocyclic group, a monovalent heterocyclic thio group, an imine residue, an amide compound residue, an acid imide residue, a carboxyl group, a nitro group and a cyano group, or a hydrogen atom . However, in the functional group having a hydrogen atom, the hydrogen atom may be substituted with a substituent.

The conjugated polymer compound preferably contains at least one group among the groups represented by the following formulas (A), (B), and (C) as the optional additional group. In the following formulae, Ar ¹ and Ar ⁵ are each independently selected from the group consisting of an arylene group, a divalent heterocyclic group composed of a 6-membered ring or more, and a divalent group having a metal complex structure. Ar ² , Ar ³ and Ar ⁴ each independently represent a functional group selected from the group consisting of an arylene group and a divalent heterocyclic group composed of a 6-membered ring or more. R ¹ and R ² each independently represents a functional group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group and an arylalkyl group, and X ¹ represents —CR ³ ═CR ⁴ A functional group selected from the group consisting of — and —C≡C— is shown. R ³ and R ⁴ each independently represent a functional group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, and a cyano group. a is 0 or 1. However, in the functional group having a hydrogen atom, the hydrogen atom may be substituted with a substituent.

Conjugation excellent in charge transport and charge injection efficiency when the conjugated polymer compound contains at least one of the optional additional groups represented by the formula (A), (B) or (C). It becomes a high molecular compound. In addition, when used in an organic light emitting device, the luminance life can be further improved.

The conjugated polymer compound has the number of moles of optional additional groups represented by the above formulas (A), (B), and (C) and the number of moles of optional additional groups other than these, N _A , N _B , When N _C and N _{M ′} are set, N ₁ , N _A , N _B , N _C and N _{M ′} preferably satisfy the following formula (II).
_{_{40 ≦ (N A + N B}} + N C) × 100 / (N 1 + N A + N B + N C + N M ') <100 (II)

The conjugated polymer compound preferably contains an optional additional group represented by the above formula (A). Thereby, it becomes a conjugated high molecular compound excellent in electron transport and electron injection efficiency, and can be used suitably for the charge transport layer (especially electron transport layer) of an organic light emitting element. The conjugated polymer compound preferably includes an arbitrary additional group represented by the formula (B). Thereby, it becomes a conjugated polymer compound excellent in hole transport and hole injection efficiency, and can be suitably used for a charge transport layer (particularly, a hole transport layer) of an organic light emitting device. The conjugated polymer compound preferably includes an optional additional group represented by the formula (A) and an optional additional group represented by the formula (B). Thereby, it becomes a conjugated high molecular compound which can form excitation energy efficiently by the coupling | bonding of a hole and an electron, and can be used suitably for the light emitting layer of an organic light emitting element.

The present invention also provides a composition comprising at least one material selected from the group consisting of a light emitting material, a hole transport material and an electron transport material, and the conjugated polymer compound. The composition of the present invention can be used for production of a light emitting layer, a charge (meaning holes or electrons, hereinafter the same) transport layer or charge injection layer of an organic light emitting device, and improves production efficiency. be able to.

The present invention also provides an ink composition comprising the conjugated polymer compound and an organic solvent. Since the ink composition contains an organic solvent, in laminating and forming the thin film containing the conjugated polymer compound, it is only necessary to remove the organic solvent by drying after applying the ink composition. It is advantageous.

The present invention also provides an organic light emitting device X and an organic light emitting device Y containing a conjugated polymer compound Z.

The present invention further provides a planar light source and a display device provided with the organic light emitting device. Since the above-mentioned organic light emitting device has a remarkably improved luminance life, a planar light source and a display device excellent in durability can be obtained.

The organic light emitting device of the present invention is a device having an improved luminance life. In addition, the luminance life of the organic light emitting device can be improved by adding the conjugated polymer compound of the present invention to the charge injection layer, the charge transport layer or the light emitting layer of the organic light emitting device.

Furthermore, according to the present invention, there are provided a composition and an ink composition containing the conjugated polymer compound, a conjugated polymer compound, a planar light source having the organic light emitting device, a display device, and the like. Can do.

It is a schematic cross section of the organic thin-film transistor which concerns on one Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on one Embodiment. It is a schematic cross section of the organic light emitting element (configuration i) according to one embodiment. It is a schematic cross section of the organic light emitting element (configuration e) according to one embodiment. It is a schematic cross section of the planar light source which concerns on one Embodiment.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the following description, the tert-butyl group may be expressed as “t-Bu” and the phenyl group as “Ph”.

<Explanation of terms>
Hereinafter, terms commonly used in this specification will be described with specific examples as necessary.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The term “C _x -C _y ” (where x and y are positive integers satisfying x <y) indicates that the number of carbon atoms in the partial structure corresponding to the functional group name described immediately after this term is It means x to y. That is, when the organic group described immediately after “C _x -C _y ” is an organic group named by combining a plurality of functional group names (for example, C _x -C _y alkoxyphenyl group), This means that the number of carbon atoms in the partial structure corresponding to the functional group name (for example, alkoxy) described immediately after “C _x -C _y ” among the functional group names is x to y. For example, “C ₁ -C ₁₂ alkyl group” means an alkyl group having 1 to 12 carbon atoms, and “C ₁ -C ₁₂ alkoxyphenyl group” means “1 to 12 carbon atoms”. It means a phenyl group having an “alkoxy group”.

The alkyl group may have a substituent, and may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group (that is, a cycloalkyl group). As the alkyl group, a linear alkyl group and a cyclic alkyl group are preferable, and an unsubstituted alkyl group and an alkyl group substituted with a halogen atom or the like are preferable.

Examples of the substituent include alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic ring Groups, heterocyclic thio groups, imine residues, amide compound residues, acid imide residues, carboxyl groups, nitro groups, cyano groups, etc., and some or all of the hydrogen atoms contained in these groups are fluorine It may be substituted with an atom (hereinafter referred to as “substituent” can be exemplified by the same group unless otherwise specified).

Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, and a hexyl group. Cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, dodecyl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl Group, perfluorooctyl group and the like.

When the alkyl group is a linear alkyl group or a branched alkyl group, it is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 12. In the case of a cyclic alkyl group, it is preferably 3 to 20, more preferably 3 to 15, and still more preferably 3 to 12. Examples of the C ₁ to C ₁₂ alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, Examples include heptyl group, octyl group, nonyl group, decyl group, dodecyl group and the like.

The alkoxy group may have a substituent, and may be any of a linear alkoxy group, a branched alkoxy group, and a cyclic alkoxy group (that is, a cycloalkoxy group). As the alkoxy group, a linear alkoxy group and a cyclic alkoxy group are preferable, and an unsubstituted alkoxy group and an alkoxy group substituted with a halogen atom, an alkoxy group, or the like are preferable.

Examples of the alkoxy group which may have a substituent include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy Group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, dodecyloxy group, trifluoromethoxy group, pentafluoroethoxy group, par Examples thereof include a fluorobutoxy group, a perfluorohexyloxy group, a perfluorooctyloxy group, a methoxymethyloxy group, and a 2-methoxyethyloxy group.

The number of carbon atoms of the alkoxy group is preferably 1-20, more preferably 1-15, still more preferably 1-12 when it is a linear alkoxy group or branched alkoxy group, and when it is a cyclic alkoxy group Preferably, it is 3 to 20, more preferably 3 to 15, and still more preferably 3 to 12. C ₁ -C ₁₂ alkoxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, cyclohexyloxy Group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, dodecyloxy group and the like.

The alkylthio group may have a substituent, and may be any of a linear alkylthio group, a molecular chain alkylthio group, and a cyclic alkylthio group (that is, a cycloalkylthio group). As the alkylthio group, a linear alkylthio group and a cyclic alkylthio group are preferable, and an unsubstituted alkylthio group and an alkylthio group substituted with a halogen atom or the like are preferable.

Examples of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, Examples include cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, dodecylthio group, trifluoromethylthio group and the like.

When the alkylthio group is a linear alkylthio group or a branched alkylthio group, it is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 12, and when it is a cyclic alkylthio group Preferably, it is 3 to 20, more preferably 3 to 15, and still more preferably 3 to 12. Examples of the C ₁ -C ₁₂ alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, Examples include heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, dodecylthio group and the like.

An aryl group is a remaining atomic group obtained by removing one hydrogen atom bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon, and may have a substituent. As the aryl group, an unsubstituted aryl group and an aryl group substituted with a halogen atom, an alkoxy group, an alkyl group or the like are preferable. The aryl group includes a group having a benzene ring, a group having a condensed ring, and two or more benzene rings and / or condensed rings, a single bond or a divalent organic group (for example, an alkylene group such as a vinylene group). And the like bonded through the like. The number of carbon atoms of the aryl group is preferably 6 to 60, more preferably 6 to 48, and still more preferably 6 to 30.

Examples of the aryl group which may have a substituent include a phenyl group, a C ₁ -C ₁₂ alkoxyphenyl group, a C ₁ -C ₁₂ alkylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 2-fluorenyl group, pentafluorophenyl group, biphenylyl group, C ₁ -C ₁₂ alkoxybiphenylyl group, C ₁ -C ₁₂ alkylbiphenylyl group, etc. A C ₁ -C ₁₂ alkoxyphenyl group, a C ₁ -C ₁₂ alkylphenyl group, a biphenylyl group, a C ₁ -C ₁₂ alkoxybiphenylyl group, and a C ₁ -C ₁₂ alkylbiphenylyl group are preferred.

C ₁ -C ₁₂ alkoxyphenyl groups include methoxyphenyl group, ethoxyphenyl group, propyloxyphenyl group, isopropyloxyphenyl group, butyloxyphenyl group, isobutyloxyphenyl group, tert-butyloxyphenyl group, pentyloxyphenyl group Hexyloxyphenyl group, octyloxyphenyl group and the like.

C ₁ -C ₁₂ alkylphenyl groups include methylphenyl, ethylphenyl, dimethylphenyl, propylphenyl, mesityl, isopropylphenyl, butylphenyl, isobutylphenyl, tert-butylphenyl, pentylphenyl Group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like.

The aryloxy group may have a substituent, and is preferably an unsubstituted aryloxy group and an aryloxy group substituted with a halogen atom, an alkoxy group, an alkyl group or the like. The number of carbon atoms of the aryloxy group is preferably 6 to 60, more preferably 6 to 48, and still more preferably 6 to 30.

The aryloxy group which may have a substituent includes a phenoxy group, a C ₁ -C ₁₂ alkoxyphenoxy group, a C ₁ -C ₁₂ alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, pentafluoro Examples thereof include a phenyloxy group, and among them, a C ₁ to C ₁₂ alkoxyphenoxy group and a C ₁ to C ₁₂ alkylphenoxy group are preferable.

C ₁ -C ₁₂ alkoxyphenoxy groups include methoxyphenoxy group, ethoxyphenoxy group, propyloxyphenoxy group, isopropyloxyphenoxy group, butyloxyphenoxy group, isobutyloxyphenoxy group, tert-butyloxyphenoxy group, pentyloxyphenoxy group Hexyloxyphenoxy group, octyloxyphenoxy group and the like.

Examples of the C ₁ -C ₁₂ alkylphenoxy group include a methylphenoxy group, an ethylphenoxy group, a dimethylphenoxy group, a propylphenoxy group, a 1,3,5-trimethylphenoxy group, a methylethylphenoxy group, an isopropylphenoxy group, a butylphenoxy group, Examples include isobutylphenoxy, sec-butylphenoxy, tert-butylphenoxy, pentylphenoxy, isoamylphenoxy, hexylphenoxy, heptylphenoxy, octylphenoxy, nonylphenoxy, decylphenoxy, dodecylphenoxy It is done.

The arylthio group may have a substituent, and is preferably an unsubstituted arylthio group and an arylthio group substituted with a halogen atom, an alkoxy group, an alkyl group, or the like. The number of carbon atoms of the arylthio group is preferably 6 to 60, more preferably 6 to 48, and still more preferably 6 to 30. Examples of the arylthio group which may have a substituent include a phenylthio group, a C ₁ to C ₁₂ alkoxyphenylthio group, a C ₁ to C ₁₂ alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and pentafluorophenyl. A thio group etc. are mentioned.

The arylalkyl group may have a substituent, and is preferably an unsubstituted arylalkyl group and an arylalkyl group substituted with a halogen atom, an alkoxy group, an alkyl group, or the like. The number of carbon atoms of the arylalkyl group is preferably 7 to 60, more preferably 7 to 48, and still more preferably 7 to 30. As the arylalkyl group which may have a substituent, a phenyl-C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkylphenyl-C Examples thereof include a ₁ to C ₁₂ alkyl group, a 1-naphthyl-C ₁ to C ₁₂ alkyl group, and a 2-naphthyl-C ₁ to C ₁₂ alkyl group.

The arylalkoxy group may have a substituent, and is preferably an unsubstituted arylalkoxy group and an arylalkoxy group substituted with a halogen atom, an alkoxy group, an alkyl group, or the like. The number of carbon atoms of the arylalkoxy group is preferably 7 to 60, more preferably 7 to 48, and still more preferably 7 to 30. The arylalkoxy group which may have a substituent includes phenyl-C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl-C Examples thereof include ₁ to C ₁₂ alkoxy groups, 1-naphthyl-C ₁ to C ₁₂ alkoxy groups, and 2-naphthyl-C ₁ to C ₁₂ alkoxy groups.

The arylalkylthio group may have a substituent, and is preferably an unsubstituted arylalkylthio group and an arylalkylthio group substituted with a halogen atom, an alkoxy group, an alkyl group or the like. The number of carbon atoms of the arylalkylthio group is preferably 7 to 60, more preferably 7 to 48, and still more preferably 7 to 30. The arylalkylthio group which may have a substituent includes phenyl-C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl-C Examples thereof include ₁ to C ₁₂ alkylthio groups, 1-naphthyl-C ₁ to C ₁₂ alkylthio groups, and 2-naphthyl-C ₁ to C ₁₂ alkylthio groups.

The alkenyl group may have a substituent, and may be any of a linear alkenyl group, a branched alkenyl group, and a cyclic alkenyl group. The number of carbon atoms of the alkenyl group is preferably 2 to 20, more preferably 2 to 15, and still more preferably 2 to 10. Examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-hexenyl, An octenyl group etc. are mentioned.

The arylalkenyl group may have a substituent, and is preferably an unsubstituted arylalkenyl group and an arylalkenyl group substituted with a halogen atom, an alkoxy group, an alkyl group, or the like. The number of carbon atoms of the arylalkenyl group is preferably 8 to 60, more preferably 8 to 48, and still more preferably 8 to 30. The arylalkenyl group which may have a substituent includes phenyl-C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl-C ₂ to C ₁₂ alkenyl groups, 1-naphthyl-C ₂ to C ₁₂ alkenyl groups, 2-naphthyl-C ₂ to C ₁₂ alkenyl groups, and the like, among others, C ₁ to C ₁₂ alkoxyphenyl-C ₂ to C ₁₂ alkenyl are mentioned. The group C ₁ -C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkenyl is preferred. C ₂ -C ₁₂ alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2- Hexenyl group, 1-octenyl group and the like can be mentioned.

The alkynyl group may have a substituent, and may be any of a linear alkynyl group, a branched alkynyl group, and a cyclic alkynyl group. The number of carbon atoms of the alkynyl group is preferably 2 to 20, more preferably 2 to 15, more preferably 2 to 10 for a linear alkynyl group and a branched alkynyl group, and preferably 10 to 10 for a cyclic alkynyl group. -20, more preferably 10-15. Examples of the alkynyl group which may have a substituent include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group and 1-hexynyl. Group, 2-hexynyl group, 1-octynyl group, arylalkynyl group and the like.

The arylalkynyl group may have a substituent, and is preferably an unsubstituted arylalkynyl group and an arylalkynyl group substituted with a halogen atom, an alkoxy group, an alkyl group, or the like. The number of carbon atoms of the arylalkynyl group is preferably 8 to 60, more preferably 8 to 48, and still more preferably 8 to 30. The arylalkynyl group which may have a substituent includes phenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl-C ₂ to C ₁₂ alkynyl groups, 1-naphthyl-C ₂ to C ₁₂ alkynyl groups, 2-naphthyl-C ₂ to C ₁₂ alkynyl groups, etc., among others, C ₁ to C ₁₂ alkoxyphenyl-C ₂ to C ₁₂ alkynyl The group C ₁ -C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkynyl is preferred. C ₂ -C ₁₂ alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 1-hexynyl, 2- Examples include a hexynyl group and a 1-octynyl group.

The monovalent heterocyclic group is a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and may have a substituent. The monovalent heterocyclic group is preferably an unsubstituted monovalent heterocyclic group or a monovalent heterocyclic group substituted with a substituent such as an alkyl group. The number of carbon atoms of the monovalent heterocyclic group is preferably 4 to 60, more preferably 4 to 30, and further preferably 4 to 20, excluding the number of carbon atoms of the substituent. Heterocyclic compounds are not only carbon atoms but also oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms, silicon atoms, selenium atoms as elements constituting the ring among organic compounds having a cyclic structure. , And those containing hetero atoms such as tellurium atoms and arsenic atoms. Examples of the monovalent heterocyclic group which may have a substituent include a thienyl group, a C ₁ to C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a C ₁ to C ₁₂ alkyl pyridyl group, and a pyridazinyl group. , pyrimidinyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, among which thienyl _group, C 1 _{~ C 12} alkyl thienyl group, a pyridyl _group, C 1 _{~ C 12} alkyl pyridyl group Is preferred. The monovalent heterocyclic group is preferably a monovalent aromatic heterocyclic group.

The monovalent heterocyclic thio group is a group in which a hydrogen atom of a thiol group is substituted with the above monovalent heterocyclic group, and may have a substituent. Examples of the monovalent heterocyclic thio group include heteroarylthio groups such as a pyridylthio group, a pyridazinylthio group, a pyrimidinylthio group, a pyrazinylthio group, and a triazinylthio group.

The amino group may have a substituent, and is preferably substituted with an unsubstituted amino group and 1 or 2 substituents selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. Amino group (hereinafter referred to as “substituted amino group”). The substituent may further have a substituent (hereinafter, the substituent that the organic group further has may be referred to as “secondary substituent”). The number of carbon atoms of the substituted amino group is preferably 1 to 60, more preferably 2 to 48, and still more preferably 2 to 40, not including the number of carbon atoms of the secondary substituent.

Examples of substituted amino groups include methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dipropylamino, isopropylamino, diisopropylamino, butylamino, isobutylamino, sec-butylamino Group, tert-butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, dodecylamino group, cyclopentyl amino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C 1 _~ C ₁₂ alkoxyphenyl amino group, bis (C ₁ C ₁₂ alkoxyphenyl) amino _group, C 1 _{~ C 12} alkyl phenyl group, bis _(C 1 _{~ C 12} alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino Group, pyridazinylamino group, pyrimidinylamino group, pyrazinylamino group, triazinylamino group, phenyl-C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkylamino group, Di (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkylphenyl-C _1- C ₁₂ alkyl) amino groups, 1-naphthyl _-C 1 _{~ C 12} alkyl group, - naphthyl _-C 1 _{~ C 12} alkylamino groups and the like.

The silyl group may have a substituent, preferably an unsubstituted silyl group, and 1 to 3 substituents selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group A silyl group substituted with (hereinafter referred to as “substituted silyl group”). The substituent may have a secondary substituent. The number of carbon atoms of the substituted silyl group does not include the number of carbon atoms of the secondary substituent, and is preferably 1 to 60, more preferably 3 to 48, and still more preferably 3 to 40.

Examples of substituted silyl groups include trimethylsilyl, triethylsilyl, tripropylsilyl, tri-isopropylsilyl, dimethyl-isopropylsilyl, diethyl-isopropylsilyl, tert-butyldimethylsilyl, pentyldimethylsilyl, hexyldimethyl Silyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, dodecyldimethylsilyl group, phenyl-C ₁ ~ _{C 12} alkylsilyl _group, C 1 _{~ C 12}

alkoxyphenyl

_-C 1 _{~ C 12} alkylsilyl _group, C 1 _{~ C 12}

alkylphenyl

_-C 1 _{~ C 12} alkylsilyl group, 1-naphthyl _-C 1 ~ C ₂ alkylsilyl group, 2-naphthyl _-C 1 _{~ C 12} alkylsilyl group, a phenyl _-C 1 _{~ C 12} alkyl dimethyl silyl group, a triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl Group, tert-butyldiphenylsilyl group, dimethylphenylsilyl group and the like.

The acyl group may have a substituent, and is preferably an unsubstituted acyl group and an acyl group substituted with a halogen atom or the like. The number of carbon atoms of the acyl group is preferably 2 to 20, more preferably 2 to 18, and still more preferably 2 to 16. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

The acyloxy group may have a substituent, and is preferably an unsubstituted acyloxy group and an acyloxy group substituted with a halogen atom or the like. The number of carbon atoms of the acyloxy group is preferably 2 to 20, more preferably 2 to 18, and still more preferably 2 to 16. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

The imine residue is represented by the general formula: H— ^N═C (R ^Y1 ) ₂ or the imine compound having a structure represented by at least one of the general formula: H—CR ^X1 ═N—R ^{Y1 in} the above general formula. It means a residue excluding a hydrogen atom. In the formula, R ^X1 represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group or an arylalkynyl group. In the formula, R ^Y1 represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, or an arylalkynyl group. However, when two R ^Y1 are present, they may be the same or different, and the two R ^Y1 are bonded together to form a divalent group such as an ethylene group, A ring may be formed as an alkylene group having 2 to 18 carbon atoms such as a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group. Examples of such imine compounds include compounds in which a hydrogen atom bonded to a nitrogen atom in aldimine, ketimine, or aldimine is substituted with an alkyl group, aryl group, arylalkyl group, arylalkenyl group, arylalkynyl group, or the like. Can be mentioned. The number of carbon atoms of the imine residue is preferably 2 to 20, more preferably 2 to 18, and still more preferably 2 to 16. Specific examples of the imine residue include groups represented by the following structural formulas.

The amide compound residue is derived from an amide compound having a structure represented by at least one of the general formula: H—NR ^X2 —COR ^Y2 and the general formula: H—CO—N (R ^Y2 ) _{2 in} the above general formula. It means a residue without an atom. In the formula, R ^X2 and R ^Y2 each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, or an arylalkynyl group. The number of carbon atoms of the amide compound residue is preferably 2 to 20, more preferably 2 to 18, and still more preferably 2 to 16. As the amide compound residue, formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, Examples include a ditrifluoroacetamide group and a dipentafluorobenzamide group.

The acid imide residue means a residue obtained by removing a hydrogen atom in the above general formula from an acid imide having a structure represented by the general formula: R ^X3 —CO—NH—CO—R ^{Y 3} . In the formula, R ^X3 and R ^Y3 each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, or an arylalkynyl group, or R ^X3 and R ^Y3 are both constituent atoms. Represents the ring structure formed. The number of carbon atoms of the acid imide residue is preferably 4 to 20, more preferably 4 to 18, and still more preferably 4 to 16. Examples of the acid imide residue include the following groups.

Arylene group means an atomic group formed by removing two hydrogen atoms from an aromatic hydrocarbon, and includes an independent benzene ring or a group having a condensed ring. The number of carbon atoms of the arylene group is preferably 6 to 60, more preferably 6 to 48, still more preferably 6 to 30, and particularly preferably 6 to 18. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the arylene group include phenylene groups such as 1,4-phenylene group, 1,3-phenylene group, and 1,2-phenylene group; biphenylylene groups such as 2,7-biphenylylene group and 3,6-biphenylylene group; 4-naphthalenediyl group, 1,5-naphthalenediyl group, naphthalenediyl group such as 2,6-naphthalenediyl group; 1,4-anthracenediyl group, 1,5-anthracenediyl group, 2,6-anthracenediyl group Anthracene diyl groups such as 9,10-anthracenediyl group; Phenanthrene diyl groups such as 2,7-phenanthrene diyl group; Groups: 2,7-fluorenediyl group, 3,6-fluorenediyl group, etc. Group: pyrenediyl group such as 1,6-pyrenediyl group, 1,8-pyrenediyl group, 2,7-pyrenediyl group, 4,9-pyrenediyl group; perylenediyl such as 3,9-perylenediyl group, 3,10-perylenediyl group, etc. Group etc. are mentioned, These may have a substituent. Of these, a phenylene group which may have a substituent and a fluorenediyl group which may have a substituent are preferable.

The divalent heterocyclic group refers to the remaining atomic group obtained by removing two hydrogen atoms from the heterocyclic compound, and may have a substituent. The divalent heterocyclic group is preferably an unsubstituted divalent heterocyclic group or a divalent heterocyclic group substituted with an alkyl group or the like. The number of carbon atoms of the divalent heterocyclic group is preferably 4 to 60, more preferably 4 to 30, and further preferably 4 to 12, excluding the number of carbon atoms of the substituent.

Examples of the divalent heterocyclic group include pyridinediyl groups such as 2,5-pyridinediyl group and 2,6-pyridinediyl group; quinolinediyl groups such as 2,6-quinolinediyl group; 1,4-isoquinolinediyl group, 1 Isoquinolinediyl groups such as 5,5-isoquinolinediyl group; quinoxalinediyl groups such as 5,8-quinoxalinediyl group; 2,1,3-benzothiadiazoles such as 2,1,3-benzothiadiazole-4,7-diyl group A benzothiazole diyl group such as a 4,7-benzothiazole diyl group; a carbazole diyl group such as a 2,7-carbazole diyl group or a 3,6-carbazole diyl group; a phenoxazine such as a 3,7-phenoxazine diyl group; Diyl group; phenothiazinediyl group such as 3,7-phenothiazinediyl group; 2,7-dibenzosiloldiyl group Dibenzosilole-diyl group and the like, and these may have a substituent. Of these, preferably 2,1,3-benzothiadiazole-4,7-diyl group which may have a substituent, phenoxazinediyl group which may have a substituent, It may be a phenothiazinediyl group. The divalent heterocyclic group is preferably a divalent aromatic heterocyclic group.

<A compound having a structure represented by the general formula (1) and a compound having a group derived from the structure represented by the general formula (1)>
A compound having a structure represented by the general formula (1) and a compound having a group derived from the structure represented by the general formula (1) will be described.

In general formula (1), R ^x represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a silyl group, a halogen atom, an acyl group, or an acyloxy group. A functional group selected from the group consisting of a monovalent heterocyclic group, a monovalent heterocyclic thio group, an imine residue, an amide compound residue, an acid imide residue, a carboxyl group, a nitro group and a cyano group, or hydrogen Indicates an atom. However, in the functional group having a hydrogen atom, the hydrogen atom may be substituted with a substituent.
R ^x is preferably a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group, more preferably a hydrogen atom, an alkyl group, or an aryl group, and still more preferably a hydrogen atom. A plurality of R ^x may be the same or different.

As a compound which has a structure represented by General formula (1), the compound represented by a following formula is mentioned, for example.

The group derived from the structure represented by the general formula (1) is a group composed of the remaining atomic groups excluding one or a plurality of R ^x in the general formula (1).

The compound having a group derived from the structure represented by the general formula (1) may be a low molecular compound or a high molecular compound. For example, it can be a compound having a molecular weight of 3,000 or less.

In the polymer compound having a group derived from the structure represented by the general formula (1), this group may be contained in the main chain of the polymer compound or in the side chain. Moreover, when contained in the main chain, it may be contained at the end of the polymer compound.

Examples of the polymer compound include a polymer compound containing a group consisting of an atomic group obtained by removing one R ^x of the general formula (1), and an atomic group obtained by removing one R ^x of the general formula (1). Examples thereof include a polymer compound containing a group at the terminal and a polymer compound containing a group consisting of an atomic group obtained by removing two R ^x in the general formula (1). These polymer compounds contain one or more groups consisting of the remaining atomic groups excluding one or more R ^x in the general formula (1).

The polymer compound containing a group consisting of an atomic group obtained by removing one R ^x of the general formula (1) contains, for example, a polymer compound containing this group in the side chain or this group at the end of the main chain. A high molecular compound is mentioned. The polymer compound containing this group at the end of the main chain includes, for example, a group consisting of an atomic group excluding one R ^x of the general formula (1) as an end-capping agent used when stopping the polymerization reaction. It can be obtained by using one.

As for the high molecular compound containing the group which consists of an atomic group remove | excluding two ^Rx of General formula (1), the high molecular compound which contains this group in a principal chain is mentioned, for example. When the polymer compound containing this group in the main chain has, for example, a portion obtained by removing two R ^{x s} in the general formula (1) to be a reaction point of polymerization, the R ^x in the general formula (1) is 2 It can be obtained when the removed part becomes a reaction point of polymerization via a linking group.

The polymer compound having a group derived from the structure represented by the general formula (1) is preferably a compound containing a group consisting of an atomic group obtained by removing two R ^x in the general formula (1), more preferably. Can be obtained in such a manner that the portion of the general formula (1) from which R ^x is removed becomes the reaction point of the polymerization.

Examples of the group consisting of an atomic group obtained by removing two R ^x in the general formula (1) include the following formula (2), formula (3), formula (4), formula (5), formula (6), or formula (7). ) Is preferred. More preferably, it is a group represented by the following formula (2), formula (3), formula (5), formula (6) or formula (7), particularly preferably a group represented by the following formula (2). is there.

Specific examples of the group represented by the above formula (2), formula (3), formula (4), formula (5), formula (6), or formula (7) include groups represented by the following formulas. It is done.

<Conjugated polymer compound having a group derived from the structure represented by the general formula (1)>
The polymer compound having a group derived from the structure represented by the general formula (1) is preferably a conjugated polymer compound because the charge injection property and the charge transport property are improved. The “conjugated polymer compound” means a polymer compound in which 50 to 100%, particularly 70 to 100%, particularly 90 to 100% of all bonds in the main chain are conjugated.

The conjugated polymer compound preferably has a group derived from the structure represented by the general formula (1) as a repeating unit. Here, “having as a repeating unit” means being included so as to constitute an electron conjugated system.

The conjugated polymer compound is synthesized by condensation polymerization, and a group derived from the structure represented by the general formula (1) and an optional additional group different from the group are introduced by the condensation polymerization. is there. Further, the number of moles of group and any additional groups derived from structures represented by the general formula (1) in the entire conjugated polymer compound, respectively, when the N ₁ and N _M, the following formula (i) The value calculated by is 0.01 or more and 20 or less.
N ₁ × 100 / (N ₁ + N _M ) (i)

The value calculated by the formula (i) is expressed by the general formula (1) when the compound subjected to the condensation polymerization is a unit and the total amount of the compounds introduced into the conjugated polymer compound by the condensation polymerization is 100 mol%. The molar content of the group derived from the structure represented by In the conjugated polymer compound of the present invention, the value calculated by the formula (i) is preferably 0.03 or more and 15 or less, more preferably 0.1 or more and 12.5 or less.

The conjugated polymer compound has a polystyrene-reduced number average molecular weight by gel permeation chromatography (hereinafter referred to as “GPC”), preferably 1 × 10 ³ to 1 × 10 ⁷ , more preferably 1 × 10 ⁴ to 5 × 10 ⁶ . When the number average molecular weight of 1 × 10 ³ or more, more excellent charge injection property and charge transport property, and facilitates improved film forming properties, in the case of 1 × 10 ⁷ or less, film forming property by coating It tends to be good. The weight average molecular weight in terms of polystyrene is preferably 1 × 10 ⁴ to 5 × 10 ⁷ , more preferably 5 × 10 ⁴ to 1 × 10 ⁷ . If the weight average molecular weight of 1 × 10 ⁴ or more, more excellent charge injection property and charge transport property, and facilitates improved film forming properties, in the case of 5 × 10 ⁷ or less, film forming property by coating It tends to be good.

Examples of the optional additional groups include “conductive polymer materials” (CMC Publishing), “latest application technology of conductive polymers” (CMC Publishing), “basic and applied conductive polymers” (stock) Company IP, edited by Katsumi Yoshino), “Conductive polymer” (edited by the Society of Polymer Science, Shinichi Yoshimura), “Polymer EL Materials” (edited by the Society of Polymer Science, Toshihiro Onishi, Tamami Ogawa), etc. Examples include a group constituting a molecular compound (a group derived from a monomer). Among these, an arylene group which may have a substituent or a divalent aromatic heterocyclic ring which may have a substituent Groups are preferred.

The conjugated polymer compound is preferably a bond between a group derived from the structure represented by the general formula (1) and an arbitrary additional group, and a bond between the arbitrary additional group and the optional additional group. Is a compound in which 50% or more, more preferably 70% or more, and still more preferably 90% or more are connected by a direct bond, a nitrogen atom, a vinylene group, or an acetylene group.

Since the above conjugated polymer compound is excellent in charge transporting property, charge injection property and luminance life, as the optional additional group, an optional additional group represented by the following general formula (A) (hereinafter referred to as “optional additional group A”). ), An optional additional group represented by the following general formula (B) (hereinafter referred to as “optional additional group B”), and an optional additional group represented by the following general formula (C) (hereinafter referred to as “optional”). It is preferable to contain at least one group selected from the group consisting of “additional group C”.

In the general formulas (A) to (C), Ar ¹ and Ar ⁵ are each independently an arylene group, a divalent heterocyclic group composed of a 6-membered ring or more, and a divalent heterocyclic group. A functional group selected from the group consisting of groups;
Ar ² , Ar ³ and Ar ⁴ each independently represent a functional group selected from the group consisting of an arylene group and a divalent heterocyclic group composed of a 6-membered ring or more.
R ¹ and R ² each independently represents a functional group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group and an arylalkyl group, and X ¹ represents —CR ³ ═CR ⁴ A functional group selected from the group consisting of — and —C≡C— is shown.
R ³ and R ⁴ each independently represent a functional group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, and a cyano group.
a is 0 or 1.
However, in the functional group having a hydrogen atom, the hydrogen atom may be substituted with a substituent. Here, the divalent heterocyclic group composed of a 6-membered ring or more is preferably a divalent heterocyclic group larger than the 6-membered ring.

Further, the number of moles of groups derived from structures represented by the general formula contained in the conjugated polymer compound of the present invention (1) and N _1, optional additional group A contained in the conjugated polymer compound, _A value calculated by the following formula (ii) when the number of moles of the optional additional group B, the optional additional group C, and the optional additional group other than these is N _A , N _B , N _C, and N _{M ′} , respectively. However, it is preferable that it is 40 or more and less than 100, More preferably, it is 50 or more and less than 100, More preferably, it is 70 or more and less than 100, Especially preferably, it is 80 or more and less than 100.
(N _A + N _B + N _C ) × 100 / (N ₁ + N _A + N _B + N _C + N _{M ′} ) (ii)

-Arbitrary additional group represented by general formula (A)-
In the general formula (A), when the group represented by Ar ¹ has a substituent, examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, and an aryl group. Examples include alkenyl groups, arylalkynyl groups, amino groups, substituted amino groups, halogen atoms, acyl groups, acyloxy groups, monovalent heterocyclic groups, carboxyl groups, nitro groups, cyano groups, and preferably alkyl groups, alkoxy groups A group, an aryl group, an aryloxy group, a substituted amino group, and a monovalent heterocyclic group, more preferably an alkyl group, an alkoxy group, and an aryl group.

In the above general formula (A), the arylene group in the arylene group which may have a substituent represented by Ar ¹ means an atomic group formed by removing two hydrogen atoms from an aromatic hydrocarbon, and independently Group having a benzene ring or condensed ring. The number of carbon atoms of the arylene group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18.
In the general formula (A), the arylene group which may have a substituent represented by Ar ¹ includes 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthalene Diyl group, 1,5-naphthalenediyl group, 2,6-naphthalenediyl group, 9,10-anthracenediyl group, 2,7-phenanthrylene group, 5,12-naphthacenylene group, 2,7-fluorenediyl group, 3,6-fluorenediyl group, 1,6-pyrene diyl group, 1,8-pyrene diyl group, 3,9-perylene diyl group, 3,10-perylene diyl group, 2,6-quinoline diyl group, 1,4-isoquinoline diyl Group, 1,5-isoquinolinediyl group, 5,8-quinoxalinediyl group and the like, preferably 1,4-phenylene group, 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 2,6-naphthalenediyl group, 9,10-anthracenediyl group, 2,7-fluorenediyl group, 1,6-pyrenediyl group, 3,9-perylenediyl group, 3,10 -Perylenediyl group, 2,6-quinolinediyl group, 1,4-isoquinolinediyl group, 5,8-quinoxalinediyl group, more preferably 1,4-phenylene group, 1,4-naphthalenediyl group, 1, 5-naphthalenediyl group, 2,6-naphthalenediyl group, 9,10-anthracenediyl group, 2,7-fluorenediyl group, 5,8-quinoxalinediyl group, particularly preferably 1,4-phenylene Group, 2,7-fluorenediyl group.

In the general formula (A), the divalent heterocyclic group composed of a 6-membered ring or more optionally having a substituent represented by Ar ¹ includes 4,7-benzo [1, 2,5] thiadiazolediyl group, 3,7-phenoxazinediyl group, 3,7-phenothiazinediyl group and the like can be mentioned, and 4,7-benzo [1,2,5] thiadiazolediyl group is preferable.

In the above general formula (A), the divalent group having a metal complex structure which may have a substituent represented by Ar ¹ is the rest of the iridium complex or the platinum complex after removing two hydrogen atoms. An atomic group (that is, a residue of an iridium complex or a platinum complex) and the like, and are represented by the following formulas M-1, M-2, M-3, M-4, M-5, M-6, and M-7. Preferred are the groups In the formula, R is an alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group A monovalent heterocyclic group, a carboxyl group, a nitro group or a cyano group is shown. A plurality of R may be the same or different.

Among these, the group represented by Ar ¹ is at least one selected from the group consisting of groups represented by the following formulas (D), (E), (F), (G) and (H). It is desirable to be.

In the formula (D), R ¹⁰ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a halogen atom, an acyl. A group, an acyloxy group, a monovalent heterocyclic group, a carboxyl group, a nitro group or a cyano group; Some or all of the hydrogen atoms contained in these groups may be substituted with fluorine atoms. f is an integer of 0-4. When a plurality of R ¹⁰ are present, they may be the same or different.

In formula (E), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group.

In the formula (F), R ¹³ and R ¹⁴ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, an amino group A group, a substituted amino group, a halogen atom, an acyl group, an acyloxy group, a monovalent heterocyclic group, a carboxyl group, a nitro group or a cyano group; Some or all of the hydrogen atoms contained in these groups may be substituted with fluorine atoms.

In formula (G), R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or an arylalkyl group.

In the formula (H), R ¹⁶ represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or an arylalkyl group.

In the above formula (D), R ¹⁰ is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, a substituted amino group, an acyl group, A monovalent heterocyclic group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a substituted amino group, an acyl group, and a monovalent heterocyclic group, still more preferably an alkyl group, an alkoxy group. A group, an aryl group, and a monovalent heterocyclic group, particularly preferably an alkyl group, an alkoxy group, and an aryl group.

In the above formula (D), f is preferably an integer of 0-2.

In the above formula (E), R ¹¹ and R ¹² are preferably an alkyl group, an aryl group, and a monovalent heterocyclic group, and more preferably an alkyl group and an aryl group.

In the above formula (F), R ¹³ and R ¹⁴ are preferably hydrogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, substituted amino group, acyl group, monovalent group. More preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a monovalent heterocyclic group, still more preferably a hydrogen atom or an alkyl group, particularly preferably. Is a hydrogen atom.

In the above formula (G), R ¹⁵ is preferably an alkyl group, an aryl group, or a monovalent heterocyclic group, more preferably an alkyl group or an aryl group, and still more preferably an aryl group.

In the above formula (H), R ¹⁶ is preferably an alkyl group, an aryl group, or a monovalent heterocyclic group, more preferably an alkyl group or an aryl group, and still more preferably an aryl group.

-Arbitrary additional group represented by general formula (B)-
In the general formula (B), when the groups represented by Ar ² , Ar ³ and Ar ⁴ have a substituent, the substituent includes an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an arylalkyl group. , Arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group, cyano group, preferably , An alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, an acyl group, and a cyano group, and more preferably an alkyl group, an alkoxy group, and an aryl group.

In the general formula (B), the arylene group in the arylene group which may have a substituent represented by Ar ² , Ar ³ and Ar ⁴ is an atom formed by removing two hydrogen atoms from an aromatic hydrocarbon. Means a group having an independent benzene ring or condensed ring. The number of carbon atoms of the arylene group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18.

In the general formula (B), the arylene group in the arylene group which may have a substituent represented by Ar ² , Ar ³ and Ar ⁴ includes a 1,3-phenylene group and a 1,4-phenylene group 1,4-naphthalenediyl group, 2,6-naphthalenediyl group, 9,10-anthracenediyl group, 2,7-phenanthenediyl group, 5,12-naphthacenediyl group, 2,7-fluorenediyl group, 3 , 8-perylenediyl group and the like.

In the general formula (B), the divalent heterocyclic in Ar ^2, Ar ³ and divalent heterocyclic group composed of the ring may also be a 6-membered ring or more, which have a substituent represented by Ar ⁴ The cyclic group usually has 4 to 60 carbon atoms, preferably 4 to 20, and more preferably 4 to 9. In the general formula (B), the divalent heterocyclic group in the divalent heterocyclic group which may have a substituent represented by Ar ² , Ar ³ and Ar ⁴ is N-methyl-2 , 5-pyrroldiyl group, 4,7-benzo [1,2,5] thiadiazolediyl group, 3,7-phenoxazinediyl group, 3,6-carbazolediyl group and the like.

In the general formula (B), Ar ² and Ar ⁴ are each independently preferably an arylene group which may have a substituent, and more preferably, an optionally substituted 1, 3-phenylene group, 1,4-phenylene group optionally having substituent, 1,4-naphthalenediyl group optionally having substituent, 2,6 optionally having substituent A naphthalenediyl group, more preferably a 1,4-phenylene group which may have a substituent, and a 1,4-naphthalenediyl group which may have a substituent, particularly preferably It is a 1,4-phenylene group which may have a substituent.

In the general formula (B), Ar ³ preferably may have a substituent group 1,3-phenylene group, which may have a substituent group 1,4-phenylene group, a substituent 1,4-naphthalenediyl group which may have, 2,7-fluorenediyl group which may have a substituent, 4,7-benzo [1,2 which may have a substituent , 5] a thiadiazole diyl group and an optionally substituted 3,7-phenoxazinediyl group, preferably an optionally substituted 1,4-phenylene group and a substituted group. An optionally substituted 1,4-naphthalenediyl group, an optionally substituted 2,7-fluorenediyl group, and more preferably an optionally substituted 1,4-phenylene It is a group.

In the general formula (B), R ¹ and R ² are preferably each independently an alkyl group, an aryl group, or a monovalent heterocyclic group, more preferably an alkyl group or an aryl group, An aryl group is preferable.

Examples of the optional additional group represented by the general formula (B) include groups represented by the following formulas (3B-1), (3B-3), and (3B-4). In the formula, R ^a represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, or a halogen atom. And a functional group selected from the group consisting of an acyl group, an acyloxy group, a monovalent heterocyclic group, a carboxyl group, a nitro group and a cyano group. However, in the functional group having a hydrogen atom, the hydrogen atom may be substituted with a substituent. A plurality of ^Ra may be the same or different.

-Arbitrary additional group represented by general formula (C)-
In the above general formula (C), a divalent heterocyclic ring composed of an arylene group which may have a substituent represented by Ar ⁵ and a ring having 6 or more members which may have a substituent. The divalent group having a metal complex structure which may have a group and a substituent is the same as the group described and exemplified in the section for Ar ¹ .

In the above general formula (C), in the functional group represented by —CR ³ ═CR ⁴ — which is X ¹ , R ³ and R ⁴ are preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably , Hydrogen atom, aryl group.

Examples of the optional additional group represented by the general formula (C) include the following formulas (4A-1), (4A-2), (4A-3), (4A-4), (4A-5), ( 4A-6), (4A-7), (4A-8), (4A-9), (4A-10) and (4A-11).

<The manufacturing method of the compound which has a structure represented by General formula (1)>
Azulene (a compound in which R ^x is all hydrogen atoms in the general formula (1)) is commercially available and available. In addition, by substituting a hydrogen atom directly bonded to the azulene ring with an arbitrary functional group from azulene by, for example, an aromatic electrophilic substitution reaction, an aromatic nucleophilic substitution reaction, or the like, the general formula (1 ) Can be produced.

<Method for Producing Compound Having Group Derived from Structure Represented by General Formula (1)>
-Polymer compound production method-
Hereinafter, the case where the compound of the present invention is a polymer compound which is a preferred embodiment (hereinafter referred to as “polymer compound of the present invention”) will be described.
When the compound having a group derived from the structure represented by the general formula (1) is a polymer compound, the polymer compound is obtained by polymerizing a monomer corresponding to the group included in the polymer compound, for example. Obtainable. As the monomer, one synthesized and isolated in advance may be used, or it may be synthesized in a reaction system and used as it is. When the obtained polymer compound is used in an organic light emitting device, the purity of the monomer may affect the performance of the organic light emitting device. Therefore, these monomers are preferably purified by methods such as distillation, sublimation purification, and recrystallization.

As a polymerization method, polymerization is performed by Suzuki coupling reaction (Chemical Review (Chem. Rev.), Vol. 95, pages 2457-2483 (1995)), polymerization is performed by Grignard reaction (Bull. Chem. Soc. Jpn., 51, 2091 (1978)), a method of polymerizing with Ni (0) catalyst (Progress in Polymer Science, 17, 173-1205, 1992), Stille Cup Examples include a method using a ring reaction (European Polymer Journal, Vol. 41, pages 2923-2933 (2005)). Among these, from the viewpoint of easy synthesis of raw materials and ease of polymerization reaction operation, a method of polymerization by Suzuki coupling reaction and a method of polymerization by Ni (0) catalyst are preferable, and the structure control of the polymer compound is preferable. From the viewpoint of ease of handling, a method of polymerizing by an aryl-aryl cross-coupling reaction such as a Suzuki coupling reaction, a Grignard reaction, or a Stille coupling reaction is more preferable, and a reaction of polymerizing by a Suzuki coupling reaction is particularly preferable.

When selecting a method for polymerization by Suzuki coupling reaction, since synthesis is simple and each compound is easy to handle, one of the monomers bonded by polymerization reaction has the following substituent A as a group that causes polymerization reaction. Preferably, the other monomer has the following substituent group B as a group that causes a polymerization reaction.
(Substituent group A)
Chlorine atom, bromine atom, iodine atom, —O—S (═O) ₂ R ^A (R ^A may be substituted with an alkyl group, or an alkyl group, an alkoxy group, a nitro group, a fluorine atom, or a cyano group. Represents an aryl group.)
(Substituent group B)
—B (OR ^B1 ) ₂ (R ^B1 represents a hydrogen atom or an alkyl group, and two R ^{B1 s} may be the same or different and may be bonded to each other to form a ring). A group represented by —BF ₄ Q ¹ (Q ¹ represents a monovalent cation of lithium, sodium, potassium, rubidium or cesium), —Sn (R ^B2 ) ₃ (R ^B2 represents A hydrogen atom or an alkyl group, and three R ^{B2 s, which} may be the same or different and may be bonded to each other to form a ring, a group represented by —MgY ¹ (Y ¹ Represents a chlorine atom, a bromine atom or an iodine atom), and a group represented by —ZnY ² (Y ² represents a chlorine atom, a bromine atom or an iodine atom).

Examples of the polymerization method include a method in which each monomer is reacted with an appropriate catalyst or base as necessary. In the case of selecting a polymerization method by Suzuki coupling reaction, in order to obtain a polymer compound having a desired molecular weight, a group selected from the substituent group A (for example, chlorine) as a group that causes a polymerization reaction that each monomer has. The ratio between the total number of moles of atoms, iodine atoms, and bromine atoms and the total number of moles of groups selected from the substituent group B (for example, —B (OR ^B1 ) ₂ ) may be adjusted. Usually, the ratio of the latter mole number to the former mole number is preferably 0.95 to 1.05, more preferably 0.98 to 1.02, and 0.99 to 1.01. More preferably.

The polymer compound of the present invention is a monomer in which one or two R ^x is substituted with a functional group selected from the group consisting of the substituent group A and the substituent group B from the structure represented by the general formula (1) And a monomer related to the present invention) and an arbitrary monomer having a functional group selected from the group consisting of the substituent group A and the substituent group B.

In the method for producing a polymer compound of the present invention, it is preferable that the charging ratio of the monomers related to the present invention to all monomers is 0.01 mol% or more and 20 mol% or less. Thus, the number of moles of group and any additional groups derived from structures represented by the general formula (1) in the entire polymer compound, respectively, when the N ₁ and N _M, by the following formula (i) A polymer compound having a calculated value of 0.01 or more and 20 or less can be easily produced.
N ₁ × 100 / (N ₁ + N _M ) (i)

-Manufacturing method of low molecular weight compounds-
A low molecular weight compound having a group derived from the structure represented by the general formula (1) can be synthesized by using a coupling reaction such as a Suzuki coupling reaction, a Yamamoto coupling reaction, or a negative coupling reaction. It is. As an example of synthesizing the low molecular weight compound using a Suzuki coupling reaction, the low molecular weight compound can be obtained by controlling the type and mole number of the monomer to be polymerized in the above-described method for producing a polymer compound. For example, from the structure represented by the general formula (1), a monomer in which one R ^x is substituted with a functional group selected from the substituent group A, and an arbitrary monomer having one functional group selected from the substituent group B Can be obtained by a Suzuki coupling reaction to obtain a compound composed of a group derived from the structure represented by the general formula (1) and an arbitrary additional group.

<Composition>
The composition of the present invention contains the conjugated polymer compound of the present invention and at least one selected from the group consisting of a light emitting material, a hole transport material and an electron transport material. The light emitting material is a polymer compound containing a group derived from a low molecular compound having a light emitting function, or a conjugated polymer having a structure different from that of the conjugated polymer compound of the present invention and having a light emitting function. Compounds are preferred. The charge transport material is a polymer compound containing a group derived from a low molecular compound having a charge transport function, or a conjugate having a structure different from that of the conjugated polymer compound of the present invention and having a charge transport function. A polymer compound is preferable.

As the light emitting material, a general light emitting material can be used. As the luminescent material, “organic EL display” (Co-authored by Shizuo Tokito, Chinami Yasada, Hideyuki Murata, published by Ohm Co., Ltd., 2004, first edition, first print) 17-48 pages, 83-99 pages, 101-120 The fluorescent material or triplet light-emitting material described on the page can be used. Examples of low-molecular fluorescent materials include perylene and its derivatives, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline metal complexes, 8-hydroxyquinoline derivative metal complexes, aromatics, and the like. Examples thereof include amines, tetraphenylcyclopentadiene and derivatives thereof, tetraphenylbutadiene and derivatives thereof, and more specifically, those described in JP-A-57-51781 and JP-A-59-194393. Etc. can be used. In addition, examples of the light emitting material include WO99 / 13692, WO99 / 48160, GB2340304A, WO00 / 53656, WO01 / 19834, WO00 / 55927, GB23448316, WO00 / 46321, WO00 / 06665, WO99 / 54943, WO99 / 5493. 54385, US5777070, WO98 / 06773, WO97 / 05184, WO00 / 35987, WO00 / 53655, WO01 / 34722, WO99 / 24526, WO00 / 22027, WO00 / 22026, WO98 / 27136, US573636, WO98 / 21262, US5741921, WO97 / 09394, WO96 / 29356, WO96 / 10617, EP07007020, WO95 / 07955 JP 2001-181618, JP 2001-123156, JP 2001-3045, JP 2000-351967, JP 2000-303066, JP 2000-299189, JP JP 2000-252065, JP 2000-136379, JP 2000-104057, JP 2000-80167, JP 10-324870, JP 10-114891, and JP 9-9. Polyfluorene, copolymers of derivatives thereof, polyarylene, copolymers of derivatives thereof, polyarylene vinylenes, copolymers of derivatives thereof, aromatics disclosed in Japanese Patent Application Laid-Open No. 11233, JP-A-9-45478, etc. Examples are (co) polymers of amines and their derivatives.

The light-emitting material is preferably a light-emitting material that is a conjugated polymer compound. The optional additional group represented by the general formula (A), the optional additional group represented by the general formula (B), and the general A light emitting material that is a polymer compound having at least one optional additional group selected from the group consisting of optional additional groups represented by formula (C) is particularly preferable.

The above hole transport material and electron transport material mainly play a role of adjusting the charge balance.

Examples of the hole transport material include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in side chains or main chains, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline And derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, and the like. In addition, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, Examples thereof include those described in JP-A-3-152184 and conjugated polymer compounds containing an arbitrary additional group represented by the above general formula (B). The hole transport material is preferably a conjugated polymer compound containing an arbitrary additional group represented by the general formula (B).

The content ratio of the hole transport material in the composition of the present invention is preferably 3 to 30 parts by mass, more preferably 3 to 30 parts by mass with respect to 100 parts by mass of the conjugated polymer compound of the present invention, since the charge balance becomes good. Is 3 to 20 parts by mass, particularly preferably 3 to 10 parts by mass.

Examples of the electron transport material include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyano Examples include ethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, and the like. In addition, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, Examples thereof include a polymer compound described in JP-A-3-152184 and a conjugated polymer compound containing an optional additional group represented by the above general formula (A). The electron transport material is preferably a conjugated polymer compound containing an arbitrary additional group represented by the general formula (A).

The content ratio of the electron transport material in the composition of the present invention is preferably 5 to 50 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the conjugated polymer compound of the present invention, so that the charge balance becomes good. The amount is 5 to 30 parts by mass, and particularly preferably 5 to 20 parts by mass.

The conjugated polymer compound of the present invention can be made into a solution or a dispersion by mixing with an organic solvent. By using a solution or dispersion, film formation by a coating method can be performed. This solution or dispersion is generally called an ink composition, a liquid composition or the like (hereinafter referred to as “ink composition”). This ink composition is also an embodiment containing an organic solvent in the above-described composition of the present invention.

Examples of the organic solvent contained in the ink composition of the present invention include chlorine-based solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, tetrahydrofuran, dioxane and the like. Ether solvents, aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, mesitylene, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane Aliphatic hydrocarbon solvents such as acetone, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, methyl benzoate and ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, Polyhydric alcohols such as lenglycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and their derivatives, methanol, ethanol, propanol And alcohol solvents such as isopropanol and cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N′-dimethylformamide. In addition, these solvents may be used individually by 1 type, or may use 2 or more types together. Among these solvents, it is preferable to include an organic solvent having a structure containing a benzene ring and having a melting point of 0 ° C. or lower and a boiling point of 100 ° C. or higher because the viscosity and film formability are excellent.

Since the ink composition of the present invention contains an organic solvent, when the thin film containing the conjugated polymer compound of the present invention is laminated and formed, after applying the ink composition of the present invention, the organic solvent is removed by drying. This is very advantageous in the manufacture of organic devices such as organic light-emitting elements. When drying, it may be dried in a state heated to 50 to 150 ° C., or may be dried under reduced pressure to about 10 ⁻³ Pa.

For lamination and film formation, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating A coating method such as a printing method, a screen printing method, a flexographic printing method, an offset printing method, an inkjet printing method, or a nozzle coating method can be used.

The preferred viscosity of the ink composition of the present invention varies depending on the coating method used, but is preferably in the range of 0.5 to 500 mPa · s at 25 ° C. The ink composition of the present invention such as an ink jet printing method passes through a discharge device. In the case of a product, the viscosity is preferably in the range of 0.5 to 20 mPa · s at 25 ° C. in order to prevent clogging and flight bending at the time of discharge.

<Thin film>
The thin film according to the present invention contains the conjugated polymer compound of the present invention. This thin film can be easily produced from the ink composition of the present invention by the above-described lamination / film formation method. Since the thin film according to the present invention includes the conjugated polymer compound of the present invention, for example, an organic light-emitting element having the thin film according to the present invention in a charge transport layer or a light-emitting layer is an element having an improved luminance life.

<Organic devices>
The configuration of the organic light emitting device of the present invention can be applied to other organic devices.

Other organic devices include organic semiconductor elements and organic light emitting elements. Examples of organic semiconductor elements include organic solar cells and organic transistors.

-Organic semiconductor device-
The organic semiconductor element includes the thin film. Examples of the organic semiconductor element include an organic thin film solar cell and an organic thin film transistor. For the production thereof, the composition of the present invention and the thin film according to the present invention are suitably used. Specifically, for example, by forming the thin film on a Si substrate on which an insulating film such as SiO ₂ and a gate electrode are formed, and forming a source electrode and a drain electrode with Au or the like, a field effect organic transistor and can do.

The organic thin film transistor includes a source electrode and a drain electrode, an organic semiconductor layer (that is, an active layer) that is a thin film serving as a current path between them, and a gate electrode that controls the amount of current passing through the current path. An electrostatic induction type is exemplified.

A field effect organic thin film transistor includes a source electrode and a drain electrode, an organic semiconductor layer serving as a current path between them, a gate electrode for controlling the amount of current passing through the current path, and an organic semiconductor layer disposed between the organic semiconductor layer and the gate electrode. It is preferable to provide an insulating layer. In particular, the source electrode and the drain electrode are preferably provided in contact with the organic semiconductor layer, and the gate electrode is preferably provided with an insulating layer in contact with the organic semiconductor layer interposed therebetween.

The electrostatic induction type organic thin film transistor has a source electrode and a drain electrode, an organic semiconductor layer serving as a current path between them, and a gate electrode for controlling an amount of current passing through the current path, and the gate electrode is in the organic semiconductor layer. Is preferably provided. In particular, the source electrode, the drain electrode, and the gate electrode provided in the organic semiconductor layer are preferably provided in contact with the organic semiconductor layer. Here, the structure of the gate electrode may be a structure in which a current path flowing from the source electrode to the drain electrode is formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. An electrode is mentioned.

FIG. 1 is a schematic cross-sectional view showing an embodiment of an organic thin film transistor (field effect organic thin film transistor). The organic thin film transistor 100 shown in FIG. 1 is formed on the substrate 1 so as to cover the substrate 1, the source electrode 5 and the drain electrode 6 formed on the substrate 1 with a predetermined interval, and the source electrode 5 and the drain electrode 6. Formed on the insulating layer 3 so as to cover the region of the insulating layer 3 formed on the organic semiconductor layer 2, the insulating layer 3 formed on the organic semiconductor layer 2, and the source electrode 5 and the drain electrode 6. A gate electrode 4.

FIG. 2 is a schematic cross-sectional view showing another embodiment of an organic thin film transistor (field effect organic thin film transistor). An organic thin film transistor 110 shown in FIG. 2 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. A part of the source electrode 5 and the drain electrode 6 and a part of the source electrode 5 and the drain electrode 6 formed on the insulating layer 3 with a predetermined interval so as to partially cover the region of the insulating layer 3 formed on An organic semiconductor layer 2 formed on the insulating layer 3 so as to cover it.

In the organic thin film transistor described above, the organic semiconductor layer 2 is composed of the thin film according to the present invention described above, and becomes a current path (channel) between the source electrode 5 and the drain electrode 6. The gate electrode 4 controls the amount of current passing through the current path (channel) in the organic semiconductor layer 2 by applying a voltage.

Among the organic thin film transistors, the field effect type organic thin film transistor can be manufactured by a known method, for example, a method described in JP-A-5-110069. The electrostatic induction organic thin film transistor can be produced by a known method, for example, a method described in JP-A-2004-006476.

-Organic light emitting device-
The organic light-emitting device according to this embodiment includes an anode, a cathode, and an organic layer present between the anode and the cathode, and the organic layer is represented by the general formula (1). A compound having a structure or a compound having a group derived from the structure represented by the general formula (1) is included. The compound having a group derived from the structure represented by the general formula (1) is preferably the conjugated polymer compound of the present invention.

Examples of the organic light emitting device according to the present embodiment include devices having the following structures (a) to (d). Note that “/” indicates that the layers before and after the adjacent layers are laminated. The same applies hereinafter.
(A) Anode / light emitting layer / cathode (b) Anode / hole transport layer / light emitting layer / cathode (c) Anode / light emitting layer / electron transport layer / cathode (d) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode

The light emitting layer is a layer having a function of emitting light.
The hole transport layer is a layer having a function of transporting holes.
The electron transport layer is a layer having a function of transporting electrons.
The hole transport layer and the electron transport layer are collectively referred to as a charge transport layer.
The hole transport layer adjacent to the light emitting layer may be referred to as an interlayer layer.
The compound having the structure represented by the general formula (1) or the compound having a group derived from the structure represented by the general formula (1) is used in the light emitting layer or the charge transport layer (particularly, the hole transport layer). It is preferably included.
When a compound having a structure represented by the general formula (1) or a compound having a group derived from the structure represented by the general formula (1) is included in the light emitting layer, the structure represented by the general formula (1) Is preferably 0.01% by mass to 20% by mass, and is derived from a compound having a structure represented by the general formula (1) or a structure represented by the general formula (1). When the compound having a group is contained in the charge transport layer (particularly the hole transport layer), the ratio of the skeleton having the structure represented by the general formula (1) is preferably 0.01% by mass to 50% by mass.

Each layer can be stacked and formed using a solution containing the material of each layer. For lamination and film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method Application methods such as spray coating, screen printing, flexographic printing, offset printing, inkjet printing, and nozzle coating can be used.

The thickness of the light emitting layer may be selected so that the driving voltage and the light emission efficiency are appropriate values, but is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm. .

When the organic light-emitting device according to this embodiment has a hole transport layer, examples of the hole transport material used include those similar to the hole transport material included in the composition of the present invention described above. The hole transport layer may be formed by any method, but when the hole transport material to be used is a low molecular compound, it is preferably formed from a mixed solution with a polymer binder. When the hole transport material used is a polymer compound, it is preferable to form a film from a solution. For film formation from a solution, a method exemplified as a coating method can be used.

The polymer binder to be mixed with the hole transport material is preferably a compound that does not extremely impede charge transport and does not strongly absorb visible light. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane, and the like.

The thickness of the hole transport layer may be selected so that the driving voltage and the light emission efficiency are appropriate values, and is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm. is there.

When the organic light emitting device according to this embodiment has an electron transport layer, examples of the electron transport material used include the same electron transport materials as those contained in the composition of the present invention described above. The electron transport layer may be formed by any method, but when the electron transport material is a low-molecular compound, a vacuum deposition method from powder or a method by film formation from a solution or a molten state is preferable. When the electron transport material is a polymer compound, a method of forming a film from a solution or a molten state is preferable. For film formation from a solution or a molten state, a polymer binder may be used in combination. For film formation from a solution, a method exemplified as a coating method can be used.

The polymer binder to be mixed with the electron transport material is preferably a compound that does not extremely inhibit charge transport and does not strongly absorb visible light. Polymeric binders include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

The thickness of the electron transport layer may be selected so that the drive voltage and the light emission efficiency are appropriate values, and is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm. .

A charge injection layer having a function of improving charge injection efficiency from the electrode may be provided between the electrode and the charge transport layer. Furthermore, in order to improve the adhesion with the electrode and the efficiency of charge injection from the electrode, the above-described charge injection layer or insulating layer may be provided adjacent to the electrode to improve the interface adhesion, prevent mixing, etc. For this purpose, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer. Note that the order and number of layers to be stacked, and the thickness of each layer may be selected in consideration of light emission efficiency and element lifetime.

Examples of the organic light emitting device provided with the charge injection layer include devices having the following structures (e) to (i).
(E) Anode / hole injection layer / hole transport layer / light emitting layer / cathode (f) Anode / light emitting layer / electron transport layer / electron injection layer / cathode (g) anode / hole injection layer / hole transport layer / Light emitting layer / electron transport layer / cathode (h) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (i) anode / hole injection layer / hole transport layer / light emitting layer / electron Transport layer / electron injection layer / cathode

The hole injection layer is a layer containing a conductive polymer, provided between the anode and the hole transport layer, and an ionization potential having an intermediate value between the anode material and the hole transport material contained in the hole transport layer. And a layer containing a material having s.

As the electron injection layer, a layer containing a conductive polymer, a material provided between the cathode and the electron transport layer, and a material having an electron affinity of an intermediate value between the cathode material and the electron transport material contained in the electron transport layer. Examples include layers.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm to 10 ³ S / cm, and the leakage current between the light emitting pixels Is preferably 10 ⁻⁵ S / cm to 10 ² S / cm, and more preferably 10 ⁻⁵ S / cm to 10 ¹ S / cm. In order to satisfy this range, the conductive polymer may be doped with an appropriate amount of ions.

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

The thickness of the charge injection layer is, for example, 1 nm to 100 nm, preferably 2 nm to 50 nm.

The material used for the charge injection layer may be selected in relation to the material of the electrode and the adjacent layer, such as polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, and polythienylene vinylene. And a derivative thereof, polyquinoline and a derivative thereof, polyquinoxaline and a derivative thereof, a conductive polymer such as a polymer having an aromatic amine structure in a main chain or a side chain, metal phthalocyanine (copper phthalocyanine, etc.), carbon and the like.

The insulating layer has a function of facilitating charge injection. The average thickness of this insulating layer is usually 0.1 nm to 20 nm, preferably 0.5 nm to 10 nm, more preferably 1 nm to 5 nm. Examples of the material used for the insulating layer include metal fluorides, metal oxides, and organic insulating materials.

Examples of the organic light emitting device provided with an insulating layer include devices having the following structures (j) to (y).
(J) Anode / insulating layer / light emitting layer / cathode (k) anode / light emitting layer / insulating layer / cathode (l) Anode / insulating layer / light emitting layer / insulating layer / cathode (m) anode / insulating layer / hole transport Layer / light emitting layer / cathode (n) anode / hole transport layer / light emitting layer / insulating layer / cathode (o) anode / insulating layer / hole transporting layer / light emitting layer / insulating layer / cathode (p) anode / insulating layer / Light emitting layer / electron transport layer / cathode (q) anode / light emitting layer / electron transport layer / insulating layer / cathode (r) anode / insulating layer / light emitting layer / electron transport layer / insulating layer / cathode (s) anode / insulating Layer / hole transport layer / light emitting layer / electron transport layer / cathode (t) anode / hole transport layer / light emitting layer / electron transport layer / insulating layer / cathode (u) anode / insulating layer / hole transport layer / light emitting Layer / electron transport layer / insulating layer / cathode (v) anode / hole injection layer / hole transport layer / light emitting layer / insulating layer / cathode (w) anode / insulating layer / light emitting layer / electron transport layer / electron injection layer Cathode (x) anode / insulating layer / hole injecting layer / hole transporting layer / light emitting layer / insulating layer / cathode (y) anode / insulating layer / light emitting layer / electron transport layer / electron injection layer / insulating layer / cathode

The substrate on which the organic light emitting device according to the present embodiment is formed may be a substrate that does not chemically change when forming the electrode and the organic layer, and examples thereof include glass, plastic, polymer film, silicon, and the like. It is done. In the case of an opaque substrate, the electrode on the opposite side to the electrode closer to the substrate is preferably transparent or translucent.

In the present embodiment, it is usually preferable that at least one of the anode and cathode electrodes is transparent or translucent, and the anode side is transparent or translucent.

As the material of the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite thereof, indium tin oxide. A film made of a conductive inorganic compound made of (ITO), indium / zinc / oxide, NESA, gold, platinum, silver, copper, or the like is used. As the anode, an organic transparent conductive film such as polyaniline and a derivative thereof, polythiophene and a derivative thereof may be used. In order to facilitate charge injection, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided on the anode.

Examples of methods for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.

The thickness of the anode can be selected in consideration of light transmittance and electric conductivity, but is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 40 nm to 500 nm. .

As a material of the cathode, a material having a small work function is preferable, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, Metals such as europium, terbium, ytterbium, and two or more alloys thereof, or one or more of them, and one of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin An alloy with a seed or more, graphite, or a graphite intercalation compound is used.

As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used.

The thickness of the cathode can be selected in consideration of electric conductivity and durability, but is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

Between the cathode and the light emitting layer or between the cathode and the electron transport layer, a layer made of a conductive polymer, or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided. A protective layer for protecting the element may be attached. In order to stably use the light emitting element for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the light emitting element from the outside.

As the protective layer, resins, metal oxides, metal fluorides, metal borides and the like can be used. As the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing the protective cover by bonding it to the element substrate with a thermosetting resin or a photocurable resin is preferable. Used. If a space is maintained using a spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, oxidation of the cathode can be prevented, and further, moisture adsorbed in the manufacturing process can be obtained by installing a desiccant such as barium oxide in the space. It becomes easy to suppress giving an image to an element.

FIG. 3 is a schematic cross-sectional view of the organic light-emitting device (organic light-emitting device having the configuration (i) above) according to this embodiment. An organic light emitting device 200 shown in FIG. 3 includes a substrate 20, an anode 22 formed on the substrate 20, a hole injection layer 23, a hole transport layer 24, a light emitting layer 25, an electron transport layer 26, and an electron injection layer 27. And a cathode 28. The anode 22 is provided on the substrate 20 so as to be in contact with the substrate 20. On the opposite side of the anode 22 from the substrate 20, a hole injection layer 23, a hole transport layer 24, a light emitting layer 25, and an electron transport layer are provided. 26, the electron injection layer 27 and the cathode 28 are laminated in this order.

FIG. 4 is a schematic cross-sectional view of the organic light emitting device (organic light emitting device having the configuration of (e) above) according to the present embodiment. An organic light emitting device 220 shown in FIG. 4 includes a substrate 20, and an anode 22, a hole injection layer 23, a hole transport layer 24, a light emitting layer 25, and a cathode 28 formed on the substrate 20. . The anode 22 is provided on the substrate 20 so as to be in contact with the substrate. On the opposite side of the anode 22 from the substrate 20, a hole injection layer 23, a hole transport layer 24, a light emitting layer 25, and a cathode 28 are provided. They are stacked in order.

In the case of an organic light emitting device, a layer containing a compound having a structure represented by the general formula (1) or a compound having a group derived from the structure represented by the general formula (1) includes a light emitting layer, a positive layer. A hole transport layer or an electron transport layer is preferred.

Further, there may be a plurality of layers containing a compound having a structure represented by the general formula (1) or a compound having a group derived from the structure represented by the general formula (1). For example, an organic light emitting device containing a compound having a structure represented by the general formula (1) or a compound having a group derived from the structure represented by the general formula (1) in the hole transport layer and the light emitting layer, Organic light-emitting devices contained in the electron transport layer and the light-emitting layer, organic light-emitting devices contained in the hole-transport layer and the electron transport layer, organic light-emitting devices contained in the hole transport layer, the light-emitting layer, and the electron transport layer .

Further, the compound having a group derived from the structure represented by the general formula (1) is preferably contained in the organic light emitting device as the conjugated polymer compound of the present invention. This further improves the luminance life of the organic light emitting device.

When the conjugated polymer compound of the present invention is contained in the hole transport layer, the conjugated polymer compound has good hole injecting property and hole transporting property, and therefore is represented by the general formula (1). A conjugated polymer compound containing a group derived from a structure and a divalent aromatic amine residue is preferable, and the divalent aromatic amine residue is represented by the above general formula (B). More preferably, it is an optional additional group represented.

When the conjugated polymer compound of the present invention is contained in the electron transport layer, the electron injecting property and the electron transporting property are improved, so that the group derived from the structure represented by the general formula (1) and the above general A conjugated polymer compound containing an arbitrary additional group represented by the formula (A) is preferable.

When the conjugated polymer compound of the present invention is contained in the light emitting layer, the charge (hole and electron) injection and transport properties are improved, and excitation energy is efficiently formed by the combination of holes and electrons. Therefore, the conjugated polymer compound is
Conjugated system containing a group derived from the structure represented by the general formula (1), an optional additional group represented by the general formula (A), and an optional additional group represented by the general formula (B) Molecular compounds,
Conjugated system containing a group derived from the structure represented by the general formula (1), an optional additional group represented by the general formula (B), and an optional additional group represented by the general formula (C) Molecular compounds,
Or a group derived from the structure represented by the general formula (1), an optional additional group represented by the general formula (A), an optional additional group represented by the general formula (B), and the general formula ( A conjugated polymer compound containing an optional additional group represented by C) is preferred.
Among these, a conjugated system containing a group derived from the structure represented by the general formula (1), an optional additional group represented by the general formula (A), and an optional additional group represented by the general formula (B) High molecular compounds are more preferred.

A layer containing a compound having a structure represented by the general formula (1) or a compound having a group derived from the structure represented by the general formula (1) is contained in an organic device such as an organic light emitting device. In this case, the content of the compound having the structure represented by the general formula (1) or the compound having a group derived from the structure represented by the general formula (1) depends on the type of the organic device and the layer used in the organic device. The type can be selected.

In the case of an organic light emitting device, the content of the compound having a structure represented by the general formula (1) or a compound having a group derived from the structure represented by the general formula (1) in each layer is as follows.
When the layer is a light emitting layer, it is 0.01% by mass to 20% by mass in terms of the structure represented by the general formula (1) with respect to the total amount of the organic compound contained in the light emitting layer. Preferably, it is 0.03% by mass to 5% by mass, more preferably 0.05% by mass to 3% by mass,
When the layer is a charge transport layer, it is 0.01% by mass to 50% by mass in terms of the structure represented by the general formula (1) with respect to the total amount of the organic compound contained in the charge transport layer. It is preferably 0.01% by mass to 20% by mass, more preferably 1% by mass to 15% by mass.
The “skeleton of the structure represented by the general formula (1)” means the remaining atomic group excluding all R ^x in the structure represented by the general formula (1).
When the layer contains both a compound having a structure represented by the general formula (1) and a compound having a group derived from the structure represented by the general formula (1), the above contents are It is the total value of the content of.

<Surface light source, display device>
The organic light emitting device according to the present invention includes a planar light source such as a curved light source and a planar light source (for example, illumination); a segment display device, a dot matrix display device (for example, a dot matrix flat display), a liquid crystal display device (for example, It is useful for display devices such as liquid crystal display devices and backlights of liquid crystal displays.

When using the organic light emitting device according to the present invention as part of white illumination, a light emitting material other than blue may be further contained in the light emitting layer of the organic light emitting device in order to obtain white color purity, or organic The light emitting element may have a second light emitting layer having a light emitting material other than blue.

In order to obtain planar light emission using the organic light emitting device according to this embodiment, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method in which a mask having a pattern-like window is provided on the surface of the planar organic light-emitting element, either the anode or the cathode, or both electrodes in a pattern form There is a method of forming. By forming a pattern by any of these methods and arranging several electrodes so that they can be turned on and off independently, a segment type display device capable of displaying numbers, letters, simple symbols, and the like can be obtained. Furthermore, in order to obtain a dot matrix display device, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of polymer compounds having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix display device can be driven passively or may be driven actively in combination with a TFT or the like. These display devices can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

FIG. 5 is a schematic cross-sectional view of a planar light source according to the present embodiment. A planar light source 300 shown in FIG. 5 includes a substrate 30, an anode 31, a hole injection layer 32, a light emitting layer 33, a cathode 34, and a protective layer 35. The anode 31 is provided on the substrate 30 so as to be in contact with the substrate 30, and a hole injection layer 32, a light emitting layer 33, and a cathode 34 are laminated in this order on the opposite side of the anode 31 from the substrate 30. . The protective layer 35 is formed so as to cover all of the anode 31, the charge injection layer 32, the light emitting layer 33, and the cathode 34 formed on the substrate 30 and in contact with the substrate 30 at the end. . The light emitting layer 33 includes a compound having a structure represented by the general formula (1) according to the present invention, a compound having a group derived from the structure represented by the general formula (1) according to the present invention, or the present invention. Conjugated polymer compounds are included.

The planar light source 300 shown in FIG. 5 further includes a plurality of light emitting layers other than the light emitting layer 33, and each light emitting layer uses a red light emitting material, a blue light emitting material, and a green light emitting material, and drives each light emitting layer. By controlling, a color display device can be obtained.

The compound having the structure represented by the general formula (1) according to the present invention or the compound having a group derived from the structure represented by the general formula (1) according to the present invention is a dye for laser, organic It is also useful as a material for a solar cell, an organic semiconductor for an organic transistor, a conductive thin film material such as a conductive thin film or an organic semiconductor thin film, a light emitting thin film material that emits fluorescence, a material for a polymer field effect transistor, or the like.

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

(Number average molecular weight and weight average molecular weight)
The number average molecular weight and weight average molecular weight in terms of polystyrene were determined by GPC (manufactured by Shimadzu Corporation, trade name: LC-10Avp). The polymer compound to be measured was dissolved in tetrahydrofuran (hereinafter referred to as “THF”) to a concentration of about 0.5% by mass, and 30 μL was injected into GPC. THF was used as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As the column, two TSKgel SuperHM-H (manufactured by Tosoh) and one TSKgel SuperH2000 (manufactured by Tosoh) were connected in series. A differential refractive index detector (manufactured by Shimadzu Corporation, trade name: RID-10A) was used as the detector.

(NMR measurement)
The NMR measurement of the monomer was performed under the following conditions.
Apparatus: Nuclear magnetic resonance apparatus, INOVA300 (trade name), manufactured by Varian Inc. Measurement solvent: Deuterated chloroform or deuterated tetrahydrofuran Sample concentration: About 1% by mass
Measurement temperature: 25 ° C

LC-MS measurement was performed by the following method. The measurement sample was dissolved in chloroform or tetrahydrofuran to a concentration of 2 mg / mL, and 1 μL was injected into LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD). As the mobile phase of LC-MS, ion-exchanged water, acetonitrile, tetrahydrofuran or a mixture thereof was used, and acetic acid was added as necessary. As the column, L-column 2 ODS (3 μm) (manufactured by Chemicals Evaluation and Research Institute, inner diameter: 2.1 mm, length: 100 mm, particle diameter: 3 μm) was used. Under these conditions, the measurement sample was measured by LC-MS and analyzed.

<Synthesis Example 1A: Synthesis of Compound 1A>
Compound 1A was prepared according to Eur. J. et al. Org. Chem. 2005, pp. Synthesized according to the method described in 2207.
In a nitrogen atmosphere, azulene (3.0 parts by mass) was charged into a three-necked eggplant flask, and hexane was added and stirred. The mixture was cooled to 0 ° C. using an ice bath, and NBS (N-bromosuccinimide) (10.4 parts by mass) was added little by little while maintaining the reaction temperature. After completion of the reaction, the resulting mixture was stirred at room temperature for 2 hours, after which the solvent was removed. The obtained solid was purified by silica gel column chromatography and recrystallization using hexane. The target compound 1A is 3.75 parts by mass (HPLC purity 100%) as a recovery from recrystallization, and 2.83 parts by mass (HPLC purity 99.6%) as a recovery from the filtrate. It was. The overall yield was 99.1%. The structure of Compound 1A was confirmed by NMR.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 8.32 (d, 12 Hz, 2H), 7.81 (s, 1H), 7.68 (t, 12 Hz, 1H), 7.27 (M, 2H).
¹³ C-NMR (75 MHz, CDCl ₃ ): δ (ppm) = 140.36, 138.50, 137.01, 136.07, 124.33, 102.99.

<Synthesis Example 1B: Synthesis of Compound 1B>
Under a stream of argon, 1-bromo-3,5-di-n-hexylbenzene (20.0 parts by mass) and tetrahydrofuran were added to the reaction vessel to prepare a homogeneous solution, and the solution was cooled to -69 ° C. A 2.76 M n-butyllithium / hexane solution (1 molar equivalent to 1-bromo-3,5-di-n-hexylbenzene) was added dropwise to the solution at −68 ° C. over 1.5 hours. The solution was further stirred at −70 ° C. for 1.5 hours. Next, a solution consisting of Compound 1B-1 (9.0 parts by mass) and tetrahydrofuran was added dropwise at −70 ° C. over 1 hour, and the mixture was stirred at −70 ° C. for 2 hours. Next, methanol and distilled water were added to the solution and stirred at −70 ° C., and then the mixture was warmed to room temperature and stirred overnight at room temperature. The reaction mixture was then filtered and the filtrate was concentrated. To the obtained concentrate, heptane and water were added and stirred, and the aqueous layer was removed from the organic layer which was allowed to stand and liquid-separated. Saturated saline was added to the organic layer, stirred, and the aqueous layer was removed from the organic layer which was allowed to stand and separate. Magnesium sulfate was added to the organic layer and stirred, and the filtrate obtained by filtration was concentrated to obtain 23.4 parts by mass of Compound 1B.

<Synthesis Example 2B: Synthesis of Compound 2B>
Under a stream of argon, Compound 1B (48.0 parts by mass) and dichloromethane were added to the reaction vessel to prepare a uniform solution and cooled to −30 ° C. Boron trifluoride diethyl ether complex (1 molar equivalent to Compound 1B) was added dropwise to the solution over 30 minutes, and the mixture was stirred overnight at room temperature. The reaction mixture was then cooled to −20 ° C., distilled water was added and stirred for 1 hour. Thereafter, the reaction solution was allowed to stand to cause liquid separation, whereby the aqueous layer was removed to obtain an organic layer. Next, water was added to the organic layer, and the mixture was stirred and allowed to stand for liquid separation, whereby the aqueous layer was removed to obtain an organic layer. A 10% by mass aqueous sodium hydrogen carbonate solution was added to the obtained organic layer, stirred, and allowed to stand for liquid separation, whereby the aqueous layer was removed to obtain an organic layer. The organic layer was concentrated to remove the solvent. Subsequently, this organic layer was purified by silica gel column chromatography using toluene and heptane as developing solvents, and concentrated to remove the solvent. Next, 23.2 parts by mass of the target compound 2B was obtained by recrystallizing the resulting concentrate using butyl acetate and methanol.

<Synthesis Example 3B: Synthesis of Compound 3B>
In a 4-necked flask under an argon stream, compound 2B (9.5 parts by mass), compound 3B-1 (6.6 parts by mass), 1,4-dioxane, potassium acetate (7.05 parts by mass), 1,1 ′ -Bis (diphenylphosphino) ferrocene (dppf, 0.1 parts by weight) and 1,1'-bis (diphenylphosphino) ferrocenedichloropalladium (II) methylene chloride complex (PdCl ₂ (dppf) · CH ₂ Cl ₂ , 0.15 parts by mass) was added and the mixture was stirred at 100 to 102 ° C. for 5 hours. Subsequently, after cooling the obtained reaction mixture to room temperature, it filtered with the filter which spread Celite and the silica gel, and the obtained filtrate was concentrated and the solvent was removed. Next, activated carbon was added to a solution prepared by adding hexane to the obtained concentrate, and the mixture was stirred at a temperature at which hexane was refluxed for 1 hour. The resulting mixture was cooled to room temperature, filtered through a filter packed with celite, and concentrated to remove the solvent. Subsequently, 10.1 mass parts of target compound 3B was obtained by recrystallizing with toluene and acetonitrile.

<Synthesis Example 1C: Synthesis of Compound 1C>
Under an inert atmosphere, 3-n-hexyl-5-methylbromobenzene (26.2 parts by mass) and anhydrous tetrahydrofuran were added to a three-necked flask to form a homogeneous solution, and the mixture was cooled to -70 ° C. To the resulting solution, a 2.5 M n-butyllithium / hexane solution (0.93 molar equivalent to 3-n-hexyl-5-methylbromobenzene) was kept at a solution temperature of −70 ° C. And stirred at the same temperature for 4 hours to prepare a solution (hereinafter referred to as “solution A”).
Separately, 2-methoxycarbonyl-4,4′-dibromobiphenyl (16.0 parts by mass) and anhydrous tetrahydrofuran were added to a two-necked flask to prepare a solution (hereinafter referred to as “solution B”).
Solution B was added dropwise to solution A so that the temperature of solution A was kept at −70 ° C. and stirred. The reaction was then stirred at room temperature for 15 hours. Next, water was added to the reaction solution at 0 ° C. and stirred. Next, the solvent was distilled off by concentration under reduced pressure, and hexane and water were added to the residue, followed by stirring. The obtained liquid mixture was allowed to stand and liquid-separated to remove the aqueous layer and obtain an organic layer. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain Compound 1C represented by the following formula as a white solid.

<Synthesis Example 2C: Synthesis of Compound 2C>
Under an inert atmosphere, Compound 1C (30.0 parts by mass) and anhydrous dichloromethane were added to a three-necked flask and cooled to 5 ° C. Boron trifluoride diethyl ether complex (4.2 molar equivalents relative to compound 1C) was added dropwise to the resulting mixture so that the temperature was kept within the range of 0 to 5 ° C., and then at room temperature overnight. Stir. The reaction solution was carefully poured into ice water, stirred for 30 minutes, and allowed to stand for liquid separation, whereby the aqueous layer was removed to obtain an organic layer. A 10% by mass aqueous potassium phosphate solution was added to the organic layer, and the mixture was stirred for 2 hours, and then allowed to stand for liquid separation, whereby the aqueous layer was removed to obtain an organic layer. The obtained organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated to distill off the solvent to obtain an oily liquid. When methanol was added to the oily liquid, a solid was formed. By recrystallizing this solid using n-butyl acetate and methanol, 24.0 parts by mass of Compound 2C represented by the following formula was obtained.

<Synthesis Example 3C: Synthesis of Compound 3C>
In a three-necked flask, compound 2C (8.0 parts by mass), bis (pinacolato) diboron (6.6 parts by mass), 1,1′-bis (diphenylphosphino) ferrocenedichloropalladium (II) methylene chloride complex (Pd (Dppf) · CH ₂ Cl ₂ , 0.15 parts by mass), 1,1′-bis (diphenylphosphino) ferrocene (0.099 parts by mass), anhydrous 1,4-dioxane and potassium acetate (7.0 parts by mass) Part) was added and stirred at 100 ° C. for 20 hours. After the reaction solution was cooled to room temperature, silica gel was passed through, the silica gel was washed with toluene, and the solvent of the obtained solution was concentrated to distill off to obtain a brown liquid. This liquid was purified by silica gel column chromatography using hexane as a developing solvent and then concentrated to a liquid obtained by concentration to obtain a solid. The solid is recrystallized once with acetonitrile and toluene, recrystallized once with dichloromethane and methanol, and the resulting organic layer is dried under reduced pressure to give a compound represented by the following formula: As a result, 2.9 parts by mass of 3C was obtained.

<Synthesis Example 1D: Synthesis of Compound 1D>
The gas in the three-necked flask was replaced with nitrogen, and 22.6 parts by mass of 1-bromo-3-n-hexylbenzene was dissolved in anhydrous tetrahydrofuran in the three-necked flask. The obtained solution was cooled to −75 ° C. or lower, and a 2.5M n-butyllithium / hexane solution (0.96 molar equivalent with respect to 1-bromo-3-n-hexylbenzene) was added dropwise, and −75 ° C. It stirred for 5 hours, keeping below. While maintaining the reaction liquid at −70 ° C., a solution prepared by dissolving 15.0 parts by mass of 2-methoxycarbonyl-4,4′-dibromobiphenyl in anhydrous tetrahydrofuran was added dropwise thereto. The resulting solution was slowly warmed to room temperature and stirred overnight. While the reaction solution was stirred at 0 ° C., water was added dropwise. After the solvent was distilled off from the reaction solution, water was added to the residue and the mixture was extracted 3 times with hexane. The obtained organic layers were combined, washed with saturated brine, and the aqueous layer was re-extracted with hexane. Then, when the obtained organic layer was dried with magnesium sulfate and then the solvent was distilled off, 26.4 parts by mass of a crude product of compound 1D was obtained.

<Synthesis Example 2D: Synthesis of Compound 2D>
In a three-necked flask, 26.4 parts by mass of the compound 1D synthesized above was dissolved in dichloromethane, and the gas in the flask was replaced with nitrogen. After cooling the obtained solution to 0 ° C. or lower, boron trifluoride diethyl ether complex (5 molar equivalents relative to Compound 1D) was added dropwise while keeping the solution at 5 ° C. or lower. The mixture was slowly warmed to room temperature and stirred overnight. The reaction solution was poured into ice water with stirring and stirred for 30 minutes. The reaction solution was separated, and the aqueous layer was extracted with dichloromethane. The organic layers were combined, 10% by mass aqueous potassium phosphate solution was added for liquid separation, and the organic layer was washed twice with water. The organic layer was dried over magnesium sulfate and then the solvent was distilled off to obtain an oily liquid. This oily liquid was dissolved in toluene, passed through a glass filter covered with silica gel, and filtered. After the solvent was distilled off from the filtrate, methanol was added and vigorously stirred to obtain crystals. The crystals were filtered and washed with methanol. The washed crystal was recrystallized with a mixed solvent of hexane and butyl acetate to obtain 12.1 parts by mass of Compound 2D.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 0.86 (t, 6H), 1.26 (m, 12H), 1.52 (m, 4H), 2.51 (t, 4H) ), 6.87 (d, 2H), 7.00 (s, 2H), 7.04 (d, 2H), 7.12 (t, 2H), 7.46 (dd, 2H), 7.48 (D, 2H), 7.55 (d, 2H).

<Synthesis Example 3D: Synthesis of Compound 3D>
5.0 parts by mass of Compound 2D was added to a three-necked flask, and the gas in the flask was replaced with nitrogen. Thereto was added anhydrous tetrahydrofuran, and the mixture was cooled to -70 ° C or lower. While maintaining the obtained solution at −70 ° C. or lower, a 2.5M n-butyllithium / hexane solution (2.2 molar equivalents relative to Compound 2D) was added dropwise. After dropping, the mixture was stirred for 4 hours while maintaining the temperature. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.8 molar equivalents relative to Compound 2D) was added thereto, and the temperature was slowly raised to room temperature. Stir overnight. The reaction solution was cooled to −30 ° C., and a 2M hydrochloric acid / diethyl ether solution was added dropwise thereto, and then the temperature was raised to room temperature. After the solvent was distilled off from the reaction solution, the resulting solid was dissolved by adding toluene. The obtained solution was filtered through a glass filter covered with silica gel, and the solvent of the filtrate was distilled off to obtain 5.0 parts by mass of a crude product. This crude product was recrystallized with a mixed solvent of toluene and acetonitrile under a nitrogen atmosphere to obtain 3.4 parts by mass of Compound 3D.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 0.86 (t, 6H), 1.26-1.29 (m, 12H), 1.31 (s, 24H), 1.52 -1.53 (m, 4H), 2.50 (t, 4H), 6.92 (d, 2H), 7.00 (d, 2H), 7.08 (t, 2H), 7.13 ( s, 2H), 7.77 (d, 2H), 7.81-7.82 (m, 4H).

<Synthesis Example 1F: Synthesis of Compound 1F>
In a three-necked flask, 9.6 parts by mass of 3,5-dibromophenol and 30.9 parts by mass of 3,5-bis (4-tert-butylphenyl) phenylboronic acid (the method described in JP-A-2005-82730) And 95.0 parts by mass of tetraethylammonium hydroxide (20% by mass aqueous solution) were added, and the gas in the flask was replaced with nitrogen. Thereto were added 0.15 parts by mass of toluene and dichlorobis (triphenylphosphine) palladium, and the mixture was heated at 100 ° C. for 8 hours. Then, when the obtained liquid mixture was allowed to cool, crystals were precipitated. The crystals were dissolved by adding chloroform, and the resulting solution was acidified with 1N hydrochloric acid and separated. The obtained aqueous layer was extracted with chloroform, and the extracted chloroform was combined with the organic layer and washed with water and saturated brine in this order. The washed organic layer was filtered through a glass filter covered with silica gel, and the solvent was distilled off from the filtrate to obtain 41.8 parts by mass of a crude product. Hexane was added thereto, the temperature was raised to reflux temperature, and then slowly cooled to room temperature, filtered, and the resulting residue was washed with hexane to obtain 28.0 parts by mass of Compound 1F represented by the following formula. It was.

LC-MS (APPI-MS, posi): 775 ([M + H] ⁺ , exact mass = 774).
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.35 (s, 36H), 5.19 (s, 1H), 7.15 (s, 2H), 7.47 (d, 8H ), 7.59 (s, 1H), 7.60 (d, 8H), 7.78 (s, 6H).
¹³ C-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 31.8, 34.9, 113.9, 119.6, 125.2, 125.7, 126.2, 127.4, 138. 6, 142.1, 142.6, 144.0, 150.9, 156.6.

<Synthesis Example 2F: Synthesis of Compound 2F>
The gas in the four-necked flask was replaced with nitrogen, and 28.0 parts by mass of Compound 1F and 13.0 parts by mass of N, N-dimethyl-4-aminopyridine were dissolved in dehydrated dichloromethane in the four-necked flask. Cooled down. There, 25.0 mass parts of trifluoromethanesulfonic anhydride was dripped over 30 minutes. And after stirring for 20 minutes, the cold bath was removed and stirring was continued for 1.5 hours. The obtained mixed solution was passed through a glass filter with silica gel and filtered, and the obtained residue was washed with toluene to obtain a mixed solution. When the solvent was distilled off from the obtained mixed liquid, 28.9 parts by mass of Compound 2F represented by the following formula was obtained.

LC-MS (ESI-MS, positive): 945 ([M + K] ⁺ , exact mass = 906).
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.38 (s, 36H), 7.52 (d, 8H), 7.57 (s, 2H), 7.64 (d, 8H) ), 7.77 (s, 4H), 7.85 (s, 2H), 7.97 (s, 1H).
¹³ C-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 31.7, 34.9, 119.3.

<Synthesis Example 3F: Synthesis of Compound 3F>
The gas in the four-neck flask was replaced with nitrogen, and 6.1 parts by mass of phenoxazine was added and dissolved in dehydrated toluene. Thereto was added 0.71 part by weight of tris (dibenzylideneacetone) dipalladium, 0.86 part by weight of 1,1′-bis (diphenylphosphino) ferrocene and 15.2 parts by weight of cesium carbonate, and the mixture was heated to 110 ° C. . A solution prepared by dissolving 28.9 parts by mass of Compound 2F in dehydrated toluene bubbled with nitrogen was added dropwise over 1 hour. Then, after stirring for 20 hours, the obtained mixture was filtered with a glass filter with silica gel while hot, and the resulting residue was washed with toluene. When the solvent was distilled off from the obtained mixed liquid, 33.0 parts by mass of a crude product was obtained. This crude product was dissolved in toluene, and the resulting solution was dropped into 1 L of methanol to cause reprecipitation. The obtained solution was filtered, and the resulting precipitate was washed with methanol to obtain 50.0 parts by mass of a crude product. Toluene was added and heated to dissolve, and ethanol was added dropwise for recrystallization. Furthermore, when the obtained product was filtered and washed with ethanol, 24.8 parts by mass of the product was obtained. When this product was recrystallized using a mixed solvent of toluene and ethanol, 16.6 parts by mass of Compound 3F represented by the following formula was obtained.

LC-MS (APCI, positive): 940 ([M + H] ⁺ , exact mass = 939).
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.37 (s, 36H), 6.13-6.16 (m, 2H), 6.62-6.71 (m, 6H) , 7.50 (d, 8H), 7.64 (d, 8H), 7.72 (s, 2H), 7.83 (s, 6H), 8.11 (s, 1H).
¹³ C-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 31.7, 34.9, 113.7, 115.8, 121.7, 123.7, 125.0, 126.0, 126. 1, 126.3, 127.4, 128.8, 134.6, 138.4, 140.4, 141.1, 142.8, 144.3, 145.3, 151.0.

<Synthesis Example 4F: Synthesis of Compound 4F>
The gas in the four-necked flask was replaced with nitrogen, and 16.6 parts by mass of Compound 3F was added and dissolved in chloroform. The obtained solution was cooled to 0 ° C. using a cold bath, and a solution in which 6.3 parts by mass of NBS was dissolved in DMF (N, N-dimethylformamide) was added dropwise over 50 minutes. And after stirring for 10 minutes, the cold bath was removed and stirring was continued for 3 hours. The obtained mixed solution was cooled again to 0 ° C., and a solution in which 0.1 part by mass of NBS was dissolved in DMF was added dropwise thereto. The mixture was stirred at room temperature for 1.5 hours, and then water was added dropwise thereto for liquid separation. The obtained aqueous layer was extracted twice with toluene, the obtained toluene solution was combined with the organic layer, and toluene was further added, and then the resulting mixture was washed with water and saturated brine in this order. The washed liquid mixture was filtered through a glass filter covered with silica gel, and the resulting residue was washed with toluene. When the solvent was distilled off from the obtained mixed liquid, 25.1 parts by mass of Compound 4F represented by the following formula was obtained.

LC-MS (APCI, positive): 1096 ([M + H] ⁺ , exact mass = 1095).
¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.37 (s, 36H), 5.99 (d, 2H), 6.75 (d, 2H), 6.85 (brs, 2H) ), 7.50 (d, 8H), 7.61-7.65 (m, 10H), 7.82 (d, 6H), 8.11 (s, 1H).
¹³ C-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 31.7, 34.9, 113.3, 114.9, 119.0, 125.0, 126.2, 126.7, 127. 3, 128.2, 129.3, 133.5, 138.3, 139.6, 140.7, 142.9, 144.5, 145.6, 151.1.

<Synthesis Example 1G: Synthesis of Compound 1G>
Under an inert atmosphere, 225 parts by mass of acetic acid was placed in a three-necked flask, and 24.3 parts by mass of 5-tert-butyl-m-xylene was added. Next, 31.2 parts by mass of bromine was added thereto, followed by reaction at 15 to 20 ° C. for 3 hours. The reaction solution was added to 500 mL of water, and the deposited precipitate was filtered. The obtained precipitate was washed twice with 250 mL of water to obtain 34.2 parts by mass of Compound 1G as a white solid.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 1.3 (s, 9H), 2.4 (s, 6H), 7.1 (s, 2H).
MS (FD +): M ^<+> 241.

<Synthesis Example 2G: Synthesis of Compound 2G>
Under an inert atmosphere, degassed dehydrated toluene was placed in a three-necked flask, and 0.63 parts by mass of tri (tert-butyl) phosphine was added. Subsequently, 0.41 part by mass of tris (dibenzylideneacetone) dipalladium, 9.6 parts by mass of compound 1G, 5.2 parts by mass of sodium tert-butoxy and 4.7 parts by mass of N, N′-diphenyl-1,4-phenylenediamine After adding a part, it was made to react at 100 degreeC for 3 hours. The reaction solution was added to saturated brine and extracted with chloroform warmed to about 50 ° C. When the solvent was distilled off from the obtained organic layer, a solid was produced. Toluene was added thereto and heated until the solid dissolved. Then, after allowing to cool, the precipitate was filtered to obtain 9.9 parts by mass of Compound 2G as a white solid.

<Synthesis Example 3G> (Synthesis of Compound 3G)
Under an inert atmosphere, dehydrated N, N-dimethylformamide was placed in a three-necked flask to dissolve 5.2 parts by mass of Compound 2G, and then 3.5 parts by mass of N-bromosuccinimide was added to the N, N— A solution dissolved in dimethylformamide was added dropwise and allowed to react all day and night. Water was added to the reaction solution, the deposited precipitate was filtered, and the obtained precipitate was washed twice with methanol to obtain 4.4 parts by mass of Compound 3G as a white solid.

¹ H-NMR (300 MHz, THF-d8): δ (ppm) = 1.3 (s, 18H), 2.0 (s, 12H), 6.6 to 6.7 (d, 4H), 6. 8 to 6.9 (br, 4H), 7.1 (s, 4H), 7.2 to 7.3 (d, 4H).
MS (FD +): M ^<+> 738.

<Polymerization Example 1: Synthesis of polymer compound 1>
Under an inert atmosphere, compound 3B (2.688 g, 2.96 mmol), the following formula:

1H (1.640 g, 1.80 mmol) represented by the following formula:

F8BR (0.411 g, 0.75 mmol) represented by the following formula:

Embedded image Compound 1J (0.238 g, 0.45 mmol), dichlorobis (triphenylphosphine) palladium (2.1 mg) and toluene (62 mL) were mixed and heated to 105 ° C. A 20% by mass aqueous tetraethylammonium hydroxide solution (10 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 3 hours and 20 minutes. After the reaction, phenylboronic acid (36.8 mg), dichlorobis (triphenylphosphine) palladium (2.1 mg), and aqueous tetraethylammonium hydroxide (10 mL) were added thereto, and the mixture was further refluxed for 16 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. The obtained mixture was cooled and then washed twice with water, twice with a 3% by mass acetic acid aqueous solution and twice with water. The obtained solution was dropped into methanol and collected by filtration to obtain a precipitate. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 3.12 g of polymer compound 1. The number average molecular weight in terms of polystyrene of the polymer compound 1 was 8.0 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 2.6 × 10 ⁵ .

The polymer compound 1 has the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

Is a random copolymer containing a repeating unit represented by a molar ratio of 50: 30: 12.5: 7.5.

<Polymerization Example 1: Synthesis of polymer compound 2>
Under an inert atmosphere, Compound 3B (1.7922 g, 1.98 mmol), Compound 1A (0.1430 g, 0.50 mmol), Compound 1H (1.0930 g, 1.20 mmol), Compound 1J (0.1584 g,. 30 mmol), palladium acetate (0.70 mg), tris (2-methoxyphenyl) phosphine (4.30 mg), 1-hexene (30.1 mg) and toluene (53 mL) were mixed and heated to 105 ° C. A 20% by mass aqueous tetraethylammonium hydroxide solution (7.5 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 3.5 hours. After the reaction, there was added phenylboronic acid (25.4 mg), palladium acetate (0.70 mg), tris (2-methoxyphenyl) phosphine (4.28 mg) and 20% by mass tetraethylammonium hydroxide aqueous solution (7.5 mL). And refluxed for a further 17 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the obtained mixture, the organic layer is washed twice with water, twice with a 3% by mass acetic acid aqueous solution and twice with water, the obtained solution is added dropwise to methanol, and the resulting precipitate is collected by filtration. A precipitate was obtained. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.95 g of polymer compound 2. The number average molecular weight in terms of polystyrene of the polymer compound 2 was 3.5 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 1.4 × 10 ⁵ .

The polymer compound 2 has the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

Is a random copolymer containing a repeating unit represented by a molar ratio of 50: 12.5: 30: 7.5.

<Polymerization Example 2: Synthesis of Polymer Compound 3>
Under an inert atmosphere, Compound 3C (2.2749 g, 2.97 mmol), F8BR (0.3290 g, 0.60 mmol), Compound 2D (1.2375 g, 1.92 mmol), Compound 3G (0.1330 g, 0.18 mmol) ), Compound 4F (0.3295 g, 0.30 mmol), dichlorobis (triphenylphosphine) palladium (2.1 mg) and toluene (76 mL) were mixed and heated to 105 ° C. A 20% by mass aqueous tetraethylammonium hydroxide solution (10 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 2 hours. After the reaction, phenylboronic acid (37 mg), dichlorobis (triphenylphosphine) palladium (2.1 mg), toluene (6 mL), 20% by mass tetraethylammonium hydroxide aqueous solution (10 mL) were added thereto, and further 14.5 hours. Refluxed. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the obtained mixture, the organic layer is washed twice with water, twice with a 3% by mass acetic acid aqueous solution and twice with water, the obtained solution is added dropwise to methanol, and the resulting precipitate is collected by filtration. A precipitate was obtained. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 2.42 g of the polymer compound 3. The polymer compound 3 had a polystyrene-equivalent number average molecular weight of 1.0 × 10 ⁵ and a polystyrene-equivalent weight average molecular weight of 2.9 × 10 ⁵ .

The polymer compound 3 has the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

Is a random copolymer containing a repeating unit represented by a molar ratio of 50: 10: 32: 3: 5.

<Polymerization Example 2: Synthesis of polymer compound 4>
Under inert atmosphere, Compound 3C (1.5135 g, 1.97 mmol), F8BR (0.2193 g, 0.40 mmol), Compound 2D (0.7477 g, 1.16 mmol), Compound 3G (0.0886 g, 0.12 mmol) ), Compound 4F (0.2196 g, 0.20 mmol), compound 1A (0.0344 g, 0.12 mmol), palladium acetate (0.62 mg), tris (2-methoxyphenyl) phosphine (4.23 mg), 1- Hexene (15.0 mg) and toluene (52 mL) were mixed and heated to 105 ° C. A 20% by mass aqueous tetraethylammonium hydroxide solution (7 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 4 hours. After the reaction, there was added phenylboronic acid (25 mg), palladium acetate (0.63 mg), tris (2-methoxyphenyl) phosphine (4.26 mg), toluene (4 mL), 20% by mass tetraethylammonium hydroxide aqueous solution (7 mL). ) And refluxed for an additional 19 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling the obtained mixture, the organic layer is washed twice with water, twice with a 3% by mass acetic acid aqueous solution and twice with water, the obtained solution is added dropwise to methanol, and the resulting precipitate is collected by filtration. A precipitate was obtained. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.55 g of polymer compound 4. The number average molecular weight of polystyrene conversion of the high molecular compound 4 was 7.9 * 10 < ⁴ >, and the weight average molecular weight of polystyrene conversion was 2.1 * 10 < ⁵ >.

The polymer compound 4 has the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

And a repeating unit represented by the following formula:

Is a random copolymer containing a repeating unit represented by a molar ratio of 50: 10: 29: 3: 5: 3.

<Example 1: Production and evaluation of organic light emitting device 1>
A glass substrate with an ITO film having a thickness of 45 nm formed by sputtering is spin-coated using AQ-1200 (manufactured by Plextronics), which is a polythiophene / sulfonic acid-based hole injecting agent, as a hole injecting material. A film was formed with a thickness and dried on a hot plate at 170 ° C. for 15 minutes.

Next, the polymer compound 2 was spin-coated in a 0.7% by mass xylene solution to form a film having a thickness of about 20 nm. Then, it heated at 180 degreeC for 60 minutes on the hotplate in nitrogen atmosphere.

Next, the polymer compound 3 was spin-coated in a 1.2% by mass xylene solution to form a film having a thickness of about 60 nm. Then, it heated at 130 degreeC for 10 minute (s) on the hotplate in nitrogen atmosphere. As a cathode, about 3 nm of sodium fluoride and then about 80 nm of aluminum were vapor-deposited, and the organic light-emitting device 1 was produced. Note that metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.

When voltage was applied to the obtained organic light emitting device 1, EL light emission having a peak at 460 nm derived from the polymer compound 3 was obtained from this device.

The organic light-emitting device 1 obtained above was set to a current value so that the initial luminance was 5000 cd / m ² , then was driven with a constant current, and the change in luminance with time was measured. As a result, the luminance was reduced by half after 257 hours.

<Comparative Example 1: Production and Evaluation of Organic Light-Emitting Element C1>
An organic light emitting device C1 was produced in the same manner as in Example 1 except that the polymer compound 1 was used in place of the polymer compound 2 in Example 1. When voltage was applied to the obtained organic light emitting device C1, EL light emission having a peak at 460 nm derived from the polymer compound 3 was obtained from this device.

The organic light-emitting device C1 obtained above was set to have a current value so that the initial luminance was 5000 cd / m ² , then was driven with a constant current, and the change in luminance with time was measured. As a result, the luminance was reduced by half after 83 hours.

<Example 2: Production and evaluation of organic light emitting device 2>
Instead of the xylene solution of the polymer compound 2 in Example 1, a solution obtained by dissolving the polymer compound 2 and the polymer compound 1 in xylene was used, and the mixing ratio was determined as polymer compound 2: polymer compound 1 = An organic light emitting device 2 was produced in the same manner as in Example 1 except that a solution having a ratio of 75:25 (mass ratio) was used. When voltage was applied to the obtained organic light emitting device 2, EL light emission having a peak at 460 nm derived from the polymer compound 3 was obtained from this device.

The organic light-emitting device 2 obtained above was set to have a current value so that the initial luminance was 5000 cd / m ² , then was driven with a constant current, and the change in luminance with time was measured. As a result, the luminance was reduced by half after 220 hours.

<Example 3: Production and evaluation of organic light emitting device 3>
Instead of the xylene solution of the polymer compound 2 in Example 1, a solution obtained by dissolving the polymer compound 2 and the polymer compound 1 in xylene was used, and the mixing ratio was determined as polymer compound 2: polymer compound 1 = An organic light emitting device 3 was produced in the same manner as in Example 1 except that a solution having a 50:50 (mass ratio) was used. When voltage was applied to the obtained organic light emitting device 3, EL light emission having a peak at 460 nm derived from the polymer compound 3 was obtained from this device.

The organic light-emitting device 3 obtained above was set to have a current value so that the initial luminance was 5000 cd / m ² , then was driven with a constant current, and the change in luminance with time was measured. As a result, the luminance was reduced by half after 222 hours.

<Example 4: Production and evaluation of organic light-emitting element 4>
Instead of the xylene solution of the polymer compound 2 in Example 1, a solution obtained by dissolving the polymer compound 2 and the polymer compound 1 in xylene was used, and the mixing ratio was determined as polymer compound 2: polymer compound 1 = An organic light emitting device 4 was produced in the same manner as in Example 1 except that a solution having a ratio of 25:75 (mass ratio) was used. When voltage was applied to the obtained organic light emitting device 4, EL light emission having a peak at 460 nm derived from the polymer compound 3 was obtained from this device.

The organic light-emitting device 4 obtained above was driven with a constant current after setting the current value so that the initial luminance was 5000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was reduced by half after 172 hours.

<Example 5: Production and evaluation of organic light-emitting element 5>
Instead of the xylene solution of the polymer compound 3 in Example 1, a solution obtained by dissolving the polymer compound 4 and the polymer compound 3 in xylene was used, and the mixing ratio was determined as polymer compound 4: polymer compound 3 = Example 1 except that a solution having a ratio of 7.5: 92.5 (mass ratio) was used and that a xylene solution of polymer compound 1 was used instead of a xylene solution of polymer compound 2 Similarly, an organic light emitting device 5 was produced. When voltage was applied to the obtained organic light emitting device 5, EL light emission having a peak at 460 nm derived from the polymer compound 3 and the polymer compound 4 was obtained from this device.

The organic light-emitting device 5 obtained above was driven with a constant current after setting the current value so that the initial luminance was 5000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was reduced by half after 206 hours.

<Example 6: Production and evaluation of organic light-emitting element 6>
Instead of the xylene solution of the polymer compound 3 in Example 1, a solution obtained by dissolving the polymer compound 4 and the polymer compound 3 in xylene was used, and the mixing ratio was determined as polymer compound 4: polymer compound 3 = Except for using a 10:90 (mass ratio) solution and using a xylene solution of polymer compound 1 instead of a xylene solution of polymer compound 2, in the same manner as in Example 1, An organic light emitting device 6 was produced. When voltage was applied to the obtained organic light emitting device 6, EL light emission having a peak at 460 nm derived from the polymer compound 3 and the polymer compound 4 was obtained from this device.

The organic light-emitting device 6 obtained above was set to have a current value so that the initial luminance was 5000 cd / m ² , then was driven with a constant current, and the change in luminance with time was measured. As a result, the luminance was reduced by half after 193 hours.

<Example 7: Production and evaluation of organic light-emitting element 7>
Instead of the xylene solution of the polymer compound 3 in Example 1, a solution obtained by dissolving the polymer compound 4 and the polymer compound 3 in xylene was used, and the mixing ratio was determined as polymer compound 4: polymer compound 3 = Example 1 except that a solution having a ratio of 12.5: 87.5 (mass ratio) was used and that a xylene solution of polymer compound 1 was used instead of a xylene solution of polymer compound 2 Similarly, an organic light emitting device 7 was produced. When voltage was applied to the obtained organic light emitting device 7, EL light emission having a peak at 460 nm derived from the polymer compound 3 and the polymer compound 4 was obtained from this device.

The organic light-emitting device 7 obtained above was driven with a constant current after setting the current value so that the initial luminance was 5000 cd / m ^2, and the change in luminance with time was measured. As a result, the luminance was reduced by half after 186 hours.

The results of Examples and Comparative Examples are summarized below.

DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Organic semiconductor layer, 3 ... Insulating layer, 4 ... Gate electrode, 5 ... Source electrode, 6 ... Drain electrode, 20 ... Substrate, 22 ... Anode, 23 ... Hole injection layer, 24 ... Hole transport Layer, 25 ... light emitting layer, 26 ... electron transport layer, 27 ... electron injection layer, 28 ... cathode, 30 ... substrate, 31 ... anode, 32 ... hole injection layer, 33 ... light emitting layer, 34 ... cathode, 35 ... protection Layer: 100... Organic thin film transistor, 110... Organic thin film transistor, 200... Organic light emitting element (configuration i), 220.

Claims

With a light emitting layer,
The light emitting layer contains a compound having a structure represented by the following general formula (1) or a compound having a group derived from the structure represented by the following general formula (1), and
The organic light-emitting device in which the ratio of the skeleton having the structure represented by the general formula (1) is 0.01% by mass to 20% by mass with respect to the total amount of the organic compound contained in the light-emitting layer in the light-emitting layer.

[Where:
R x is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group A functional group selected from the group consisting of a monovalent heterocyclic thio group, an imine residue, an amide compound residue, an acid imide residue, a carboxyl group, a nitro group and a cyano group, or a hydrogen atom.
However, in the functional group having a hydrogen atom, the hydrogen atom may be substituted with a substituent. A plurality of R x may be the same or different. ]
A light emitting layer, and a charge transport layer adjacent to the light emitting layer,
The charge transport layer contains a compound having a structure represented by the following general formula (1) or a compound having a group derived from the structure represented by the following general formula (1), and
In the charge transport layer, the ratio of the skeleton having the structure represented by the general formula (1) to the total amount of the organic compound contained in the charge transport layer is 0.01% by mass to 50% by mass. .

[Where:
R x is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group A functional group selected from the group consisting of a monovalent heterocyclic thio group, an imine residue, an amide compound residue, an acid imide residue, a carboxyl group, a nitro group and a cyano group, or a hydrogen atom.
However, in the functional group having a hydrogen atom, the hydrogen atom may be substituted with a substituent. A plurality of R x may be the same or different. ]
The organic light-emitting device according to claim 1 or 2, wherein the compound having a group derived from the structure represented by the general formula (1) is a conjugated polymer compound.
The organic light-emitting device according to claim 3, wherein the conjugated polymer compound has a group derived from the structure represented by the general formula (1) as a repeating unit.
Synthesized by condensation polymerization,
A group derived from the structure represented by the following general formula (1) and an optional additional group different from the group are introduced by the condensation polymerization,
The number of moles of group and the optional additional groups derived from structures represented by the general formula (1), when the N 1 and N M, respectively, N 1 and N M satisfies the following formula (I) Conjugated polymer compounds.
0.01 ≦ N 1 × 100 / (N 1 + N M ) ≦ 20 (I)

[Where:
R x is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group A functional group selected from the group consisting of a monovalent heterocyclic thio group, an imine residue, an amide compound residue, an acid imide residue, a carboxyl group, a nitro group and a cyano group, or a hydrogen atom.
However, in the functional group having a hydrogen atom, the hydrogen atom may be substituted with a substituent. A plurality of R x may be the same or different. ]
The group derived from the structure represented by the general formula (1) is represented by the following formula (2), formula (3), formula (4), formula (5), formula (6), or formula (7). The conjugated polymer compound according to claim 5.

[Where:
R x is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group A functional group selected from the group consisting of a monovalent heterocyclic thio group, an imine residue, an amide compound residue, an acid imide residue, a carboxyl group, a nitro group and a cyano group, or a hydrogen atom.
However, in the functional group having a hydrogen atom, the hydrogen atom may be substituted with a substituent. A plurality of R x may be the same or different. ]
The conjugated polymer compound according to claim 5 or 6, comprising at least one group among groups represented by the following formulas (A), (B), and (C) as the optional additional group.

[Where:
Ar 1 and Ar 5 each independently represent a functional group selected from the group consisting of an arylene group, a divalent heterocyclic group composed of a 6-membered ring or more, and a divalent group having a metal complex structure. , Ar 2 , Ar 3 and Ar 4 each independently represent a functional group selected from the group consisting of an arylene group and a divalent heterocyclic group composed of a 6-membered ring or more.
R 1 and R 2 each independently represent a functional group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group and an arylalkyl group;
X 1 represents a functional group selected from the group consisting of —CR 3 ═CR 4 — and —C≡C—. R 3 and R 4 each independently represent a functional group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, and a cyano group.
a is 0 or 1.
However, in the functional group having a hydrogen atom, the hydrogen atom may be substituted with a substituent. ]
The number of moles of the optional additional group represented by the formulas (A), (B), and (C) and the number of moles of the optional additional group other than these are N A , N B , N C, and N M ′ , respectively. The conjugated polymer compound according to claim 7, wherein the N 1 , N A , N B , N C and N M ′ sometimes satisfy the following formula (II).
40 ≦ (N A + N B + N C) × 100 / (N 1 + N A + N B + N C + N M ') <100 (II)
The conjugated polymer compound according to claim 7 or 8, comprising an arbitrary additional group represented by the formula (A).
The conjugated polymer compound according to any one of claims 7 to 9, comprising an optional additional group represented by the formula (B).
The conjugated polymer compound according to any one of claims 7 to 10, comprising an optional additional group represented by the formula (A) and an optional additional group represented by the formula (B).
At least one material selected from the group consisting of a light emitting material, a hole transport material and an electron transport material;
A composition comprising the conjugated polymer compound according to any one of claims 5 to 11.
An ink composition comprising the conjugated polymer compound according to any one of claims 5 to 11 and an organic solvent.
The organic light-emitting device according to claim 3, comprising the conjugated polymer compound according to any one of claims 5 to 11.
A planar light source comprising the organic light emitting device according to any one of claims 1 to 4 and 14.
A display device comprising the organic light-emitting element according to any one of claims 1 to 4 and 14.