JP5617150B2 - Conjugated polymer compound and polymer light emitting device using the same - Google Patents

Description

  The present invention relates to a conjugated polymer compound and a polymer light emitting device (polymer LED) using the conjugated polymer compound.

Various studies have been made on high-molecular-weight light-emitting materials and charge transporting materials that are soluble in a solvent because they can form an organic layer in a light-emitting element by a coating method. A polymer compound having a structure in which a ring is condensed is known (for example, Non-Patent Document 1 and Patent Document 1).

Advanced Materials 1997, Vol. 9, No. 10, 798 International Publication No. 99/54385 Pamphlet

  However, the conjugated polymer compound has a problem that its electron injection property is not always sufficient. An object of the present invention is to provide a polymer compound that is useful as a light-emitting material or a charge transport material and has excellent electron injection properties.

〔式中、Ａ環およびＢ環は、それぞれ独立に、置換基を有していてもよい芳香族環または置換基を有していてもよい非芳香族環を表し、Ａ環およびＢ環の少なくとも一方は芳香族環である。また、Ｃ環は置換基を有していてもよい芳香族環を表す。Ｚ₁は炭素原子、酸素原子、硫黄原子、窒素原子、珪素原子、硼素原子、燐原子、セレン原子から選ばれる原子または該原子を含む基を表し、Ｚ₂〜Ｚ₆はそれぞれ独立に炭素原子、珪素原子、窒素原子および硼素原子から選ばれる原子または該原子を含む基を表す。また、Ｂ環及びＣ環が置換基を有する場合これらが結合して環を形成してもよい。〕


That is, the present invention provides a conjugated polymer compound containing a structure represented by the following formula (a) as a partial structure.

[In the formula, A ring and B ring each independently represent an aromatic ring which may have a substituent or a non-aromatic ring which may have a substituent. At least one is an aromatic ring. Moreover, C ring represents the aromatic ring which may have a substituent. Z ₁ represents a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, a boron atom, a phosphorus atom or a selenium atom or a group containing the atom, and Z _{2 to} Z ₆ are each independently a carbon atom. Represents an atom selected from a silicon atom, a nitrogen atom and a boron atom, or a group containing the atom. Moreover, when B ring and C ring have a substituent, these may combine and form a ring. ]

  The conjugated polymer compound of the present invention is useful as a light emitting material or a charge transport material, and is excellent in electron injection property. Therefore, the polymer LED containing the conjugated polymer compound of the present invention can be used for curved or flat light sources for liquid crystal display backlights or illumination, segment type display elements, dot matrix flat panel displays, and the like. .

〔式中、Ａ環、Ｂ環、Ｃ環、Ｚ₁、Ｚ₂およびＺ₃の定義は前記と同じである。〕 The following formula (1) shows a structure when Z _{4 to} Z ₆ are carbon atoms in the formula (a).

[Wherein, the definitions of A ring, B ring, C ring, Z ₁ , Z ₂ and Z ₃ are the same as above. ]

In the formula (1), Z ₁ is —C (R _w ) (R _x ) —,> C═C (R _w ) (R _x ), —O—, _—S— , —S (═O) — , -S (= O) (= O) -, - N (R w) -, - Si (R w) (R x) -, - P (= O) (R w) -, - P (R w _{) -, - B (R w} ) -, - C (R w) (R x) -O -, - C (= O) -O -, - C (R w) = N-, or -Se- in It is preferable that -C ( _Rw ) ( _Rx )-,> C = C ( _Rw ) ( _Rx ), -Si ( _Rw ) ( _Rx )-.
Here, R _w and R _x are each independently a hydrogen atom, or an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group , Arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, nitro group, amide group, acid imide group, monovalent heterocyclic group, carboxyl Represents a substituent such as a group, a substituted carboxyl group or a cyano group.

R _w and R _{x in} the formula (1) are an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, and an arylalkynyl group. , Amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, nitro group, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl Or an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, or an arylalkynyl group. To be chosen Preferred.

From the viewpoint of solubility, R _w and R _x are more preferably selected from an alkyl group and an arylalkyl group.

In the formula (1), Z ₁ preferably has one or more substituents and more preferably has two substituents from the viewpoint of heat resistance and light emission characteristics.

In the formula (1), Z ₂ and Z ₃ each independently represent an atom selected from a carbon atom, a silicon atom, a nitrogen atom, and a boron atom or a group containing the atom. For example,>CH-,>CR'-,> C =,>SiH-,>SiR'- or nitrogen (> N-) are preferred, and all are> CH- from the viewpoint of heat resistance and light emission characteristics. ,>CR′−,> C = are more preferable.
R ′ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, or a substituted amino group. Group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, nitro group, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group Represent.

Examples of the aromatic ring which may have a substituent in the formula (1) include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The aromatic hydrocarbon ring is preferably a benzene ring alone or condensed with two or more benzene rings. Examples thereof include benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, phenanthrene ring. Aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, and phenanthrene ring are preferable. Aromatic heterocycles include pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, phenanthroline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, indole ring, thiazole ring, oxazole ring, etc. Can be given.

Examples of the non-aromatic ring which may have a substituent include an aliphatic hydrocarbon ring and a non-aromatic heterocyclic ring. Examples of the aliphatic hydrocarbon ring include a cyclopentane ring, a cyclohexane ring, a cyclopeptane ring, and a cyclononane ring. Non-aromatic heterocycles include tetrahydrofuran ring, tetrahydrothiofuran ring, pyrrolidine ring, phosphorolane ring, silolane ring, borolane ring, tetrahydropyran ring, tetrahydrothiopyran ring, piperidine ring, phosphinane ring, borinane ring, sirinane ring, etc. can give.

In the structure represented by the formula (1), it is preferable that all elements constituting the A ring, the B ring, and the C ring are carbon.
From the viewpoint of luminescent properties, the A ring, the B ring and the C ring are preferably all aromatic hydrocarbon rings, and may each independently have a benzene ring or a substituent which may have a substituent. It is preferably selected from a naphthalene ring and an anthracene ring which may have a substituent.
It is more preferable that the A ring, the B ring and the C ring are each independently a benzene ring or a naphthalene ring, and it is further preferable that the A ring, the B ring and the C ring are all benzene rings.

The structure represented by the formula (1) may be contained in the side chain when it is contained as a repeating unit when it is contained in the main chain in the conjugated polymer compound. From the viewpoint of device characteristics such as heat resistance, solubility, light emission characteristics, and luminance half-life, it is preferable to be included in the conjugated polymer compound as a repeating unit.

  Examples of the conjugated polymer compound of the present invention include those containing the structure represented by the formula (1) as a repeating unit.

〔式中、Ｂ’環およびＣ’環はそれぞれ独立に置換基を有していてもよい芳香族環を表し、Ａ’環は置換基を有していてもよい芳香族環または置換基を有していてもよい非芳香族環を表す。２つの結合手はそれぞれＢ’環およびＣ’環上に存在する。Ｚ₁〜Ｚ₃はそれぞれ前記と同じ意味を表す。〕
As an example, a structure represented by the following formula (2) can be given.

[Wherein, the B ′ ring and the C ′ ring each independently represent an aromatic ring which may have a substituent, and the A ′ ring represents an aromatic ring or a substituent which may have a substituent. It represents a non-aromatic ring that may have. Two bonds are present on the B ′ ring and the C ′ ring, respectively. Z _{1 to} Z ₃ each have the same meaning as described above. ]

〔式中、Ａ''環およびＣ''環はそれぞれ独立に置換基を有していてもよい芳香族環を表し、Ｂ''環は置換基を有していてもよい芳香族環または置換基を有していてもよい非芳香族環を表す。２つの結合手はそれぞれＡ''環およびＣ''環上に存在する。Ｚ₁〜Ｚ₃はそれぞれ前記と同じ意味を表す。〕
式（２）、（３）における置換基を有していてもよい芳香族環、置換基を有していてもよい非芳香族環の定義、具体例等は、上記式（１）におけるそれらについての定義、具体例と同様である。 Another example is a structure represented by the following formula (3).

[Wherein, the ring A ″ and the ring C ″ each independently represent an optionally substituted aromatic ring, and the ring B ″ represents an optionally substituted aromatic ring or The non-aromatic ring which may have a substituent is represented. Two bonds are present on the A ″ ring and the C ″ ring, respectively. Z _{1 to} Z ₃ each have the same meaning as described above. ]
Definitions and specific examples of the aromatic ring which may have a substituent in formulas (2) and (3) and the non-aromatic ring which may have a substituent are those in formula (1) above. This is the same as the definition and specific example.

When the conjugated polymer compound of the present invention contains the structure represented by the formula (2) and / or (3) as a repeating unit, the amount of these repeating units of the conjugated polymer compound of the present invention is the total repeating unit. The total amount is usually 1 mol% or more and 100 mol% or less, preferably 20 mol% or more, and more preferably 50 mol% or more and 100 mol% or less.

As specific examples when Z2 and Z3 are other than carbon in the structures represented by the formulas (2) and (3), the following formulas (1V-1) to (1V-9) and The thing which has. In the following, each bond in the aromatic hydrocarbon ring represents an arbitrary position.

  Specific examples in which Z1 is carbon in the structures represented by the formulas (2) and (3) include the following formulas (1A-1) to (1J-12) and those having a substituent. . In the following, each bond in the aromatic hydrocarbon ring represents an arbitrary position.

  In the structures represented by the formulas (2) and (3), specific examples of the ring B substituent and the C ring substituent bonded to each other to form a ring include the following (1K-1) to (1K-3), (1L-1) to (1L-3), and those having a substituent in the following. In the following, each bond in the aromatic hydrocarbon ring represents an arbitrary position.

〔式中、RwおよびRxの定義は前記と同じ。Rw’およびRx’はRw、Rxと同様の置換基を表す。〕

[Wherein, Rw and Rx are as defined above. Rw ′ and Rx ′ represent the same substituents as Rw and Rx. ]

〔式中、Rw、Rx、Rw’およびRx’の定義は前記と同じ。Rw’’およびRx’’はRw、Rxと同様の置換基を表す。〕

[Wherein, definitions of Rw, Rx, Rw ′ and Rx ′ are the same as described above. Rw ″ and Rx ″ represent the same substituents as Rw and Rx. ]

In the structures represented by the above formulas (2) and (3), the case where Z1 is silicon includes the following formulas (1M-1) to (1M-5) and those having a substituent. In the following, each bond in the aromatic hydrocarbon ring represents an arbitrary position.

In the structures represented by the above formulas (2) and (3), the case where Z1 is nitrogen includes the following formulas (1N-1) to (1N-5) and those having a substituent. In the following, each bond in the aromatic hydrocarbon ring represents an arbitrary position.

In the structures represented by the formulas (2) and (3), examples of the case where Z1 is oxygen include the following formulas (1O-1) to (1O-5) and those having a substituent. In the following, each bond in the aromatic hydrocarbon ring represents an arbitrary position.

In the structures represented by the formulas (2) and (3), examples of the compound in which Z1 is boron include the following formulas (1P-1) to (1P-5) and those having a substituent. In the following, each bond in the aromatic hydrocarbon ring represents an arbitrary position.

In the structures represented by the formulas (2) and (3), examples of the case where Z1 is carbon include the following formulas (1Q-1) to (1Q-5) and those having a substituent. In the following, each bond in the aromatic hydrocarbon ring represents an arbitrary position.

In the structures represented by the above formulas (2) and (3), Z1 is carbon and the B ′ ring and the B ″ ring are 5-membered rings. The following formulas (1R-1) to (1R-8) And those having a substituent. In the following, each bond in the aromatic hydrocarbon ring represents an arbitrary position.

In the structures represented by the above formulas (2) and (3), Z1 is carbon and the B ′ ring and the B ″ ring are thiophene rings. The following formulas (1S-1) to (1S-3), And those having a substituent. In the following, each bond in the aromatic hydrocarbon ring represents an arbitrary position.

In the structures represented by the above formulas (2) and (3), Z1 is carbon and the B ′ ring and the B ″ ring are furan rings. The following formulas (1T-1) to (1T-3) And those having a substituent. In the following, each bond in the aromatic hydrocarbon ring represents an arbitrary position.

In addition, examples of the structure represented by the formulas (2) and (3) in which Z1 is carbon include the following formulas (1U-1) to (1U-3) and those having a substituent. . In the following, each bond in the aromatic hydrocarbon ring represents an arbitrary position.

  From the viewpoint of the stability of the compound, it is preferable that Z1 to Z3 are all carbon atoms in the structures represented by the formulas (1), (2) and (3).

In the structure represented by the above formula (1), from the viewpoint of heat resistance, fluorescence intensity, etc., the A ring, the B ring and the C ring are preferably all aromatic hydrocarbon rings, such as a benzene ring, a naphthalene ring and an anthracene ring. It is more preferable that A ring, B ring and C ring are all benzene rings.

In the structures represented by the above formulas (2) and (3), more preferably, the A ′ ring, the B ′ ring, the C ′ ring, the A ″ ring, the B ″ ring, and the C ″ ring are all from the benzene ring. More preferably, from the viewpoint of electron injection, two bonds are present on each of the B ring and C ring, or one on each of the A ring and C ring. Those are preferred.

（６） （７）

〔式中、Ｒ_p1、Ｒ_q1、Ｒ_p2、Ｒ_q2、Ｒ_w1、Ｒ_x1、Ｒ_w2およびＲ_x2はそれぞれ独立に置換基を表す。ａおよびｃは０〜５の整数を表し、ｂおよびｄは０〜３の整数を表す。Ｒ_p1とＲ_q1、Ｒ_p2とＲ_q2、Ｒ_w1とＲ_x1およびＲ_w2とＲ_x2はそれぞれ互いに結合して環を形成していてもよい。〕
式（６）、（７）の中で、Ｒ_w1とＲ_x1の少なくとも１つ、およびＲ_w2とＲ_x2の少なくとも１つの炭素数が２以上であるものが好ましい。 Especially, the conjugated polymer compound containing the repeating unit shown by following formula (6), (7) is preferable.

(6) (7)

[Wherein, R _p1 , R _q1 , R _p2 , R _q2 , R _w1 , R _x1 , R _w2 and R _x2 each independently represent a substituent. a and c represent an integer of 0 to 5, and b and d represent an integer of 0 to 3. R _p1 and R _q1 , R _p2 and R _q2 , R _w1 and R _x1, and R _w2 and R _x2 may be bonded to each other to form a ring. ]
Among the formulas (6) and (7), those in which at least one of R _w1 and R _x1 and at least one of R _w2 and R _x2 have 2 or more carbon atoms are preferable.

In the above formulas (6) and (7), R _p1 , R _q1 , R _p2 , R _q2 , R _w1 , R _x1 , R _w2 and R _x2 are alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy Group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue Group, nitro group, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group and cyano group are preferred, and aryl group and arylalkyl group are more preferred. As the aryl group, more specifically, a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group (C ₁ -C ₁₂ is also shown. Hereinafter it is 1 to 12 carbon atoms.), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, 9-anthracenyl group, an aryl group having a carbon number of usually about 6 to 60, such as a pentafluorophenyl group Is exemplified.
More specifically, as the arylalkyl group, 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 ₁ -C _{A 12} alkyl group, a 1-naphthyl-C ₁ -C ₁₂ alkyl group, a 2-naphthyl-C ₁ -C ₁₂ alkyl group or the like, which usually has about 7 to 60 carbon atoms, preferably about 7 to 48 carbon atoms. An alkyl group is exemplified.

A conjugated polymer compound containing a repeating unit represented by the above formula (6) is preferable from the viewpoint of ease of synthesis.

In the case where the aromatic ring, non-aromatic ring, or Z ₁ in formula (1) has a substituent, the substituent is alkyl from the viewpoint of solubility in organic solvents, device characteristics, ease of synthesis, and the like. Group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group Group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, nitro group and cyano group are preferred. . The hydrogen atom contained in these substituents may be replaced with a fluorine atom.

  The alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, i -Propyl group, n-butyl group, i-butyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3, 7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, and the like. Solubility in organic solvents, device characteristics, synthesis From the viewpoint of ease of operation and the balance between heat resistance, pentyl group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group, Sill group, 3,7-dimethyl octyl group are preferable.

  The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group Etc., solubility in organic solvents, device characteristics, From the balance between the viewpoint and the heat resistance of the easiness of the formation, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyl group, decyloxy group, 3,7-dimethyl octyloxy group are preferable.

  The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, a propylthio group, i -Propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyl Octylthio group, laurylthio group, trifluoromethylthio group and the like. From the viewpoint of solubility in organic solvents, device characteristics, ease of synthesis and heat resistance, pentylthio group, hexylthio group, octylthio group, etc. Group, 2-ethylhexylthio group, decylthio group, 3,7-dimethyloctyl Lucio group is preferred.

An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and having a condensed ring, two or more independent benzene rings or condensed rings bonded directly or through a group such as vinylene. Also included. The aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenyl group and a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ have 1 to indicates a 12. the same applies is less.), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, 9-anthracenyl group, penta A fluorophenyl group and the like are exemplified, and from the viewpoints of solubility in an organic solvent, device characteristics, easiness of synthesis, etc., a C _{1 to} C ₁₂ alkoxyphenyl group and a C _{1 to} C ₁₂ alkylphenyl group are preferable. Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkylphenyl group as specifically methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, i- propylphenyl group, butylphenyl group, i- butyl Examples include phenyl group, t-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like.

The aryloxy group usually has about 6 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include phenoxy group, C _{1 to} C ₁₂ alkoxyphenoxy group, C _{1 to} C ₁₂ alkylphenoxy group, 1 - naphthyloxy group, 2-naphthyloxy group, are exemplified such as pentafluorophenyl group is, solubility in organic solvents, device properties, from the standpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxy phenoxy group , C ₁ -C ₁₂ alkylphenoxy group are preferable.
Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkylphenoxy such as methyl phenoxy groups as group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, i- propyl phenoxy group, Examples include butylphenoxy, i-butylphenoxy, t-butylphenoxy, pentylphenoxy, isoamylphenoxy, hexylphenoxy, heptylphenoxy, octylphenoxy, nonylphenoxy, decylphenoxy, dodecylphenoxy Is done.

Arylthio group has a carbon number of usually about 6 to 60, and specific examples thereof include a phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2 - naphthylthio group, are exemplified such as pentafluorophenyl thio group, solubility in organic solvents, device properties, from the standpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ An alkylphenylthio group is preferred.

The arylalkyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include a phenyl-C ₁ -C ₁₂ alkyl group and a C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C. ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl groups and the like, organic solvents From the viewpoints of solubility in water, device characteristics, easiness of synthesis, etc., C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl group Is preferred.

The arylalkoxy group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenylmethoxy group, a phenylethoxy group, a phenylbutoxy group, a phenylpentyloxy group, and a phenylhexyloxy group. group, phenyl heptene Ciro alkoxy group, a phenyl -C ₁ -C ₁₂ alkoxy groups such as phenyl Ok Ciro alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, are exemplified 2-naphthyl -C ₁ -C ₁₂ alkoxy group, solubility in organic solvents, device properties, synthesis easiness from the point of view, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group preferably .

The arylalkylthio group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkylthio group and a C ₁ -C ₁₂ alkoxyphenyl-C _1. -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio groups and the like, From the viewpoint of solubility in organic solvent, device characteristics, easiness of synthesis, etc., C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ Alkylthio groups are preferred.

Arylalkenyl group has a carbon number of usually about 8 to 60, and examples thereof include 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 -C ₁₂ alkenyl group, 1-naphthyl-C ₂ -C ₁₂ alkenyl group, 2-naphthyl-C ₂ -C ₁₂ alkenyl group, etc., and solubility in organic solvents, device properties, from the standpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, a C ₂ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl group are preferred.

Arylalkynyl group has a carbon number of usually about 8 to 60, and examples thereof include 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 -C ₁₂ alkynyl group, 1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl groups and the like, solubility in organic solvents, device properties, from the standpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, a C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferred.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl The group or the monovalent heterocyclic group may have a substituent. The carbon number of the substituted amino group is usually about 1 to 60, preferably 2 to 48, not including the carbon number of the substituent.
Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino group, butylamino group, i-butylamino group, t -Butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group , pyrimidylamino group, Pirajiruamino group, triazyl amino group phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkylamino groups, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino groups, 1-naphthyl - C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino groups.

Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. The substituted silyl group usually has about 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
Specifically, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethyl Silyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, a 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 ₁₂ alkylsilyl group, 2-naphthyl C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, t- butyl diphenyl silyl group, Examples thereof include a dimethylphenylsilyl group.

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

  The acyl group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group. Group, pentafluorobenzoyl group and the like.

  The acyloxy group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group. Group, trifluoroacetyloxy group, pentafluorobenzoyloxy group and the like.

As the imine residue, an imine compound (refers to an organic compound having —N═C— in the molecule. For example, aldimine, ketimine, and hydrogen atoms on these N are substituted with alkyl groups or the like. And a residue obtained by removing one hydrogen atom from the compound, usually having about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples include groups represented by the following structural formulas.

  The amide group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, penta Examples include a fluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, a dipentafluorobenzamide group, and the like.

Examples of the acid imide group include residues obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, having about 4 to 20 carbon atoms, and specific examples include the groups shown below. The

The monovalent heterocyclic group refers to a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms, preferably 4 to 20 carbon atoms. The carbon number of the heterocyclic group does not include the carbon number of the substituent. Here, the heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and silicon in the ring. Say things. Specifically, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, a thienyl group , C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

  Examples of the substituted carboxyl group include a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and usually has about 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms. Specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group. Cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycal Nyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group, etc. Is mentioned. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent.

In the conjugated polymer compound of the present invention, from the viewpoint of electron injection properties, it is preferable that Rw, Rx, Rw1, Rx1, Rw2, and Rx2 are each independently an aryl group or an arylalkyl group, and Rw and Rx are the same aryl. In the case of a group, when R _w1 and R _x1 are the same aryl group, it is more preferable that R _w2 and R _x2 are the same aryl group.
Here, the definition and specific examples of the aryl group and arylalkyl group are the same as described above.
As the aryl group, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, 3, 5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,6-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,6-dipropylphenyl group, 3,5-dipropylphenyl group, 2,4,6-tripropylphenyl group, 2-isopropyl Phenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,6-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2,4,6-triisopropylphenyl group, 2-butylphenyl group, 3- Butylphenyl group, 4- Butylphenyl group, 2,6-butylphenyl group, 3,5-butylphenyl group, 2,4,6-butylphenyl group, 2-t-butylphenyl group, 3-t-butylphenyl group, 4-t- Butylphenyl group, 2,6-di-t-butylphenyl group, 3,5-di-t-butylphenyl group, 2,4,6-tri-t-butylphenyl group, etc., preferably carbon number Is about 6 to 20, and a phenyl group is more preferable.

（２A−１） （２A−２） （２A−３） From the viewpoint of the solubility of the compound, examples of the specific structure of the repeating unit represented by the above formula (2) include the following formulas (2A-1) to (2A-3).

(2A-1) (2A-2) (2A-3)

（３A−１） （３A−２） （３A−３）
From the viewpoint of the solubility of the compound, examples of the specific structure of the repeating unit represented by the above formula (3) include the following formulas (3A-1) to (3A-3).

(3A-1) (3A-2) (3A-3)

（２B−１） （２B−２） （２B−３） （２B−４）
。 As a specific structure of the repeating unit represented by the above formula (6) having excellent electron injection properties, those in which R _w1 and R _x1 each have the same aryl group can be mentioned, and the following formulas (2B-1) to (2B) -4) is exemplified

(2B-1) (2B-2) (2B-3) (2B-4)
.

（３B−１） （３B−２） （３B−３） （３B−４） Specific structures of the repeating unit represented by the above formula (7) having excellent electron injection properties include those in which R _w1 and R _x1 each have the same aryl group, and the following formulas (3B-1) to (3B) -4) is exemplified.

(3B-1) (3B-2) (3B-3) (3B-4)

（２C−１） （２C−２） （２C−３） （２C−４）
As specific examples of the repeating unit represented by the above formula (2), those in which R _w and R _x are bonded to each other to form a ring include the following formulas (2C-1) to (2C-4): Illustrated.

(2C-1) (2C-2) (2C-3) (2C-4)

（３C−１） （３C−２） （３C−３） （３C−４）
As specific examples of the repeating unit represented by the above formula (3), those in which R _w and R _x are bonded to each other to form a ring include the following formulas (3C-1) to (3C-4): Illustrated.

(3C-1) (3C-2) (3C-3) (3C-4)

（２D−１） （２D−２） （２D−３） （２D−４）

As specific examples of the repeating unit represented by the above formula (2), the substituents of the B ′ ring and the C ′ ring are bonded to each other to form a ring, the following formulas (2D-1) to (2D— The structure shown in 4) is exemplified.

(2D-1) (2D-2) (2D-3) (2D-4)

（３D−１） （３D−２） （３D−３） （３D−３）
As specific examples of the repeating unit represented by the above formula (3), the substituents of the B ″ ring and the C ″ ring are bonded to each other to form a ring, the following formulas (3D-1) to ( The structure shown by 3D-4) is exemplified.

(3D-1) (3D-2) (3D-3) (3D-3)

Specific examples in the case where Rw1 and R1x among the repeating units represented by the above formula (6) are non-aromatic rings such as an aliphatic hydrocarbon ring and a non-aromatic heterocyclic ring include the following.

Of the repeating units represented by the above formula (7), specific examples in the case where Rw1 and R1x are non-aromatic rings such as aliphatic hydrocarbon rings and non-aromatic heterocycles include the following.

From the viewpoint of the heat resistance of the compound, at least one of R _w1 and R _x1 or at least one of R _w2 and R _x2 is preferably a substituent having 2 or more carbon atoms, and preferably has 4 to 12 carbon atoms. More preferred.

〔式中、Ａ'''環およびＢ'''環は、置換基を有していてもよい芳香族環または置換基を有していてもよい非芳香族環を表し、Ａ'''環およびＢ'''環の少なくとも一方は置換基を有していてもよい芳香族環である。また、Ｃ'''環は置換基を有していてもよい芳香族環を表す。結合手はＡ'''環、Ｂ'''環またはＣ'''環上に存在する。Ｚ₁〜Ｚ₃はそれぞれ前記と同じ意味を表す。〕
式（４）における置換基を有していてもよい芳香族環、置換基を有していてもよい非芳香族環の定義、具体例等は、上記式（1）におけるそれらについての定義、具体例と同様である。
Another preferred structure of the formula (1) is a structure represented by the following formula (4).

[In the formula, A ′ ″ ring and B ′ ″ ring represent an aromatic ring which may have a substituent or a non-aromatic ring which may have a substituent, and A ′ ″ At least one of the ring and the B ′ ″ ring is an aromatic ring which may have a substituent. The C ′ ″ ring represents an aromatic ring which may have a substituent. The bond is present on the A ′ ″ ring, the B ′ ″ ring or the C ′ ″ ring. Z _{1 to} Z ₃ each have the same meaning as described above. ]
Definitions, specific examples and the like of the aromatic ring that may have a substituent in formula (4) and the non-aromatic ring that may have a substituent are the definitions for those in the above formula (1), The same as the specific example.

The structure represented by the above formula (4) exists in the side chain or terminal of the conjugated polymer compound. In these cases, the repeating unit of the conjugated polymer compound may or may not contain the structure represented by the formula (2) or (3).

  Specific examples of the structure represented by the formula (4) include the structures (1A-1) to (1U-3) described above and a structure in which one bond is deleted from the structure having a substituent in the structure described above. It is done.

〔式中、Ａ''''環およびＢ''''環は、それぞれ独立に置換基を有していてもよい芳香族環または置換基を有していてもよい非芳香族環を表し、Ａ環およびＢ環の少なくとも一方は置換基を有していてもよい芳香族環である。また、Ｃ''''環は置換基を有していてもよい芳香族炭化水素環を表す。３つの結合手はそれぞれＡ''''環、Ｂ''''環またはＣ''''環上のいずれかに存在し、Ｚ₁〜Ｚ₃は前記と同じ意味を表す。〕
またＡ''''環、Ｂ''''環またはＣ''''環のいずれか一つの環が結合手を複数個有していても良い。
式（５）における置換基を有していてもよい芳香族環、置換基を有していてもよい非芳香族環の定義、具体例等は、上記式（1）におけるそれらについての定義、具体例と同様である。
Another preferred structure of the formula (1) is a structure represented by the following formula (5).

[In the formula, A ″ ″ ring and B ″ ″ ring each independently represent an aromatic ring which may have a substituent or a non-aromatic ring which may have a substituent. At least one of the A ring and the B ring is an aromatic ring which may have a substituent. The C ″ ″ ring represents an aromatic hydrocarbon ring which may have a substituent. Each of the three bonds is present on either the A ″ ″ ring, the B ″ ″ ring or the C ″ ″ ring, and Z _{1 to} Z ₃ represent the same meaning as described above. ]
In addition, any one of the A ″ ″ ring, the B ″ ″ ring, and the C ″ ″ ring may have a plurality of bonds.
Definitions, specific examples and the like of the aromatic ring which may have a substituent in formula (5) and the non-aromatic ring which may have a substituent are the definitions for those in the above formula (1), The same as the specific example.

When the structure represented by the formula (5) is included, the conjugated polymer compound usually has a branched structure. When the formula (5) is contained as a repeating unit, the repeating unit represented by the formula (5) is preferably 10 mol% or less, and preferably 1 mol% or less of all repeating units from the viewpoint of solubility and the like. It is more preferable.

Specific examples of the structure represented by the formula (5) include a structure in which one bond is added to either the A ring, the B ring or the C ring of the structures (1A-1) to (1U-3) described above. Is mentioned.

  The conjugated polymer compound of the present invention preferably contains at least one structure other than the above formula (1) from the viewpoint of light emission characteristics.

〔式中、Ａｒ₁、Ａｒ₂、Ａｒ₃およびＡｒ₄はそれぞれ独立にアリーレン基、２価の複素環基または金属錯体構造を有する２価の基を示す。Ｘ₁、Ｘ₂およびＸ₃はそれぞれ独立に−ＣＲ₉＝ＣＲ₁₀−、−Ｃ≡Ｃ−、−Ｎ（Ｒ₁₁）−、または−（ＳｉＲ₁₂Ｒ₁₃）_m−を示す。Ｒ₉およびＲ₁₀は、それぞれ独立に水素原子、アルキル基、アリール基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。Ｒ₁₁、Ｒ₁₂およびＲ₁₃は、それぞれ独立に水素原子、アルキル基、アリール基、１価の複素環基、アリールアルキル基または置換アミノ基を含む基を示す。ｆｆは１または２を示す。ｍは１〜１２の整数を示す。Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂およびＲ₁₃がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。〕 Furthermore, it is preferable that at least one type of repeating unit having a structure other than (1) is included.
Examples of the repeating unit having a structure other than the above formula (1) include repeating units represented by the following formulas (8) to (11).

[Wherein, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. X ₁ , X ₂ and X ₃ each independently represent —CR ₉ ═CR ₁₀ —, —C≡C—, —N (R ₁₁ ) —, or — (SiR ₁₂ R ₁₃ ) _m —. R ₉ and R ₁₀ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, an arylalkyl group or a group containing a substituted amino group. ff represents 1 or 2. m shows the integer of 1-12. When there are a plurality of R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ , they may be the same or different. ]

Here, an arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and those having a condensed ring, two or more independent benzene rings or condensed rings are directly or via a group such as vinylene. Are also included. The arylene group may have a substituent.
Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, and a substituted amino group. Silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, and cyano group.
Carbon number of the part except the substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. Moreover, the total carbon number including the substituent of an arylene group is about 6-100 normally.
As an arylene group, a phenylene group (for example, the following formulas 1 to 3), a naphthalenediyl group (the following formulas 4 to 13), an anthracene-diyl group (the following formulas 14 to 19), a biphenyl-diyl group (the following formulas 20 to 25) ), Fluorene-diyl group (formula 36-38), terphenyl-diyl group (formula 26-28), condensed ring compound group (formula 29-35), stilbene-diyl (formula AD), Examples include distilbene-diyl (formulas E and F). Of these, a phenylene group, a biphenylene group, a fluorene-diyl group, and a stilbene-diyl group are preferable.

The divalent heterocyclic group in Ar ₁ , Ar ₂ , Ar _3, and Ar ₄ refers to the remaining atomic group obtained by removing two hydrogen atoms from the heterocyclic compound, and the group has a substituent. May be.
Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. Say things. Of the divalent heterocyclic groups, an aromatic heterocyclic group is preferable.
Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, and a substituted amino group. Silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, and cyano group.
Carbon number of the part except the substituent in a bivalent heterocyclic group is about 3-60 normally. Moreover, the total carbon number including the substituent of a bivalent heterocyclic group is about 3-100 normally.

Examples of the divalent heterocyclic group include the following.
Divalent heterocyclic group containing nitrogen as a hetero atom; pyridine-diyl group (formula 39 to 44), diazaphenylene group (formula 45 to 48), quinoline diyl group (formula 49 to 63), quinoxaline diyl group ( The following formulas 64-68), acridinediyl groups (the following formulas 69-72), bipyridyldiyl groups (the following formulas 73-75), phenanthroline diyl groups (the following formulas 76-78), and the like.
Groups having a fluorene structure containing oxygen, silicon, nitrogen, selenium and the like as a hetero atom (the following formulas 79 to 93).
5-membered ring heterocyclic groups containing oxygen, silicon, nitrogen, sulfur, selenium and the like as a hetero atom: (the following formulas 94 to 98).
5-membered ring condensed hetero groups containing oxygen, silicon, nitrogen, selenium and the like as a hetero atom: (the following formulas 99 to 110).
A 5-membered ring heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium, etc. as a heteroatom and bonded in the α-position of the heteroatom to form a dimer or oligomer: (Formulas 111 to 112) Is mentioned.
And groups having the 5-membered ring heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium and the like as a hetero atom and bonded to the phenyl group at the α-position of the hetero atom (the following formulas 113 to 119).
Examples include groups in which a phenyl group, a furyl group, or a thienyl group is substituted on a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, etc. as a hetero atom (the following formulas 120 to 125).

The divalent group having a metal complex structure in Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ is the remaining 2 obtained by removing two hydrogen atoms from the organic ligand of the metal complex having an organic ligand. Is a valent group.
The organic ligand usually has about 4 to 60 carbon atoms. Examples thereof include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, and 2-phenyl-benzo. Examples include thiazole and its derivatives, 2-phenyl-benzoxazole and its derivatives, porphyrin and its derivatives.
Examples of the central metal of the complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium.
Examples of the metal complex having an organic ligand include a low-molecular fluorescent material, a metal complex known as a phosphorescent material, and a triplet light-emitting complex.
Specific examples of the divalent group having a metal complex structure include the following (126 to 132).

In the above formulas 1 to 132, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group. , Arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substitution A carboxyl group, a nitro group or a cyano group is shown. Moreover, the carbon atom which the group of Formula 1-132 has may be substituted with the nitrogen atom, the oxygen atom, or the sulfur atom, and the hydrogen atom may be substituted with the fluorine atom.
Here, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, Definitions, specific examples, and preferred examples of a halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, and substituted carboxyl group include the aromatic hydrocarbon ring having a substituent. It is the same as those in the case of having.

〔式中、E1環およびF1環はそれぞれ独立にベンゼン環またはナフタレン環であることがより好ましく、E1環およびF1環が全てベンゼン環であることがさらに好ましい。２つの結合手はそれぞれＥ１環またはＦ１環上に存在する。Ｚ₄は−Ｃ（Ｒa）（Ｒ_b）−、＞Ｃ＝Ｃ（Ｒ_a）（Ｒ_b）、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）（＝Ｏ）−、−Ｎ（Ｒ_a）−、−Si（Ｒ_a）（Ｒ_b）−、−Ｐ（＝Ｏ）(Ｒ_a)−、−Ｐ（Ｒ_a）−、−Ｂ（Ｒ_a）−、−Ｃ（Ｒ_a）（Ｒ_b）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（Ｒ_a）＝Ｎ−または−Ｓｅ−を表す。また、（Ｒ_a）、（Ｒ_b）はそれぞれ独立に置換基を表す。〕
From the viewpoints of solubility, device characteristics and the like, the formula (8) is preferably a repeating unit represented by the following formula (12).

[Wherein, the E1 ring and the F1 ring are each independently more preferably a benzene ring or a naphthalene ring, and more preferably all of the E1 ring and the F1 ring are benzene rings. Two bonds are present on the E1 ring or the F1 ring, respectively. Z ₄ represents —C (Ra) (R _b ) —,> C═C (R _a ) (R _b ), —O—, _—S— , —S (═O) —, —S (═O) ( = O)-, -N (R _a )-, -Si (R _a ) (R _b )-, -P (= O) (R _a )-, -P (R _a )-, -B (R _{a ) -, - C (R a} ) (R b) -O -, - C (= O) -O -, - C (R a) = represents the N- or -Se-. Further, (R _a ) and (R _b ) each independently represent a substituent. ]

Specific examples of the structure in which Z4 is carbon in the repeating unit represented by the formula (12) include the following structures (12-1 to 12-73) and structures having substituents in the following structures. Examples of the types of substituents that the E1 ring and F1 ring have include the same groups as the substituents that the A ring to C ring have.

The formula Ra, Rb, and R ₆ to R ₇ each independently represents a substituent. Examples of the substituent include alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, Examples include silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, nitro group, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group. .

Specific examples of the structure in which Z4 is an atom other than carbon in the repeating unit represented by the formula (12) include the following structures (12-74 to 12-85) and structures having substituents in the following structures. . Examples of the type of substituent include the same groups as the substituents of the aforementioned E ring and F ring.

〔上記式中Ｒw3、Ｒx3はそれぞれ独立に置換基を表す。置換基としてはアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、ニトロ基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基などがあげられる〕

[In the above formula, Rw3 and Rx3 each independently represents a substituent. Examples of the substituent include alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, Examples include silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, nitro group, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group. ]

〔式中、Ｒ₁₄は、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。ｎは０〜４の整数を示す。Ｒ₁₄が複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₁₅およびＲ₁₆は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。ｏおよびｐはそれぞれ独立に０〜３の整数を示す。Ｒ₁₅およびＲ₁₆がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₁₇およびＲ₂₀は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。ｑおよびｒはそれぞれ独立に０〜４の整数を示す。Ｒ₁₈およびＲ₁₉は、それぞれ独立に水素原子、アルキル基、アリール基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。Ｒ₁₇およびＲ₂₀が複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₂₁は、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。sは０〜２の整数を示す。Ａｒ₁₃およびＡｒ₁₄はそれぞれ独立にアリーレン基、２価の複素環基または金属錯体構造を有する２価の基を示す。ｓｓおよびｔｔはそれぞれ独立に０または１を示す。
Ｘ₄は、Ｏ、Ｓ、ＳＯ、ＳＯ₂、Ｓｅ，またはＴｅを示す。Ｒ₂₁が複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₃₄は、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を表す。ｈは０〜４の整数を表す。Ｒ₃₄が複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₂₂およびＲ₂₅は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。tおよびuはそれぞれ独立に０〜４の整数を示す。Ｘ₅は、Ｏ、Ｓ、ＳＯ₂、Ｓｅ，Ｔｅ、Ｎ−Ｒ₂₄、またはＳｉＲ₂₅Ｒ₂₆を示す。Ｘ₆およびＸ₇は、それぞれ独立にＮまたはＣ−Ｒ₂₇を示す。Ｒ₂₄、Ｒ_25、Ｒ₂₆およびＲ₂₇はそれぞれ独立に水素原子、アルキル基、アリール基、アリールアルキル基または１価の複素環基を示す。Ｒ₂₂、Ｒ₂₃およびＲ₂₇が複数存在する場合、それらは同一でも異なっていてもよい。〕
式（１８）で示される繰り返し単位の中央の５員環の例としては、チアジアゾール、オキサジアゾール、トリアゾール、チオフェン、フラン、シロールなどが挙げられる。 The repeating unit represented by the formula (8) is preferably a repeating unit represented by the following formulas (13) to (19).

[Wherein, R ₁₄ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, A substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group are shown. n shows the integer of 0-4. When a plurality of R ₁₄ are present, they may be the same or different. ]

Wherein R ₁₅ and R ₁₆ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Or a cyano group is shown. o and p each independently represent an integer of 0 to 3. When a plurality of R ₁₅ and R ₁₆ are present, they may be the same or different. ]

[Wherein, R ₁₇ and R ₂₀ are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an aryl group. Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Or a cyano group is shown. q and r each independently represents an integer of 0 to 4. R ₁₈ and R ₁₉ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. When a plurality of R ₁₇ and R ₂₀ are present, they may be the same or different. ]

[Wherein, R ₂₁ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, A substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group are shown. s shows the integer of 0-2. Ar ₁₃ and Ar ₁₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. ss and tt each independently represent 0 or 1.
X ₄ represents O, S, SO, SO ₂ , Se, or Te. When a plurality of R ₂₁ are present, they may be the same or different. ]

[Wherein, R ₃₄ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, It represents a substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group. h represents an integer of 0 to 4. When a plurality of R ₃₄ are present, they may be the same or different. ]

[Wherein R ₂₂ and R ₂₅ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Or a cyano group is shown. t and u each independently represents an integer of 0 to 4. X ₅ represents O, S, SO ₂ , Se, Te, N—R ₂₄ , or SiR ₂₅ R ₂₆ . X ₆ and X ₇ each independently represent N or C—R ₂₇ . R ₂₄ , R _25, R ₂₆ and R ₂₇ each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. When a plurality of R ₂₂ , R ₂₃ and R ₂₇ are present, they may be the same or different. ]
Examples of the central 5-membered ring of the repeating unit represented by the formula (18) include thiadiazole, oxadiazole, triazole, thiophene, furan, silole and the like.

〔式中、Ｒ₂₈およびＲ₃₃は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。vおよびwはそれぞれ独立に０〜４の整数を示す。Ｒ₂₉、Ｒ₃₀、Ｒ₃₁およびＲ₃₆は、それぞれ独立に水素原子、アルキル基、アリール基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。Ａｒ₅はアリーレン基、２価の複素環基または金属錯体構造を有する２価の基を示す。Ｒ₂₈およびＲ₃₃が複数存在する場合、それらは同一でも異なっていてもよい。〕

Wherein R ₂₈ and R ₃₃ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Or a cyano group is shown. v and w each independently represent an integer of 0 to 4. R ₂₉ , R ₃₀ , R ₃₁ and R ₃₆ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. Ar ₅ represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. When a plurality of R ₂₈ and R ₃₃ are present, they may be the same or different. ]

〔式中、Ａｒ₆、Ａｒ₇、Ａｒ₈およびＡｒ₉はそれぞれ独立にアリーレン基または２価の複素環基を示す。Ａｒ₁₀、Ａｒ₁₁およびＡｒ₁₂はそれぞれ独立にアリール基、または１価の複素環基を示す。Ａｒ₆、Ａｒ₇、Ａｒ₈、Ａｒ₉、Ａｒ₁₀、Ａｒ₁₁およびＡｒ₁₂は置換基を有していてもよい。ｘおよびｙはそれぞれ独立に０または正の整数を示す。〕 Among the repeating units represented by the above formula (9), the repeating unit represented by the following formula (20) is also preferable from the viewpoint of changing the emission wavelength, increasing the luminous efficiency, and improving the heat resistance. .

[Wherein, Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ each independently represent an arylene group or a divalent heterocyclic group. Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an aryl group or a monovalent heterocyclic group. Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , Ar ₁₀ , Ar ₁₁ and Ar ₁₂ may have a substituent. x and y each independently represent 0 or a positive integer. ]

  From the viewpoint of stability of the light-emitting element and ease of synthesis, it is preferable to include one or more and three or less repeating units represented by the formula (20), more preferably one or two. More preferably, it is a case where one type of repeating unit represented by the formula (20) is included.

  In the conjugated polymer compound of the present invention, when two types of repeating units represented by the formula (20) are included as repeating units, x = y = 0 from the viewpoint of adjusting the emission wavelength, device characteristics, and the like. It is preferable to select from a combination of a repeating unit shown and a repeating unit shown by x = 1 and y = 0, or a combination of two repeating units shown by x = 1 and y = 0.

In the present invention, when the repeating unit represented by the formula (2) or (3) and the repeating unit represented by the formula (9) are included, the molar ratio is preferably 98: 2 to 60:40.
From the viewpoint of fluorescence intensity, device characteristics, etc., the repeating unit represented by the formula (9) is the sum of the repeating unit represented by the formula (2) or (3) and the repeating unit represented by the formula (20). More preferably, it is 30 mol% or less. When an EL device is produced using only one kind of the conjugated polymer compound of the present invention, the repeating unit represented by the formula (2) or (3) and the formula (20) are used from the viewpoint of device characteristics and the like. The ratio of repeating units is preferably 95: 5 to 70:30.

In the present invention, when the repeating unit represented by the formula (2) or (3) and the repeating unit represented by the formula (8), (10), (11) are included, the molar ratio is 90:10 to 10: 90 is preferable.
In the present invention, the repeating unit represented by the formula (2) or (3) and the formulas (8) to (11) (wherein the formula (8) is represented by the formulas (8), (10), and (11)). In some cases and when the formula (9) includes the repeating unit represented by the formula (20)), the molar ratio is preferably 99: 1 to 60:40, 99: 1 to More preferably, it is 70:30.

Specific examples of the repeating unit represented by the above formula (9) include those represented by the following (formulas 133 to 140).

  In the above formula, R is the same as that in formulas 1-132. In order to increase the solubility in an organic solvent, it is preferable to have at least one other than a hydrogen atom, and it is preferable that the symmetry of the shape of the repeating unit including a substituent is small.

  In the above-described formula, in the substituent in which R contains alkyl, it is preferable that one or more alkyls having a cyclic or branched structure are contained in order to enhance the solubility of the conjugated polymer compound in an organic solvent. Furthermore, in the above formula, when R contains an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents. Among the structures represented by the above formulas 133 to 140, the structures represented by the above formula 134 and the above formula 137 are preferable from the viewpoint of adjusting the emission wavelength.

In the repeating unit represented by the above formula (20), Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ are each independently an arylene group from the viewpoints of adjusting the emission wavelength, device characteristics, and the like, and Ar ₁₀ , Ar It is preferable that ₁₁ and Ar ₁₂ each independently represent an aryl group.

Ar ₆ , Ar ₇ , and Ar ₈ are each independently preferably an unsubstituted phenylene group, an unsubstituted biphenyl group, an unsubstituted naphthylene group, or an unsubstituted anthracenediyl group.

Ar ₁₀ , Ar _11, and Ar ₁₂ are each preferably an aryl group having three or more substituents independently from the viewpoints of solubility in _an organic solvent, device characteristics, and the like. Ar ₁₀ , Ar ₁₁ And Ar ₁₂ is more preferably a phenyl group having 3 or more substituents, a naphthyl group having 3 or more substituents, or an anthranyl group having 3 or more substituents. Ar ₁₀ , Ar ₁₁ and Ar ₁₂ Is more preferably a phenyl group having three or more substituents.

〔式中、Ｒe、ＲfおよびＲgは、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、シリルオキシ基、置換シリルオキシ基、１価の複素環基またはハロゲン原子を表す。Ｒe、ＲfおよびＲgに含まれる水素原子はフッ素原子に置換されていてもよい。〕 Among them, Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are each independently the following formula (35) and preferably x + y ≦ 3, more preferably x + y = 1, and further preferably x = 1. This is the case when y = 0.

[In the formula, Re, Rf and Rg are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an aryl group. An alkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a silyloxy group, a substituted silyloxy group, a monovalent heterocyclic group, or a halogen atom is represented. Hydrogen atoms contained in Re, Rf and Rg may be substituted with fluorine atoms. ]

More preferably, in the above formula (35), Re and Rf are each independently an alkyl group having 3 or less carbon atoms, an alkoxy group having 3 or less carbon atoms, or an alkylthio group having 3 or less carbon atoms, and Rg is 3 carbon atoms. Examples thereof include an alkyl group having ˜20, an alkoxy group having 3 to 20 carbon atoms, and an alkylthio group having 3 to 20 carbon atoms.

〔ここで、(３６−１)、(３６−２)で示される構造に含まれるベンゼン環は、それぞれ独立に１個以上４個以下の置換基を有していてもよい。それら置換基は、互いに同一であっても、異なっていても良い。また、複数の置換基が連結して環を形成していても良い。さらに、該ベンゼン環に隣接して他の芳香族炭化水素環または複素環が結合していても良い。〕 In the repeating unit represented by the formula (20), Ar ₇ is preferably the following formula (36-1) or (36-2).

[Here, the benzene rings contained in the structures represented by (36-1) and (36-2) may each independently have 1 or more and 4 or less substituents. These substituents may be the same as or different from each other. A plurality of substituents may be connected to form a ring. Further, another aromatic hydrocarbon ring or heterocyclic ring may be bonded adjacent to the benzene ring. ]

Specific examples of the repeating unit represented by the formula (20) include those represented by the following (formulas 141 to 142).

Examples of the conjugated polymer compound containing a repeating unit other than the repeating unit represented by the formula (2) or (3) include the repeating units represented by the formulas (6) and (7) from the viewpoint of fluorescence characteristics and device characteristics. Those composed of one or more repeating units selected from the units and one or more repeating units represented by the above formulas (12), (14) to (20) are preferable. They are represented by formulas 133, 134, 137, and 138. More preferably, any one of the repeating units represented by formula (6) or (7) and any one of the repeating units represented by formula 134 and 137 and formula (6) Or what consists of a repeating unit shown by (7) is still more preferable.

In the conjugated polymer compound of the present invention, all the bonds between the aromatic rings constituting the main chain are substantially directly bonded, or -O-, -N (R)-( R represents a substituent, and those bonded via —S—, —CR═CR— or —C≡C— are preferred.

The conjugated polymer compound of the present invention includes one or more repeating units selected from the repeating units represented by the above formulas (6) and (7) and the above formulas (12), ( 14) to (20) are preferable, and any one of the repeating units represented by Formulas 133, 134, 137, and 138 and Formula (6) or (7) are preferable. What consists of the repeating unit shown is more preferable, and what consists of any one kind of the repeating unit shown by Formula 134 and Formula 137 and the repeating unit shown by Formula (6) or (7) is still more preferable.

〔式中Ａ環、Ｂ環、Ｃ環およびＺ₁〜Ｚ₃については前述のとおり。Ｙ_tおよびＹ_uはそれぞれ独立に縮合重合に関与する置換基を表す。ｅ、ｆは０以上の整数値を示し、ｅ＋ｆ≧１かつｅ≦2、ｆ≦1である。〕 Next, the manufacturing method of the conjugated polymer compound of this invention is demonstrated.
Among the conjugated polymer compounds of the present invention, the conjugated polymer compound having a repeating unit having the structure represented by formulas (2) to (3) is, for example, a compound represented by formula (27) as one of the raw materials. It can manufacture by polymerizing using.

[Wherein, A ring, B ring, C ring and Z _{1 to} Z ₃ are as described above. Y _t and Y _u represents a substituent participating in condensation polymerization are each independently. e and f represent integer values of 0 or more, and e + f ≧ 1, e ≦ 2, and f ≦ 1. ]

（３８） （３９）
〔式中、Ａ環、Ｂ環およびＣ環は前述と同様である。Ｙ_t、Ｙ_Uはそれぞれ独立に置換基を表し、Ｙ_tはＡ環またはＢ環と、Ｙ_uはＣ環と結合している。〕
Among the compounds represented by the above formula (27), polymerization is performed using compounds represented by the following formulas (38) and (39) from the viewpoint of ease of raising the degree of polymerization and ease of controlling the polymerization. Is preferred.

(38) (39)
[Wherein, A ring, B ring and C ring are the same as described above. Y _t, Y _U each independently represents a substituent, Y _t is attached with ring A or ring B, Y _u is the C ring. ]

（２８） （２９）
〔式中、Ｒ_w1、Ｒ_x1、Ｒ_w2、Ｒ_x2はそれぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、ニトロ基またはシアノ基を表し、ａおよびｃは０〜５の整数を表し、ｂおよびｄは０〜３の整数を表し、Ｒ_p1、Ｒ_q1、Ｒ_p2、Ｒ_q2がそれぞれ複数個存在する場合、それらは同一でも異なっていてもよい。Ｙ_t1、Ｙ_u1、Ｙ_t2、Ｙ_u2はそれぞれ独立に縮合重合に関与する置換基を表す。〕で示される化合物を原料の一つとして用いて重合させることにより製造することができる。 Examples of the raw material of the conjugated polymer compound having a repeating unit represented by the formulas (6) and (7) include compounds represented by the following formulas (28) and (29).

(28) (29)
[Wherein R _w1 , R _x1 , R _w2 and R _x2 are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, Arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl Represents a group, a substituted carboxyl group, a nitro group or a cyano group, a and c represent an integer of 0 to 5, b and d represent an integer of 0 to 3, and R _p1 , R _q1 , R _p2 and R _q2 represent When there are a plurality of each, they may be the same or different. _{Y t1, Y u1, Y t2} , Y u2 represents a substituent participating in condensation polymerization are each independently. ] Can be produced by polymerization using one of the raw materials as a raw material.

A conjugated polymer compound containing a repeating unit represented by the above formula (29) is preferred from the viewpoint of ease of synthesis.

_Rw1 , _Rx1 , _Rw2 , _Rx2 and _Rp1 , _Rq1 , _Rp2 , _Rq2 alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group , Arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent The definitions and specific examples of the heterocyclic group and the substituted carboxyl group are the same as those definitions and specific examples of the substituent in the case where the A ring and the B ring in the formula (1) have a substituent.

If Y _t, Y _u, Y _t1, Y _u1, Y _t2 and Y substituents capable of participating in polymerization in _u2 is independently a halogen atom, alkyl sulfonate group are selected from aryl sulfonate groups and aryl alkyl sulfonate groups, synthetic Is preferable because it can be used as a raw material for various polymerization reactions.

In addition, in (28), when Y _t1 and Yu ₁ are bromine atoms, it is preferable from the viewpoint that synthesis is easy, functional group conversion is easy, and that they can be used as raw materials for various polymerization reactions.

If addition is Y _t2, Y _u2 in (29) is a bromine atom, the point can be easily synthesized from the viewpoint which can be used as a raw material for functional group transformation easiness and various polymerization reactions.

Moreover, it is preferable that a = b = 0 from the viewpoint of improving the heat resistance in (28).

From the viewpoint of improving heat resistance in (29), it is preferable that c = d = 0.

（４０）

〔式中、Ｙ_t、Ｙ_u、Y_vはそれぞれ縮合重合に関与する置換基を表す。ｅ、ｆは０又は正の整数を表す。〕で示される化合物を原料の一つとして用いて重合させることにより製造することができる。 In the case of producing a conjugated polymer compound or dendrimer having a branched main chain and three or more terminal portions, it is produced by polymerizing using a compound represented by the following formula (40) as one of the raw materials. can do.

(40)

[Wherein Y _t , Yu _and Y _v each represent a substituent involved in condensation polymerization. e and f represent 0 or a positive integer. ] Can be produced by polymerization using one of the raw materials as a raw material.

（４１）
化合物が挙げられる。
〔式中、Ｒ_w1、Ｒ_x1、Ｒ_p1、Ｒ_q1、Ｙ_t1、Ｙ_u1、Ｙ_v1はそれぞれ置換基を表し、ａ’は０〜４の整数を表し、ｂ’は０〜３の整数を表しす。Ｒ_p1、Ｒ_q1がそれぞれ複数個存在する場合、それらは同一でも異なっていてもよい。〕 The raw material represented by the formula (40) is preferably represented by the following formulas (41) and (42).

(41)
Compounds.
[Wherein, R _w1 , R _x1 , R _p1 , R _q1 , Y _t1 , Yu ₁ , Y _v1 each represents a substituent, a ′ represents an integer of 0 to 4, and b ′ represents an integer of 0 to 3 Represents When a plurality of R _p1 and R _q1 are present, they may be the same or different. ]

（４２）

化合物が挙げられる。
〔式中、Ｒ_w2、Ｒ_x2、Ｒ_p2、Ｒ_q2、Ｙ_t2、Ｙ_u2、およびＹ_v2はそれぞれ置換基を表し、ｃ’は０〜４の整数を表し、ｄ’は０〜３の整数を表しす。Ｒ_p2、Ｒ_q2がそれぞれ複数個存在する場合、それらは同一でも異なっていてもよい。〕 The raw material represented by the formula (40) is preferably represented by the following formula (42).

(42)

Compounds.
_{Wherein, R w2, R x2, R} p2, R q2, Y t2, Y u2, and Y _v2 each represent a substituent, c 'is an integer of 0 to 4, d' is from 0 to 3 Represents an integer. When a plurality of R _p2 and R _q2 are present, they may be the same or different. ]

Further, in (41), from the viewpoint of improving the heat resistance, it is preferable that a ′ = b ′ = 0.

Further, from the viewpoint of improving heat resistance in (42), it is preferable that c ′ = d ′ = 0.

  In the production of the conjugated polymer compound of the present invention, a conjugated polymer compound having a higher molecular weight is obtained when the compound represented by the formula (40) or (41) or (42) is contained in the monomer as a raw material. It is done. In this case, the compound represented by the formula (40) or (41) or (42) is preferably used in the range of 10 mol% or less when the compound represented by the formula (28) is 100 mol%. It contains in a certain monomer, More preferably, it contains in 1 mol% or less.

  In addition, when the conjugated polymer compound of the present invention has a repeating unit other than the formula (2) or (3), it participates in two polymerizations that become a repeating unit other than the formula (41) or (42). The polymerization may be carried out in the presence of a compound having a substituent.

〔式中、Ａｒ₁、Ａｒ₂、Ａｒ₃、Ａｒ₄、ｆｆ、Ｘ₁、Ｘ₂およびＸ₃は前記と同じである。Ｙ₅、Ｙ₆、Ｙ₇、Ｙ₈、Ｙ₉、Ｙ₁₀、Ｙ₁₁、およびＹ₁₂はそれぞれ独立に重合に関与する置換基を表す。〕 Examples of the compound having two polymerizable substituents that become a repeating unit other than the repeating unit represented by the above formula (2) or (3) include compounds of the following formulas (31) to (34). .
In addition to the compound represented by the above formula (40), the compound represented by any of the following formulas (31) to (34) is polymerized to be added to the unit represented by the above formula (2) or (3). Thus, a conjugated polymer compound having one or more units of (8) to (11) in order can be produced.

[Wherein, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ ff, X ₁ , X ₂ and X ₃ are the same as described above. Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , and Y ₁₂ each independently represent a substituent involved in polymerization. ]

Conjugated polymer compounds whose ends are sealed are the above formulas (38), (39), (28), (29), (40), (41), (42), and the above formulas (31) to (34). In addition to the above, the compounds represented by the following formulas (43) and (44) can be used as a raw material for polymerization.

E ₁ -Y ₁₅ (43)
E ₂ -Y ₁₆ (44)

(E ₁ and E ₂ each represent a monovalent group derived from a monovalent heterocyclic ring, an aryl group having a substituent, a monovalent aromatic amine group or a heterocyclic coordination metal complex; Y ₁₅ , Y ₁₆ Each independently represents a substituent capable of participating in polymerization.)

〔式中、Ａｒ₆、Ａｒ₇、Ａｒ₈、Ａｒ₉、Ａｒ₁₀、Ａｒ₁₁、Ａｒ₁₂、ｘおよびｙの定義および好ましい例については前記と同じ。Ｙ₁₃およびＹ₁₄はそれぞれ独立に重合に関与しうる置換基を示す。〕 In addition, as a compound having two substituents involved in the condensation corresponding to the above formula (20), which is a repeating unit other than the repeating unit represented by the above formula (2) or (3), the following formula (45) ).

[Wherein, definitions and preferred examples of Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , Ar ₁₀ , Ar ₁₁ , Ar ₁₂ , x and y are the same as described above. Y ₁₃ and Y ₁₄ each independently represent a substituent capable of participating in polymerization. ]

In particular, a conjugated polymer having a chain represented by the following formula (46) by copolymerization using the compound represented by the above formula (38) or (39) and the compound represented by the above formula (45). Can be obtained.

Among the substituents that can participate in the polymerization in the production method of the present invention, the substituents that can participate in the polymerization include halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, aryl alkyl sulfonate groups, borate ester groups, sulfoniums. Examples thereof include a methyl group, a phosphonium methyl group, a phosphonate methyl group, a monohalogenated methyl group, -B (OH) ₂ , a formyl group, a cyano group, and a vinyl group.

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

  Examples of the alkyl sulfonate group include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group. Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group. Examples of the aryl sulfonate group include benzyl. Examples include sulfonate groups.

ホウ酸エステル基としては、下記式で示される基が例示される。

式中、Ｍｅはメチル基を、Ｅｔはエチル基を示す。

Examples of the borate group include groups represented by the following formula.

In the formula, Me represents a methyl group, and Et represents an ethyl group.

Examples of the sulfonium methyl group include groups represented by the following formula.
_{^{-CH 2 S + Me 2 X -}} , -CH 2 S + Ph 2 X -
(X represents a halogen atom, and Ph represents a phenyl group.)

Examples of the phosphonium methyl group include groups represented by the following formula.
_{^{-CH 2 P + Ph 3 X -}} (X represents a halogen atom.)

Examples of the phosphonate methyl group include groups represented by the following formula.
—CH ₂ PO (OR ′) ₂ (X represents a halogen atom, R ′ represents an alkyl group, an aryl group, or an arylalkyl group.)

  Examples of the monohalogenated methyl group include a methyl fluoride group, a methyl chloride group, a methyl bromide group, and a methyl iodide group.

The preferred substituents involved in the condensation polymerization vary depending on the type of polymerization reaction. For example, when using a zerovalent nickel complex such as a Yamamoto coupling reaction, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate. Groups. In the case of using a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction, an alkyl sulfonate group, a halogen atom, a borate group, -B (OH) _{2 and the} like can be mentioned.

  Specifically, in the production method of the present invention, a compound having a plurality of substituents involved in polymerization, which is a monomer, is dissolved in an organic solvent as necessary. For example, using an alkali or a suitable catalyst, It can be carried out at a melting point or higher and a boiling point or lower. For example, “Organic Reactions”, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965, “Organic Synthesis”, Collective No. 6 (Collective Volume VI), 407-411, John Wiley & Sons, Inc., 1988, Chemical Review (Chem. Rev.), 95, 2457 (1995), Journal of Organometallic Chemistry (J. Organomet. Chem.), 576, 147 (1999), Macromolecular Chemistry Kuromorekyura Symposium (Makromol., Macromol.Symp.), Vol. 12, page 229 (1987) may be a known method described, for example.

In the method for producing a conjugated polymer compound of the present invention, the condensation polymerization can be carried out by using a known condensation reaction depending on the substituent involved in the condensation polymerization of the raw material compound.
When the conjugated polymer compound of the present invention forms a double bond in condensation polymerization, for example, a method described in JP-A-5-202355 can be mentioned. That is, polymerization by Wittig reaction of a compound having a formyl group and a compound having a phosphonium methyl group, or a compound having a formyl group and a phosphonium methyl group, by Heck reaction between a compound having a vinyl group and a compound having a halogen atom. Polymerization, polycondensation of compounds having two or more monohalogenated methyl groups by dehydrohalogenation method, polycondensation of compounds having two or more sulfonium methyl groups by decomposing sulfonium salt, having a formyl group Examples include a method such as polymerization by a Knoevenagel reaction between a compound and a compound having a cyano group, and a method such as polymerization by a McMurry reaction of a compound having two or more formyl groups.
When the conjugated polymer compound of the present invention generates a triple bond in the main chain by condensation polymerization, for example, Heck reaction and Sonogashira reaction can be used.

Further, when a double bond or triple bond is not generated, for example, a method of polymerizing from a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) complex, FeCl ₃ or the like Examples thereof include a method of polymerizing with an oxidizing agent, a method of electrochemically oxidatively polymerizing, a method of decomposing an intermediate polymer having an appropriate leaving group, and the like.

  Among these, the structure is controlled by polymerization by Wittig reaction, polymerization by Heck reaction, polymerization by Knoevenagel reaction, polymerization by Suzuki coupling reaction, polymerization by Grignard reaction, and polymerization by nickel zero-valent complex. It is preferable because it is easy. Among them, a method of polymerizing with a nickel zeroized complex is preferable from the viewpoints of ease of molecular weight control, device characteristics such as polymer LED lifetime, light emission starting voltage, current density, voltage increase during driving, and heat resistance. .

  Since the conjugated polymer compound of the present invention has an asymmetric skeleton as shown in the formula (2) or (3) in the repeating unit, the direction of the repeating unit exists in the conjugated polymer compound. In the case of controlling the orientation of these repeating units, for example, there is a method of polymerizing by controlling the orientation of the repeating units by selecting the combination of the substituent involved in the condensation polymerization of the corresponding monomer and the polymerization reaction used. Illustrated.

  In the case of controlling the sequence of two or more kinds of repeating units in the conjugated polymer compound of the present invention, a method of polymerizing after synthesizing an oligomer having a part or all of the repeating units in the target sequence Examples include a method of polymerizing by selecting a substituent involved in condensation polymerization of each monomer to be used and a polymerization reaction to be used and controlling a sequence of repeating units.

Among the production methods of the present invention, a production method in which the substituent involved in the condensation polymerization is selected from a halogen atom, an alkyl sulfonate group, an aryl sulfonate group or an aryl alkyl sulfonate group, and the condensation polymerization is performed in the presence of a nickel zero-valent complex is preferred. .
As raw material compounds, dihalogenated compounds, bis (alkyl sulfonate) compounds, bis (aryl sulfonate) compounds, bis (aryl alkyl sulfonate) compounds or halogen-alkyl sulfonate compounds, halogen-aryl sulfonate compounds, halogen-aryl alkyl sulfonate compounds, Examples include alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds, and aryl sulfonate-aryl alkyl sulfonate compounds.

  In this case, for example, a halogen-alkyl sulfonate compound, a halogen-aryl sulfonate compound, a halogen-aryl alkyl sulfonate compound, an alkyl sulfonate-aryl sulfonate compound, an alkyl sulfonate-aryl alkyl sulfonate compound, or an aryl sulfonate-aryl alkyl sulfonate compound is used as a raw material compound. Thus, a method for producing a conjugated polymer compound in which the direction and sequence of repeating units are controlled can be mentioned.

In the production method of the present invention, the substituent involved in the condensation polymerization is selected from a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl sulfonate group, a boric acid group, or a boric acid ester group. The total number of moles of halogen atom, alkyl sulfonate group, aryl sulfonate group and arylalkyl sulfonate group (J) of the compound, and the total number of moles of boric acid group (-B (OH) ₂ ) and boric acid ester group A production method in which the ratio of (K) is substantially 1 (usually K / J is in the range of 0.7 to 1.2) and condensation polymerization using a nickel catalyst or a palladium catalyst is preferred.
Specific combinations of raw material compounds include a combination of a dihalogenated compound, a bis (alkyl sulfonate) compound, a bis (aryl sulfonate) compound or a bis (aryl alkyl sulfonate) compound and a diboric acid compound or a diboric acid ester compound. .
Also, halogen-boric acid compounds, halogen-boric acid ester compounds, alkyl sulfonate-boric acid compounds, alkyl sulfonate-boric acid ester compounds, aryl sulfonate-boric acid compounds, aryl sulfonate-boric acid ester compounds, arylalkyl sulfonate-borates Examples include acid compounds, arylalkyl sulfonate-boric acid compounds, and arylalkyl sulfonate-boric acid ester compounds.

  In this case, for example, as a raw material compound, a halogen-boric acid compound, a halogen-boric acid ester compound, an alkyl sulfonate-boric acid compound, an alkyl sulfonate-boric acid ester compound, an aryl sulfonate-boric acid compound, an aryl sulfonate-boric acid ester compound, Examples thereof include a method of producing a conjugated polymer compound in which the orientation and sequence of repeating units are controlled by using an arylalkyl sulfonate-boric acid compound, an arylalkyl sulfonate-boric acid compound, and an arylalkyl sulfonate-boric acid ester compound.

  The organic solvent varies depending on the compound and reaction to be used, but it is generally preferable that the solvent to be used is sufficiently deoxygenated and the reaction proceeds in an inert atmosphere in order to suppress side reactions. Similarly, it is preferable to perform a dehydration treatment. However, this is not the case in the case of a two-phase reaction with water, such as the Suzuki coupling reaction.

  Solvents include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloropentane and bromopentane. Halogenated saturated hydrocarbons such as chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene, methanol, ethanol, propanol, isopropanol, butanol, t-butyl alcohol Alcohols such as formic acid, acetic acid, propionic acid, dimethyl ether, diethyl ether, methyl-t-butyl ether, tetra Ethers such as drofuran, tetrahydropyran, dioxane, trimethylamine, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, amines such as pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N , N-diethylacetamide, amides such as N-methylmorpholine oxide, etc. are exemplified, and a single solvent or a mixed solvent thereof may be used. Of these, ethers are preferable, and tetrahydrofuran and diethyl ether are more preferable.

  In order to make it react, an alkali and a suitable catalyst are added suitably. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. As a method of mixing the alkali or catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or conversely, slowly add the reaction solution to the alkali or catalyst solution. And the method of adding.

  The conjugated polymer compound of the present invention may be a random, block or graft copolymer, or a polymer having an intermediate structure thereof, for example, a random copolymer having a block property. Also good. From the viewpoint of obtaining a polymer light emitter having a high quantum yield of fluorescence or phosphorescence, a random copolymer having a block property and a block or graft copolymer are preferable to a complete random copolymer. A case in which the main chain is branched and there are three or more terminal portions and dendrimers are also included.

In the structure represented by the formula (2), when two formulas (2) are adjacent to each other, the structure is represented by any one of the following formulas (21), (22), and (23). From the viewpoint of electron injecting property and transporting property, the conjugated polymer compound preferably contains at least one of (21) to (23).

In the structure represented by the formula (3), the structure when two formulas (3) are adjacent to each other is a structure represented by any of the following formulas (24), (25), and (26). From the viewpoint of electron injecting property and transporting property, the conjugated polymer compound preferably contains at least one of (24) to (26).

  In order to withstand various processes for producing a light emitting element or the like, the glass transition temperature of the conjugated polymer compound is preferably about 100 ° C. or higher, more preferably 130 ° C. or higher, and 150 ° C. or higher. More preferably.

The number average molecular weight in terms of polystyrene of the conjugated polymer compound of the present invention is usually about 10 ³ to 10 ⁸ , preferably 10 ⁴ to 10 ⁶ . Further, the weight average molecular weight in terms of polystyrene is usually about 10 ³ to 10 ⁸ , and preferably 5 × 10 ⁴ or more, more preferably 10 ⁵ or more from the viewpoint of film formability and efficiency when used as an element. preferable. Moreover, it is preferable that it is 10 < ⁵ > -5 * 10 < ⁶ > from a soluble viewpoint. A preferred range of the conjugated polymer compound has high efficiency even when used alone in an element or when two or more kinds are mixed and used in an element. Similarly, from the viewpoint of improving the film formability of the conjugated polymer compound, the dispersity (weight average molecular weight / number average molecular weight) is preferably 1.5 or more.

  In addition, the conjugated polymer compound of the present invention may have a branched structure in the main chain, and examples of the branched structure include a structure represented by the above formula (5). It is preferable that one or more rings are included and one or more rings are included in the C ring.

〔式中、Ｒ_p1、Ｒ_q1、R_w1およびR_x1は前記と同様の意味を表す。ａは０〜４の整数値を表し、ｂは０〜３の整数値を表す。〕 More preferably, the branched structure is represented by the following formula (37).

[Wherein, R _p1 , R _q1 , R _w1 and R _x1 represent the same meaning as described above. a represents an integer value of 0 to 4, and b represents an integer value of 0 to 3. ]

  In addition, the terminal group of the conjugated polymer compound of the present invention is protected with a stable group, because if the polymerization active group remains as it is, there is a possibility that the light emission characteristics and lifetime when the device is made will be reduced. It is preferable. Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and examples thereof include a structure in which an aryl group or a heterocyclic group is bonded via a carbon-carbon bond. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478.

  In the conjugated polymer compound of the present invention, at least one of the molecular chain ends is a monovalent heterocyclic group, a monovalent aromatic amine group, a monovalent group derived from a heterocyclic coordination metal complex, or a formula weight It preferably has an aromatic end group selected from 90 or more aryl groups. This aromatic terminal group may be one type or two or more types. The terminal groups other than the aromatic terminal group are preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less of all terminals from the viewpoint of fluorescence characteristics and device characteristics. More preferably, it is substantially absent. Here, the molecular chain terminal is an aromatic terminal group present at the terminal of the conjugated polymer compound by the production method of the present invention, a leaving group of the monomer used for the polymerization, and is conjugated without being released during the polymerization. A leaving group that exists at the end of a polymer compound, or a proton that is bonded to a monomer that exists at the end of a conjugated polymer compound, but the aromatic terminal group is not bonded to the polymer but the leaving group of the polymer is removed. . Among these molecular chain ends, the leaving group of the monomer used for the polymerization, which does not leave at the time of polymerization and exists at the end of the conjugated polymer compound, for example, a single group having a halogen atom as a raw material. In the case of producing the conjugated polymer compound of the present invention using a monomer, etc., if halogen remains at the end of the conjugated polymer compound, the fluorescence characteristics and the like tend to deteriorate. It is preferred that substantially no leaving group remains.

  In the conjugated polymer compound of the present invention, at least one of the molecular chain ends is a monovalent heterocyclic group, a monovalent aromatic amine group, a monovalent group derived from a heterocyclic coordination metal complex, or a formula weight. It is expected that various properties are added to the conjugated polymer compound by sealing with an aromatic terminal group selected from 90 or more aryl groups. Specifically, the effect of increasing the time required to reduce the luminance of the device, the effect of increasing the charge injection property, the charge transport property, the light emission property, the effect of increasing the compatibility and interaction between the copolymers, the anchor effect Etc.

Examples of the monovalent heterocyclic group include the groups described above, and specific examples thereof include the following structures.

  Examples of the monovalent aromatic amine group include a structure in which one of the two bonds having the two in the structure of the formula (20) is sealed with R.

  Examples of the monovalent group derived from the heterocyclic coordination metal complex include a structure in which one of two bonds in the divalent group having the above metal complex structure is sealed with R. .

  Among the terminal groups, the aryl group having a formula weight of 90 or more usually has about 6 to 60 carbon atoms. Here, the formula weight of the aryl group means the sum of the number of atoms of each element multiplied by the atomic weight of each element in the chemical formula when the aryl group is represented by a chemical formula.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a group having a fluorene structure, and a condensed ring compound group.

があげられる。 Examples of the phenyl group for sealing the end include

Can be given.

があげられる。 As a naphthyl group for sealing the end, for example,

Can be given.

があげられる。 As an anthracenyl group, for example,

Can be given.

があげられる。
Examples of the group containing a fluorene structure include:

Can be given.

があげられる。 As the condensed ring compound group, for example,

Can be given.

  As the terminal group for enhancing the charge injection property and the charge transport property, a monovalent heterocyclic group, a monovalent aromatic amine group, and a condensed ring compound group are preferable, and a monovalent heterocyclic group and a condensed ring compound group are more preferable. .

  As the terminal group for enhancing the light emission characteristics, a monovalent group derived from a naphthyl group, an anthracenyl group, a condensed ring compound group or a heterocyclic coordination metal complex is preferable.

  As the terminal group having an effect of prolonging the time required for reducing the luminance of the element, an aryl group having a substituent is preferable, and a phenyl group having 1 to 3 alkyl groups is preferable.

共役高分子化合物間の相溶性や相互作用を高める効果がある末端基としては、置換基を有するアリール基が好ましい。また、炭素数６以上のアルキル基が置換したフェニル基を用いることによりアンカー的な効果を奏することができる。アンカー効果とは末端基がポリマーの凝集体に対してアンカー的な役割をし、相互作用を高める効果をいう。

The terminal group having an effect of enhancing the compatibility and interaction between the conjugated polymer compounds is preferably an aryl group having a substituent. An anchor effect can be obtained by using a phenyl group substituted with an alkyl group having 6 or more carbon atoms. The anchor effect means an effect in which the end group plays an anchor role with respect to the polymer aggregate and enhances the interaction.

〔式中のＲは前述のＲが例示されるが、水素、シアノ基、炭素数１〜２０のアルキル基、アルコキシ基、アルキルチオ基、炭素数６〜１８のアリール基、アリールオキシ基、炭素数４〜１４の複素環基が好ましい。〕 As the group for enhancing the element characteristics, the following structure is preferable.

[R in the formula is exemplified by the aforementioned R, but hydrogen, cyano group, alkyl group having 1 to 20 carbon atoms, alkoxy group, alkylthio group, aryl group having 6 to 18 carbon atoms, aryloxy group, carbon number 4-14 heterocyclic groups are preferred. ]

As the group for enhancing the element characteristics, the following structure is more preferable.

  Examples of the good solvent for the conjugated polymer compound of the present invention include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, and n-butylbenzene. Although depending on the structure and molecular weight of the conjugated polymer compound, it can usually be dissolved in these solvents in an amount of 0.1% by weight or more.

The conjugated polymer compound of the present invention preferably has a fluorescence quantum yield of 30% or more, more preferably 50% or more, and further preferably 60% or more from the viewpoint of fluorescence intensity, device characteristics, and the like.
One of the properties desired for a conjugated polymer compound for polymer LED is electron injection. The electron injection property generally depends on the value of the lowest unoccupied molecular orbital (LUMO) of the conjugated polymer compound, and the larger the LUMO absolute value, the better the electron injection property. The absolute value of LUMO is preferably 2.5 eV or more, more preferably 2.7 eV or more, and even more preferably 2.8 eV or more.

  When the conjugated polymer compound of the present invention is used for a polymer LED or the like, since the purity affects the performance of the device such as the light emission characteristics, the monomer before polymerization is purified by a method such as distillation, sublimation purification, and recrystallization. It is preferable to polymerize later. Further, after the polymerization, it is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography. Among the conjugated polymer compounds of the present invention, those produced by a method of polymerizing with a nickel zero-valent complex are element characteristics such as lifetime of polymer LED, light emission starting voltage, current density, voltage increase during driving, or It is preferable from the viewpoint of heat resistance and the like.

When the substituent involved in condensation polymerization in the raw material of the conjugated polymer compound of the present invention is halogen, for example, (38), (39), (28), (29), (38), (39), (28), (29), Y _r1 , Y _s1, Y _r2 , Y of (40), (41), (42), (31), (32), (33), (34), (43), (44), (45) _{s2, Y t, Y u,} Y v, after synthesizing the _{Y t1, Y u1, Y v1} , Y t2, Y u2, Y v2, a compound of structure by replacing the hydrogen atom, for example, chlorine, bromine, iodine , N-chlorosuccinimide, N-bromosuccinimide, benzyltrimethylammonium tribromide and the like.

  The substituent that participates in the condensation polymerization in the raw material of the conjugated polymer compound of the present invention is preferably halogen. From the viewpoint of increasing the molecular weight and the ease of purification after completion of the reaction, the halogen may be bromine. preferable.

In addition, those in which the substituent involved in the condensation polymerization in the raw material of the conjugated polymer compound of the present invention is an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate group can be derived, for example, into a hydroxyl group such as an alkoxy group. A compound having a functional group is subjected to a coupling reaction, a ring closure reaction, or the like, and (38), (39), (28), (29), (40), (41), (42), (31), (32), (33), (34), (43), (44), in _{(45), Y r1, Y} s1, Y r2, Y s2, Y t, Y u, Y v, Y t1 _{, Y u1, Y v1, Y} t2, Y u2, Y v2, after synthesizing a compound obtained by replacing a functional group capable of inducing the hydroxyl group, such as alkoxy groups, for example such as using dealkylation agent by boron tribromide, etc. Y _r1 , Y _s1 by various reactions of _{, Y r2, Y s2, Y} t, Y u, Y v, Y t1, Y u1, Y v1, Y t2, Y u2, Y v2, was synthesized compound is replaced with a hydroxyl group, then, for example, various It can be obtained by sulfonylating the hydroxyl group with sulfonyl chloride, sulfonic acid anhydride or the like.

In addition, when the substituent involved in the condensation polymerization in the raw material of the conjugated polymer compound of the present invention is a boric acid group or a boric acid ester group, (38), (39), (28 ), (29), (40), (41), (42), (31), (32), (33), (34), (43), (44), (45), Y _{r1, Y s1, Y r2,} Y s2, Y t, Y u, Y v, Y t1, Y u1, Y v1, Y t2, Y u2, Y v2, after synthesizing a compound obtained by replacing the halogen atom, Converting halogen atoms to boric acid groups by reacting with alkyllithium, magnesium metal, etc., and further boring with trimethylborate, and boric acid esterification by boric acid oxidation Is obtained. Moreover, (38), (39), (28), (29), (40), (41), (42), (31), (32), (33), (34) by the above method or the like. ), (43), (44), in _{(45), Y r1, Y} s1, Y r2, Y s2, Y t, Y u, Y v, Y t1, Y u1, Y v1, Y t2, Y _u2, Y _v2, to synthesize a halogen compound is replaced with trifluoromethane sulfonate group or the like, then, non-patent literature [Journal of Organic Chemistry, 11995,60,7508-7510, Tetrahedoron Letters, 1997,28 (19) , 3447-3450] and the like. Among the conjugated polymer compounds of the present invention, those produced by a method of polymerizing with a nickel zero-valent complex are preferable from the viewpoint of lifetime characteristics.

Next, the use of the conjugated polymer compound of the present invention will be described.
The conjugated polymer compound of the present invention usually emits fluorescence or phosphorescence in a solid state and can be used as a polymer light emitter (high molecular weight light emitting material).
Further, the conjugated polymer compound has an excellent charge transporting ability, and can be suitably used as a polymer LED material or a charge transporting material. The polymer LED using the polymer light emitter is a high-performance polymer LED that can be driven with low voltage and high efficiency. Therefore, the polymer LED can be preferably used for a backlight of a liquid crystal display, or a device such as a curved or flat light source for illumination, a segment type display element, a dot matrix flat panel display.
The conjugated polymer compound of the present invention can also be used as a material for conductive thin films such as laser dyes, organic solar cell materials, organic semiconductors for organic transistors, conductive thin films, and organic semiconductor thin films.
Furthermore, it can also be used as a light-emitting thin film material that emits fluorescence or phosphorescence.

Next, the polymer LED of the present invention will be described.
The polymer LED of the present invention has an organic layer between electrodes composed of an anode and a cathode, and the organic layer contains the conjugated polymer compound of the present invention.
The organic layer (a layer containing an organic substance) may be any of a light emitting layer, a hole transport layer, an electron transport layer, and the like, but the organic layer is preferably a light emitting layer.

  Here, the light emitting layer refers to a layer having a function of emitting light, the hole transporting layer refers to a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. Say. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently.

When the organic layer is a light emitting layer, the light emitting layer that is an organic layer may further contain a hole transporting material, an electron transporting material, or a light emitting material. Here, the light-emitting material refers to a material that exhibits fluorescence and / or phosphorescence.
When the conjugated polymer compound of the present invention and the hole transporting material are mixed, the mixing ratio of the hole transporting material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt% with respect to the entire mixture. %. When the polymer material of the present invention and the electron transporting material are mixed, the mixing ratio of the electron transporting material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt% with respect to the entire mixture. Further, when the conjugated polymer compound of the present invention and the luminescent material are mixed, the mixing ratio of the luminescent material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt%, with respect to the entire mixture. When the conjugated polymer compound of the present invention is mixed with a light emitting material, a hole transporting material and / or an electron transporting material, the mixing ratio of the light emitting material is 1 wt% to 50 wt% with respect to the entire mixture. , Preferably 5 wt% to 40 wt%, and the total of the hole transporting material and the electron transporting material is 1 wt% to 50 wt%, preferably 5 wt% to 40 wt%. The content of the compound is 99 wt% to 20 wt%.

As the hole-transporting material, electron-transporting material, and light-emitting material to be mixed, known low-molecular compounds, triplet light-emitting complexes, or conjugated polymer compounds can be used, but conjugated polymer compounds are preferably used. As the hole transporting material, electron transporting material and light emitting material of the conjugated polymer compound, WO99 / 13692, WO99 / 48160, GB2340304A, WO00 / 53656, WO01 / 19834, WO00 / 55927, GB2348316, WO00 / 46321, WO00 / 06665, WO99 / 54943, WO99 / 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, EP07 7020, WO 95/07955, JP 2001-181618, JP 2001-123156, JP 2001-3045, JP 2000-351967, JP 2000-303066, JP 2000-299189, JP 2000-252065, JP 2000-252065, JP 2000-136379, JP 2000-104057, JP 2000-80167, JP 10-324870, JP 10-114891, JP 9-111233, JP 9-45478, and the like, and derivatives thereof And copolymers, polyarylenes, derivatives and copolymers thereof, polyarylene vinylenes, derivatives and copolymers thereof, (co) polymers of aromatic amines and derivatives thereof.
Examples of low molecular weight fluorescent materials include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or its derivatives of metals. A complex, an aromatic amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.
Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

Examples of triplet light-emitting complexes include Ir (ppy) ₃ , Btp ₂ Ir (acac) having iridium as a central metal, PtOEP having platinum as a central metal, Eu (TTA) ₃ phen having a central metal as europium, and the like. Can be mentioned.

三重項発光錯体として具体的には、例えばＮａｔｕｒｅ，（１９９８），３９５，１５１、Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．（１９９９），７５（１），４、Ｐｒｏｃ．ＳＰＩＥ−Ｉｎｔ．Ｓｏｃ．Ｏｐｔ．Ｅｎｇ．（２００１），４１０５（Ｏｒｇａｎｉｃ Ｌｉｇｈｔ−Ｅｍｉｔｔｉｎｇ Ｍａｔｅｒｉａｌｓ ａｎｄ Ｄｅｖｉｃｅｓ ＩＶ），１１９、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，（２００１），１２３，４３０４、Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，（１９９７），７１（１８），２５９６、Ｓｙｎ．Ｍｅｔ．，（１９９８），９４（１），１０３、Ｓｙｎ．Ｍｅｔ．，（１９９９），９９（２），１３６１、Ａｄｖ．Ｍａｔｅｒ．，（１９９９），１１（１０），８５２、Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ．，３４，１８８３（１９９５）などに記載されている。

Specific examples of the triplet light-emitting complex include, for example, Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105 (Organic Light-Emitting Materials and Devices IV), 119, J. MoI. Am. Chem. Soc. , (2001), 123, 4304, Appl. Phys. Lett. , (1997), 71 (18), 2596, Syn. Met. , (1998), 94 (1), 103, Syn. Met. , (1999), 99 (2), 1361, Adv. Mater. , (1999), 11 (10), 852, Jpn. J. et al. Appl. Phys. 34, 1883 (1995).

The conjugated polymer compound of the present invention can be excellent in heat resistance by having the structure of the formula (1).
Among the conjugated polymer compounds of the present invention, the glass transition temperature is preferably 130 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 160 ° C. or higher.

The polymer composition of the present invention contains at least one material selected from a hole transport material, an electron transport material and a light emitting material and the conjugated polymer compound of the present invention, and can be used as a light emitting material or a charge transport material. it can.
The content ratio of the conjugated polymer compound of the present invention and at least one material selected from the hole transport material, electron transport material, and luminescent material may be determined according to the use. The same content ratio as in the above light emitting layer is preferable.

Another embodiment of the present invention is exemplified by a polymer composition containing two or more conjugated polymer compounds of the present invention.
Specifically, a polymer comprising two or more kinds of conjugated polymer compounds containing the repeating unit represented by the formula (2) or (3), wherein the total amount of the conjugated polymer compounds is 50% by weight or more of the whole. When the composition is used as a light emitting material of a polymer LED, it is excellent in terms of luminous efficiency, life characteristics and the like, which is preferable. More preferably, the total amount of the conjugated polymer compound is 70% by weight or more of the total.
The polymer composition of the present invention can enhance device characteristics such as lifetime as compared with the case where a conjugated polymer compound is used alone for a polymer LED.

  When the conjugated polymer compound of the present invention is used as a polymer composition, it is represented by the above formula (2) or (3) from the viewpoint of solubility in an organic solvent and device characteristics such as light emission efficiency and lifetime characteristics. The repeating unit is preferably selected from the repeating unit represented by the formula (6) or the repeating unit represented by the formula (7), more preferably the repeating unit represented by the formula (6), ), And a and b are more preferably 0. The repeating unit represented by the formula (20) is more preferably a repeating unit represented by the formula 134 or a repeating unit represented by the formula 137.

The number average molecular weight in terms of polystyrene of the polymer composition of the present invention is usually about 10 ³ to 10 ⁸ , preferably 10 ⁴ to 10 ⁶ . The weight average molecular weight in terms of polystyrene is usually about 10 ³ to 10 ⁸ , and preferably 5 × 10 ^{4 to} 5 × 10 ⁶ from the viewpoint of film formability and efficiency in the case of an element. ^{5 to} 5 × 10 ⁶ is more preferable. Here, the average molecular weight of the polymer composition refers to a value obtained by analyzing a composition obtained by mixing two or more conjugated polymer compounds by GPC.

  As the film thickness of the light emitting layer of the polymer LED of the present invention, the optimum value varies depending on the material used, and it may be selected so that the drive voltage and the light emission efficiency are appropriate values. Preferably it is 2 nm-500 nm, More preferably, it is 2 nm-200 nm.

  Examples of the method for forming the light emitting layer include a method by film formation from a solution. As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, Application methods such as a flexographic printing method, an offset printing method, and an ink jet printing method can be used. Printing methods such as a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method are preferable in that pattern formation and multicolor coating are easy.

The solution (ink composition) used in the printing method or the like may contain at least one conjugated polymer compound of the present invention. In addition to the conjugated polymer compound of the present invention, a hole transport material, electron transport Additives such as materials, luminescent materials, solvents, stabilizers and the like may be included.
The ratio of the conjugated polymer compound of the present invention in the ink composition is usually 20 wt% to 100 wt%, preferably 40 wt% to 100 wt%, based on the total weight of the composition excluding the solvent.
When the solvent is contained in the ink composition, the ratio of the solvent is 1 wt% to 99.9 wt% with respect to the total weight of the composition.
The viscosity of the ink composition varies depending on the printing method. However, when the ink composition passes through a discharge device such as an ink jet printing method, the viscosity is 1 at 25 ° C. in order to prevent clogging at the time of discharge and flight bending. It is preferably in the range of ˜20 mPa · s, and more preferably in the range of 5 to 20 mPa · s.

  The solution of the present invention may contain additives for adjusting viscosity and / or surface tension in addition to the conjugated polymer compound of the present invention. As the additive, a high molecular weight conjugated polymer compound (thickener) for increasing the viscosity, a poor solvent, a low molecular weight compound for decreasing the viscosity, a surfactant for decreasing the surface tension, and the like are appropriately combined. And use it.

The high molecular weight conjugated polymer compound may be any compound that is soluble in the same solvent as the conjugated polymer compound of the present invention and does not inhibit light emission or charge transport. For example, high molecular weight polystyrene, polymethyl methacrylate, or a conjugated polymer compound of the present invention having a high molecular weight can be used. The weight average molecular weight is preferably 500,000 or more, more preferably 1,000,000 or more.
A poor solvent can also be used as a thickener. That is, the viscosity can be increased by adding a small amount of a poor solvent for the solid content in the solution. When a poor solvent is added for this purpose, the type and amount of the solvent may be selected as long as the solid content in the solution does not precipitate. Considering stability during storage, the amount of the poor solvent is preferably 50 wt% or less based on the entire solution.

  The solution of the present invention may contain an antioxidant in addition to the conjugated polymer compound of the present invention in order to improve storage stability. The antioxidant is not particularly limited as long as it is soluble in the same solvent as the conjugated polymer compound of the present invention and does not inhibit light emission or charge transport, and examples thereof include phenol-based antioxidants and phosphorus-based antioxidants.

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing the conjugated polymer compound of the present invention is preferable. Chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and aromatic solvents such as toluene and xylene. Hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane Polyhydric alcohols such as propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, dimethyl sulfoxide, etc. And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination. Of the above solvents, it is preferable to include one or more organic solvents having a structure containing at least one benzene ring, a melting point of 0 ° C. or lower, and a boiling point of 100 ° C. or higher.

  As the type of solvent, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents are preferable from the viewpoints of solubility in organic solvents, uniformity during film formation, viscosity characteristics, and the like. , Toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, i-butylbenzene, s-butylbenzene, anisole, ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone Cyclohexylbenzene, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, 2-propylcyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, - decanone, tetralin, dicyclohexyl ketone, cyclohexanone, phenyl hexane, decalin are preferable, xylene, anisole, cyclohexylbenzene, bicyclohexyl, cyclohexanone, phenyl hexane, more preferably contains at least one of the decalin.

  The number of solvents in the solution is preferably two or more, more preferably two to three, and even more preferably two from the viewpoints of film formability and device characteristics.

  When two kinds of solvents are contained in the solution, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, one type of solvent is preferably a solvent having a boiling point of 180 ° C. or higher, and the other one type of solvent is preferably a solvent having a boiling point of 180 ° C. or lower. It is more preferable that the solvent is a solvent having a boiling point of 180 ° C. or lower. From the viewpoint of viscosity, it is preferable that 1 wt% or more of the conjugated polymer compound dissolves at 60 ° C. in one of the two solvents, and one solvent out of the two solvents contains 1 wt% at 25 ° C. The above conjugated polymer compound is preferably dissolved.

  When three types of solvents are contained in the solution, one or two of them may be in a solid state at 25 ° C. From the viewpoint of film formability, at least one of the three solvents is preferably a solvent having a boiling point of 180 ° C. or higher, and at least one solvent is preferably a solvent having a boiling point of 180 ° C. or lower. At least one of the types of solvents is a solvent having a boiling point of 200 ° C. or more and 300 ° C. or less, and at least one of the solvents is more preferably a solvent having a boiling point of 180 ° C. or less. From the viewpoint of viscosity, it is preferable that 1 wt% or more of the conjugated polymer compound is dissolved in two of the three types of solvents at 60 ° C. One type of the three types of solvents It is preferable that 1 wt% or more of the conjugated polymer compound is dissolved at 25 ° C.

  When two or more kinds of solvents are contained in the solution, the solvent having the highest boiling point is preferably 40 to 90 wt% of the weight of all the solvents in the solution, from the viewpoint of viscosity and film formability, and 50 to 90 wt% % Is more preferable.

  Examples of the solution of the present invention include a solution composed of anisole and bicyclohexyl, a solution composed of anisole and cyclohexylbenzene, a solution composed of xylene and bicyclohexyl, xylene and cyclohexylbenzene, and the like from the viewpoint of viscosity and film formability.

  From the viewpoint of solubility of the conjugated polymer compound in the solvent, the difference between the solubility parameter of the solvent and the solubility parameter of the conjugated polymer compound is preferably 10 or less, and more preferably 7 or less.

The solubility parameter of the solvent and the solubility parameter of the conjugated polymer compound can be determined by the methods described in “Solvent Handbook (Kodansha, 1976)”.

  The conjugated polymer compound of the present invention contained in the solution may be one type or two or more types, and may contain a conjugated polymer compound other than the conjugated polymer compound of the present invention as long as the device characteristics and the like are not impaired. .

  The solution of the present invention may contain water, metal and a salt thereof in the range of 1 to 1000 ppm. Specific examples of the metal include lithium, sodium, calcium, potassium, iron, copper, nickel, aluminum, zinc, chromium, manganese, cobalt, platinum, iridium and the like. Moreover, silicon, phosphorus, fluorine, chlorine, bromine may be included in a range of 1 to 1000 ppm.

  Using the solution of the present invention, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method A thin film can be produced by a printing method, an offset printing method, an inkjet printing method, or the like. Among these, the solution of the present invention is preferably used for a film forming method by a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method, and more preferably used for a film forming by an ink jet method.

  When a thin film is produced using the solution of the present invention, since the glass transition temperature of the conjugated polymer compound contained in the solution is high, it can be baked at a temperature of 100 ° C. or higher, and baked at a temperature of 130 ° C. However, the deterioration of the element characteristics is very small. Depending on the type of the conjugated polymer compound, baking at a temperature of 160 ° C. or higher is also possible.

  Examples of thin films that can be produced using the solution of the present invention include luminescent thin films, conductive thin films, and organic semiconductor thin films.

  In the luminescent thin film of the present invention, the quantum yield of light emission is preferably 50% or more, more preferably 60% or more, and 70% or more from the viewpoint of the brightness of the device, light emission voltage, and the like. Is more preferable.

  The conductive thin film of the present invention preferably has a surface resistance of 1 KΩ / □ or less. The electrical conductivity can be increased by doping the thin film with a Lewis acid, an ionic compound, or the like. The surface resistance is more preferably 100Ω / □ or less, and further preferably 10Ω / □.

In the organic semiconductor thin film of the present invention, the higher one of the electron mobility and the hole mobility is preferably 10 ⁻⁵ cm ² / V / second or more. More preferably, it is 10 ^<-3 > cm < ² > / V / second or more, More preferably, it is 10 ^<-1 > cm < ² > / V / second or more.
An organic transistor can be formed by forming the organic semiconductor thin film on a Si substrate on which an insulating film such as SiO2 and a gate electrode are formed, and forming a source electrode and a drain electrode with Au or the like.

  The polymer light-emitting device of the present invention preferably has a maximum external quantum yield of 1% or more when a voltage of 3.5 V or more is applied between the anode and the cathode from the viewpoint of device brightness and the like. More preferably 5% or more.

  The polymer light-emitting device of the present invention (hereinafter referred to as polymer LED) is a polymer LED in which an electron transport layer is provided between the cathode and the light-emitting layer, and hole transport between the anode and the light-emitting layer. Examples include a polymer LED provided with a layer, a polymer LED provided with an electron transport layer between a cathode and a light-emitting layer, and a hole transport layer provided between an anode and a light-emitting layer.

For example, the following structures a) to d) are specifically exemplified.
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 (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)

The polymer LED of the present invention includes those in which the conjugated polymer compound of the present invention is contained in a hole transport layer and / or an electron transport layer.
When the conjugated polymer compound of the present invention is used for a hole transport layer, the conjugated polymer compound of the present invention is preferably a conjugated polymer compound containing a hole transporting group, and specific examples thereof include: Examples thereof include a copolymer with an aromatic amine and a copolymer with stilbene.
Further, when the conjugated polymer compound of the present invention is used for an electron transport layer, the conjugated polymer compound of the present invention is preferably a conjugated polymer compound containing an electron transporting group, and specific examples thereof include: Examples thereof include a copolymer with oxadiazole, a copolymer with triazole, a copolymer with quinoline, a copolymer with quinoxaline, and a copolymer with benzothiadiazole.

  When the polymer LED of the present invention has a hole transport layer, the hole transport material used is polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, polysiloxane having an aromatic amine in a side chain or a main chain. Derivatives, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5- Thienylene vinylene) or a derivative thereof.

  Specifically, as the hole transporting material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2-209988 are disclosed. Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

  Among these, as a hole transporting material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, a polyaniline or a derivative thereof , Polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or a polymer hole transporting material such as poly (2,5-thienylene vinylene) or a derivative thereof is preferable, and polyvinyl carbazole or a derivative thereof is more preferable Derivatives, polysilanes or derivatives thereof, and polysiloxane derivatives having an aromatic amine in the side chain or main chain.

Examples of the hole transport material of the low molecular weight compound include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and triphenyldiamine derivatives. In the case of a low molecular weight hole transporting material, it is preferably used by being dispersed in a polymer binder.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used. As the polymer binder, poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, poly (2,5-thienylenevinylene) or a derivative thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  Polyvinylcarbazole or a derivative thereof is obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

  Examples of polysilane or derivatives thereof include compounds described in Chem. Rev. 89, 1359 (1989) and GB 2300196 published specification. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

  Since polysiloxane or a derivative thereof has almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular hole transporting material in the side chain or main chain are preferably used. Particularly, those having a hole transporting aromatic amine in the side chain or main chain are exemplified.

  Although there is no restriction | limiting in the film-forming method of a positive hole transport layer, The method by the film-forming from a mixed solution with a polymer binder is illustrated with a low molecular hole transport material. In the case of a polymer hole transporting material, a method by film formation from a solution is exemplified.

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing a hole transporting material is preferable. Chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and aromatic solvents such as toluene and xylene. Hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane Polyhydric alcohols such as propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, dimethyl sulfoxide, etc. And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination.

  Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  The film thickness of the hole transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If it is too thick, the driving voltage of the element becomes high, which is not preferable. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the polymer LED of the present invention has an electron transport layer, known materials can be used as the electron transport material used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or Derivatives thereof, anthraquinone or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline Alternatively, derivatives thereof, polyfluorene or derivatives thereof, and the like are exemplified.

  Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, The thing etc. which are described in the same 3-152184 gazette are illustrated.

  Of these, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  There are no particular restrictions on the method of forming the electron transport layer, but for low molecular weight electron transport materials, vacuum deposition from powder, or by film formation from a solution or molten state, solution for polymer electron transport materials is possible. Or the method by the film-forming from a molten state is illustrated, respectively. When forming a film from a solution or a molten state, the above polymer binder may be used in combination.

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing an electron transport material and / or a polymer binder is preferable. Chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and aromatic solvents such as toluene and xylene. Hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane Polyhydric alcohols such as propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, dimethyl sulfoxide, etc. And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination.

  Examples of film formation methods from a solution or a molten state include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  The conjugated polymer compound of the present invention can also be used as a polymer field effect transistor. As a structure of a polymer field effect transistor, a source electrode and a drain electrode are usually provided in contact with an active layer made of a polymer, and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween. Just do it.

  The polymer field effect transistor is usually formed on a supporting substrate. The material of the supporting substrate is not particularly limited as long as the characteristics as a field effect transistor are not impaired, but a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

  The field effect transistor can be manufactured by a known method, for example, a method described in JP-A-5-110069.

  In forming the active layer, it is very advantageous and preferable to use an organic solvent-soluble polymer. As a film forming method from a solution in which a polymer is dissolved in an organic solvent, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, Coating methods such as spray coating, screen printing, flexographic printing, offset printing, and inkjet printing can be used.

A sealed polymer field effect transistor obtained by sealing a polymer field effect transistor after forming the polymer field effect transistor is preferable. Thereby, the polymer field effect transistor is shielded from the atmosphere, and the deterioration of the characteristics of the polymer field transistor can be suppressed.
Examples of the sealing method include a method of covering with a UV curable resin, a thermosetting resin or an inorganic SiONx film, and a method of bonding a glass plate or film with a UV curable resin or a thermosetting resin. In order to effectively shut off from the atmosphere, it is preferable to perform the steps from the preparation of the polymer field-effect transistor to the sealing without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

  The film thickness of the electron transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  Further, among the charge transport layers provided adjacent to the electrodes, those having a function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers). , An electron injection layer).

Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be improved. In order to prevent mixing, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.
The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

In the present invention, a polymer LED provided with a charge injection layer (electron injection layer, hole injection layer) includes a polymer LED provided with a charge injection layer adjacent to the cathode, and a charge injection layer adjacent to the anode. The provided polymer LED is mentioned.
For example, the following structures e) to p) are specifically mentioned.
e) Anode / hole injection layer / light emitting layer / cathode f) Anode / light emitting layer / electron injection layer / cathode g) Anode / hole injection layer / light emitting layer / electron injection layer / cathode h) Anode / hole injection layer / Hole transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / electron injection layer / cathode j) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode k ) Anode / hole injection layer / light emitting layer / electron transport layer / cathode l) Anode / light emitting layer / electron transport layer / electron injection layer / cathode m) Anode / hole injection layer / light emitting layer / electron transport layer / electron injection Layer / cathode n) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode p) anode / Hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

As described above, the polymer LED of the present invention includes those in which the conjugated polymer compound of the present invention is contained in a hole transport layer and / or an electron transport layer.
The polymer LED of the present invention includes those in which the conjugated polymer compound of the present invention is contained in a hole injection layer and / or an electron injection layer. When the conjugated polymer compound of the present invention is used for a hole injection layer, it is preferably used simultaneously with an electron accepting compound. In addition, when the conjugated polymer compound of the present invention is used in an electron transport layer, it is preferably used simultaneously with an electron donating compound. Here, for simultaneous use, there are methods such as mixing, copolymerization and introduction as a side chain.

  Specific examples of the charge injection layer include a layer containing a conductive polymer, an intermediate between the anode material and the hole transporting material included in the hole transporting layer, provided between the anode and the hole transporting layer. A layer containing a material having an ionization potential of the value, 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 or more and 10 ³ or less, and the leakage current between the light emitting pixels is reduced. In order to achieve this, 10 ⁻⁵ S / cm to 10 ² is more preferable, and 10 ⁻⁵ S / cm to 10 ¹ is more preferable.

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 or more and 10 ³ S / cm or less. in order to reduce the current, more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably less 10 ^-5 S / cm or more and 10 ¹ S / cm.
Usually, in order to make the electric conductivity of the conductive polymer 10 ⁻⁵ S / cm or more and 10 ³ or less, the conductive polymer is doped with an appropriate amount of ions.

The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions, and the like.
The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

  The material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer. Polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene And derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanines (such as copper phthalocyanine), and carbon .

  An insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. As the polymer LED provided with the insulating layer having a thickness of 2 nm or less, the polymer LED provided with the insulating layer having a thickness of 2 nm or less adjacent to the cathode, or the insulating layer having a thickness of 2 nm or less provided adjacent to the anode. Polymer LED is mentioned.

Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode u) Anode / hole transporting layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode w) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode x) anode / Light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode y) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode z) anode / film Insulating layer / hole transport layer / light-emitting layer / light-emitting layer / electron transport layer / cathode aa) anode / hole transport layer / light-emitting layer / electron transport Layer / insulating layer with a film thickness of 2 nm or less / cathode ab) anode / insulating layer with a film thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / insulating layer with a film thickness of 2 nm or less / cathode Includes the polymer compound of the present invention in any of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer in the element structures exemplified in the above a) to ab). Things can be raised.

  The substrate on which the polymer LED of the present invention is formed may be any substrate that does not change when the electrode is formed and the organic layer is formed, and examples thereof include glass, plastic, polymer film, and silicon substrate. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

Usually, at least one of the anode and the cathode of the polymer LED of the present invention is transparent or translucent. The anode side is preferably 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 film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Further, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.
The film thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there.
Further, in order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

As a material of the cathode used in the polymer LED of the present invention, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and their Two or more of these alloys, or an alloy of one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. Is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The cathode may have a laminated structure of two or more layers.
The thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  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. Further, 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 having an average film thickness of 2 nm or less may be provided between the cathode and the organic material layer. A protective layer for protecting the polymer LED may be attached. In order to use the polymer LED stably for a long period of time, it is preferable to attach a protective layer and / or protective cover in order to protect the element from the outside.

  As the protective layer, conjugated polymer compounds, metal oxides, metal fluorides, metal borides and the like can be used. Further, 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 cover by bonding it to the element substrate with a heat effect resin or a photo-curing resin is preferable. Used for. 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, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It is easy to suppress damage to the element. Among these, it is preferable to take any one or more measures.

The polymer LED of the present invention can be used as a backlight for a planar light source, a segment display device, a dot matrix display device, and a liquid crystal display device.
In order to obtain planar light emission using the polymer LED of the present invention, 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 of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic material layer of a non-light-emitting portion is formed extremely thick and substantially non- There are a method of emitting light and a method of forming either one of the anode or the cathode or both electrodes in a pattern. A segment type display element capable of displaying numbers, letters, simple symbols, etc. can be obtained by forming a pattern by any of these methods and arranging several electrodes so that they can be turned ON / OFF independently. Further, in order to obtain a dot matrix element, 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 multi-color display are possible by a method of separately coating a plurality of types of polymeric fluorescent substances having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively or may be driven actively in combination with TFTs. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

  Furthermore, the planar light-emitting element is a self-luminous thin type, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
(Number average molecular weight and weight average molecular weight)
Here, regarding the number average molecular weight and the weight average molecular weight, the polystyrene-equivalent number average molecular weight and weight average molecular weight were determined by GPC (manufactured by Shimadzu Corporation: LC-10Avp). The polymer to be measured was dissolved in tetrahydrofuran to a concentration of about 0.5 wt%, and 50 μL was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As for 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: RID-10A) was used as the detector.

(Fluorescence spectrum)
The fluorescence spectrum was measured by the following method. A polymer thin film was prepared by spin-coating a 0.8 wt% toluene or chloroform solution of the polymer on quartz. This thin film was excited at a wavelength of 350 nm, and the fluorescence spectrum was measured using a fluorescence spectrophotometer (Fluorolog manufactured by Horiba, Ltd.). In order to obtain the relative fluorescence intensity in the thin film, the intensity of the Raman line of water is used as a standard, the fluorescence spectrum plotted with wavenumber is integrated in the spectrum measurement range, and measured using a spectrophotometer (Varian Cary 5E). The value assigned by the absorbance at the excitation wavelength was determined.

(Glass-transition temperature)
The glass transition temperature was determined by DSC (DSC2920, manufactured by TA Instruments).

(Measurement of LUMO)
The LUMO of the conjugated conjugated polymer compound was measured using cyclic voltammetry (manufactured by BAS: ALS600) in an acetonitrile solvent containing 0.1 wt% tetrabutylammonium tetrafluoroborate. After the conjugated conjugated polymer compound is dissolved in chloroform so that the concentration is about 0.2 wt%, 1 mL of a chloroform solution of the conjugated conjugated polymer compound is applied on the working electrode, and the conjugated conjugated polymer compound is vaporized by vaporizing chloroform. Formed. The measurement was carried out in a glove box in which a silver / silver ion electrode was used as a reference electrode, a glassy carbon electrode as a working electrode, and a platinum electrode as a counter electrode, and was replaced with nitrogen. The potential sweep rate was both measured at 50 mV / s. LUMO was calculated from the reduction potential obtained from cyclic voltammetry.

化合物１
アルゴンガスで置換した１０Ｌセパラブルフラスコにブロモ安息香酸メチル６１９ｇ、炭酸カリウム９０４ｇ、1-ナフチルボロン酸４５０ｇを加え、トルエン３６００ｍｌおよび水４０００ｍｌを加えて攪拌する。テトラキストリフェニルホスフィンパラジウム(0)３０ｇを加えてから加熱還流し、そのまま３時間攪拌した。室温まで冷却後分液し、水２０００ｍｌで洗浄した。溶媒を留去したのち、トルエンを用いてシリカゲルカラム精製を行った。得られたクルドを濃縮しヘキサン７７４ｍｌで２回洗浄し、乾燥することにより化合物１を５９６．９ｇ白色固体として得た。
Synthesis example 1
(Synthesis of Compound 1)

Compound 1
To a 10 L separable flask substituted with argon gas, 619 g of methyl bromobenzoate, 904 g of potassium carbonate, and 450 g of 1-naphthylboronic acid are added, and 3600 ml of toluene and 4000 ml of water are added and stirred. After adding 30 g of tetrakistriphenylphosphine palladium (0), the mixture was heated to reflux and stirred for 3 hours. After cooling to room temperature, the solution was separated and washed with 2000 ml of water. After the solvent was distilled off, silica gel column purification was performed using toluene. The obtained kurd was concentrated, washed twice with 774 ml of hexane, and dried to obtain 596.9 g of Compound 1 as a white solid.

化合物２
３Lの３口フラスコに4-t-ブチルフェニルブロミド １１３g、テトラヒドロフラン１５００ｍｌを加え窒素雰囲気下で−７８℃まで冷却する。ｎ-ブチルリチウムを滴下漏斗に６００mlとり系内の温度が変化しないようにゆっくりと滴下する。滴下後室温で２時間攪拌したのち、−78℃に冷却し化合物１３４．６ｇをテトラヒドロフラン５００ｍｌに溶解した溶液を６０分かけて滴下した。さらに−７８℃で２時間攪拌した後、飽和塩化アンモニウム水溶液を５００ｍｌ用いて反応を停止し、トルエン１０００ｍｌで抽出した。水で洗浄後、シリカゲルショートカラムを通して不純物を取り除き、化合物２を６１．５g得た。 (Synthesis of Compound 2)

Compound 2
Add 113 g of 4-t-butylphenyl bromide and 1500 ml of tetrahydrofuran to a 3 L three-necked flask and cool to −78 ° C. under a nitrogen atmosphere. Add 600 ml of n-butyllithium to the dropping funnel and slowly drop it so that the temperature in the system does not change. After the dropwise addition, the mixture was stirred at room temperature for 2 hours, cooled to -78 ° C, and a solution of 134.6 g of the compound dissolved in 500 ml of tetrahydrofuran was added dropwise over 60 minutes. After further stirring at −78 ° C. for 2 hours, the reaction was stopped with 500 ml of saturated aqueous ammonium chloride solution, and extracted with 1000 ml of toluene. After washing with water, impurities were removed through a silica gel short column to obtain 61.5 g of Compound 2.

化合物３
三フッ化ホウ素エーテル錯体３２５ｍＬを入れた２０００ｍｌの三口フラスコに、ジクロロメタンを１５００ml加え、氷浴で十分に冷却した。化合物２を１３２ｇをジクロロメタン溶液とし、等圧でない滴下漏斗を用いて1時間かけて滴下した。氷浴をはずし、室温で２時間攪拌した後、水を加えて反応を停止した。クロロホルムを用いて抽出し、有機層を濃縮後、橙色の油状物を得た。トルエン２４０ml、2-プロパノール５０mlを用いて再結晶することにより目的とする化合物３を36.2ｇ得た。
(Synthesis of Compound 3)

Compound 3
To a 2000 ml three-necked flask containing 325 ml of boron trifluoride ether complex, 1500 ml of dichloromethane was added and sufficiently cooled in an ice bath. 132 g of Compound 2 was made into a dichloromethane solution and added dropwise over 1 hour using a dropping funnel that was not isobaric. After removing the ice bath and stirring at room temperature for 2 hours, water was added to stop the reaction. Extraction was performed using chloroform, and the organic layer was concentrated to obtain an orange oil. By recrystallization using 240 ml of toluene and 50 ml of 2-propanol, 36.2 g of the target compound 3 was obtained.

化合物４
窒素雰囲気下、１０００ｍｌ3口フラスコに閉環体３を２０ｇ(純度99.6%)を仕込み、ジクロロメタン100ｍｌを加えて溶解し、酢酸を259ｍｌ加えて油浴中50℃に加熱した。加熱しながら塩化亜鉛11.2ｇを加えて攪拌し、ベンジルトリメチルアンモニウムトリブロミド35.4ｇをジクロロメタン150ｍｌに溶かした溶液を加熱還流しながら60分かけて加えた。さらに1時間50℃で攪拌し、室温まで冷却した後、水200ｍｌを加えて反応を停止した。分液し、水層はクロロホルム300ｍｌで抽出し、有機層を合一した。有機層は飽和チオ硫酸ナトリウム水溶液300ｍｌで洗浄後、飽和炭酸水素ナトリウム水溶液500ｍｌ、水200ｍｌで洗浄した。得られた有機層はプレコートしたシリカゲルを通してろ過した。溶媒を留去し、得られた混合物をヘキサンより再結晶し、目的化合物４を白色の固体として17.2g得た。
<分析>
¹H-NMR（300MHz／CDCl₃）：δ1.27 (s, 18H), 6.79(dd, 2H), 7.15-7.23 (m, 3H), 7.48 (ddd, 1H), 7.54 (td, 1H), 7.81 (dd, 1H), 7.86 (d, 1H), 7.88 (d, 1H), 8.16 (dt, 1H).
LC/MS(APPI(pos))： m/z calcd for [C₃₇H₃₄Br₂]^+・, 638.47; found, 638.0. Example 1
(Synthesis of Compound 4)

Compound 4
Under a nitrogen atmosphere, 20 g (purity 99.6%) of Ring Closure 3 was charged in a 1000 ml three-necked flask, dissolved by adding 100 ml of dichloromethane, added with 259 ml of acetic acid, and heated to 50 ° C. in an oil bath. While heating, 11.2 g of zinc chloride was added and stirred, and a solution of 35.4 g of benzyltrimethylammonium tribromide in 150 ml of dichloromethane was added over 60 minutes while heating to reflux. The mixture was further stirred for 1 hour at 50 ° C., cooled to room temperature, and then 200 ml of water was added to stop the reaction. The aqueous layer was extracted with 300 ml of chloroform, and the organic layers were combined. The organic layer was washed with 300 ml of a saturated aqueous sodium thiosulfate solution, and then washed with 500 ml of a saturated aqueous sodium bicarbonate solution and 200 ml of water. The resulting organic layer was filtered through precoated silica gel. The solvent was distilled off, and the resulting mixture was recrystallized from hexane to obtain 17.2 g of the objective compound 4 as a white solid.
<Analysis>
¹ H-NMR (300 MHz / CDCl ₃ ): δ 1.27 (s, 18H), 6.79 (dd, 2H), 7.15-7.23 (m, 3H), 7.48 (ddd, 1H), 7.54 (td, 1H), 7.81 (dd, 1H), 7.86 (d, 1H), 7.88 (d, 1H), 8.16 (dt, 1H).
LC / MS (APPI (pos)): m / z calcd for [C ₃₇ H ₃₄ Br ₂ ] ⁺ , 638.47; found, 638.0.

化合物５
不活性雰囲気下で、５００ｍｌの３つ口フラスコに酢酸２２５ｇを入れ、５−ｔ−ブチル−ｍ−キシレン２４．３ｇを加えた。続いて臭素３１．２ｇを加えた後、１５〜２０℃で３時間反応させた。
反応液を水５００ｍｌに加え析出した沈殿をろ過した。水２５０ｍｌで２回洗浄し、化合物５を白色の固体３４．２ｇを得た。 Synthesis example 2
(Synthesis of 1-bromo-4-t-butyl-2,6-dimethylbenzene)

Compound 5
Under an inert atmosphere, 225 g of acetic acid was placed in a 500 ml three-necked flask, and 24.3 g of 5-t-butyl-m-xylene was added. Then, after adding 31.2 g of bromine, it was made to react at 15-20 degreeC for 3 hours.
The reaction solution was added to 500 ml of water, and the deposited precipitate was filtered. This was washed twice with 250 ml of water to obtain 34.2 g of compound 5 as a white solid.

化合物６
不活性雰囲気下で、３００ｍｌの３つ口フラスコに脱気した脱水トルエン１６６０ｍｌを入れ、Ｎ，Ｎ’−ジフェニルベンジジン２７５．０ｇ、４−ｔ−ブチル−２，６−ジメチルブロモベンゼン４４９．０ｇを加えた。続いてトリス（ジベンジリデンアセトン）ジパラジウム７．４８ｇ、ｔ−ブトキシナトリウム１９６．４ｇ、を加えた後、トリ（ｔ−ブチル）ホスフィン５．０ｇを加えた。その後、１０５℃で７時間反応させた。
反応液にトルエン２０００ｍｌを加え、セライト濾過し、濾液を水１０００ｍｌで３回洗浄した後、７００ｍｌまで濃縮した。これにトルエン／メタノール（１：１）溶液１６００ｍｌを加え、析出した結晶を濾過し、メタノールで洗浄した。白色の固体４７９．４ｇを得た。
(Synthesis of Compound 6)

Compound 6
In an inert atmosphere, 1660 ml of degassed toluene was put into a 300 ml three-necked flask, and 275.0 g of N, N′-diphenylbenzidine and 449.0 g of 4-t-butyl-2,6-dimethylbromobenzene were added. added. Subsequently, 7.48 g of tris (dibenzylideneacetone) dipalladium and 196.4 g of sodium t-butoxy were added, and 5.0 g of tri (t-butyl) phosphine was added. Then, it was made to react at 105 degreeC for 7 hours.
Toluene (2000 ml) was added to the reaction mixture, and the mixture was filtered through Celite. The filtrate was washed with 1000 ml of water three times and then concentrated to 700 ml. To this was added 1600 ml of a toluene / methanol (1: 1) solution, and the precipitated crystals were filtered and washed with methanol. 479.4 g of a white solid was obtained.

化合物７
不活性雰囲気下で、クロロホルム４７３０ｇに、上記Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（４−ｔ‐ブチル−２，６−ジメチルフェニル）−ベンジジン４７２．８ｇを溶解した後、遮光および氷浴下でＮ−ブロモスクシンイミド２８１．８ｇを１２分割で１時間かけて仕込み、３時間反応させた。
クロロホルム１４３９ｍｌを反応液に加え、濾過し、濾液のクロロホルム溶液を５％チオ硫酸ナトリウム２１５９ｍｌで洗浄し、トルエンを溶媒留去して白色結晶を得た。得られた白色結晶をトルエン／エタノールで再結晶し、白色結晶６７８．７ｇを得た。
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ８１５．２ (Synthesis of Compound 7)

Compound 7
In an inert atmosphere, 472.8 g of N, N′-diphenyl-N, N′-bis (4-t-butyl-2,6-dimethylphenyl) -benzidine was dissolved in 4730 g of chloroform, In an ice bath, 281.8 g of N-bromosuccinimide was charged in 12 portions over 1 hour and reacted for 3 hours.
Chloroform 1439 ml was added to the reaction solution, followed by filtration. The chloroform solution of the filtrate was washed with 2159 ml of 5% sodium thiosulfate, and toluene was distilled off to obtain white crystals. The obtained white crystals were recrystallized with toluene / ethanol to obtain 678.7 g of white crystals.
MS (APCI (+)): (M + H) ^<+ > 815.2

Example 2 <Synthesis of Polymer Compound 1>
Compound 4 (1.92 g) and 2,2′-bipyridyl (1.27 g) were dissolved in 216 mL of dehydrated tetrahydrofuran, and then bubbled with nitrogen to purge the system with nitrogen. In a nitrogen atmosphere, this solution was heated to 60 ° C., bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (2.23 g) was added, and the mixture was stirred at 60 ° C. for 3 hours. Reacted for hours. The reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 11 mL / methanol 216 mL / ion exchanged water 216 mL and stirred for 1 hour, and then the deposited precipitate was filtered and reduced in pressure for 2 hours. The solution was dried and then dissolved in about 100 mL of toluene, followed by filtration. The filtrate was purified through an alumina column, added with about 200 ml of 5.2% hydrochloric acid and stirred for 3 hours, and then the aqueous layer was removed. Next, about 200 mL of 4% aqueous ammonia was added and stirred for 2 hours, and then the aqueous layer was removed. Further, about 200 mL of ion-exchanged water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. The organic layer was dropped into about 600 mL of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained copolymer (hereinafter referred to as polymer compound 1) was 0.080 g. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 6.5 × 10 ⁴ and Mw = 3.0 × 10 ⁵ , respectively.

Example 3 <Synthesis of Polymer Compound 2>
Compound 4 (0.89 g), N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) -benzidine (0.49 g) (compound 7) and 2,2′-bipyridyl (0.84 g) were dissolved in 144 mL of dehydrated tetrahydrofuran, and the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, the temperature of the solution was raised to 60 ° C., bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (1.49 g) was added, and the mixture was stirred at 60 ° C. for 3 hours. Reacted for hours. The reaction solution was cooled to room temperature (about 25 ° C.) and dropped into a mixed solution of 25% aqueous ammonia 7 mL / methanol 144 mL / ion exchanged water 144 mL and stirred for 1 hour, and then the deposited precipitate was filtered and decompressed for 2 hours. The solution was dried and then dissolved in about 60 mL of toluene, followed by filtration. The filtrate was purified through an alumina column, added with about 120 ml of 5.2% hydrochloric acid and stirred for 3 hours, and then the aqueous layer was removed. Then, about 120 mL of 4% aqueous ammonia was added and stirred for 2 hours, and then the aqueous layer was removed. Further, about 120 mL of ion-exchanged water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. The organic layer was dropped into about 400 mL of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained copolymer (hereinafter referred to as polymer compound 2) was 0.420 g. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 2.0 × 10 ⁴ and Mw = 1.5 × 10 ⁵ , respectively.

Synthesis Example 4 (Synthesis of polymer compound 3)
2,7-dibromo-9,9-dioctylfluorene (287 mg, 0.523 mmol), 2,7- (9,9-dioctyl) fluorenediboronic acid ethylene glycol cyclic ester (305 mg, 0. 0) under inert atmosphere. 575 mmol), aliquot 336 (15 mg) was dissolved in toluene (4.3 g), and potassium carbonate (231 mg, 1.67 mmol) was added to this as an approximately 1 g aqueous solution. Further, tetrakis (triphenylphosphine) palladium (0.39 mg, 0.00034 mmol) was added, and the mixture was heated to reflux for 20 hours. Subsequently, bromobenzene (11.5 mg) was added, and the mixture was further heated to reflux for 5 hours. After completion of the heating, the reaction mass was added dropwise to a mixed solution of methanol (40 ml) and 1N aqueous hydrochloric acid (2.2 ml), and the deposited precipitate was separated by filtration. The resulting precipitate was washed with methanol and water and dried under reduced pressure to obtain a solid. Subsequently, the solid was dissolved in 50 ml of toluene, passed through a silica column, and concentrated to 20 ml. The concentrated solution was added dropwise to methanol, and the deposited precipitate was filtered off and dried under reduced pressure to obtain polymer compound 3. Yield 340 mg.
The obtained polymer compound 3 had a molecular weight in terms of polystyrene of Mn = 1.2 × 10 ³ and Mw = 3.2 × 10 ³ .

Example 4 (Measurement of fluorescence spectrum)
When the fluorescence spectrum of the polymer compound 1 was measured by the method described above, a fluorescence spectrum having a peak at 470 nm was obtained.

Example 5 (Measurement of fluorescence spectrum)
When the fluorescence spectrum of the polymer compound 2 was measured by the above-described method, a fluorescence spectrum having a peak at 478 nm was obtained.

Example 6 (Evaluation of electron injection property)
When the LUMO value of the polymer compound 1 was measured under the above-mentioned conditions, it was 2.93 eV.

Example 7 (Electron injection property evaluation)
When the LUMO value of the polymer compound 2 was measured under the above-mentioned conditions, it was 2.92 eV.

Comparative Example 1
When the LUMO value of the polymer compound 3 was measured under the above-mentioned conditions, it was 2.44 eV.

It can be seen that the polymer compounds 1, 2, 4, and 5 all exhibit excellent electron injection properties.

化合物７−２
三口の丸底フラスコ（５００ｍｌ）に２−ブロモヨードベンゼン２５．１ｇ、ナフタレンボロン酸２０．０ｇ、テトラキストリフェニルホスフィンパラジウム（０）０．４２７ｇおよび炭酸カリウム２５．５ｇを加えた後、トルエン９２ｍｌ、水９１ｍｌを加え加熱還流した。２４時間攪拌した後、室温まで冷却した。反応溶液をシリカゲルを通してろ過し、溶媒を留去し組成生物２５ｇを得た。シリカゲルカラムクロマトグラフィーにて精製した後、ヘキサンを用いて再結晶を行い、化合物７−２を白色固体として１２．２ｇ得た。
Synthesis example 5
(Synthesis of Compound 7-2)

Compound 7-2
After adding 25.1 g of 2-bromoiodobenzene, 20.0 g of naphthaleneboronic acid, 0.427 g of tetrakistriphenylphosphine palladium (0) and 25.5 g of potassium carbonate to a three-necked round bottom flask (500 ml), 92 ml of toluene, 91 ml of water was added and heated to reflux. After stirring for 24 hours, it was cooled to room temperature. The reaction solution was filtered through silica gel, and the solvent was distilled off to obtain 25 g of a composition product. After purification by silica gel column chromatography, recrystallization was performed using hexane to obtain 12.2 g of compound 7-2 as a white solid.

化合物８
窒素雰囲気下、３口フラスコ（２００ｍｌ）に化合物７−２（７．３ｇ）を仕込み、テトラヒドロフラン７３ｍｌを加えて溶解した。−７８℃に冷却した後、n-ブチルリチウム１８．１４ｍｌを加えた。３０分攪拌後、プロピルシクロヘキサノンを６．３８ｍLのＴＨＦに溶かして加えた。室温まで昇温した後、飽和塩化アンモニウム水溶液を５０ｍｌ加えて反応を停止し、ＴＨＦ１００ｍｌで抽出した。得られた有機層をプレコートしたシリカゲルを通し、濃縮した。シリカゲルカラムクロマトグラフィーにて精製し、化合物８を７．５ｇ得た。
＜分析＞
¹H-NMR（300MHz／CDCl₃）
δ0.86-0.94 (m, 3H), 1.28-1.90 (m, 17H), 1.95-2.10 (m, 1H), 2.15-2.35 (m, 1H), 7.10 (d, 1H), 7.26-7.51 (m, 7H), 7.61 (dd, 1H), 7.86 (t, 1H), 7.86 (t, 1H).
LC-MS（APPI-posi）：m/z calcd. for [C28H34O], 386.57, found for [C28H34O]+・, 387.2
(Synthesis of Compound 8)

Compound 8
In a nitrogen atmosphere, compound 7-2 (7.3 g) was charged into a three-necked flask (200 ml), and 73 ml of tetrahydrofuran was added and dissolved. After cooling to −78 ° C., 18.14 ml of n-butyllithium was added. After stirring for 30 minutes, propylcyclohexanone was dissolved in 6.38 mL of THF and added. After raising the temperature to room temperature, 50 ml of a saturated aqueous ammonium chloride solution was added to stop the reaction, and the mixture was extracted with 100 ml of THF. The obtained organic layer was passed through precoated silica gel and concentrated. Purification by silica gel column chromatography gave 7.5 g of compound 8.
<Analysis>
¹ H-NMR (300 MHz / CDCl ₃ )
δ0.86-0.94 (m, 3H), 1.28-1.90 (m, 17H), 1.95-2.10 (m, 1H), 2.15-2.35 (m, 1H), 7.10 (d, 1H), 7.26-7.51 (m , 7H), 7.61 (dd, 1H), 7.86 (t, 1H), 7.86 (t, 1H).
LC-MS (APPI-posi): m / z calcd. For [C28H34O], 386.57, found for [C28H34O] +, 387.2

化合物９
窒素雰囲気下、１００ｍｌ2口フラスコにBF3Et2Oを１２．５ｇ、ジクロロメタン４０ｍｌを仕込み、水浴で冷却した。化合物８をジクロロメタン１５ｍｌにとかして滴下し、30分撹拌した。水５０ｍLを加えて反応を停止し、クロロホルム５０ｍLで二回抽出した。得られた溶液を濃縮し、シリカゲルカラムクロマトグラフィーにて精製し、化合物９を２g得た。
＜分析＞
¹H-NMR（300MHz／CDCl₃）
δ0.80 (t, 3H), 1.09-1.26 (m, 10H), 1.31-1.45 (m, 4H), 1.63-1.78 (m, 1H), 1.84 (q, 1H), 2.05 (m, 1H), 2.54 (m, 1H), 2.84 (t, 1H), 7.23-7.35 (m, 3H), 7.42-7.53 (m, 2H), 7.56 (d, 1H), 7.77 (d, 1H), 7.85 (t, 1H, 7.91 (d, 1H), 8.54-8.57 (m, 1H). (Synthesis of Compound 9)

Compound 9
Under a nitrogen atmosphere, 12.5 g of BF3Et2O and 40 ml of dichloromethane were charged into a 100 ml two-necked flask and cooled in a water bath. Compound 8 was added dropwise in 15 ml of dichloromethane and stirred for 30 minutes. The reaction was stopped by adding 50 mL of water, and extracted twice with 50 mL of chloroform. The resulting solution was concentrated and purified by silica gel column chromatography to obtain 2 g of compound 9.
<Analysis>
¹ H-NMR (300 MHz / CDCl ₃ )
δ0.80 (t, 3H), 1.09-1.26 (m, 10H), 1.31-1.45 (m, 4H), 1.63-1.78 (m, 1H), 1.84 (q, 1H), 2.05 (m, 1H), 2.54 (m, 1H), 2.84 (t, 1H), 7.23-7.35 (m, 3H), 7.42-7.53 (m, 2H), 7.56 (d, 1H), 7.77 (d, 1H), 7.85 (t, 1H, 7.91 (d, 1H), 8.54-8.57 (m, 1H).

（化合物１０の合成）
化合物１０
窒素雰囲気下、１００ｍｌ３口フラスコに化合物９を仕込み、ジクロロメタン３３ｍ、酢酸３３ｍｌを加えて50℃に加熱した。加熱下、塩化亜鉛を仕込み、ベンジルトリメチルアンモニウムトリブロミド４．４５ｇをジクロロメタン３３ｍｌに溶かして溶液とし、加熱還流しながら滴下した。３０分攪拌後、室温まで放冷し、水を加えて反応を停止し、クロロホルムを用いて抽出した。得られた有機層は飽和チオ硫酸ナトリウム水溶液５０ｍｌで2回洗浄し、さらに飽和炭酸水素ナトリウム水溶液１００ｍｌ、水５０ｍｌで洗浄した。有機溶媒を濃縮した。シリカゲルカラムクロマトグラフィーにて精製した後、再結晶を行い、化合物１０を１ｇ得た。
＜分析＞
¹H-NMR（300MHz／CDCl₃）
δ0.83 (t, 3H), 1.0-1.24 (m, 11H), 1.3-1.53 (m, 3H), 1.6-1.77 (m, 1H), 1.8-1.94 (m, 1H), 2.0-2.12 (m, 1H), 2.4-2.54 (dd, 1H), 2.56-2.85 (t, 1H), 7.43-7.47 (m, 1H), 7.50 (s, 1H), 7.50-7.61 (m, 2H), 7.70 (d, 1H), 7.83 (s, 1H), 8.29 (d, 1H), 8.43 (d, 1H).再測定中
LC-MS（APPI-posi）：m/z calcd for [C28H30Br2], 526.35; found for [C28H30Br2]+・, 524. Example 8

(Synthesis of Compound 10)
Compound 10
Under a nitrogen atmosphere, Compound 9 was charged into a 100 ml three-necked flask, and 33 m of dichloromethane and 33 ml of acetic acid were added and heated to 50 ° C. Zinc chloride was charged under heating, and 4.45 g of benzyltrimethylammonium tribromide was dissolved in 33 ml of dichloromethane to form a solution, which was added dropwise while heating under reflux. After stirring for 30 minutes, the mixture was allowed to cool to room temperature, water was added to stop the reaction, and the mixture was extracted with chloroform. The obtained organic layer was washed twice with 50 ml of a saturated aqueous sodium thiosulfate solution, and further washed with 100 ml of a saturated aqueous sodium bicarbonate solution and 50 ml of water. The organic solvent was concentrated. After purification by silica gel column chromatography, recrystallization was performed to obtain 1 g of compound 10.
<Analysis>
¹ H-NMR (300 MHz / CDCl ₃ )
δ0.83 (t, 3H), 1.0-1.24 (m, 11H), 1.3-1.53 (m, 3H), 1.6-1.77 (m, 1H), 1.8-1.94 (m, 1H), 2.0-2.12 (m , 1H), 2.4-2.54 (dd, 1H), 2.56-2.85 (t, 1H), 7.43-7.47 (m, 1H), 7.50 (s, 1H), 7.50-7.61 (m, 2H), 7.70 (d , 1H), 7.83 (s, 1H), 8.29 (d, 1H), 8.43 (d, 1H).
LC-MS (APPI-posi): m / z calcd for [C28H30Br2], 526.35; found for [C28H30Br2] + ・, 524.

Example 9 (Synthesis of Polymer Compound 4)
A reaction vessel (200 mL) was charged with 0.316 g of compound 10 and 2,2'-bipyridyl (0.159 g) in a nitrogen atmosphere, and then tetrahydrofuran (43 mL) was added to form a solution to obtain bis (1,5-cyclooctadiene. ) Nickel (0) {Ni (COD) ₂ } 0.281 g was charged. The temperature was raised to 60 ° C. with stirring, and the mixture was stirred for 3 hours. The reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 2 mL / methanol 43 mL / ion exchange water 43 mL and stirred for 1 hour, and then the deposited precipitate was filtered and reduced in pressure for 2 hours. It was dried, and then filtered using a glass filter pre-coated with radiolite after being dissolved in about 20 mL of toluene. The filtrate was purified through an alumina column, and about 35 ml of 5.2% hydrochloric acid was added and stirred for 3 hours. The aqueous layer was later removed. Next, about 35 mL of 4% aqueous ammonia was added, and after stirring for 2 hours, the aqueous layer was removed. Further, about 35 mL of ion-exchanged water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. The organic layer was dropped into about 120 mL of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained polymer compound 4 was 0.140 g. The number-average molecular weight, weight-average molecular weight, and z-average molecular weight in terms of polystyrene were Mn = 1.56 × 10 ⁵ , Mw = 7.19 × 10 ⁵ , and Mz = 1.66 × 10 ⁶ , respectively.

Example 10 (Synthesis of Polymer Compound 5)
0.184 g of compound 10 in a reaction vessel (200 mL), N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) -benzidine (0. 49 g) (Compound 7) (0.111 g) and 2,2′-bipyridyl (0.133 g) were charged, and dehydrated tetrahydrofuran (54 mL) previously bubbled with argon gas (10 minutes) under a nitrogen atmosphere was added to make a solution. Bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.234 g) was charged. The temperature was raised to 60 ° C. with stirring, and the mixture was stirred for 3 hours. The reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 2 mL / methanol 54 mL / ion exchanged water 54 mL and stirred for 1 hour, and then the deposited precipitate was filtered and decompressed for 2 hours. It was dried, and then filtered using a glass filter pre-coated with radiolite after being dissolved in about 20 mL of toluene. The filtrate was purified through an alumina column, added with about 30 ml of 5.2% hydrochloric acid and stirred for 3 hours. The aqueous layer was later removed. Next, about 30 mL of 4% aqueous ammonia was added, and after stirring for 2 hours, the aqueous layer was removed. Further, about 30 mL of ion-exchanged water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. The organic layer was dropped into about 50 mL of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer compound 5 was 0.150 g (yield 70%). The number-average molecular weight, weight-average molecular weight, and z-average molecular weight in terms of polystyrene were Mn = 2.1 × 10 ⁴ , Mw = 8.2 × 10 ⁴ , and Mz = 1.7 × 10 ⁵ , respectively.

Synthesis Example 6 (Synthesis of Polymer Compound 6)
After charging Compound 10 (53 mg), 2,7-dibromo-9,9-dioctylfluorene (332 mg), and 2,2′-bipyridyl (266 mg) into a small-scale six-reaction vessel (200 mL), Under a nitrogen atmosphere, dehydrated tetrahydrofuran (47 mL) previously bubbled with argon gas (10 minutes) was added to make a solution, and bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (468 mg) was added. Prepared. The temperature was raised to 60 ° C. with stirring, and the mixture was stirred for 3 hours. The reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 4 mL / methanol 72 mL / ion exchanged water 72 mL, stirred for 1 hour, and then the deposited precipitate was filtered and decompressed for 2 hours. Dry, then dissolve in about 30 mL of toluene, add 120 mg of radiolite, stir, filter using a Kiriyama funnel pre-coated with radiolite (2 mm), purify the filtrate through an alumina column, 5.2% About 59 ml of aqueous hydrochloric acid was added and stirred for 3 hours, and then the aqueous layer was removed. Next, about 59 mL of 4% ammonia water was added and stirred for 2 hours, and then the aqueous layer was removed. Further, about 59 mL of ion-exchanged water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. The organic layer was dropped into about 94 mL of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained polymer compound 6 was 0.186 g. The number average molecular weight, weight average molecular weight and z average molecular weight in terms of polystyrene were Mn = 1.28 × 10 ⁵ , Mw = 3.15 × 10 ⁵ and Mz = 5.27 × 10 ⁵ , respectively.

Example 11 (Measurement of fluorescence spectrum)
When the fluorescence spectrum of the polymer compound 4 was measured by the method described above, a fluorescence spectrum having a peak at 454 nm was obtained.

Example 12 (Measurement of fluorescence spectrum)
When the fluorescence spectrum of the polymer compound 5 was measured by the method described above, a fluorescence spectrum having a peak at 478 nm was obtained.

Example 13 (Evaluation of electron injection property)
When the LUMO value of the polymer compound 4 was measured under the above-mentioned conditions, it was 2.83 eV.

Example 14 (Electron injection property evaluation)
When the LUMO value of the polymer compound 5 was measured under the above-mentioned conditions, it was 2.75 eV.

Example 15 (Evaluation of heat resistance)
It was 267 degreeC when the glass transition point of the high molecular compound 4 was measured on the above-mentioned conditions.

Example 16 (Evaluation of heat resistance)
It was 295 degreeC when the glass transition point of the high molecular compound 5 was measured on the above-mentioned conditions.

Comparative Example 2 (Heat resistance evaluation)
It was 73 degreeC when the glass transition point of the high molecular compound 3 was measured on the above-mentioned conditions.

It can be seen that both of the polymer compounds 4 and 5 exhibit excellent heat resistance.

Claims (31)

A conjugated polymer compound comprising a structure represented by the following formula (2 ′) as a repeating unit.

[Wherein, the B ′ ring and the C ′ ring each independently represent a benzene ring or a naphthalene ring which may have a substituent, and the A ′ ring represents a benzene ring or a naphthalene ring which may have a substituent. Represents. Two bonds are present on the B ′ ring and the C ′ ring, respectively. ] A conjugated polymer compound comprising a structure represented by the following formula (3 ′) as a repeating unit.

[In the formula, A ″ ring and C ″ ring each independently represent a benzene ring or a naphthalene ring which may have a substituent, and B ″ ring may have a substituent. Or represents a naphthalene ring. Two bonds are present on the A ″ ring and the C ″ ring, respectively. ]   The A ′ ring, the B ring ′ and the C ′ ring are all benzene rings, or the A ″ ring, the B ″ ring and the C ″ ring are all benzene rings. 2. The conjugated polymer compound according to 2. The conjugated polymer compound according to any one of claims 1 to 3, comprising a repeating unit represented by the following formula (6) or (7).

(6) (7)
[Wherein, R _p1 , R _q1 , R _p2 , R _q2 , R _w1 , R _x1 , R _w2 and R _x2 each independently represent a substituent, and a and c each independently represent an integer of 0 to 5 , B and d each independently represents an integer of 0 to 3. R _p1 and R _q1 , R _p2 and R _q2 , R _w1 and R _x1, and R _w2 and R _x2 may be bonded to each other to form a ring. ] The conjugated polymer compound according to claim 4, wherein at least one carbon number of R _w1 and R _x1 is 2 or more, or at least one carbon number of R _w2 and R _x2 is 2 or more. . Furthermore, as a repeating unit other than the above formulas (2 ′) and (3 ′), at least one repeating unit selected from repeating units represented by the following formulas (8) to (11) is included. The conjugated polymer compound according to any one of -5.

[Wherein, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. X ₁ , X ₂ and X ₃ each independently represent —CR ₁ ═CR ₂ —, —C≡C— or —N (R ₃ ) —. R ₁ and R ₂ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. R ₃ represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, an arylalkyl group or a substituted amino group. e represents an integer of 0 to 2; When a plurality of R ₁ , R ₂ and R ₃ are present, they may be the same or different. ] The conjugated polymer compound according to claim 6, wherein the repeating unit represented by the formula (8) is a repeating unit represented by the following formula (12).

[In the formula, E ring and F ring represent an aromatic ring, two bonds exist on E ring or F ring, Z ₄ represents —C (R _w ) (R _x ) —,> C═ C ( _Rw ) ( _Rx ), -O-, _-S- , -S (= O)-, -S (= O) (= O)-, -N ( _Rw )-, -Si (R _w ) ( _Rx )-, -P (= O) ( _Rw )-, -P ( _Rw )-, -B ( _Rw )-, -C ( _Rw ) ( _Rx ) -O-, -C (= O) -O -, - C (R w) = represents the N- or -Se-. R _w and R _x each independently represents a substituent. ] The conjugated polymer compound according to claim 6, wherein the repeating unit represented by the formula (8) is a repeating unit represented by any of the following formulas (13) to (20).

[Wherein, R ₁₄ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, It represents a substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group. n represents an integer of 0 to 4. When a plurality of R ₁₄ are present, they may be the same or different. ]

Wherein R ₁₅ and R ₁₆ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Or represents a cyano group. o and p each independently represent an integer of 0 to 3. When a plurality of R ₁₅ and R ₁₆ are present, they may be the same or different. ]

[Wherein, R ₁₇ and R ₂₀ are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an aryl group. Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Or represents a cyano group. q and r each independently represents an integer of 0 to 4. R ₁₈ and R ₁₉ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. When a plurality of R ₁₇ and R ₂₀ are present, they may be the same or different. ]

[Wherein, R ₂₁ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, It represents a substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group. g represents the integer of 0-2. Ar ₁₃ and Ar ₁₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. e and f each independently represents 0 or 1; X ₄ represents O, S, SO, SO ₂ , Se, or Te. When a plurality of R ₂₁ are present, they may be the same or different. ]

[Wherein, R ₃₄ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, It represents a substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group. h represents an integer of 0 to 4. When a plurality of R ₃₄ are present, they may be the same or different. ]

[Wherein R ₂₂ and R ₂₃ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Or represents a cyano group. i and j each independently represents an integer of 0 to 4. X ₅ represents O, S, SO ₂ , Se, Te, N—R ₂₄ , or SiR ₂₅ R ₂₆ . X ₆ and X ₇ each independently represent N or C—R ₂₇ . R ₂₄ , R _25, R ₂₆ and R ₂₇ each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. When a plurality of R ₂₅ , R ₂₆ and R ₂₇ are present, they may be the same or different.
]

Wherein R ₂₈ and R ₃₃ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl Alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group Or represents a cyano group. k and l each independently represents an integer of 0 to 4. R ₂₉ , R ₃₀ , R ₃₁ and R ₃₂ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. Ar ₅ represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. When a plurality of R ₂₈ and R ₃₃ are present, they may be the same or different. ] The conjugated polymer compound according to claim 6, wherein the repeating unit represented by the formula (9) is a repeating unit represented by the following formula (20).

[Wherein, Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ each independently represent an arylene group or a divalent heterocyclic group. Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an aryl group or a monovalent heterocyclic group. Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , and Ar ₁₀ may have a substituent. x and y each independently represents 0 or 1, and 0 ≦ x + y ≦ 1. ] The conjugated polymer compound according to any one of 1 to 9 , wherein the number average molecular weight in terms of polystyrene is from 10 ³ to 10 ⁸ . Formula (38 '), (39'), to any one of claims 1 to 10, characterized in that the polymerization by using as one of raw materials for any of the compounds represented by (28) and (29) The manufacturing method of the conjugated polymer compound of description.

(38 ') (39')
[Wherein, A ring, B ring and C ring each independently represents a benzene ring or a naphthalene ring which may have a substituent. Y _t and Y _U are each independently a halogen atom, a thiol group, an alkoxy group, a phenoxy group, an alkyl phenoxy group, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid ester group, a sulfonium methyl group, a phosphonium methyl group, phosphonate methyl group, monohalogenated methyl group, boric acid group, formyl group, a cyano group, a vinyl group or a triazene group, Y _t is attached with ring a or ring B, Y _u is the C ring. ]

(28) (29)
[In the formula, R _p1 , R _q1 , R _p2 and R _q2 are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, Arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl A group, a substituted carboxyl group or a cyano group, a and c each independently represent an integer of 0 to 5, b and d each independently represent an integer of 0 to 3, R _p1 , R _q1 , R _p2 and When a plurality of R _q2 are present, they may be the same or different. R _w1 , R _x1 , R _w2 and R _x2 are each independently an alkyl group having 3 or more carbon atoms, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group , Arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, Represents a carboxyl group, a substituted carboxyl group or a cyano group, and R _p1 and R _q1 , R _p2 and R _q2 , R _w1 and R _x1, and R _w2 and R _x2 may be bonded to each other to form a ring. Y _t1, Y _u1, Y _t2 and Y _u2 are each independently a halogen atom, a thiol group, an alkoxy group, a phenoxy group, Arukirufunokishi group, an alkyl sulfonate group, aryl sulfonate group, arylalkyl sulfonate group, borate group, a sulfonium methyl Represents a group, phosphonium methyl group, phosphonate methyl group, monohalogenated methyl group, boric acid group, formyl group, cyano group, vinyl group or triazene group. ] 12. The production method according to claim 11 , wherein the compound is polymerized with a compound represented by any one of the following formulas (30) to (33) in addition to the compound represented by the formula (28) and / or (29). .

[Wherein, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , X ₁ , X ₂ and X ₃ represent the same meaning as described above. ff represents an integer of 0-2. Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ and Y ₁₄ each independently represent a substituent involved in the polymerization. ] Substituent participating in polymerization is each independently a halogen atom, alkyl sulfonate group, selected from aryl sulfonate groups and aryl alkyl sulfonate groups, according to claim 11 or 12, characterized in that the polymerization in the presence of a nickel zero-valent complex Manufacturing method. The substituents involved in the polymerization are each independently selected from halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, aryl alkyl sulfonate groups, boric acid groups, or boric acid ester groups, and halogen atoms and alkyl sulfonate groups possessed by all raw material compounds. The ratio of the total number of moles of aryl sulfonate group and arylalkyl sulfonate group to the total number of moles of boric acid group and boric acid ester group is in the range of 0.7 to 1.2, and a nickel or palladium catalyst is used. The production method according to claim 11 , wherein polymerization is performed. A polymer composition comprising at least one material selected from a hole transport material, an electron transport material, and a light emitting material, and the conjugated polymer compound according to any one of claims 1 to 10 . A polymer composition comprising two or more conjugated polymer compounds according to any one of claims 1 to 10 . A solution comprising the conjugated polymer compound according to any one of claims 1 to 10 or the polymer composition according to claim 15 or 16 . The solution according to claim 17 , wherein the viscosity is 1 to 20 mPa · s at 25 ° C. A luminescent thin film containing the conjugated polymer compound according to any one of claims 1 to 10 or the polymer composition according to claim 15 or 16 . The electroconductive thin film containing the conjugated polymer compound in any one of Claims 1-10 , or the polymer composition of Claim 15 or 16 . An organic semiconductor thin film containing the conjugated polymer compound according to any one of claims 1 to 10 or the polymer composition according to claim 15 or 16 . An organic transistor comprising the organic semiconductor thin film according to claim 21 . It has an organic layer between the electrodes which consist of an anode and a cathode, and this organic layer contains the conjugated polymer compound in any one of Claims 1-10 , or the polymer composition of Claim 15 or 16. A polymer light emitting device characterized by the above. 24. The polymer light emitting device according to claim 23 , wherein the organic layer is a light emitting layer. The polymer light-emitting device according to claim 24 , wherein the light-emitting layer further contains a hole transport material, an electron transport material, or a light-emitting material. It has a light emitting layer and a charge transport layer between the electrodes which consist of an anode and a cathode, and this charge transport layer is a conjugated polymer compound in any one of Claims 1-10 , or the polymer of Claim 15 or 16. 26. The polymer light emitting device according to claim 25 , comprising a composition. A light-emitting layer and a charge transport layer are provided between electrodes composed of an anode and a cathode, a charge injection layer is provided between the charge transport layer and the electrode, and the charge injection layer is any one of claims 1 to 10 . 27. The polymer light-emitting device according to claim 26 , comprising the conjugated polymer compound according to claim 15 or the polymer composition according to claim 15 or 16 . A planar light source comprising the polymer light-emitting device according to any one of claims 23 to 27 . A segment display device comprising the polymer light-emitting device according to any one of claims 23 to 27 . A dot matrix display using the polymer light emitting device according to any one of claims 23 to 27 . 28. A liquid crystal display device comprising the polymer light-emitting device according to claim 23 as a backlight.