JP2005206826A - Method for producing polymer compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a high-molecular-weight polymer compound by the condensation polymerization of at least one kind of monomer having two eliminable groups in the presence of a metal condensation agent. <P>SOLUTION: In producing a polymer compound having at least one kind of repeating units represented by formula (6): -Z<SB>1</SB>-A-Z<SB>2</SB>- by the condensation polymerization of at least one kind of monomer represented by formula (1): Y<SB>1</SB>-Z<SB>1</SB>-A-Z<SB>2</SB>-Y<SB>2</SB>in the presence of a metallic condensation agent selected from metals and metal compounds, the temperature in causing the metallic condensation agent to act on the monomer is 45°C or higher. In formula (1), Y<SB>1</SB>and Y<SB>2</SB>are each an atom or an atomic group eliminable by the action of the condensation agent; -A- is an arylene group, a divalent heterocyclic group, or the like; and -Z<SB>1</SB>- and -Z<SB>2</SB>- are each a direct bond, -C≡C-, or the like. In formula (6), -A-, -Z<SB>1</SB>-, and -Z<SB>2</SB>- are each the same as above-described. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a polymer compound.

As a method for producing a polymer compound, for example, a conjugated polymer compound such as polyphenylene, polyfluorene, and polythiophene, a zero-valent nickel complex as a metal condensing agent in a monomer having two halogen atoms as a leaving group Is known to be allowed to act at room temperature of about 25 ° C., then heated to the reaction temperature and subjected to condensation polymerization (Non-patent Document 1, Patent Document 1, Patent Document 2).
Macromolecules 1992, 25, 1214-1223. JP-A-7-247344 JP 2002-284862 A

  However, the above method has a problem that the molecular weight of the obtained polymer compound does not always increase to a satisfactory level.

  An object of the present invention is to provide a method for producing a high molecular weight polymer compound by subjecting one or more monomers having two leaving groups to condensation polymerization in the presence of a metal condensing agent.

  As a result of intensive studies to solve the above problems, the present inventors have made the molecular weight of the resulting polymer compound high by setting the temperature at which the metal condensing agent is allowed to act on the monomer to 45 ° C. or higher. As a result, the present invention has been completed.

That is, the present invention
One or more monomers selected from the following formula (1) are subjected to condensation polymerization in the presence of a metal condensing agent selected from a metal and a metal compound, and the polymer has one or more repeating units represented by the following formula (6). In producing molecular compounds,
A temperature at which the metal condensing agent is allowed to act on the monomer is 45 ° C. or higher, and a method for producing a polymer compound is provided.

Y ₁ -Z ₁ -AZ ₂ -Y ₂ (1)
[Wherein, Y ₁ and Y ₂ each independently represent an atom or an atomic group that can be removed by the action of the condensing agent,
-A- is
-Ar _1- (2),
—Ar ₂ —X ₁ — (Ar ₃ —X ₂ ) _w —Ar ₄ — (3),
—Ar ₅ —X ₃ — (4)
Or -X ₄ - (5)
_{(Wherein, Ar 1, Ar 2, Ar} 3, Ar 4, and Ar ₅ represent each independently an arylene group, a divalent group having a divalent heterocyclic group or a metal complex structure, X ₁ is - C≡C—, —N (R ₁ ) —, or — (SiR ₂ R ₃ ) _y —, wherein X ₂ and X ₃ are —CR ₄ ═CR ₅ —, —C≡C—, —N (R ₁ ) — or — (SiR ₂ R ₃ ) _y —, and X ₄ represents —CR ₄ ═CR ₅ —, —C≡C—, or — (SiR ₂ R ₃ ) _y —, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or an arylalkyl group, and R ₄ and R ₅ 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, w represents an integer of 0 to 1, y Represents an integer of 1 to 12. When a plurality of R _{2 s} and R _{3 s} are present, they may be the same or different.
—Z ₁ — and —Z ₂ — each independently represents a direct bond, —C≡C—, or —CR ₆ ═CR ₇ —, and R ₆ and R ₇ each independently represents a hydrogen atom, an alkyl group, or aryl. Represents a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group]

-Z ₁ -AZ _2- (6)
[Wherein, -A-, -Z _1-, and -Z _2- represent the same meaning as described above. ]

  According to the present invention, a high molecular weight polymer compound can be produced by subjecting one or more monomers having two leaving groups to condensation polymerization using a metal condensing agent.

In the monomer represented by the formula (1) used in the present invention, Y ₁ and Y ₂ each independently represent a leaving group.
As the leaving group, a hydrogen atom, a halogen _{atom, -OSO 2 R 8, -B (} OR 9) 2, -Sn (R 10) 3, -MgX , and the like.
(Wherein R ₈ represents an alkyl group, an aryl group, or an arylalkyl group. R ₉ represents a hydrogen atom, an alkyl group, or an aryl group, and two R _{9 s} may be the same or different, and together, , May form a ring.
R ₁₀ represents an alkyl group or an aryl group, and X represents a halogen atom).

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

Examples of —OSO ₂ R ₈ include a methanesulfonate group, an ethanesulfonate group, a trifluoromethanesulfonate group, a benzenesulfonate group, a p-toluenesulfonate group, a p-nitrobenzenesulfonate group, and a benzylsulfonate group.

式中、Ｍｅはメチル基を、Ｅｔはエチル基を示す。 Examples of —B (OR ₉ ) ₂ include groups represented by the following formulae.

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

Examples of —Sn (R ₁₀ ) ₃ include —Sn (n—Bu) ₃ , —Sn (Me) ₃ , and —Sn (Ph) ₃ . In the formula, n-Bu represents a normal butyl group, Me represents a methyl group, and Ph represents a phenyl group.

-MgX is exemplified by -MgCl, -MgBr, and -MgI.

In the monomer represented by the formula (1) used in the present invention,
-A- is
-Ar _1- (2),
—Ar ₂ —X ₁ — (Ar ₃ —X ₂ ) _w —Ar ₄ — (3),
—Ar ₅ —X ₃ — (4)
Or -X ₄ - (5)
_{(Wherein, Ar 1, Ar 2, Ar} 3, Ar 4, and Ar ₅ represent each independently an arylene group, a divalent group having a divalent heterocyclic group or a metal complex structure, X ₁ is - C≡C—, —N (R ₁ ) —, or — (SiR ₂ R ₃ ) _y —, wherein X ₂ and X ₃ are —CR ₄ ═CR ₅ —, —C≡C—, —N (R ₁ ) — or — (SiR ₂ R ₃ ) _y —, and X ₄ represents —CR ₄ ═CR ₅ —, —C≡C—, or — (SiR ₂ R ₃ ) _y —, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or an arylalkyl group, and R ₄ and R ₅ 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, w represents an integer of 0 to 1, y Represents an integer of 1 to 12. When a plurality of R ₂ and R ₃ are present, they may be the same or different.

Among the arylene groups represented by Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ , a divalent heterocyclic group or a divalent group having a metal complex structure, an arylene group or a divalent heterocyclic group Is preferred.
Here, the 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, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano And an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a substituted amino group, a substituted silyl group, a substituted silyloxy group, and a monovalent heterocyclic group are preferable.

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.

  Examples of the arylene group include a phenylene group (for example, formulas 1 to 3 in the following figure), a naphthalene-diyl group (formulas 4 to 13 in the following figure), an anthracene-diyl group (formulas 14 to 19 in the following figure), Formulas 20-25), terphenyl-diyl groups (formulas 26-28 in the figure below), condensed ring compound groups (formulas 29-35 in the figure below), fluorene-diyl groups (formulas 36-38 in the figure below), indenofluorene -Diyl (lower figures 38A-38B), stilbene-diyl (formulas A-D in the lower figure), distilbene-diyl (formulas E, F in the lower figure) and the like. Of these, a phenylene group, a biphenyl-diyl group, a fluorene-diyl group, and a stilbene-diyl group are preferable.

In the above formulas (2) to (5), the divalent heterocyclic group represented by Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , and Ar ₅ is the remainder obtained by removing two hydrogen atoms from the heterocyclic compound. The group may have a substituent.
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, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano And an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a substituted amino group, a substituted silyl group, a substituted silyloxy group, and a monovalent heterocyclic group are preferable.
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 in the following figure), diazaphenylene group (formula 45 to 48 in the figure below), quinoline diyl group (formula 49 to 63 in the figure below), quinoxaline Diyl groups (formulas 64 to 68 in the lower figure), acridine diyl groups (formulas 69 to 72 in the lower figure), bipyridyldiyl groups (formulas 73 to 75 in the lower figure), phenanthroline diyl groups (formulas 76 to 78 in the lower figure), and the like.
Groups having a fluorene structure containing silicon, nitrogen, boron, sulfur, selenium and the like as a hetero atom (formulas 79 to 93 in the following figure).
A group containing silicon, nitrogen, boron, sulfur, selenium and the like as a hetero atom and having an indenofluorene structure (formulas J to O in the following figure).
5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom: (Formulas 94 to 98 in the following figure).
5-membered ring condensed heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom: (Formulas 99 to 110 in the following figure).
A 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, and bonded to the α-position of the heteroatom to form a dimer or oligomer: (Formulas 111 to 112 in the following figure).
A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a hetero atom, and bonded to the phenyl group at the α-position of the hetero atom: (Formulas 113 to 119 in the following figure).
A group obtained by substituting a phenyl group, a furyl group, or a thienyl group with a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, or the like as a hetero atom (formulas 120 to 125 in the following figure).

The divalent group having a metal complex structure represented by Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , and Ar ₅ is a group obtained by removing two hydrogen atoms from an organic ligand of a metal complex having an organic ligand. The remaining divalent group.
Carbon number of the organic ligand of the metal complex having an organic ligand is usually about 4 to 60. Examples of organic ligands include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenyl-benzothiazole and derivatives thereof, 2-phenyl-benzoxazole and derivatives thereof. Derivatives, porphyrins and derivatives thereof.
Examples of the central metal of the metal complex having an organic ligand include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium.
Examples of the metal complex having an organic ligand include low-molecular fluorescent materials and phosphorescent materials known as so-called triplet light-emitting complexes.

  Examples of the divalent group having a metal complex structure include the following (126 to 132).

  In the above formulas 1-132 and J-O, 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, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, A monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, or a cyano group is shown.

In the example of the substituent, a plurality of Rs are contained in one structural formula, but a plurality of Rs out of these Rs may be linked or condensed to form a ring. Further, when R contains alkyl, a part of the methyl group or methylene group of alkyl may be replaced with a group containing a hetero atom or a methyl group or methylene group substituted with one or more fluorine atoms. Examples of these heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms and the like.
Furthermore, when R contains an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents.
In order to increase the solubility in a solvent, it is preferable that at least one of a plurality of Rs in one structural formula is other than a hydrogen atom, and the symmetry of the shape of the repeating unit including a substituent is Less is preferred. Moreover, it is preferable that one or more of R in one structural formula is a group containing a linear or cyclic or branched alkyl group having 3 or more carbon atoms.

Among the substituents that Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , and Ar ₅ may have, the alkyl group may be linear, branched, or cyclic, and usually has 1 to 20 carbon atoms. The degree is preferably 3 to 20, and specific examples thereof include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, isoamyl group, hexyl. Group, a cyclohexyl group, a 4-C ₁ -C ₁₂ alkylcyclohexyl group (C ₁ -C ₁₂ indicate that it has 1 to 12 carbon atoms, the same applies hereinafter), a heptyl group, an octyl group, 2- Ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl And the like, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, decyl 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, and specific examples thereof include methoxy group, ethoxy group, 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. Pentyloxy group, hexyloxy group Octyloxy group, a 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, and specific examples thereof include methylthio group, ethylthio group, propylthio group, i-propylthio group. 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-dimethyloctylthio Group, laurylthio group, trifluoromethylthio group and the like, and pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group, and 3,7-dimethyloctylthio group are preferable.

The aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group, a C _{1 to} C ₁₂ alkylphenyl group, 1- Examples include a naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, and a pentafluorophenyl group, and a C _{1 to} C ₁₂ alkoxyphenyl group and a C _{1 to} C ₁₂ alkylphenyl group preferable. Here, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and those having a condensed ring, two or more independent benzene rings or condensed rings are directly or a group such as vinylene. The thing couple | bonded through is also included.
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.
Specific examples of C ₁ -C ₁₂ alkyl include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, Examples include 3,7-dimethyloctyl and lauryl.

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, pentafluorophenyloxy group are exemplified, C ₁ -C ₁₂ alkoxy phenoxy group, a C ₁ -C ₁₂ alkylphenoxy group are preferable.

Arylthio group, usually about 6 to 60 carbon atoms, preferably 7 to 48, 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, pentafluorophenylthio group and the like, C ₁ -C ₁₂ alkoxyphenyl-thio group, a C ₁ -C ₁₂ alkyl phenylthio group are preferable.

The arylalkyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include phenylmethyl group, phenylethyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, phenylhexyl group. Puchichiru group, a phenyl -C ₁ -C ₁₂ alkyl group such as a phenyl octyl group, a phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ Examples include alkylphenyl-C ₁ -C ₁₂ alkyl group, 1-naphthyl-C ₁ -C ₁₂ alkyl group, 2-naphthyl-C ₁ -C ₁₂ alkyl group, etc., and C ₁ -C ₁₂ alkoxyphenyl-C _1- C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group are preferable.

The arylalkoxy group usually has about 7 to 60 carbon atoms, preferably 7 to 48. Specific examples thereof include phenylmethoxy group, phenylethoxy group, phenylbutoxy group, phenylpentyloxy group, phenylhexyloxy 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 Examples include ₁₂ alkoxy groups, 1-naphthyl-C ₁ -C ₁₂ alkoxy groups, 2-naphthyl-C ₁ -C ₁₂ alkoxy groups, etc., C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy groups, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group are preferable.

Arylalkylthio group has usually about 7 to 60 carbon atoms, preferably 7 to 48, and examples thereof include phenyl -C ₁ -C ₁₂ alkylthio group, 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, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group are preferable.

Arylalkenyl group has usually about 8 to 60 carbon atoms, preferably 8 to 48, 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 groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl groups are preferred.

The arylalkynyl group has usually about 8 to 60 carbon atoms, preferably 8 to 48, and examples thereof include phenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl, 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, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.

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, and a monovalent heterocyclic group.
The substituted amino group usually has about 1 to 60 carbon atoms, preferably 2 to 48, and specific examples thereof include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group. 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 Basic Feni Amino 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 group, 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, such as carbazolyl 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 and a monovalent heterocyclic group.
The substituted silyl group usually has about 1 to 60 carbon atoms, preferably 3 to 48, and specific examples thereof include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, dimethyl- i-propylsilyl group, diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyl dimethylsilyl group, decyldimethylsilyl group, a 3,7-- dimethylsilyl group, lauryldimethylsilyl group, a phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl silyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ ~ 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-xylylsilyl group, tribenzylsilyl group, diphenylmethylsilyl group, t-butyldiphenylsilyl group, dimethylphenylsilyl group, trimethoxysilyl group, triethoxysilyl group, tripropyloxysilyl group, tri-i-propylsilyl group Dimethyl-i-propylsilyl group, methyldimethoxysilyl group, ethyldimethoxysilyl group, and the like.

Examples of the substituted silyloxy group include a silyloxy group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The substituted silyloxy group usually has about 1 to 60 carbon atoms, preferably 3 to 48. Specific examples thereof include trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, tri-i-propylsilyloxy group. Group, dimethyl-i-propylsilyloxy group, diethyl-i-propylsilyloxy group, t-butylsilyldimethylsilyloxy group, pentyldimethylsilyloxy group, hexyldimethylsilyloxy group, heptyldimethylsilyloxy group, octyldimethyl silyloxy group, 2-ethylhexyl - butyldimethylsilyloxy group, nonyldimethylsilyl group, decyldimethylsilyl group, a 3,7-- butyldimethylsilyloxy group, lauryl dimethyl silyloxy group, a phenyl -C ₁ -C ₁₂ Alkyl Riruokishi group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl silyloxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl silyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl oxy group, 2-naphthyl -C ₁ -C ₁₂ alkyl silyloxy group, phenyl -C ₁ -C ₁₂ alkyl dimethyl silyloxy group, triphenyl silyloxy group, tri -p- xylyl silyloxy group, tribenzylsilyloxy Group, diphenylmethylsilyloxy group, t-butyldiphenylsilyloxy group, dimethylphenylsilyloxy group, trimethoxysilyloxy group, triethoxysilyloxy group, tripropyloxysilyloxy group, tri-i-propylsilyloxy group, Dimethyl-i-propylsilyloxy group, methyldimethoxysilylo Shi, ethyl dimethoxy silyl group, and the like are exemplified.

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

  The acyl group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms, and specific examples thereof include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group, Examples thereof include a pentafluorobenzoyl group.

  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, a benzoyloxy group, Examples thereof include a trifluoroacetyloxy group and a pentafluorobenzoyloxy group.

The imine residue refers to an imine compound (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 60 carbon atoms, preferably 2 to 20 carbon atoms. Specific examples thereof are shown by the following structural formulas: And the like are exemplified.

  The amide group usually has about 1 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, pentafluorobenzamide. Group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoroacetamide group, dipentafluorobenzamide group and the like.

上記例示において、Ｍｅはメチル基を示す。 The acid imide group includes a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, and usually has about 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms. Specific examples include the following groups.

In the above examples, Me represents a methyl group.

The monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 3 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 hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, etc. in the ring. Say.
Monovalent Specific examples of the heterocyclic group are thienyl groups, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are thienyl groups, C _{A 1 to} C ₁₂ alkyl thienyl group, a pyridyl group, and a C _{1 to} C ₁₂ alkyl pyridyl group are preferred.

Examples of the substituted carboxyl group include an alkyl group, an aryl group, an arylalkyl group, or a carboxyl group substituted with a monovalent heterocyclic group.
The substituted carboxyl group usually has about 2 to 60 carbon atoms, preferably 2 to 48, and 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, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group Perfluorobutoxycarbonyl group, perfluorooctyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group, and the like.

Among the above formulas (2) to (5), the above formulas (2) and (3) are more preferable.

  Among the above formulas (2), the following formulas (8), (9), (10), (11), (12), and (13) are preferable.

式中、Ｒ₂₅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、シリルオキシ基、置換シリルオキシ基、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。ｚは０〜４の整数を示す。Ｒ₂₅が複数存在する場合、それらは同一であっても異なっていてもよい。
（８）の具体例としては、

があげられる。

In the formula, R ₂₅ is 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, silyloxy group, substituted silyloxy 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. z shows the integer of 0-4. When a plurality of R ₂₅ are present, they may be the same or different.
As a specific example of (8),

Is given.

〔式中、Ｒ₂₆およびＲ₂₇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、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。aaおよびbbはそれぞれ独立に０〜３の整数を示す。Ｒ₂₆およびＲ₂₇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。
（９）の具体例としては

があげられる。

[Wherein R ₂₆ and R ₂₇ 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, silyloxy group, substituted silyloxy 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. aa and bb each independently represent an integer of 0 to 3. When a plurality of R ₂₆ and R ₂₇ are present, they may be the same or different.
As a specific example of (9)

Is given.

〔式中、Ｒ₂₈およびＲ₃₁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、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。Ｒ₂₉およびＲ₃₀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。ｃｃおよびｄｄはそれぞれ独立に０〜４の整数を示す。Ｒ₂₈およびＲ₃₁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。〕


（10）の具体例としては

があげられる。

Wherein R ₂₈ and R ₃₁ 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, silyloxy group, substituted silyloxy 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. R ₂₉ and R ₃₀ 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. cc and dd each independently represents an integer of 0 to 4. When a plurality of R ₂₈ and R ₃₁ are present, they may be the same or different. ]


As a specific example of (10)

Is given.

式中、Ｒ₃₂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。eeは０〜２の整数を示す。Ａｒ₆ およびＡｒ₇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。ｓaおよびsbはそれぞれ独立に０または１を示す。Ｘ₈は、Ｏ、Ｓ、ＳＯ、ＳＯ₂、Ｓｅ，またはＴｅを示す。Ｒ₃₂が複数存在する場合、それらは同一であっても異なっていてもよい。
（11）の具体例としては

があげられる。

In the formula, R ₃₂ is 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 group, substituted carboxyl group or cyano group are shown. ee represents an integer of 0-2. Ar ₆ and Ar ₇ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. sa and sb each independently represent 0 or 1; X ₈ represents O, S, SO, SO ₂ , Se, or Te. When a plurality of R ₃₂ are present, they may be the same or different.
As a concrete example of (11)

Is given.

式中、Ｒ₃₃およびＲ₃₄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、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。ffおよびggはそれぞれ独立に０〜４の整数を示す。Ｘ₅は、Ｏ、Ｓ、ＳＯ、ＳＯ₂、Ｓｅ，Ｔｅ、Ｎ−Ｒ₃₅、またはＳｉＲ₃₆Ｒ₃₇を示す。Ｘ₆およびＸ₇は、それぞれ独立に、ＮまたはＣ−Ｒ₃₈を示す。Ｒ₃₅、Ｒ₃₆、Ｒ₃₇およびＲ₃₈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。Ｒ₃₃、Ｒ₃₄、Ｒ₃₆およびＲ₃₇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（１２）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、シロールなどがあげられる。
（12）の具体例としては

があげられる。

In the formula, each of R ₃₃ and R ₃₄ independently 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, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, A carboxyl group, a substituted carboxyl group or a cyano group is shown. ff and gg each independently represent an integer of 0 to 4. X ₅ represents O, S, SO, SO ₂ , Se, Te, N—R ₃₅ , or SiR ₃₆ R ₃₇ . X ₆ and X ₇ each independently represent N or C—R ₃₈ . R ₃₅ , R ₃₆ , R ₃₇ and R ₃₈ 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 ₃₃ , R ₃₄ , R ₃₆ and R ₃₇ are present, they may be the same or different. ]

Examples of the central 5-membered ring in the formula (12) include thiadiazole, oxadiazole, triazole, thiophene, furan, silole and the like.
As a specific example of (12)

Is given.

式中、Ｒ₃₉およびＲ₄₄は、それぞれ独立に式（８）のＲ₂₅と同じ基を示す。hhおよびjjはそれぞれ独立に０〜４の整数を示す。Ｒ₄₀、Ｒ₄₁、Ｒ₄₂およびＲ₄₃は、それぞれ独立に式（１０）のＲ₂₉と同じ基を示す。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。Ｒ₃₉およびＲ₄₄が複数存在する場合、それらは同一であっても異なっていてもよい。
(12)の具体例としては

があげられる。

In the formula, R ₃₉ and R ₄₄ each independently represent the same group as R ₂₅ in the formula (8). hh and jj each independently represents an integer of 0 to 4. R ₄₀ , R ₄₁ , R ₄₂ and R ₄₃ each independently represent the same group as R ₂₉ in formula (10). Ar ₅ represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. When a plurality of R ₃₉ and R ₄₄ are present, they may be the same or different.
As a specific example of (12)

Is given.

式中、Ａｒ₁₁、Ａｒ₁₂、Ａｒ₁₃およびＡｒ₁₄は、それぞれ独立にアリーレン基または２価の複素環基を表す。Ａｒ₁₅、Ａｒ₁₆およびＡｒ₁₇は、それぞれ独立にアリール基または１価の複素環基を表す。ｑｑおよびｒｒはそれぞれ独立に０または１を表し、０≦ｑｑ＋ｒｒ≦１である。
In the above formula (3), the following formula (14) is preferable.

In the formula, Ar ₁₁ , Ar ₁₂ , Ar ₁₃ and Ar ₁₄ each independently represent an arylene group or a divalent heterocyclic group. Ar ₁₅ , Ar ₁₆ and Ar ₁₇ each independently represents an aryl group or a monovalent heterocyclic group. qq and rr each independently represent 0 or 1, and 0 ≦ qq + rr ≦ 1.

Specific examples of the above (14) include the following diagrams (Formulas 133 to 140).

上記式においてＲは、前記式１〜１３２、Ｊ〜Ｏのそれと同じ意味を表す。

In the above formula, R represents the same meaning as in formulas 1-132 and J-O.

式中、Ｒ₄₅、Ｒ₄₆およびＲ₄₇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、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。kkおよびmmはそれぞれ独立に０〜４の整数を示す。ppは１〜２の整数を示す。nnは０〜５の整数を示す。Ｒ₄₅、Ｒ₄₆およびＲ₄₇が複数存在する場合、それらは同一であっても異なっていてもよい。 Of the formula (14), the following formula (14-2) is preferable.

In the formula, R ₄₅ , R ₄₆ and R ₄₇ 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, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent complex A cyclic group, a carboxyl group, a substituted carboxyl group or a cyano group is shown. kk and mm each independently represent an integer of 0 to 4. pp represents an integer of 1 to 2. nn represents an integer of 0 to 5. When a plurality of R ₄₅ , R ₄₆ and R ₄₇ are present, they may be the same or different.

In the monomer represented by the formula (1) used in the present invention, —Z ₁ — and —Z ₂ — each independently represents a direct bond, —C≡C—, or —CR ₆ ═CR ₇ —. R ₆ and R ₇ 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.

Here, the alkyl group represented by R ₆ and R ₇ may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. group, an ethyl group, a propyl group, i- propyl group, butyl group, i- butyl, t- butyl group, a pentyl group, an isoamyl group, a hexyl group, a cyclohexyl group, 4-C ₁ ~C ₁₂ alkyl 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 Groups such as pentyl, hexyl, octyl, 2-ethylhexyl, decyl, and 3,7-dimethyloctyl. Preferred.

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 such as fluorophenyl group and the like, C ₁ -C ₁₂ alkoxyphenyl group, is C ₁ -C ₁₂ alkylphenyl group are preferable. Here, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and those having a condensed ring, two or more independent benzene rings or condensed rings are directly or a group such as vinylene. The thing couple | bonded through is also included.
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.
Specific examples of C ₁ -C ₁₂ alkyl include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, Examples include 3,7-dimethyloctyl and lauryl.

The monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 3 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 hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, etc. in the ring. Say.
Monovalent Specific examples of the heterocyclic group are thienyl groups, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are thienyl groups, C _{A 1 to} C ₁₂ alkyl thienyl group, a pyridyl group, and a C _{1 to} C ₁₂ alkyl pyridyl group are preferred.

Examples of the substituted carboxyl group include an alkyl group, an aryl group, an arylalkyl group, or a carboxyl group substituted with a monovalent heterocyclic group.
The substituted carboxyl group usually has about 2 to 60 carbon atoms, preferably 2 to 48, and 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, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group Perfluorobutoxycarbonyl group, perfluorooctyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group, and the like.

Next, a method for producing the monomer represented by the above formula (1) will be described.
The method for producing the monomer represented by the above formula (1) varies depending on the type of leaving group represented by Y ₁ and Y _2. For example, the first production method is represented by the following formula (1 ′). And a method of substituting W in the compound with Y ₁ and Y ₂ .

WZ ₁ -AZ ₂ -W (1 ′)
Here, -Z _1- , -Z ₂ -and A represent the same meaning as described above, and W represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a trialkylsilyl group, a trifluoromethanesulfonyl group, a formyl group, or the like. Represent.

The first production method will be specifically described.
The compound represented by the formula (1) (—Z ₁ —, —Z ₂ — is a direct bond, and Y ₁ and Y ₂ are halogen atoms) is the compound represented by the formula (1 ′) (—Z ₁ —, —Z _2- is a direct bond and W is a hydrogen atom) and a halogenating agent such as chlorine, bromine, N-bromosuccinimide, iodine-silver trifluoroacetate and the like. In this case, if necessary, the compound represented by the formula (1 ′) may be reacted with a halogenated reagent after reacting with a base.

The compound represented by formula (1) (Y ₁ and Y ₂ are halogen atoms) is obtained by reducing the compound represented by formula (1 ′) (W is a nitro group) with a catalyst such as Ru / C. Amino form, and the amino form is diazotized with nitrous acid or the like to form a diazo form, which is treated with a halogenating agent such as hydrogen chloride, hydrogen bromide, sodium chloride, sodium bromide, iodine or potassium iodide. Can be manufactured.

Further, the compound represented by the formula (1) (Y ₁ and Y ₂ are halogen atoms) includes a compound represented by the formula (1 ′) (W is a trialkylsilyl group), sodium iodide-N-chlorosuccinimide, It can be produced by reacting with a halogenated reagent such as iodine monochloride.

The compound represented by the formula (1) (Y ₁ , Y ₂ is —B (OR ₉ ) ₂ ) is obtained by reacting the compound represented by (1 ′) (W is a hydrogen atom) with, for example, a base. , Trimethoxyborane, triethoxyborane, and other boric acid compounds can be used for the reaction (wherein R ₉ represents the same meaning as described above).

The compound represented by the formula (1) (Y ₁ and Y ₂ are —B (OR ₉ ) ₂ ) is the same as the compound represented by (1) (W is a halogen atom, a trifluoromethanesulfonyl group, etc.)
For example, it can be produced by reacting with a boric acid compound such as bispinacolatodiborane (wherein R ₉ represents the same meaning as described above).

Further, the compound (Y ₁ , Y ₂ is —OSO ₂ R ₈ ) represented by the formula (1) exceeds the compound (Y ₁ , Y ₂ is —B (OR ₉ ) ₂ ) represented by the formula (1). It can be produced by reacting with hydrogen oxide or the like and then sulfonated with a sulfonated reagent such as sulfonyl halide (wherein R ₈ represents the same meaning as described above).

In addition, the compound represented by the formula (1) (—Z ₁ —, —Z ₂ — is —CR ₆ ═CR ₇ —, or —C≡C—, Y ₁ , Y ₂ is a hydrogen atom) is represented by the formula (1 The compound represented by the formula (1 ′) (W ₁ ) is subjected to a Vilsmeier reaction and the like (—Z ₁ —, —Z ₂ — are a direct bond, W ₁ , W ₂ are hydrogen atoms). , W ₂ is formyl group), and this formyl form is subjected to Wittig reaction, Corey-Fuchs acetylene synthesis reaction, and the like. (Wherein R ₆ and R ₇ represent the same meaning as described above).

As a second method for producing the monomer represented by the formula (1), an intermediate having a leaving group represented by Y ₁ or Y _{2 represented} by the following formula (1 ″) is synthesized, and then D is prepared. Examples of the production method include conversion to A by various ring closure reactions, functional group conversion reactions, substitution reactions, elimination reactions and the like.
Y ₁ −Z ₁ −DZ ₂ −Y ₂ (1 ″)

In the method for producing a polymer compound of the present invention, when a monomer selected from the above formula (1) is subjected to condensation polymerization using a metal condensing agent selected from metals and metal compounds, the metal condensing agent is used as a monomer. The temperature at the time of making it act is 45 degreeC or more, It is characterized by the above-mentioned. This temperature should just be substantially 45 degreeC or more.
As temperature at the time of making it act on a monomer, 50 degreeC or more is preferable and 60 degreeC or more is more preferable.

More than half amount, preferably 60% by weight or more, more preferably 90% by weight or more, and particularly preferably the temperature at which the whole amount is allowed to act on the monomer with respect to the total amount of the metal condensing agent used in the condensation polymerization. It is preferable that it is 45 degreeC or more.
When the condensation polymerization is an equivalent reaction, usually, the total amount of the metal condensing agent used in the condensation polymerization is
When the condensation polymerization is a catalytic reaction, the total amount of the metal condensing agent used for the condensation polymerization is usually sufficient to catalyze the reaction. The amount is, for example, about 0.001 to 1 equivalent with respect to the monomer.

“The temperature when the metal condensing agent is allowed to act on the monomer is substantially 45 ° C. or higher” means that the substantial temperature in the vicinity of the place where the metal condensing agent is allowed to act is 45 ° C. or higher. For example, when the metal condensing agent is allowed to act on the monomer by mixing with stirring in a solvent, the “substantial temperature” may be the reaction solution temperature.

The upper limit of the “temperature at which the metal condensing agent is allowed to act on the monomer” varies depending on the monomer used, the condensation reaction used in the condensation polymerization, and the solvent, but is preferably 250 ° C. or lower.
In the method for producing a polymer compound of the present invention, as a method for allowing a metal condensing agent to act on a monomer at 45 ° C. or higher, for example, when a solvent is used, (a) a mixture containing a monomer and a solvent A method in which the metal condensing agent is mixed with the liquid mixture as a solid or as a liquid mixture with a solvent while maintaining the temperature of the liquid at 45 ° C. or higher,
(B) A method of mixing a monomer in the mixed solution as a solid or as a mixed solution with a solvent while keeping the mixed solution containing the metal condensing agent and the solvent at 45 ° C. or higher,
(C) While maintaining the temperature of the mixed liquid containing a part of the monomer and the solvent at 45 ° C. or higher, the mixed liquid is mixed with a metal condensing agent (in a solid or as a mixed liquid with an organic solvent) and the remaining A method of separately mixing monomers (in a solid or as a mixed solution with a solvent).
(D) While maintaining the temperature of the solvent at 45 ° C. or higher, the metal condensing agent (in solid or as a mixed solution with an organic solvent) and the monomer (in solid or as a mixed solution with a solvent), A method of charging separately with a solid or a mixed solution with an organic solvent can be mentioned. From the viewpoint of increasing the molecular weight, while maintaining the temperature of the mixed solution containing the monomer and the solvent at 45 ° C. or higher, the mixed solution The method ((a) or (c)) in which a metal condensing agent (preferably a zero-valent nickel complex) is charged is preferable. Is more preferable.
Further, the metal condensing agent may be allowed to act on the monomer a plurality of times.
As the reaction method, any of batch, semi-batch and continuous methods can be adopted.
A batch system is preferred.

In the method for producing a polymer compound of the present invention, in the presence of a metal condensing agent selected from metals and metal compounds, when one or more monomers selected from the formula (1) are subjected to condensation polymerization, a metal condensing agent is used. The temperature at which the monomer is allowed to act on is substantially 45 ° C. or higher, and the condensation reaction used for the condensation polymerization is not particularly limited.
A Yamamoto coupling reaction, a Suzuki coupling reaction, a transmetallation reaction, a Heck reaction, a Sonogashira reaction, a Stille reaction, a condensation reaction using a metal condensing agent such as a Ullmann reaction are exemplified, and the Yamamoto coupling reaction is preferable.

  The metal condensing agent selected from the metals and metal compounds used in the production method of the present invention is selected according to the type of condensation reaction used in the condensation polymerization.

As the metal condensing agent, for example, in the case of using a Yamamoto coupling reaction as a condensation reaction, a zerovalent nickel complex may be mentioned,
When using a Suzuki coupling reaction, a transmetalation reaction, a Stille reaction, a Heck reaction, a Sonogashira reaction, etc. as a condensation reaction, a transition metal compound such as a nickel catalyst or a palladium catalyst, and a co-catalyst or base in each reaction as necessary. In the case of using the Ullmann reaction as the condensation reaction, metals such as copper and nickel are exemplified.

  The metal condensing agent can be used alone or in a mixed solution or mixture containing the metal condensing agent. It can also be used in the state of a precursor capable of generating a metal condensing agent in the system.

  Hereinafter, typical condensation polymerization will be described.

（式中、Ｘはそれぞれ独立にハロゲン原子を表し、Ａ、Ｒ₈はそれぞれ独立に前記と同じ意味を表す。） When the condensation reaction used for the condensation polymerization is a Yamamoto coupling reaction,
In the monomer represented by the formula (1), Y ₁ and Y ₂ are preferably each independently a halogen atom or —OSO ₂ R ₈ , and more preferably a halogen atom. (Wherein R ₈ represents the same meaning as described above). Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. However, because of high reactivity, a chlorine atom and a bromine atom are preferable, and a bromine atom is particularly preferable.
In this case, examples of the monomer represented by the formula (1) include compounds represented by the following formulas.

(In the formula, each X independently represents a halogen atom, and A and R ₈ each independently represent the same meaning as described above.)

Among the monomers represented by the formula (1), those in which -Z ₁ -and -Z ₂ -are direct bonds are preferable.

When the condensation reaction used for the condensation polymerization is a Yamamoto coupling reaction, a zero-valent nickel complex is usually used as the metal condensing agent.
As the zero-valent nickel complex, a method using a zero-valent nickel complex and a method in which a divalent nickel compound is reacted in the presence of a reducing agent such as zinc or hydrazine to generate a zero-valent nickel compound in the system and reacting the same. However, it is preferable to use a zero-valent nickel complex as it is without using a reducing agent.

The amount of the zero-valent nickel complex is usually 0.01 mol or more with respect to 1 mol of the monomer represented by the formula (1). When a reducing agent such as zinc or hydrazine is not used, the molecular weight tends to be small if the amount used is too small. Therefore, it is preferably 1.5 mol or more, more preferably 1.8 mol or more, and even more preferably 2 .1 mole or more. The upper limit of the amount used is not limited, but if the amount used is too large, post-treatment tends to be difficult, and therefore it is preferably 5.0 mol or less. When carried out in the presence of a reducing agent such as zinc or hydrazine, the zero-valent nickel complex is preferably about 0.01 to 1 mol, more preferably about 0.01 to 0.5 mol in order to act catalytically. .

  Examples of the zero-valent nickel complex include bis (1,5-cyclooctadiene) nickel (0), (ethylene) bis (triphenylphosphine) nickel (0), tetrakis (triphenylphosphine) nickel, Bis (1,5-cyclooctadiene) nickel (0) is preferred from the viewpoint of versatility and low cost.

Moreover, it is preferable from a viewpoint of a yield improvement to add a neutral ligand.
Here, the neutral ligand is a ligand having no anion or cation, and 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N′-tetramethylethylenediamine. Nitrogen-containing ligands such as triphenylphosphine, tolylphosphine, tributylphosphine, triphenoxyphosphine, 1,2-bisdiphenylphosphinoethane, 1,3-bisdiphenylphosphinopropane and other tertiary phosphine coordination A nitrogen-containing ligand is preferable in terms of versatility and low cost, and 2,2′-bipyridyl is particularly preferable in terms of high reactivity and high yield. In particular, from the viewpoint of improving the yield of the polymer, a system in which 2,2′-bipyridyl is added as a neutral ligand to a system containing bis (1,5-cyclooctadiene) nickel (0) is preferable. In the method in which zero-valent nickel is produced and reacted in the system, examples of the divalent nickel compound include nickel chloride and nickel acetate. Examples of the reducing agent include zinc, sodium hydride, hydrazine and derivatives thereof, lithium aluminum hydride, and the like, and ammonium iodide, lithium iodide, potassium iodide and the like are used as additives as necessary.

The reaction is usually carried out in a solvent. Examples of the solvent include aprotic polarities such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide, and dimethyl sulfoxide. Solvent, aromatic hydrocarbon solvent such as toluene, xylene, mesitylene, benzene, n-butylbenzene, aliphatic hydrocarbon solvent such as tetralin, decalin, tetrahydrofuran, 1,4-dioxane, dibutyl ether, tert-butylmethyl Examples include ether solvents such as ether and dimethoxyethane, ester solvents such as ethyl acetate, butyl acetate and methyl benzoate, and alkyl halide solvents such as chloroform and dichloroethane.
Among these, ether solvents and aromatic hydrocarbon solvents are preferable from the viewpoint of increasing the molecular weight. Moreover, ether solvents, such as tetrahydrofuran and 1, 4- dioxane, are more preferable from the surface of the ease in taking out the product by filtration.

These solvents can be used alone or as a mixed solvent by mixing two or more kinds of solvents at an arbitrary ratio. The amount of the solvent is not particularly limited, but if the concentration is too low, it may be difficult to recover the produced polymer compound, and if the concentration is too high, stirring may be difficult. , Solvent, monomer represented by formula (1), and metal condensing agent are 100% by weight, preferably 0.05 to 40% by weight, more preferably 0.1 to 25% by weight. A large amount of solvent is desirable.

The reaction temperature is not particularly limited. When a solvent is used, although it depends on the solvent to be used, it is usually about 45 to 200 ° C, preferably about 45 to 160 ° C from the viewpoint of low heating cost, and 50 to 100 A temperature of about ° C is more preferable. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.

The reaction time is usually about 0.25 to 200 hours, and preferably about 0.25 to 50 hours from the viewpoint of productivity and the like.

The Yamamoto coupling reaction is described in, for example, Macromolecules 1992, 25, 1214-1223.

When the condensation reaction used in the condensation polymerization is a Suzuki coupling reaction, Y ₁ and Y ₂ are each independently a halogen atom, —OSO ₂ R ₈ , or a monomer represented by the formula (1) A monomer that is -B (OR ₉ ) ₂ is used. Usually, the total amount (J) of the total number of moles of halogen atoms and -OSO ₂ R ₈ of the monomer, and -B (OR ₉ ) ₂ The ratio of the total number of moles (K) is substantially 1 (usually K / J is in the range of 0.7 to 1.2). (Wherein R ₈ and R ₉ each independently represent the same meaning as described above)

In this case, as the monomer represented by the formula (1), for example,
One or more selected from X-A-X, R ₈ O ₂ SO-A-OSO ₂ R ₈ and XA-OSO ₂ R _8, and (R ₉ O) ₂ BAB (OR ₉ ) ₂ A combination with one or more selected from:
X-A-B, etc. (OR _{9) 2} and _{R 8 O 2 SO-A-} B (OR 9) 2 from one or more selected thereof.
Among the monomers represented by the formula (1), those in which -Z ₁ -and -Z ₂ -are direct bonds are preferable.

When the condensation polymerization is a Suzuki coupling reaction, the metal condensing agent is preferably a nickel catalyst or a palladium catalyst.

Examples of the nickel catalyst include bis (1,5-cyclooctadiene) nickel (0) and nickel (II) dichloride. Examples of the palladium catalyst include palladium [tetrakis (triphenylphosphine)], palladium acetate. And the like.
The amount of the metal condensing agent used is usually 0.001 mol or more per 1 mol of the monomer represented by the formula (1). The upper limit is not limited, but is preferably 0.1 mol or less from the viewpoint of raw material costs.

Moreover, as a metal condensing agent, for example, when using bis (1,5-cyclooctadiene) nickel (0), nickel (II) dichloride or the like, it is desirable to add a neutral ligand as necessary. You may use the metal condensing agent which coordinated the neutral ligand previously.
Here, the neutral ligand is a ligand having no anion or cation, and 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N′-tetramethylethylenediamine. Nitrogen-containing ligands such as triethylamine; triphenylphosphine, tolylphosphine, tributylphosphine, triphenoxyphosphine, tricyclohexylphosphine, 1,2-bisdiphenylphosphinoethane, 1,3-bisdiphenylphosphinopropane, etc. Examples include tertiary phosphine ligands.
Usually, an inorganic base such as potassium carbonate, sodium carbonate, and barium hydroxide, an organic base such as triethylamine, and an inorganic salt such as cesium fluoride are added in an amount equal to or more, preferably 1 to 10 equivalents, relative to the monomer. An inorganic salt may be used as an aqueous solution and reacted in a two-phase system. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. As the reaction temperature, when a solvent is used, a temperature of about 45 to 160 ° C. is preferably used although it depends on the solvent. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours.
The Suzuki coupling reaction is described, for example, in Chemical Review (Chem. Rev.), Vol. 95, p. 2457 (1995).

When the condensation reaction used for the condensation polymerization is a transmetalation reaction, the monomer represented by the formula (1) is usually a monomer having Y ₁ and Y ₂ independently of each other a halogen atom and —MgX. The ratio of the total number of moles of halogen atoms (J) to the total number of moles of -MgX (K) in the total amount of monomers is usually substantially 1 (usually K / J is 0). In the range of 7 to 1.2). (In the formula, each X independently represents the same meaning as described above.)

In this case, as the monomer represented by the formula (1), for example,
One or more selected from X-A-X,
One or more combinations selected from XMg-A-MgX;
One or more selected from X-A-MgX;
Is mentioned.
(In the formula, A and X each independently represent the same meaning as described above.)
The -Z ₁ -, - Z ₂ - is preferably is a direct bond.

Examples of the metal condensing agent used when the condensation reaction used in the condensation polymerization is a transmetalation reaction include transition metal compounds such as nickel catalysts.
Examples of the nickel catalyst include transition metal compounds such as nickel chloride, nickel bromide, and bis (1,5-cyclooctadiene) nickel (0).
As a solvent, in a solvent such as tetrahydrofuran, toluene, N, N-dimethylformamide, the reaction time is about 1 hour to 200 hours, and the reaction is performed at a temperature of about 45 to 160 ° C.
In order to promote the reaction, iodide such as iodine, tetraethylammonium iodide, potassium iodide, sodium iodide or the like may coexist in the reaction system. Moreover, you may add neutral ligands, such as 2,2'- bipyridyl, as needed.
The transmetalation reaction is described, for example, in Polymer, 46, 68 (1997).

When the condensation reaction used in the condensation polymerization is a Stille reaction, usually, Y ₁ and Y ₂ are each independently a halogen atom, —OSO ₂ R ₈ , or —Sn as the monomer represented by the formula (1). (R ₁₀ ) ₃ is used, but usually the total number of moles of halogen atoms and —OSO ₂ R _{8 in} the total amount of monomers (J) and the number of moles of —Sn (R ₁₀ ) ₃ The total (K) ratio is substantially 1 (usually K / J is in the range of 0.7 to 1.2). Examples of the metal condensing agent include transition metal compounds such as a palladium catalyst (wherein R ₈ and R ₁₀ independently represent the same meaning as described above). The -Z ₁ -, - Z ₂ - is preferably is a direct bond.

In this case, as the monomer represented by the formula (1), for example,
X-A-X, combinations of the _{R 8 O 2 SO-A-} OSO 2 R 8 from at least one member selected _{(R 10) 3 Sn-A} -Sn (R 10) 3 of one or more selected ;

One or more selected from X-A-Sn (R ₁₀ ) ₃ and R ₈ O ₂ SO-A-Sn (R ₁₀ ) ₃ ;
(In the formula, A, X, R ₈ and R ₁₀ each independently represent the same meaning as described above.)

Is mentioned.

When the condensation reaction used for the condensation polymerization is a Stille reaction, a transition metal compound such as a palladium catalyst is used as the metal condensing agent.
As the metal condensing agent, for example, a transition metal compound such as palladium [tetrakis (triphenylphosphine)] is used, and the reaction is performed in a solvent such as tetrahydrofuran, toluene, N, N-dimethylformamide at a temperature of about 45 to 200 ° C. In the reaction system, an inorganic salt such as lithium chloride may coexist if necessary in order to promote the reaction. The reaction time is about 1 hour to 200 hours.
The Stille reaction is described, for example, in Polymers, Vol. 46, p. 68 (1997).

When the condensation reaction used in the condensation polymerization is an Ullmann reaction, the monomer represented by the formula (1) is preferably one in which Y ₁ and Y ₂ are each independently a halogen atom.
The -Z ₁ -, - Z ₂ - is preferably is a direct bond.
Examples of the metal condensing agent include metals such as copper. The amount of the metal condensing agent used is about 0.8 to 10 mol with respect to 1 mol of the monomer represented by the formula (1), and in a solvent such as tetrahydrofuran, toluene, chlorobenzene, N, N-dimethylformamide. , At a temperature of about 80 to 200 ° C. The reaction time is about 1 hour to 200 hours.
The Ullmann reaction is described, for example, in Chemical Reviews, 2002, 102 (5), 1359-1469.

When the condensation reaction used in the condensation polymerization is a Heck reaction, as the monomer represented by the formula (1), —Z ₁ — and —Z ₂ — are each independently directly bonded, or —CR ₆ ═CR ₇ — And at least one of —Z ₁ — and —Z ₂ — is used as —CR ₆ ═CR ₇ —.
-Z ₁ -, - when it is a direct bond, preferably Y ₁ and Y ₂ are each independently a halogen _{atom, -Z 1 - - Z 2,} - Z 2 - is -CR ₆ = CR ₇ - In this case, Y ₁ and Y ₂ are each preferably a hydrogen atom. (Wherein R ₆ and R ₇ have the same meaning as described above.)

In this case, as the monomer represented by the formula (1), for example,
X-A-X of one or more selected the _{H-R 7 C = CR 6} -A-CR 6 = combination of at least one member selected from CR ₇ -H;
_{X-A-CR 6 = CR} 7 1 or more selected from -H;
Is mentioned.
(In the formula, A, X, R ₆ and R ₇ each independently represent the same meaning as described above.)

  An example of the metal condensing agent is a palladium catalyst. For example, using a palladium (II) acetate catalyst, the monomer is reacted in the presence of a base such as triethylamine. A relatively high boiling point solvent such as N, N-dimethylformamide or N-methylpyrrolidone is used, the reaction temperature is about 80 to 160 ° C., and the reaction time is about 1 to 100 hours. The Heck reaction is described in, for example, Polymer, Vol. 39, pages 5241-5244 (1998).

When the condensation reaction used in the condensation polymerization is a Sonogashira reaction, as the monomer represented by the formula (1), -Z _1- , -Z ₂ -may be a direct bond, or -C≡C-. Preferably, at least one of -Z ₁ -and -Z _2- is used as at least one monomer.
When -Z ₁ -and -Z ₂ -are direct bonds, Y ₁ and Y ₂ are each independently a halogen atom, and -Z ₁ -and -Z ₂ -are -C≡C-. In this case, it is preferable that Y ₁ and Y ₂ are each independently a hydrogen atom.

In this case, as the monomer represented by the formula (1), for example,
A combination of one or more selected from X-A-X and one or more selected from HC≡C—A—C≡C—H;
One or more selected from X-A-C≡C—H;
Is mentioned. (In the formula, A and X each independently represent the same meaning as described above.)

  As the metal condensing agent, generally, a palladium catalyst and cuprous iodide are used, and in the presence of a base such as triethylamine, N, N-dimethylformamide, an amine solvent or an ether solvent is used, The monomer is reacted. Depending on the reaction conditions and the reactivity of the polymerizable substituent of the monomer, the reaction temperature is usually about 45 to 120 ° C., and the reaction time is about 1 to 100 hours. The Sonogashira reaction is described, for example, in Tetrahedron Letters, 40, 3347-3350 (1999), Tetrahedron Letters, 16, 4467-4470 (1975).

The condensation polymerization of the present invention is usually performed in a solvent.
The solvent to be used varies depending on the type of condensation reaction and the type of monomer used in the condensation polymerization to be used. In general, in order to suppress side reactions, sufficient deoxygenation treatment is performed and the reaction proceeds in an inert atmosphere. It is desirable. Similarly, it is preferable to perform a dehydration treatment. However, this is not the case when water is present in the system in advance, as in the case of performing a two-phase reaction with water in the Suzuki coupling reaction.

When the polymer compound produced by the method of the present invention is used in a polymer LED, the purity of the polymer compound affects the performance of the device such as light emission characteristics. Therefore, the monomer before polymerization is distilled, sublimated, purified, recrystallized, etc. Polymerization after purification by a graphic method is preferred.
The polymer compound of the present invention is polymerized, for example, a reaction mass is poured into a mixed solution of a large excess of methanol, water, and ammonia water to precipitate a crude polymer, which is collected by filtration, dried, and then dissolved in an organic solvent. It is possible to obtain by an operation of filtering insoluble metal, etc., performing acid washing, alkali washing, etc., if necessary, and then pouring it in a large excess of methanol to precipitate the polymer and filter it. it can. In addition, after the polymerization, purification is performed by conventional separation operations such as acid washing, alkali washing, neutralization, water washing, organic solvent washing, reprecipitation, centrifugation, extraction, column chromatography, and dialysis, purification operation, drying and other operations. It is preferable to

The polymer compound of the present invention is a polymer compound obtained by the above-described production method of the present invention, and contains one or more types of repeating units represented by the following formula (6) derived from the raw material monomer.
-Z ₁ -AZ _2- (6)
[Wherein, -A-, -Z _1-, and -Z _2- represent the same meaning as described above. ]

When one kind of the monomer represented by the general formula (1) is used, a homopolymer is formed.
In addition, when two or more types having different A as monomers are used, a copolymer is formed.
For example, two different monomers represented by the above formula (1) are
Y ₁ -Z ₁ -A ₁ -Z ₂ -Y ₂
Y ₁ -Z ₁ -A ₂ -Z ₂ -Y ₂
In this case, a copolymer having —Z ₁ —A ₁ —Z ₂ — and —Z ₁ —A ₂ —Z ₂ — as repeating units is obtained.

  In the polymer compound obtained by the production method of the present invention, the total number of repeating units represented by (6) is usually 10 mol% or more and 100 mol% or less, and 30 mol% or more and 100 mol% or less of all repeating units. It is more preferable that it is 50 mol% or more and 100 mol% or less.

The polymer compound may contain a repeating unit other than the repeating unit represented by (6) as long as the fluorescence property and the charge transport property are not impaired. Moreover, the repeating unit may be connected by a non-conjugated unit, or the non-conjugated part may be contained in the repeating unit. Examples of the binding structure include those shown below and combinations of two or more of the following. Here, R is a group selected from the same substituents as described above, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms.

The polymer compound may be a random, block or graft copolymer, or may be a polymer having an intermediate structure thereof, for example, a random copolymer having a block property. From the viewpoint of obtaining polymer light emitters (high-molecular-weight light-emitting materials) with high quantum yield of fluorescence or phosphorescence, random copolymers with block properties and block or graft copolymers are more suitable than completely random copolymers. preferable. A case in which the main chain is branched and there are three or more terminal portions and dendrimers are also included.

  In addition, the terminal group of the polymer compound of the present invention may be 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. . 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.

The polymer compound obtained by the production method of the present invention usually emits fluorescence and / or phosphorescence in the solid state, and the weight average molecular weight in terms of polystyrene is usually from 10 ³ to 10 ⁸ and from 10 ⁴ to 10 ⁷ . It is preferably 6 × 10 ⁴ to 10 ⁷ .
The number average molecular weight in terms of polystyrene is usually 10 ² to 10 ^7, preferably 10 ³ to 10 ^6, more preferably from 6x10 ³ to 10 ^6.

Next, the use of the polymer compound of the present invention will be described.
The polymer compound obtained by the production method 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). 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 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 polymer compound of the present invention.
The organic layer 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 exhibiting fluorescence and / or phosphorescence.

  When the 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. It is. 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 polymer compound of the present invention and the light emitting material are mixed, the mixing ratio of the light emitting material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt% with respect to the entire mixture. When the 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 fluorescent material is 1 wt% to 50 wt% with respect to the entire mixture, preferably Is 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%, and contains the polymer compound of the present invention. The amount 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 and high-molecular compounds can be used, but it is preferable to use high-molecular compounds. As the hole transporting material, electron transporting material and light emitting material of the polymer compound, WO99 / 13692, WO99 / 48160, GB2340304A, WO00 / 53656, WO01 / 19834, WO00 / 55927, GB23448316, 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, EP07070 0, WO95 / 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) with iridium as the central metal, PtOEP with platinum as the central metal, and Eu (TTA) 3phen with europium as the central metal. It is done.

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 DevicesＩＶ), 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。
本発明の組成物は、正孔輸送材料、電子輸送材料および発光材料から選ばれる少なくとも１種類の材料と本発明の高分子化合物の少なくとも1種類を含有するものであり、発光材料や電荷輸送材料として用いることができる。
正孔輸送材料、電子輸送材料、発光材料から選ばれる少なくとも１種類の材料と本発明の高分子化合物の含有比率は、用途に応じて決めればよいが、発光材料の用途の場合は、上記の発光層におけると同じ含有比率が好ましい。

Specific examples of triplet light emitting complexes include 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).
The 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 at least one polymer compound of the present invention. Can be used as
The content ratio of at least one material selected from a hole transport material, an electron transport material, and a light emitting material and the polymer compound of the present invention may be determined according to the use. The same content ratio as in the light emitting layer is preferable.

  The film thickness of the light emitting layer in the polymer LED of the present invention varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate values. For example, the film thickness is preferably 1 nm to 1 μm, preferably Is 2 nm to 500 nm, more preferably 5 nm to 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 ink composition used in the printing method or the like only needs to contain at least one polymer compound of the present invention. Besides the polymer compound of the present invention, a hole transport material, an electron transport material, a light emitting material, Additives such as solvents and stabilizers may be included.
The ratio of the polymer compound of the present invention in the ink composition is 20 wt% to 100 wt%, preferably 40 wt% to 100 wt%, based on the total weight of the composition excluding the solvent.

Further, when the solvent is contained in the ink composition, the ratio of the solvent is 1 wt% to 99.9 wt%, preferably 60 wt% to 99.5 wt%, and more preferably 80 wt% with respect to the total weight of the composition. % To 99.0 wt%.
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. to prevent clogging during flight and flight bending. It is preferably in the range of ˜20 mPa · s.

  Although there is no restriction | limiting in particular as a solvent used as an ink composition, The thing which can melt | dissolve or disperse | distribute materials other than the solvent which comprises this ink composition is preferable. When the material constituting the ink composition is soluble in a nonpolar solvent, the solvent is a chlorinated solvent such as chloroform, methylene chloride or dichloroethane, an ether solvent such as tetrahydrofuran, or an aromatic such as toluene or xylene. Examples include aromatic hydrocarbon solvents, ketone solvents such as acetone and methyl ethyl ketone, and ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate.

  In addition, as the polymer LED of the present invention, a polymer LED having an electron transport layer provided between the cathode and the light emitting layer, a polymer LED having a hole transport layer provided between the anode and the light emitting layer, Examples include a polymer LED in which an electron transport layer is provided between the cathode and the light emitting layer, and a hole transport layer is provided between the anode and the 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.)

  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.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transporting material. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  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, anthraquinones 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.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve an electron transport material and / or a polymer binder. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  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 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 / charge injection layer / light emitting layer / cathode f) Anode / light emitting layer / charge injection layer / cathode g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode h) Anode / charge injection layer / hole Transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / charge injection layer / cathode j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode k) anode / charge Injection layer / light emitting layer / electron transport layer / cathode l) anode / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode n) anode / Charge injection layer / hole transport layer / light emitting layer / electron transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) anode / charge injection layer / hole transport Layer / light emitting layer / electron transport layer / charge injection layer / cathode

  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 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 with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode aa) anode / hole transport layer / light emitting layer / electron transport Layer / thickness 2nm or less of the insulating layer / cathode ab) anode / thickness 2nm or less of the insulating layer / hole transport layer / light emitting layer / electron transporting layer / thickness 2nm or less of the insulating layer / cathode

  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, a polymer compound, metal oxide, metal fluoride, metal boride 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 becomes easy to suppress giving an image to an 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. By forming a pattern by any of these methods and arranging some electrodes so that they can be turned on / off independently, a segment type display element capable of displaying numbers, letters, simple symbols, and the like can be obtained. 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 multicolor display are possible by a method of separately coating a plurality of types of polymer light emitters 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. 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. Regarding the number average molecular weight and the weight average molecular weight, the number average molecular weight in terms of polystyrene (hereinafter referred to as Mn) and the weight average molecular weight in terms of polystyrene (hereinafter referred to as Mw) by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. Asked.

Example 1
Condensation polymerization of 2,7-dibromo-9,9-di-n-octylfluorene and 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene (60 ° C.)
2,7-dibromo-9,9-di-n-octylfluorene 4.00 g (7.3 mmol) and 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene 0.85 g (1.8 mmol) And 2,2′-bipyridyl (3.42 g, 21.9 mmol) were charged into a reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. To this, 240 g of tetrahydrofuran (dehydrated solvent) was added and dissolved by stirring. This mixed solution was deaerated by bubbling with argon gas, and then the mixed solution was heated to 60 ° C. Next, 6.02 g (21.9 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to the mixed solution and reacted at the same temperature for 5 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled, then poured into a mixed solution of 79 g of methanol / 100 g of ion-exchanged water / 18.2 g of 25% aqueous ammonia, and stirred for about 1 hour. Next, the deposited precipitate was filtered and dried under reduced pressure for 2 hours to obtain 5.3 g of a crude polymer. In the crude polymer, the ratio of the repeating units of 9,9-di-n-octylfluorene and 9,9-bis (3-methylbutyl) fluorene is 80:20. This crude polymer had a polystyrene-equivalent number average molecular weight (hereinafter referred to as Mn) of 3.3 × 10 ⁵ and a polystyrene-equivalent weight average molecular weight (hereinafter referred to as Mw) of 1.2 × 10 ⁶ . .
After 0.57 g of the crude polymer was dissolved in 160 g of toluene, the insoluble matter was filtered off with a filter paper. The filtrate was purified by passing through an alumina column. 79% of 6% hydrochloric acid was added to the recovered toluene solution and stirred for 30 minutes. The aqueous layer was removed, and 76 g of 3% aqueous ammonia was added to the organic layer, followed by stirring for 30 minutes. Thereafter, the aqueous layer was removed, and 67 g of ion-exchanged water was added to the organic layer. After stirring for 30 minutes, the aqueous layer was removed. 320 g of methanol was poured into the obtained toluene solution 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 was 0.24 g. In the copolymer, the ratio of the repeating units of 9,9-di-n-octylfluorene and 9,9-bis (3-methylbutyl) fluorene is 80:20. Mn of this copolymer was 3.7 × 10 ⁵ and Mw was 1.2 × 10 ⁶ .

Example 2
Condensation polymerization of 2,7-dibromo-9,9-di-n-octylfluorene and 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene (50 ° C.)
2,7-dibromo-9,9-di-n-octylfluorene 4.00 g (7.3 mmol) and 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene 0.85 g (1.8 mmol) And 2,2′-bipyridyl (3.42 g, 21.9 mmol) were charged into a reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. To this, 240 g of tetrahydrofuran (dehydrated solvent) was added and dissolved by stirring. The mixed solution was degassed by bubbling with argon gas, and then the mixed solution was heated to 50 ° C. Next, 6.02 g (21.9 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and reacted at the same temperature for 5 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled, then poured into a mixed solution of 79 g of methanol / 100 g of ion-exchanged water / 18.2 g of 25% aqueous ammonia, and stirred for about 1 hour. Next, the deposited precipitate was filtered and dried under reduced pressure for 2 hours to obtain 3.8 g of a crude polymer. In the crude polymer, the ratio of the repeating units of 9,9-di-n-octylfluorene and 9,9-bis (3-methylbutyl) fluorene is 80:20. Mn of this crude polymer was 3.9 × 10 ⁵ and Mw was 1.2 × 10 ⁶ .

Comparative Example 1
Condensation polymerization of 2,7-dibromo-9,9-di-n-octylfluorene and 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene (temperature rising from room temperature to 60 ° C.)
2,7-dibromo-9,9-di-n-octylfluorene 4.00 g (7.3 mmol) and 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene 0.85 g (1.8 mmol) And 2,2′-bipyridyl (3.42 g, 21.9 mmol) were charged into a reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. To this, 240 g of tetrahydrofuran (dehydrated solvent) was added and dissolved by stirring. This mixed solution was deaerated by bubbling with argon gas. Next, 6.02 g (21.9 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, stirred for 10 minutes at room temperature, then heated to 60 ° C. over 45 minutes, The reaction was carried out at the same temperature for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled and then poured into a mixed solution of 79 g of methanol / 100 g of ion-exchanged water / 18.2 g of 25% aqueous ammonia and stirred for about 2 hours. Next, the deposited precipitate was filtered and dried under reduced pressure for 8 hours to obtain 5.2 g of a crude polymer. In the crude polymer, the ratio of the repeating units of 9,9-di-n-octylfluorene and 9,9-bis (3-methylbutyl) fluorene is 80:20. The crude polymer had an Mn of 1.1 × 10 ⁵ and an Mw of 3.1 × 10 ⁵ .
After dissolving 1.74 g of the crude polymer in 80 g of toluene, the insoluble matter was filtered off with a filter paper. The filtrate was purified by passing through an alumina column. 79% of 6% hydrochloric acid was added to the recovered toluene solution and stirred for 30 minutes. The aqueous layer was removed, and 76 g of 3% aqueous ammonia was added to the organic layer, followed by stirring for 30 minutes. Thereafter, the aqueous layer was removed, and 67 g of ion-exchanged water was added to the organic layer. After stirring for 30 minutes, the aqueous layer was removed. 158 g of methanol was poured into the obtained toluene solution 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 was 0.30 g. In the copolymer, the ratio of the repeating units of 9,9-di-n-octylfluorene and 9,9-bis (3-methylbutyl) fluorene is 80:20. Mn of this copolymer was 1.1 × 10 ⁵ and Mw was 2.9 × 10 ⁵ .

Comparative Example 2
Condensation polymerization of 2,7-dibromo-9,9-di-n-octylfluorene and 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene (28 ° C.)
2,7-dibromo-9,9-di-n-octylfluorene 4.00 g (7.3 mmol) and 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene 0.85 g (1.8 mmol) And 2,2′-bipyridyl (3.42 g, 21.9 mmol) were charged into a reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. To this, 240 g of tetrahydrofuran (dehydrated solvent) was added and dissolved by stirring. This mixed solution was deaerated by bubbling with argon gas. Next, 6.02 g (21.9 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution at room temperature (28 ° C.), and reacted at room temperature (28 ° C.) for 5 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled, then poured into a mixed solution of 79 g of methanol / 100 g of ion-exchanged water / 18.2 g of 25% aqueous ammonia, and stirred for about 1 hour. Next, the deposited precipitate was filtered and dried under reduced pressure for 2 hours to obtain 3.2 g of a crude polymer. In the crude polymer, the ratio of the repeating units of 9,9-di-n-octylfluorene and 9,9-bis (3-methylbutyl) fluorene is 80:20. The crude polymer had an Mn of 5.5 × 10 ³ and an Mw of 1.4 × 10 ⁴ .

Comparative Example 3
Condensation polymerization of 2,7-dibromo-9,9-di-n-octylfluorene and 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene (40 ° C.)
2,7-dibromo-9,9-di-n-octylfluorene 4.00 g (7.3 mmol) and 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene 0.85 g (1.8 mmol) And 2,2′-bipyridyl (3.42 g, 21.9 mmol) were charged into a reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. To this, 240 g of tetrahydrofuran (dehydrated solvent) was added and dissolved by stirring. This mixed solution was deaerated by bubbling with argon gas. Next, 6.02 g (21.9 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution at 40 ° C., and reacted at the same temperature for 5 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled, then poured into a mixed solution of 79 g of methanol / 100 g of ion-exchanged water / 18.2 g of 25% aqueous ammonia, and stirred for about 1 hour. Next, the deposited precipitate was filtered and dried under reduced pressure for 2 hours to obtain 4.9 g of a crude polymer. In the crude polymer, the ratio of the repeating units of 9,9-di-n-octylfluorene and 9,9-bis (3-methylbutyl) fluorene is 80:20. The crude polymer had an Mn of 1.2 × 10 ⁴ and an Mw of 2.4 × 10 ⁴ .

Reference example 3
Synthesis of Compound C (Dibenzothiophene Derivative)

（化合物Ｃ−１）
不活性雰囲気下１ｌの四つ口フラスコに２，８−ジブロモジベンゾチオフェン ７ｇとＴＨＦ ２８０ｍｌを入れ、室温で撹拌、溶かした後、−７８℃まで冷却した。ｎ−ブチルリチウム ２９ｍｌ（１．６モルヘキサン溶液）を滴下した。滴下終了後、温度を保持したまま２時間撹拌し、トリメトキシボロン酸 １３ｇを滴下した。滴下終了後、ゆっくり室温まで戻した。３時間室温で撹拌後、ＴＬＣで原料の消失を確認した。５％硫酸 １００ｍｌを加えて反応を終了させ、室温で１２時間撹拌した。水を加えて洗浄し、有機層を分液した。溶媒を酢酸エチルに置換した後、３０％過酸化水素水 ５ｍｌを加え、４０℃で５時間撹拌した。その後有機層を分液し、１０％硫酸アンモニウム鉄（II）水溶液で洗浄後乾燥、溶媒を留去することにより、茶色の固体 ４．４３ｇを得た。ＬＣ−ＭＳ測定からは二量体などの副生成物も生成しており、化合物Ｃ−１の純度は７７％であった（ＬＣ面百）。
ＭＳ（ＡＰＣＩ（−））：（Ｍ−Ｈ）^- ２１５ Reference Example 3-1 (Synthesis of Compound C-1)

(Compound C-1)
Under an inert atmosphere, 7 g of 2,8-dibromodibenzothiophene and 280 ml of THF were placed in a 1 l four-necked flask, stirred and dissolved at room temperature, and then cooled to -78 ° C. 29 ml of n-butyllithium (1.6 molar hexane solution) was added dropwise. After completion of dropping, the mixture was stirred for 2 hours while maintaining the temperature, and 13 g of trimethoxyboronic acid was added dropwise. After completion of dropping, the temperature was slowly returned to room temperature. After stirring at room temperature for 3 hours, disappearance of the raw material was confirmed by TLC. The reaction was terminated by adding 100 ml of 5% sulfuric acid and stirred at room temperature for 12 hours. Water was added for washing, and the organic layer was separated. After replacing the solvent with ethyl acetate, 5 ml of 30% aqueous hydrogen peroxide was added and stirred at 40 ° C. for 5 hours. Thereafter, the organic layer was separated, washed with a 10% aqueous ammonium iron (II) sulfate solution, dried, and the solvent was distilled off to obtain 4.43 g of a brown solid. By-products such as dimers were also produced from LC-MS measurement, and the purity of compound C-1 was 77% (LC area percentage).
MS (APCI (-)) :( M-H) - 215

（化合物Ｃ−２）
不活性雰囲気下で２００ｍｌの三つ口フラスコに上記化合物Ｃ−１ ４．４３ｇと臭化ｎ−オクチル ２５．１ｇ、および炭酸カリウム １２．５ｇ（２３．５ｍｍｏｌ）を入れ、溶媒としてメチルイソブチルケトン ５０ｍｌを加えて１２５℃で６時間加熱還流した。反応終了後、溶媒を留去、クロロホルムと水を加えて、有機層を分液し、さらに水で２回洗浄した。無水硫酸ナトリウムで乾燥後、シリカゲルカラム（展開溶媒：トルエン／シクロヘキサン＝１／１０）で精製することにより、８．４９ｇ（ＬＣ面百９７％、収率９４％）の化合物Ｃ−２を得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９１（ｔ、６Ｈ）、１．３１〜１．９０（ｍ、２４Ｈ）、４．０８（ｔ、４Ｈ）、７．０７（ｄｄ、２Ｈ）、７．５５（ｄ、２Ｈ）、７．６８（ｄ、２Ｈ） Reference Example 3-2 (Synthesis of Compound C-2)

(Compound C-2)
Under an inert atmosphere, 4.43 g of the above compound C-1, 25.1 g of n-octyl bromide, and 12.5 g (23.5 mmol) of potassium carbonate were placed in a 200 ml three-necked flask, and methyl isobutyl ketone 50 ml as a solvent. And heated to reflux at 125 ° C. for 6 hours. After completion of the reaction, the solvent was distilled off, chloroform and water were added, the organic layer was separated, and further washed twice with water. After drying over anhydrous sodium sulfate, purification was performed with a silica gel column (developing solvent: toluene / cyclohexane = 1/10) to obtain 8.49 g (LC area percentage 97%, yield 94%) of compound C-2. .
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.91 (t, 6H), 1.31-1.90 (m, 24H), 4.08 (t, 4H), 7.07 (dd, 2H), 7.55 (d, 2H), 7 .68 (d, 2H)

（化合物Ｃ−３） Reference Example 3-3 (Synthesis of Compound C-3)

(Compound C-3)

In a 100 ml three-necked flask, 6.67 g of compound C-2 and 40 ml of acetic acid were placed, and the temperature was raised to 140 ° C. in an oil bath. Subsequently, 13 ml of 30% aqueous hydrogen peroxide was added from the condenser, and after vigorously stirring for 1 hour, the reaction was terminated by pouring into 180 ml of cold water. After extraction with chloroform and drying, the solvent was distilled off to obtain 6.96 g (LC area percentage 90%, yield 97%) of compound C-3.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.87 (m, 24H), 4.06 (t, 4H), 7.19 (dd, 2H), 7.69 (d, 2H), 7 .84 (d, 2H)
MS (APCI (+)): (M + H) ^<+> 473

（化合物Ｃ−４）
不活性雰囲気下２００ｍｌ四つ口フラスコに化合物Ｃ−３ ３．９６ｇと酢酸／クロロホルム＝１：１混合液 １５ｍｌを加え、７０℃で撹拌し、溶解させた。続いて、臭素 ６．０２ｇを上記の溶媒 ３ｍｌに溶かして加え、３時間撹拌した。チオ硫酸ナトリウム水溶液を加えて未反応の臭素を除き、クロロホルムと水を加えて、有機層を分液し乾燥した。溶媒を留去し、シリカゲルカラム（展開溶媒：クロロホルム／ヘキサン＝１／４）で精製することにより、４．４６ｇ（ＬＣ面百９８％、収率８４％）の化合物Ｃ−４を得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９５（ｔ、６Ｈ）、１．３０〜１．９９（ｍ、２４Ｈ）、４．１９（ｔ、４Ｈ）、７．０４（ｓ、２Ｈ）、７．８９（ｓ、２Ｈ）
ＭＳ（ＦＤ＋）Ｍ＋ ６３０

参考例３−５＜化合物Ｃ（ジベンゾチオフェン誘導体）の合成＞

＜化合物Ｃ（ジベンゾチオフェン誘導体）＞
不活性雰囲気下２００ｍｌ三つ口フラスコに化合物Ｃ−４ ３．９ｇとジエチルエーテル ５０ｍｌを入れ、４０℃まで昇温、撹拌した。水素化アルミニウムリチウム １．１７ｇを少量ずつ加え、５時間反応させた。水を少量ずつ加えることによって過剰な水素化アルミニウムリチウムを分解し、３６％塩酸 ５．７ｍｌで洗浄した。クロロホルム、水を加えて、有機層を分液し乾燥した。シリカゲルカラム（展開溶媒：クロロホルム／ヘキサン＝１／５）で精製することにより、１．８ｇ（ＬＣ面百９９％、収率４９％）の化合物Ｃを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、６Ｈ）、１．２６〜１．９７（ｍ、２４Ｈ）、４．１５（ｔ、４Ｈ）、７．４５（ｓ、２Ｈ）、７．９４（ｓ、２Ｈ）
ＭＳ（ＦＤ⁺）Ｍ⁺ ５９８ Reference Example 3-4 (Synthesis of Compound C-4)

(Compound C-4)
Under an inert atmosphere, 3.96 g of Compound C-3 and 15 ml of a mixed solution of acetic acid / chloroform = 1: 1 were added to a 200 ml four-necked flask and stirred at 70 ° C. to dissolve. Subsequently, 6.02 g of bromine was dissolved in 3 ml of the above solvent, and the mixture was stirred for 3 hours. A sodium thiosulfate aqueous solution was added to remove unreacted bromine, chloroform and water were added, and the organic layer was separated and dried. The solvent was distilled off and purified by a silica gel column (developing solvent: chloroform / hexane = 1/4) to obtain 4.46 g (LC area percentage 98%, yield 84%) of compound C-4.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.95 (t, 6H), 1.30 to 1.99 (m, 24H), 4.19 (t, 4H), 7.04 (s, 2H), 7.89 (s, 2H)
MS (FD +) M + 630

Reference Example 3-5 <Synthesis of Compound C (Dibenzothiophene Derivative)>

<Compound C (dibenzothiophene derivative)>
Under an inert atmosphere, 3.9 g of Compound C-4 and 50 ml of diethyl ether were placed in a 200 ml three-necked flask, heated to 40 ° C. and stirred. Lithium aluminum hydride 1.17 g was added little by little and allowed to react for 5 hours. Excess lithium aluminum hydride was decomposed by adding water little by little and washed with 5.7 ml of 36% hydrochloric acid. Chloroform and water were added, and the organic layer was separated and dried. By purification with a silica gel column (developing solvent: chloroform / hexane = 1/5), 1.8 g (LC area percentage 99%, yield 49%) of compound C was obtained.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.97 (m, 24H), 4.15 (t, 4H), 7.45 (s, 2H), 7.94 (s, 2H)
MS (FD ⁺ ) M ⁺ 598

（化合物Ｄ−１）
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、白色の固体３４．２ｇを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ(ｐｐｍ) ＝ １．３〔ｓ，９Ｈ〕、２．４〔ｓ，６Ｈ〕、７．１〔ｓ，２Ｈ〕
ＭＳ（ＦＤ⁺）Ｍ⁺ ２４１ Reference example 4
Synthesis Reference Example 4-1 of Compound D (Phenylenediamine Derivative)
<Synthesis of Compound D-1>

(Compound D-1)
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 a white solid.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ (ppm) = 1.3 [s, 9H], 2.4 [s, 6H], 7.1 [s, 2H]
MS (FD ⁺ ) M ⁺ 241

（化合物Ｄ−２）
不活性雰囲気下で、１００ｍｌの３つ口フラスコに脱気した脱水トルエン３６ｍｌを入れ、トリ（ｔ−ブチル）ホスフィン０．６３ｇ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０．４１ｇ、上記の化合物Ｄ−１ ９．６ｇ、ｔ−ブトキシナトリウム５．２ｇ、Ｎ，Ｎ’−ジフェニル−１，４−フェニレンジアミン４．７ｇを加えた後、１００℃で３時間反応させた。
反応液を飽和食塩水３００ｍｌに加え、約５０℃に温めたクロロホルム３００ｍｌで抽出した。溶媒を留去した後、トルエン１００ｍｌを加えて、固体が溶解するまで加熱、放冷した後、沈殿をろ過し、白色の固体９．９ｇを得た。 Reference Example 4-2
<Synthesis of Compound D-2>

(Compound D-2)
Under an inert atmosphere, 36 ml of degassed dehydrated toluene was placed in a 100 ml three-necked flask, and 0.63 g of tri (t-butyl) phosphine was added. Subsequently, 0.41 g of tris (dibenzylideneacetone) dipalladium, 9.6 g of the above compound D-1, 5.2 g of sodium t-butoxy, and 4.7 g of N, N′-diphenyl-1,4-phenylenediamine were added. And then reacted at 100 ° C. for 3 hours.
The reaction solution was added to 300 ml of saturated brine and extracted with 300 ml of chloroform warmed to about 50 ° C. After the solvent was distilled off, 100 ml of toluene was added, and the mixture was heated and allowed to cool until the solid was dissolved, and then the precipitate was filtered to obtain 9.9 g of a white solid.

（化合物Ｄ：フェニレンジアミン誘導体）
不活性雰囲気下で、１０００ｍｌの３つ口フラスコに脱水Ｎ，Ｎ−ジメチルホルムアミド３５０ｍｌを入れ、上記の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）−１，４−フェニレンジアミン５．２ｇを溶解した後、氷浴下でＮ−ブロモスクシンイミド３．５ｇ／Ｎ，Ｎ−ジメチルホルムアミド溶液を滴下し、一昼夜反応させた。
反応液に水１５０ｍｌを加え、析出した沈殿をろ過し、メタノール５０ｍｌで２回洗浄し化合物Ｄの白色の固体４．４ｇを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＴＨＦ−ｄ８）：
δ(ｐｐｍ) ＝ １．３〔ｓ，１８Ｈ〕、２．０〔ｓ，１２Ｈ〕、６．６〜６．７〔ｄ，４Ｈ〕、６．８〜６．９〔ｂｒ，４Ｈ〕、７．１〔ｓ，４Ｈ〕、７．２〜７．３〔ｄ，４Ｈ〕
ＭＳ（ＦＤ⁺）Ｍ⁺ ７３８ Reference Example 4-3
<Synthesis of Compound D (Phenylenediamine Derivative)>

(Compound D: phenylenediamine derivative)
Under an inert atmosphere, 350 ml of dehydrated N, N-dimethylformamide was placed in a 1000 ml three-necked flask and the above N, N′-diphenyl-N, N′-bis (4-t-butyl-2,6- After dissolving 5.2 g of (dimethylphenyl) -1,4-phenylenediamine, a 3.5 g / N, N-dimethylformamide solution of N-bromosuccinimide was added dropwise in an ice bath and allowed to react overnight.
150 ml of water was added to the reaction solution, and the deposited precipitate was filtered and washed twice with 50 ml of methanol to obtain 4.4 g of Compound D white solid.
¹ H-NMR (300 MHz / THF-d8):
δ (ppm) = 1.3 [s, 18H], 2.0 [s, 12H], 6.6 to 6.7 [d, 4H], 6.8 to 6.9 [br, 4H], 7 .1 [s, 4H], 7.2 to 7.3 [d, 4H]
MS (FD ⁺ ) M ⁺ 738

Example 3
Condensation polymerization of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) (60 ° C.)
2.73 g (4.6 mmol) of compound C (dibenzothiophene derivative), 3.37 g (4.6 mmol) of compound D (phenylenediamine derivative) and 3.42 g (21.9 mmol) of 2,2′-bipyridyl Then, the inside of the reaction system was replaced with nitrogen gas. To this, 214 g of tetrahydrofuran (dehydrated solvent) was added and dissolved by stirring. This mixed solution was deaerated by bubbling with argon gas, and then the mixed solution was heated to 60 ° C. Next, 6.02 g (21.9 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to the mixed solution and reacted at the same temperature for 5 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled, then poured into a mixed solution of 79 g of methanol / 100 g of ion-exchanged water / 18.2 g of 25% aqueous ammonia, and stirred for about 1 hour. Next, the deposited precipitate was filtered and dried under reduced pressure for 5 hours to obtain 5.6 g of a crude polymer. In the crude polymer, the ratio of the repeating units of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) is 50:50. The crude polymer had an Mn of 2.7 × 10 ⁴ and an Mw of 2.4 × 10 ⁵ .

Comparative Example 4
Condensation polymerization of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) (temperature rising from room temperature to 60 ° C.)
A reaction vessel containing 1.8 g (3.0 mmol) of compound C (dibenzothiophene derivative), 2.2 g (3.0 mmol) of compound D (phenylenediamine derivative) and 1.84 g (11.8 mmol) of 2,2′-bipyridyl Then, the inside of the reaction system was replaced with nitrogen gas. To this, 160 ml of tetrahydrofuran (dehydrated solvent) was added and dissolved by stirring. This mixed solution was deaerated by bubbling with argon gas, and then the mixed solution was heated to 60 ° C. Next, 3.4 g (11.8 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution and reacted at the same temperature for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled and then poured into a mixed solution of methanol 100 ml / ion-exchanged water 200 ml / 25% aqueous ammonia 30 ml and stirred for about 2 hours. Next, the deposited precipitate was filtered, washed with methanol, and then dried under reduced pressure for 5 hours to obtain 2.7 g of a crude polymer.
The whole amount of the crude polymer was dissolved in 150 g of toluene, and the insoluble matter was filtered off with a filter paper. The filtrate was purified by passing through an alumina column, 45 ml of 25% aqueous ammonia and 200 ml of ion exchange water were added to the recovered toluene solution, stirred for 2 hours, the aqueous layer was removed, and 200 ml of ion exchange water was added to the organic layer. In addition, the aqueous layer was removed after stirring for 30 minutes. The obtained toluene solution was poured into 450 ml of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure for 5 hours. The yield of the obtained copolymer was 1.20 g. In the copolymer, the ratio of the repeating units of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) is 50:50. Mn of this polymer was 1.8 × 10 ⁴ , and Mw was 4.9 × 10 ⁴ .

Example 4
Condensation polymerization of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) (60 ° C metal condensing material preparation)
Compound C (dibenzothiophene derivative) 1.616 g (2.7 mmol), compound D (phenylenediamine derivative) 1.330 g (1.8 mmol) and 2,2′-bipyridyl 1.688 g (10.8 mmol) Then, the inside of the reaction system was replaced with nitrogen gas. To this, 115 g of tetrahydrofuran (dehydrated solvent) was added and dissolved by stirring. This mixed solution was deaerated by bubbling with argon gas, and then the mixed solution was heated to 60 ° C. Next, 2.971 g (10.8 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution and reacted at the same temperature for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled and then poured into a mixed solution of methanol 102 g / ion exchanged water 130 g / 25% ammonia water 8.9 g and stirred for about 1 hour. Next, the deposited precipitate was filtered and dried under reduced pressure to obtain 2.76 g of a crude polymer. In the crude polymer, the ratio of the repeating units of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) is 60:40. The crude polymer had Mn of 2.8 × 10 ⁴ and Mw of 2.3 × 10 ⁵ .

Example 5
The reaction vessel was charged with 1.688 g (10.8 mmol) of 2,2′-bipyridyl condensation polymerization of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative), and the reaction system was replaced with nitrogen gas. To this, 115 g of tetrahydrofuran (dehydrated solvent) was added and dissolved by stirring. This mixed solution was degassed by bubbling with argon gas, and then 2.971 g (10.8 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added, and the temperature was raised to 60 ° C. After the temperature increase, 1.616 g (2.7 mmol) of compound C (dibenzothiophene derivative) and 1.330 g (1.8 mmol) of compound D (phenylenediamine derivative) were added and reacted at the same temperature for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled and then poured into a mixed solution of methanol 102 g / ion exchanged water 130 g / 25% ammonia water 8.9 g and stirred for about 1 hour. Next, the deposited precipitate was filtered and dried under reduced pressure to obtain 1.80 g of a crude polymer. In the crude polymer, the ratio of the repeating units of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) is 60:40. Mn of this crude polymer was 1.1 × 10 ⁴ and Mw was 1.3 × 10 ⁵ .

Example 6
Condensation polymerization of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) 0.592 g (0.99 mmol) of compound C (dibenzothiophene derivative) and 0.598 g (8.1 mmol) of compound D (phenylenediamine derivative) After charging 0.675 g (4.32 mmol) of 2,2′-bipyridyl into the reaction vessel, the inside of the reaction system was replaced with nitrogen gas. To this, 52 ml of tetrahydrofuran (dehydrated solvent) was added and dissolved by stirring, and then the mixed solution was heated to 60 ° C. Next, 1.188 g (4.32 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution and reacted at the same temperature for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled and then poured into a mixed solution of methanol 41 g / ion-exchanged water 52 g / 25% ammonia water 3.6 g and stirred for about 1 hour. Next, the deposited precipitate was filtered and dried under reduced pressure to obtain 1.11 g of a crude polymer. In the crude polymer, the ratio of the repeating units of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) is 55:45. The crude polymer had an Mn of 2.3 × 10 ⁴ and an Mw of 2.0 × 10 ⁵ .

Example 7
Condensation polymerization of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) 0.592 g (0.99 mmol) of compound C (dibenzothiophene derivative) and 0.598 g (8.1 mmol) of compound D (phenylenediamine derivative) After charging 0.675 g (4.32 mmol) of 2,2′-bipyridyl into the reaction vessel, the inside of the reaction system was replaced with nitrogen gas. To this, 52 ml of toluene (dehydrated solvent) was added and dissolved by stirring, and then the mixed solution was heated to 60 ° C. Next, 1.188 g (4.32 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution and reacted at the same temperature for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled and then poured into a mixed solution of methanol 41 g / ion-exchanged water 52 g / 25% ammonia water 3.6 g and stirred for about 1 hour. In this reaction, the deposited precipitate was fine and it was difficult to filter out as in Example 6. Therefore, after standing, the aqueous layer was separated, and the obtained organic layer was dried under reduced pressure to obtain 1.57 g of crude polymer. Got. In the crude polymer, the ratio of the repeating units of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) is 55:45. The crude polymer had an Mn of 2.5 × 10 ⁴ and an Mw of 3.2 × 10 ⁵ .

Example 8
Condensation polymerization of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) 0.592 g (0.99 mmol) of compound C (dibenzothiophene derivative) and 0.598 g (8.1 mmol) of compound D (phenylenediamine derivative) After charging 0.675 g (4.32 mmol) of 2,2′-bipyridyl into the reaction vessel, the inside of the reaction system was replaced with nitrogen gas. To this, 52 ml of N, N-dimethylformamide (dehydrated solvent) was added and dissolved by stirring, and then the temperature of the mixed solution was raised to 60 ° C. Next, 1.188 g (4.32 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution and reacted at the same temperature for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled and then poured into a mixed solution of methanol 41 g / ion-exchanged water 52 g / 25% ammonia water 3.6 g and stirred for about 1 hour. Next, the deposited precipitate was filtered and dried under reduced pressure to obtain 1.08 g of a crude polymer. In the crude polymer, the ratio of the repeating units of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) is 55:45. The crude polymer had an Mn of 7.9 × 10 ³ and an Mw of 2.0 × 10 ⁴ .

Example 9
Condensation polymerization of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) 0.592 g (0.99 mmol) of compound C (dibenzothiophene derivative) and 0.598 g (8.1 mmol) of compound D (phenylenediamine derivative) After charging 0.675 g (4.32 mmol) of 2,2′-bipyridyl into the reaction vessel, the inside of the reaction system was replaced with nitrogen gas. To this, 52 ml of 1,4-dioxane (dehydrated solvent) was added and dissolved by stirring, and then the mixed solution was heated to 60 ° C. Next, 1.188 g (4.32 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution and reacted at the same temperature for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled and then poured into a mixed solution of methanol 41 g / ion-exchanged water 52 g / 25% ammonia water 3.6 g and stirred for about 1 hour. Next, the deposited precipitate was filtered and dried under reduced pressure to obtain 1.05 g of a crude polymer. In the crude polymer, the ratio of the repeating units of compound C (dibenzothiophene derivative) and compound D (phenylenediamine derivative) is 55:45. The crude polymer had Mn of 2.8 × 10 ⁴ and Mw of 2.5 × 10 ⁵ .

Claims (21)

One or more monomers selected from the following formula (1) are subjected to condensation polymerization in the presence of a metal condensing agent selected from a metal and a metal compound, and the polymer has one or more repeating units represented by the following formula (6). In producing molecular compounds,
A method for producing a polymer compound, wherein a temperature at which the metal condensing agent is allowed to act on a monomer is 45 ° C or higher.

Y ₁ -Z ₁ -AZ ₂ -Y ₂ (1)
[Wherein, Y ₁ and Y ₂ each independently represent an atom or an atomic group that can be removed by the action of the condensing agent,
-A- is
-Ar _1- (2),
—Ar ₂ —X ₁ — (Ar ₃ —X ₂ ) _w —Ar ₄ — (3),
—Ar ₅ —X ₃ — (4)
Or -X ₄ - (5)
_{(Wherein, Ar 1, Ar 2, Ar} 3, Ar 4, and Ar ₅ represent each independently an arylene group, a divalent group having a divalent heterocyclic group or a metal complex structure, X ₁ is - C≡C—, —N (R ₁ ) —, or — (SiR ₂ R ₃ ) _y —, wherein X ₂ and X ₃ are —CR ₄ ═CR ₅ —, —C≡C—, —N (R ₁ ) — or — (SiR ₂ R ₃ ) _y —, and X ₄ represents —CR ₄ ═CR ₅ —, —C≡C—, or — (SiR ₂ R ₃ ) _y —, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or an arylalkyl group, and R ₄ and R ₅ 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, w represents an integer of 0 to 1, y Represents an integer of 1 to 12. When a plurality of R _{2 s} and R _{3 s} are present, they may be the same or different.
—Z ₁ — and —Z ₂ — each independently represents a direct bond, —C≡C—, or —CR ₆ ═CR ₇ —, and R ₆ and R ₇ each independently represents a hydrogen atom, an alkyl group, or aryl. Represents a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group]

-Z ₁ -AZ _2- (6)
[Wherein, -A-, -Z _1-, and -Z _2- represent the same meaning as described above. ]
_{2. The} process according to claim 1, wherein the metal condensing agent is a zero-valent nickel complex, and Y ₁ and Y ₂ are each independently a halogen atom or —OSO ₂ R ₈ , wherein R ₈ is an alkyl group Represents an aryl group or an arylalkyl group.   The production method according to claim 2, wherein the amount of the zerovalent nickel complex is in the range of 0.01 to 5 mol with respect to 1 mol of the monomer of the formula (1).   4. The production method according to claim 2, wherein the condensation polymerization is carried out in the presence of an ether solvent or an aromatic hydrocarbon solvent.   3. A zero-valent nickel complex is mixed with the liquid mixture as a solid or as a liquid mixture with a solvent while maintaining the temperature of the liquid mixture containing the monomer and the solvent at 45 ° C. or higher. The manufacturing method of -4. The metal condensing agent is a nickel catalyst or a palladium catalyst, Y ₁ and Y ₂ are each independently a halogen atom, —OSO ₂ R ₈ or —B (OR ₉ ) ₂ , and a halogen atom, —OSO ₂ R ₈ The production method according to claim 1, wherein the ratio of the total number of moles to the total number of moles of -B (OR ₉ ) ₂ is 1, wherein R ₈ is an alkyl group, aryl Represents a group or an arylalkyl group, R ₉ represents a hydrogen atom, an alkyl group, or an aryl group, and two R _{9 s} may be the same or different and may together form a ring. ].   The production method according to claim 6, wherein the amount of the nickel catalyst or the palladium catalyst is in the range of 0.001 to 0.1 mol with respect to 1 mol of the monomer of the formula (1).   A polymer compound produced by the production method according to claim 1.   A composition comprising at least one material selected from a hole transport material, an electron transport material, and a light-emitting material and at least one polymer compound according to claim 8.   An ink composition comprising the polymer compound according to claim 8.   The ink composition according to claim 10, wherein the viscosity is 1 to 20 mPa · s at 25 ° C.   A luminescent thin film containing the polymer compound according to claim 8.   A conductive thin film containing the polymer compound according to claim 8.   An organic semiconductor thin film containing the polymer compound according to claim 8.   A polymer light emitting device comprising a layer containing the polymer compound according to claim 8 between electrodes composed of an anode and a cathode.   The polymer light-emitting device according to claim 15, wherein the layer containing the polymer compound according to claim 8 is a light-emitting layer.   16. The polymer light emitting device according to claim 15, wherein the light emitting layer further contains a hole transporting material, an electron transporting material or a light emitting material.   A planar light source comprising the polymer light-emitting device according to claim 15.   A segment display device comprising the polymer light-emitting device according to claim 15.   A dot matrix display device comprising the polymer light emitting device according to claim 15. A liquid crystal display device comprising the polymer light emitting device according to claim 15 as a backlight.