JP5457619B2 - Polyarylene - Google Patents

Description

  The present invention relates to polyarylene.

It has an asymmetric divalent aromatic group as a repeating unit, and the divalent aromatic group is numbered by a carbon atom according to the IUPAC organic chemical nomenclature, and among the two carbon atoms having a free valence, A regioregular polyarylene having a high proportion of head-to-tail bonds formed between the head and the tail when the lower carbon atom is the head and the higher carbon atom is the tail is It is known that, due to high regularity, functions such as improved crystallinity, improved orientation, and improved conductivity are exhibited (see Non-Patent Documents 1 and 2).
As a regioregular polyarylene having a head-to-tail bond at a high ratio, those having a heterocyclic ring such as thiophene, pyridine, quinoline, and furan have been known (see Non-Patent Document 1).
In addition, as polyarylene having a divalent aromatic group whose aromatic ring is an aromatic hydrocarbon ring as a repeating unit, polyphenylene described in Non-Patent Document 3 is known, but these have a head-to-tail bond. There is no description about positional regularity. Furthermore, although the polyphenylene described in Non-Patent Document 3 has an alkoxymethyl group or an acyloxymethyl group as a substituent, these substituents are easily cleaved in both oxidizing and reducing atmospheres, and so on. It is not suitable for use as a charge transport material, an organic semiconductor material, a polymer electrolyte membrane or the like.
Adv. Mater. 1998, 10, 93 Appl. Phys. Lett. 1996, 69, 4108 Polymeric Materials Science and Engineering 1999, 80, 229

  Therefore, as a polymer material such as a light emitting material, a charge transport material, an organic semiconductor material, and a polymer electrolyte membrane having excellent stability, a divalent aromatic group whose aromatic ring is an aromatic hydrocarbon ring is used as a repeating unit. There has been a desire for polyarylenes containing regioregular chains with a high proportion of head-to-tail bonds.

  As a result of intensive studies to solve the above problems, the present inventors have a substituent that is difficult to decompose in an oxidizing or reducing atmosphere, and there is no sulfur atom, nitrogen atom, or oxygen atom on the aromatic ring. A polyarylene containing a regioregular chain having a divalent aromatic group as a repeating unit and having a head-to-tail bond at a high ratio was found.

That is, the present invention may be referred to as a chain composed of only repeating units represented by the following formula (1) (generally sometimes referred to as a structural unit) (generally referred to as a structural chain). And the average value of the number of repeating units forming the chain is 3 or more, and of the total bonds formed between the repeating units, the ratio of the bonds formed between the head and tail is The present invention relates to a polymer compound (polyarylene) characterized by being 85% or more.

(Wherein, Ar ¹ in the formula (1) is a divalent aromatic group, the aromatic ring is an aromatic hydrocarbon ring (i.e., an aromatic ring consists only of carbon atoms.). R ¹ is Represents a substituent on Ar ¹ , each independently a hydrocarbon group, hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, nitro group, cyano group, hydroxyl group, mercapto group, acyl group, A formyl group, a carboxyl group, a hydrocarbon oxycarbonyl group, an amino group, an aminocarbonyl group, an imidoyl group, an azo group, an acyloxy group, a phosphonic acid group, or a sulfonic acid group, where n represents an integer of 0 to 30. In the case of representing an integer of 2 or more, a plurality of R ¹ may be the same or different, and the carbon atom is represented by the IUPAC organic chemical nomenclature using the repeating unit represented by formula (1) as a divalent group. Numbered Of the two carbon atoms having a free valence, the carbon atom with the lower number is the head and the carbon atom with the higher number is the tail. (In no case has a two-fold symmetry axis perpendicular to the straight line at the midpoint of the straight line connecting the tail and the tail.)

  The polymer compound (polyarylene) of the present invention is excellent in stability such as thermal stability and chemical stability, and is useful as a light emitting material and a charge transporting material, and is a laser dye, an organic solar cell material, and an organic transistor. It can be used as materials for electrically conductive thin films such as organic semiconductors, conductive thin films, organic semiconductor thin films, and polymer electrolyte materials such as polymer electrolyte membranes such as metal ion and proton conductive membranes.

The polymer compound of the present invention (hereinafter also referred to as polyarylene of the present invention) includes a repeating unit represented by the formula (1). Ar ¹ in the formula (1) is a divalent aromatic group, and the aromatic ring is an aromatic hydrocarbon ring.

  Here, the divalent aromatic group means the remaining atomic group obtained by removing two hydrogen atoms bonded to the carbon atom of benzene, or a carbon atom of an aromatic ring from a condensed ring containing one or more aromatic rings. The remaining atomic group after removing two hydrogen atoms bonded to. The divalent aromatic group usually has 6 to 100 carbon atoms, preferably 6 to 60 carbon atoms, more preferably 6 to 45 carbon atoms, and still more preferably 6 to 30 carbon atoms. The carbon number of the divalent aromatic group does not include the carbon number of the substituent.

Here, as the remaining atomic group obtained by removing two hydrogen atoms bonded to the carbon atom of benzene, an atomic group of the following formula (1A-1) is exemplified, and an aromatic group is condensed from a condensed ring including one or more aromatic rings. The remaining atomic groups after removing two hydrogen atoms bonded to the ring carbon atoms include the following formulas (1B-1) to (1B-36) and (1C-1) to (1C-37) A group is illustrated.
The divalent aromatic group is preferably an atomic group of formulas (1B-1) to (1B-36) and formulas (1C-1) to (1C-37), more preferably formula (1B-1). ) To (1B-13) and formulas (1C-1) to (1C-37), more preferably formulas (1B-8) to (1B-13) and formulas (1C-1) to (1C-13) 1C-37), more preferably atomic groups of formulas (1C-1) to (1C-37), even more preferably atoms of formulas (1C-4) to (1C-12) A group.

R ¹ in the formula (1) represents a substituent on Ar ¹ and each independently represents a hydrocarbon group, a hydrocarbon oxy group, a hydrocarbon thio group, a trialkylsilyl group, a halogen atom, a nitro group, a cyano group, It represents a hydroxyl group, mercapto group, acyl group, formyl group, carboxyl group, hydrocarbon oxycarbonyl group, amino group, aminocarbonyl group, imidoyl group, azo group, acyloxy group, phosphonic acid group or sulfonic acid group.

Examples of the hydrocarbon group for R ¹ in the formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, and a cyclo group. Linear, branched or cyclic alkyl groups having about 1 to 50 carbon atoms such as hexyl group, norbornyl group, nonyl group, decyl group and 3,7-dimethyloctyl group; phenyl group, 4-methylphenyl group, 4 -Isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-adamantylphenyl group, 4-phenylphenyl group, 1-naphthyl group, 2- Aryl groups having about 6 to 60 carbon atoms such as naphthyl group; phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1- Phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 1-phenyl-3-propyl group, 1-phenyl-4-butyl group, 1-phenyl-5-pentyl And an aralkyl group having about 7 to 50 carbon atoms such as 1-phenyl-6-hexyl group, etc. The hydrocarbon group is preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably 1 carbon atom. Is a hydrocarbon group having ˜22, and more preferably a hydrocarbon group having 1 to 16 carbon atoms.

  The hydrocarbon group further includes a hydrocarbon thio group, trialkylsilyl group, halogen atom, nitro group, cyano group, hydroxyl group, mercapto group, acyl group, formyl group, carboxyl group, hydrocarbon oxycarbonyl group, amino group, It may be substituted with an aminocarbonyl group, imidoyl group, azo group, phosphonic acid group or sulfonic acid group.

Examples of the hydrocarbon thio group that may be substituted with the hydrocarbon group for R ¹ in (1) include, for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, t-butylthio group, Pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, cyclohexylmethylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, dodecylthio group, pentadecylthio group, octadecylthio group, docosylthio group, phenylthio group, 4-butyl A hydrocarbon thio group having about 1 to 50 carbon atoms in total, such as a phenylthio group.
As this hydrocarbon thio group, C1-C30 is preferable, More preferably, it is C1-C22, More preferably, it is C1-C16.

Examples of the alkyl group of the trialkylsilyl group that may be substituted for the hydrocarbon group in R ¹ in (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. , A pentyl group, a hexyl group, a nonyl group, a dodecyl group, a pentadecyl group, an octadecyl group, a docosyl group and the like, and an alkyl group having about 1 to 50 carbon atoms. The three alkyl groups of the trialkylsilyl group may be the same or different.

Examples of the halogen atom that may be substituted for the hydrocarbon group in R ¹ in (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the acyl group that may be substituted for the hydrocarbon group in R ¹ in (1) include an acetyl group, a propanoyl group, a hexanoyl group, an octanoyl group, a 2-ethylhexanoyl group, a benzoyl group, and a 4-butylbenzoyl group. And an acyl group having 2 to 30 carbon atoms in total.

Examples of the hydrocarbon oxycarbonyl group that may be substituted for the hydrocarbon group represented by R ¹ in (1) include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, a t-butoxycarbonyl group, and a cyclohexylmethyloxycarbonyl group. Group, n-octyloxycarbonyl group, phenyloxycarbonyl group, 4-butylphenyloxycarbonyl group and the like hydrocarbon oxycarbonyl groups having 1 to 30 carbon atoms in total.

The two hydrogen atoms on the nitrogen atom of the amino group that may be substituted with the hydrocarbon group in R ¹ in (1) may be independently replaced by a hydrocarbon group, an acyl group, or a hydrocarbon oxycarbonyl group. Good. Examples of the hydrocarbon group, acyl group, and hydrocarbon oxycarbonyl group include those described above.

The aminocarbonyl group which may be substituted with the hydrocarbon group in R ¹ in (1) is a carbonyl group substituted with the above amino group having about 1 to 30 carbon atoms.

Examples of the imidoyl group that may be substituted for the hydrocarbon group in R ¹ in (1) include formimidoyl group, acetimidyl group, propionimidoyl group, benzimidoyl group, N-methylacetimidoyl group, N -Imidoyl groups having about 1 to 30 total carbon atoms such as phenylacetimidoyl group.

Examples of the azo group that may be substituted with the hydrocarbon group in R ¹ in (1) include azo groups having about 1 to 30 carbon atoms such as a diazenyl group, a methylazo group, a propylazo group, and a phenylazo group.

Examples of the hydrocarbon oxy group in R ¹ in the formula (1) include a methyloxy group, an ethyloxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a t-butyloxy group, a pentyloxy group, and hexyl. Linear, branched or cyclic alkyloxy groups having about 1 to 50 carbon atoms, such as oxy group and cyclohexyloxy group; phenoxy group, 4-methylphenoxy group, 4-propylphenoxy group, 4-isopropylphenoxy group, 4- About 6 to 60 carbon atoms such as butylphenoxy group, 4-t-butylphenoxy group, 4-hexylphenoxy group, 4-cyclohexylphenoxy group, 4-phenoxyphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, etc. Aryloxy group; phenylmethyloxy group, 1-phenylethyl Oxy group, 2-phenylethyloxy group, 1-phenyl-1-propyloxy group, 1-phenyl-2-propyloxy group, 2-phenyl-2-propyloxy group, 1-phenyl-3-propyloxy group, Examples include aralkyloxy groups having about 7 to 60 carbon atoms such as 1-phenyl-4-butyloxy group, 1-phenyl-5-pentyloxy group, 1-phenyl-6-hexyloxy group.
The hydrocarbon oxy group is preferably a hydrocarbon oxy group having 1 to 40 carbon atoms, more preferably a hydrocarbon oxy group having 1 to 30 carbon atoms, and still more preferably a hydrocarbon having 1 to 20 carbon atoms. It is an oxy group.

The hydrocarbon oxy group further includes hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, nitro group, cyano group, hydroxyl group, mercapto group, acyl group, formyl group, carboxyl group, hydrocarbon oxy group. It may be substituted with a carbonyl group, amino group, aminocarbonyl group, imidoyl group, azo group, phosphonic acid group or sulfonic acid group.
Here, the hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, acyl group, hydrocarbon oxycarbonyl group, amino group, aminocarbonyl group, imidoyl group, and azo group are the same as described above. Can be mentioned.

Examples of the hydrocarbon thio group in R ¹ in the formula (1) include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a t-butylthio group, a pentylthio group, a hexylthio group, and a cyclohexyl group. All carbon such as thio, heptylthio, cyclohexylmethylthio, octylthio, 2-ethylhexylthio, nonylthio, dodecylthio, pentadecylthio, octadecylthio, docosylthio, phenylthio, 4-butylphenylthio A hydrocarbon thio group of about 1 to 50 is mentioned.
As this hydrocarbon thio group, C1-C30 is preferable, More preferably, it is C1-C22, More preferably, it is C1-C16.

The hydrocarbon thio group further includes hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, nitro group, cyano group, hydroxyl group, mercapto group, acyl group, formyl group, carboxyl group, hydrocarbon oxy group. It may be substituted with a carbonyl group, amino group, aminocarbonyl group, imidoyl group, azo group, phosphonic acid group, or sulfonic acid group.
Here, the hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, acyl group, hydrocarbon oxycarbonyl group, amino group, aminocarbonyl group, imidoyl group, azo group are the same as described above. Is mentioned.

Examples of the alkyl group of the trialkylsilyl group in R ¹ in the formula (1) include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, Examples thereof include alkyl groups having about 1 to 50 carbon atoms such as nonyl group, dodecyl group, pentadecyl group, octadecyl group and docosyl group. The three alkyl groups of the trialkylsilyl group may be the same or different.

As a halogen atom in R < ¹ > in Formula (1), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

Examples of the acyl group in R ¹ in the formula (1) include acyl groups having about 2 to 50 carbon atoms such as acetyl group, propanoyl group, butanoyl group, cyclohexylacetyl group, benzoyl group and 4-butylbenzoyl group. Can be mentioned.
As this acyl group, C2-C30 is preferable, More preferably, it is C2-C22, More preferably, it is C2-C16.

The acyl group further includes a hydrocarbon oxy group, a hydrocarbon thio group, a trialkylsilyl group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a mercapto group, an acyl group, a formyl group, a carboxyl group, and a hydrocarbon oxycarbonyl group. , An amino group, an aminocarbonyl group, an imidoyl group, an azo group, a phosphonic acid group, or a sulfonic acid group.
Here, the hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, acyl group, hydrocarbon oxycarbonyl group, amino group, aminocarbonyl group, imidoyl group, azo group are the same as described above. Is mentioned.

Examples of the hydrocarbon oxycarbonyl group in R ¹ in the formula (1) include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, a t-butoxycarbonyl group, a cyclohexylmethyloxycarbonyl group, and an n-octyloxycarbonyl group. Group, a phenyloxycarbonyl group, a 4-butylphenyloxycarbonyl group, a 1-naphthyloxycarbonyl group and the like, and a hydrocarbon oxycarbonyl group having about 2 to 50 carbon atoms in total.
As this hydrocarbon oxycarbonyl group, C2-C30 is preferable, More preferably, it is C2-C22, More preferably, it is C2-C16.

The hydrocarbon oxycarbonyl group further includes hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, nitro group, cyano group, hydroxyl group, mercapto group, acyl group, formyl group, carboxyl group, hydrocarbon. It may be substituted with an oxycarbonyl group, amino group, aminocarbonyl group, imidoyl group, azo group, phosphonic acid group, or sulfonic acid group.
Here, the hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, acyl group, hydrocarbon oxycarbonyl group, amino group, aminocarbonyl group, imidoyl group, azo group are the same as described above. Is mentioned.

In the amino group at R ¹ in formula (1), two hydrogen atoms on the nitrogen atom may each independently be replaced by a hydrocarbon group, an acyl group, or a hydrocarbon oxycarbonyl group, and the total number of carbon atoms is It is about 0-50. The above-mentioned thing is mentioned as a hydrocarbon group and an acyl group.
The amino group preferably has 0 to 30 carbon atoms, more preferably 0 to 22 carbon atoms, and still more preferably 0 to 16 carbon atoms.

The aminocarbonyl group in R ¹ in Formula (1) is a carbonyl group substituted with the amino group, and has a total carbon number of about 1 to 50.
As this aminocarbonyl group, C1-C30 is preferable, More preferably, it is C1-C22, More preferably, it is C1-C16.

Examples of the imidoyl group in R ¹ in the formula (1) include formimidoyl group, acetimidoyl group, propionimidoyl group, benzimidoyl group, N-methylacetimidoyl group, N-phenylacetimidoyl group, and the like. And an imidoyl group having about 1 to 50 total carbon atoms.
As this imidoyl group, C1-C30 is preferable, More preferably, it is C1-C22, More preferably, it is C1-C16.

The imidoyl group further includes hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, nitro group, cyano group, hydroxyl group, mercapto group, acyl group, formyl group, carboxyl group, hydrocarbon oxycarbonyl group. , An amino group, an aminocarbonyl group, an imidoyl group, an azo group, a phosphonic acid group, or a sulfonic acid group.
Here, the hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, acyl group, hydrocarbon oxycarbonyl group, amino group, aminocarbonyl group, imidoyl group, azo group are the same as described above. Is mentioned.

Examples of the azo group for R ¹ in formula (1) include azo groups having about 1 to 50 carbon atoms such as a methylazo group, a propylazo group, and a phenylazo group.
As this azo group, C1-C30 is preferable, More preferably, it is C1-C22, More preferably, it is C1-C16.

The azo group further includes a hydrocarbon oxy group, a hydrocarbon thio group, a trialkylsilyl group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a mercapto group, an acyl group, a formyl group, a carboxyl group, and a hydrocarbon oxycarbonyl group. , An amino group, an aminocarbonyl group, an imidoyl group, an azo group, a phosphonic acid group, or a sulfonic acid group.
Here, the hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, acyl group, hydrocarbon oxycarbonyl group, amino group, aminocarbonyl group, imidoyl group, azo group are the same as described above. Is mentioned.

Examples of the acyloxy group in R ¹ in the formula (1) include all carbons such as acetyloxy group, butyryloxy group, octanoyloxy group, 2-ethylhexanoyloxy group, benzoyloxy group, 4-butylbenzoyloxy group, and the like. An acyloxy group of about 1 to 50 is mentioned.
As this acyloxy group, C2-C30 is preferable, More preferably, it is C2-C22, More preferably, it is C2-C16.

The acyloxy group further includes a hydrocarbon oxy group, a hydrocarbon thio group, a trialkylsilyl group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a mercapto group, an acyl group, a formyl group, a carboxyl group, and a hydrocarbon oxycarbonyl group. , An amino group, an aminocarbonyl group, an imidoyl group, an azo group, a phosphonic acid group, or a sulfonic acid group.
Here, the hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, acyl group, hydrocarbon oxycarbonyl group, amino group, aminocarbonyl group, imidoyl group, azo group are the same as described above. Is mentioned.

From the viewpoint of stability, R ¹ in formula (1) is preferably a hydrocarbon group, hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, nitro group, cyano group, hydroxyl group, mercapto group. An acyl group, a carboxyl group, a phosphonic acid group, and a sulfonic acid group, more preferably a hydrocarbon group, a hydrocarbon oxy group, a hydrocarbon thio group, a trialkylsilyl group, a nitro group, a cyano group, and an acyl group, More preferred are a hydrocarbon group and a hydrocarbon oxy group.

N in the formula (1) represents an integer of 0 to 30. The number of n is preferably an integer of 0 to 20, more preferably an integer of 0 to 10, and further preferably an integer of 0 to 5. When n represents an integer of 2 or more, the plurality of R ¹ may be the same as or different from each other.

In the case where Ar ¹ in formula (1) is an atomic group obtained by removing two hydrogen atoms from a benzene ring, n represents an integer of 1 to 4. At this time, the number of n is preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and particularly preferably 1. When n is 1, the polyarylene of the present invention has a structure in which the effect of positional regularity of the head-to-tail bond is more likely to occur.

Ar ¹ in formula (1) is a remaining atomic group obtained by removing two hydrogen atoms bonded to a carbon atom of an aromatic ring from a condensed ring containing one or more aromatic rings, and one Ar ¹ When two R ¹ are present on the sp ³ carbon, a spiro ring may be formed between the two R ¹ .

  In accordance with the IUPAC organic chemical nomenclature described in Rules A-13 and A-24 of Organic Chemistry / Biochemical Nomenclature (above) (Revised 2nd Edition, Nanedo, 1988), the repetition represented by formula (1) When the number of a carbon atom is given with the unit as a divalent group, out of the two carbon atoms having a free valence, the carbon atom with the lower number is the head and the carbon atom with the higher number is the tail. As used herein, the free valence refers to those that can form bonds with other free valences as described in Organic Chemistry / Biochemical Nomenclature (above) (Revised 2nd Edition, Nankodo, 1988).

For example, in the case of the divalent group represented by the formula (2), the number of carbon atoms is given according to the IUPAC organic chemical nomenclature, and the carbon atom of the number ^m is represented by C ^{m as} in the formula (2-a) Become. (Here, in formulas (2) and (2-a), R ² represents a substituent and represents the same substituent as the substituent represented by R ¹ in formula (1). M represents an integer of 1 or more. ) In formula (2-a), the two carbons with free valences are C ¹ and C ⁴ , and among these, C ¹ with the smallest number of carbon atoms is the head, and the number of carbon atoms The big C ⁴ is the tail.

In the present invention, the repeating unit represented by the formula (1) does not have any two-fold symmetry axis perpendicular to the straight line at the midpoint of the straight line connecting the head and tail.
Here, the two-fold symmetry axis means that when an object is rotated 180 ° around its axis as described in Atkins physical chemistry (top) (4th edition, Tokyo Kagaku Dojin, 1993) page 633 This is the axis where the object looks the same as the original.

For example, in the case of the divalent group represented by the formula (2-a), the midpoint of the straight line connecting the head and tail connects carbon atom C ¹ and carbon atom C ⁴ in the same divalent group. It is a point that is at an equal distance from the carbon atoms C ¹ and C ⁴ on the straight line. Here, at the midpoint of the straight line connecting the head and tail, the object before rotating and the object after rotating do not overlap even if rotated 180 ° around any straight line orthogonal to the straight line. In no case can a two-fold symmetry axis exist. Therefore, the divalent group represented by the formula (2-a) is included in the repeating unit represented by the formula (1).

Further, for example, in the case of the divalent group represented by the formula (3), the number of carbon atoms is attached according to the IUPAC organic chemical nomenclature, and the carbon atom of the number ^m is represented by C ^{m as shown} in the formula (3-a) become. (Here, m represents an integer of 1 or more.) In the formula (3-a), the two carbons having free valences are C ¹ and C ⁴ , and of these, the number of the carbon atom The smaller C ^{1 is the} head and the larger carbon atom C ⁴ is the tail. Here, the straight line connecting the head and tail is a straight line connecting carbon atom C ¹ and carbon atom C ⁴ in the same divalent group. At this time, if the center point of the straight line connecting the head and tail is rotated by 180 ° about the straight line orthogonal to the straight line, the object before the rotation and the object after the rotation overlap, so this axis is symmetric twice It can be an axis. Therefore, the divalent group represented by the formula (3) is not included in the repeating unit represented by the formula (1).

When confirming the presence or absence of the above two-fold symmetry axis, it is easier to confirm by substituting a substituent different from R ² and a free valence among the substituents represented by R ¹ .

Specific examples of the repeating unit represented by the formula (1) contained in the polyarylene in the present invention include the following formulas (4A-1) to (4A-9), (4B-1) to (4B-12), (4C-1) to (4C-24), (4D-1) to (4D-25), (4E-1) to (4E-5), (4F-1) to (4F-3), (4G -1) to (4G-10) and (4H-1) to (4H-50). Here, R ³ , R ⁴ and R ⁵ each represent the same substituent as the substituent represented by R ¹ in Formula (1). When a plurality of R ³ are present in one repeating unit, R ³ may be the same as or different from each other. If R ³ and R ⁴ coexist within one repeating unit represent different substituents R ³ and R ⁴ each, in one of the repeat units R ^3, R ^4, and when R ⁵ coexist R ³ , R ⁴ , and R ⁵ each represent a different substituent.

  The repeating unit represented by the formula (1) contained in the polyarylene of the present invention is preferably a formula (4B-1) to (4B-12), (4C-1) to (4C-24), (4D- 1) to (4D-25), (4E-1) to (4E-5), (4F-1) to (4F-3), (4G-1) to (4G-10), and (4H-1 ) To (4H-50), more preferably represented by formulas (4B-1) to (4B-12), (4C-1) to (4C-24), (4G-1) to (4G-10) and repeating units represented by (4H-1) to (4H-50), more preferably formulas (4C-15) to (4C-24), (4G-1) to (4 4G-10) and repeating units represented by (4H-1) to (4H-50), more preferably (4G-1) to (4G-10), and (4H-1) to (4H -50), more preferably repeating units represented by formulas (4H-1) to (4H-50).

The number average molecular weight (Mn) in terms of polystyrene by size exclusion chromatography (hereinafter referred to as SEC) of polyarylene in the present invention is 5.0 × 10 ² to 1.0 × 10 ⁶ , from the viewpoint of stability, solubility, and the like. , Preferably 1.0 × 10 ³ to 5.0 × 10 ⁵ , more preferably 2.0 × 10 ³ to 2.0 × 10 ⁵ . The weight average molecular weight (Mw) in terms of polystyrene of the polyarylene in the present invention by SEC is 1.0 × 10 ³ to 2.0 × 10 ⁶ , and preferably 2.0 from the viewpoint of stability, solubility, film forming property, and the like. × 10 ³ to 1.0 × 10 ⁶ , more preferably 5.0 × 10 ³ to 5.0 × 10 ⁵ .

  The polyarylene of the present invention contains a chain composed of only one kind of repeating unit represented by the formula (1), and the average value of the number of repeating units forming the chain (hereinafter referred to as the average number of linkages) Is 3 or more.

Here, when the repeating unit contained in the polyarylene of the present invention is only one kind of repeating unit represented by the formula (1), the average number of connections is represented by the following formula (A1), for example. .

Average number of connections = Mn / FW ₁ (A1)

(In formula (A1), Mn represents the number average molecular weight in terms of polystyrene measured by SEC of the polyarylene of the present invention, and FW ₁ represents the formula weight of one kind of repeating unit represented by formula (1). .)

In the polyarylene of the present invention, one type of repeating unit represented by the formula (1) (referred to as “repeating unit Q” in the following formula (A2)) and a repeating unit other than the repeating unit are: when included, (referred to as N _Q) average chain number, for example, represented by the following formula (A2).

Average number of connections (N _Q ) = N1 / N2 (A2)

(In the formula, N1 is the number of repeating units Q contained per unit amount of the polyarylene of the present invention, and N2 is the number of blocks formed of the repeating units Q contained per unit amount of the polyarylene of the present invention. Here, the block formed of the repeating unit Q is represented by the following formula (BR).)

(In the formula, Ar ₆ represents one kind of repeating unit represented by the formula (1), and g represents an integer of 1 or more. In the block, a repeating unit other than the repeating unit represented by Ar ₆ or The end groups are adjacent.)

The lower limit of the average number of connections in the polyarylene of the present invention is preferably 5 from the viewpoints of crystallinity, orientation, conductivity, etc., more preferably 6, more preferably 7, even more preferably. 8, even more preferably 10, still more preferably 12, still more preferably 15, still more preferably 20, even more preferably 30, and even more preferably 50. Yes, more preferably 100.
The upper limit of the average number of connections in the polyarylene of the present invention is preferably 5000, more preferably 1000, and even more preferably 500.

  In the polyarylene of the present invention, the ratio of the number of bonds formed between the head and tail to the total number of bonds formed between one type of repeating unit represented by the formula (1) is 85%. It is necessary to be above. From the viewpoint of stability, the ratio of the number of bonds formed between the head and tail to the total number of bonds formed between the repeating units represented by formula (1) is preferably 90% or more, more Preferably it is 95% or more, Most preferably, it is 98% or more.

As the bond formed between adjacent repeating units, for example, in the case of the repeating unit represented by the above formula (2), the following formulas (2-b), (2-c), and (2-d There are three types of bonds represented by: Among these, the bond represented by the formula (2-b) is a bond formed between the head and the tail.

  The polyarylene of the present invention contains a chain composed of only one kind of repeating unit represented by the formula (1), and the repeating unit is an average number of repeating units forming the chain is 3 or more. Other repeating units may be included. The total of one type of repeating unit represented by the formula (1) is preferably 50 mol% or more of all repeating units, more preferably 70 mol%, still more preferably 80 mol% or more, Preferably it is 90 mol% or more.

Examples of the repeating unit other than the repeating unit represented by the formula (1) that may be included in the polyarylene of the present invention include the following formulas (5), (6), (7), and (8). Is done. The repeating units represented by the following formulas (5), (6), (7), and (8) do not include the repeating units represented by the formula (1).

In the formula, Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. When a plurality of Ar ₃ are present, they may be the same or different. X ₁ , X ₂ and X ₃ are each independently —CR _a ═CR _b —, —C≡C—, —N (R _c ) —, —O—, —S—, —SO—, —SO _2. -, or _{- (SiR d R e) q} - shows a. R _a and R _b are each independently a hydrogen atom, monovalent hydrocarbon group (alkyl group, aryl group, etc.), monovalent heterocyclic group, carboxyl group, hydrocarbon oxycarbonyl group (substituted carboxyl group, etc.) Or a cyano group is shown. R _c , R _d and R _e each independently represent a hydrogen atom, a monovalent hydrocarbon group, (an alkyl group, an aryl group, an arylalkyl group, etc.), or a monovalent heterocyclic group. p represents 1 or 2. q represents an integer of 1 to 12. When there are a plurality of R _a , R _b , R _c , R _d, and R _e , they may be the same or different. Specific examples of the monovalent hydrocarbon group represented by R _a , R _b , R _c , R _d and R _e include the examples of the monovalent hydrocarbon group represented by R ¹ in the formula (1). Can be mentioned. Specific examples of the hydrocarbon oxycarbonyl group represented by R _a and R _b include the hydrocarbon oxycarbonyl group represented by R ¹ in Formula (1).

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 a substituent represented by R ¹ in formula (1) and a monovalent heterocyclic group, preferably a hydrocarbon group, a hydrocarbon oxy group, a hydrocarbon thio group, a trialkylsilyl group, Halogen atom, nitro group, cyano group, hydroxyl group, mercapto group, acyl group, carboxyl group, phosphonic acid group, sulfonic acid group, more preferably hydrocarbon group, hydrocarbon oxy group, hydrocarbon thio group, trialkyl A silyl group, a nitro group, a cyano group, and an acyl group are preferable, and a hydrocarbon group and a hydrocarbon oxy group are more 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.
As an arylene group, a phenylene group (for example, the following formulas (9A-1) to (9A-3)), a naphthalenediyl group (the following formulas (9B-1) to (9B-6)), an anthracene-diyl group (lower Formulas (9C-1) to (9C-5)), biphenyl-diyl groups (the following formulas (9D-1) to (9D-6)), terphenyl-diyl groups (the following formulas (9E-1) to (9E) -3)), condensed ring compound groups (following formulas (9F-1) to (9F-6)), fluorene-diyl groups (following formulas (9F-7) to (9F-9)), stilbene-diyl (lower Formulas (9G-1) to (9G-4)), distilbene-diyl (the following formulas (9G-5), (9G-6)) and the like are exemplified. Among them, a phenylene group, a biphenylene group, a fluorene-diyl group, and a stilbene-diyl group are preferable, a phenylene group, a biphenylene group, and a fluorene-diyl group are more preferable, a phenylene group and a fluorene-diyl group are further preferable, and a fluorene-diyl group. Is particularly preferred.

The divalent heterocyclic group in Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ is the remaining atomic group obtained by removing two hydrogen atoms from the heterocyclic compound, and the group has a substituent. May be.
Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. Say things. Of the divalent heterocyclic groups, an aromatic heterocyclic group is preferable.
Examples of the substituent include a substituent represented by R ¹ in Formula (1) and a monovalent heterocyclic group, and preferably a hydrocarbon group, a hydrocarbon oxy group, a hydrocarbon thio group, a trialkylsilyl group, a halogen atom. , Nitro group, cyano group, hydroxyl group, mercapto group, acyl group, carboxyl group, phosphonic acid group, sulfonic acid group, more preferably hydrocarbon group, hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group , A nitro group, a cyano group and an acyl group, more preferably a hydrocarbon group and a hydrocarbon oxy group.
Carbon number of the part except the substituent in a bivalent heterocyclic group is about 3-60 normally. Moreover, the total carbon number including the substituent of a bivalent heterocyclic group is about 3-100 normally.

Examples of the divalent heterocyclic group include the following.
Divalent heterocyclic group containing nitrogen as a hetero atom; pyridine-diyl group (the following formula (9H-1) to (9H-6)), diazaphenylene group (the following formula (9H-7) to (9H-10) ), Quinoline diyl group (following formula (9I-1) to (9I-15)), quinoxaline diyl group (following formula (9I-16) to (9I-20)), acridine diyl group (following formula (9I-21) To (9I-24)), bipyridyldiyl groups (the following formulas (9J-1) to (9J-3)), phenanthroline diyl groups (the following formulas (9J-4) to (9J-6)), and the like.
Groups having a fluorene structure containing oxygen, silicon, nitrogen, sulfur, selenium and the like as a hetero atom (the following formulas (9J-7) to (9J-21)).
5-membered ring heterocyclic groups (the following formulas (9K-1) to (9K-5)) containing oxygen, silicon, nitrogen, sulfur, selenium and the like as a heteroatom are exemplified.
5-membered ring condensed hetero groups containing oxygen, silicon, nitrogen, sulfur, selenium and the like as a hetero atom (the following formulas (9K-6) to (9K-16)) can be mentioned.
A 5-membered ring heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, which is bonded at the α-position of the heteroatom to form a dimer or oligomer (formula (9L-1) to (9L-2)).
5-membered heterocyclic groups containing oxygen, silicon, nitrogen, sulfur, selenium, etc. as heteroatoms, which are bonded to the phenyl group at the α-position of the heteroatoms (the following formulas (9L-3) to (9L-9) )).
Examples include groups (following formulas (9M-1) to (9M-6)) in which a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, etc. as a hetero atom is substituted with a phenyl group, a furyl group, or a thienyl group. .
Examples include groups (the following formulas (9M-7) to (9M-15)) in which a phenyl group is condensed to a 6-membered heterocyclic group containing oxygen, nitrogen, sulfur and the like as a hetero atom.

The divalent group having a metal complex structure in Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ is
This is a remaining divalent group obtained by removing two hydrogen atoms from an organic ligand of a metal complex having an organic ligand.
The organic ligand usually has about 4 to 60 carbon atoms. Examples thereof include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, and 2-phenyl-benzo. Examples include thiazole and derivatives thereof, 2-phenyl-benzoxazole and derivatives thereof, porphyrin and derivatives thereof.
Examples of the central metal of the complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium.
Examples of the metal complex having an organic ligand include a low-molecular fluorescent material, a metal complex known as a phosphorescent material, and a triplet light-emitting complex.

Specific examples of the divalent group having a metal complex structure include (9N-1) to (9N-7) of the following formulas.

Formulas (9A-1) to (9A-3), (9B-1) to (9B-6), (9C-1) to (9C-5), (9D-1) to (9D-6), (9E-1) to (9E-3), (9F-1) to (9F-9), (9G-1) to (9G-6), (9H-1) to (9H-10), (9I -1) to (9I-24), (9J-1) to (9J-21), (9K-1) to (9K-16), (9L-1) to (9L-9), (9M-1 ) To (9M-6), (9M-7) to (9M-15), and (9N-1) to (9N-7), each R _A is independently a hydrogen atom or in formula (1) R ¹ represents a substituent, preferably a hydrogen atom, hydrocarbon group, hydrocarbon oxy group, hydrocarbon thio group, trialkylsilyl group, halogen atom, nitro group, cyano group, hydroxyl group, mercapto group, acyl group A carboxyl group, a phosphonic acid group, and a sulfonic acid group, more preferably a hydrogen atom, a hydrocarbon group, or a hydrocarbon group. Shi group, hydrocarbon thio group, trialkylsilyl group, a nitro group, a cyano group, an acyl group, more preferably a hydrogen atom, a hydrocarbon group, a hydrocarbon oxy group. Formulas (9A-1) to (9A-3), (9B-1) to (9B-10), (9C-1) to (9C-6), (9D-1) to (9D-6), ( 9E-1) to (9E-3), (9F-1) to (9F-9), (9G-1) to (9G-6), (9H-1) to (9H-10), (9I- 1) to (9I-24), (9J-1) to (9J-21), (9K-1) to (9K-16), (9L-1) to (9L-9), (9M-1) The carbon atoms of the groups (9M-6), (9M-7) to (9M-15), and (9N-1) to (9N-7) are replaced with nitrogen atoms, oxygen atoms or sulfur atoms. The hydrogen atom may be substituted with a fluorine atom.
Specific examples of the repeating unit represented by the formula (5) include an arylene group represented by Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ , a divalent heterocyclic group, or a divalent group having a metal complex structure. And preferably (9A-1) to (9A-3), (9B-1) to (9B-6), (9C-1) to (9C-5), (9D- 1) to (9D-6), (9F-1) to (9F-9), (9G-1) to (9G-6), (9I-1) to (9I-24), (9J-7) (9J-21), (9K-6) to (9K-16), (9L-3) to (9L-9), (9M-1) to (9M-6), and (9M-7) to A group represented by (9M-15), more preferably formulas (9A-1) to (9A-3), (9B-1) to (9B-6), (9C-1) to (9C- 5), (9F-7) to (9F-9), (9G-1) to (9G-4), (9J-13) to (9J-15), (9J-19) to (9J-21) , (9K-15) to (9K-16) Groups represented by (9L-3) to (9L-9), (9M-1) to (9M-6), and (9M-7) to (9M-12), and more preferably a group represented by the formula (9A -1) to (9A-3), (9F-7) to (9F-9), (9J-13) to (9J-15), (9J-19) to (9J-21), (9K-15) ) To (9K-16), (9M-1) to (9M-6), and (9M-7) to (9M-12), and among them, the formula (9F-7) to (9F-9), (9J-13) to (9J-15), (9J-19) to (9J-21), (9K-15) to (9K-16), (9M-1) to (9M -6), and groups represented by (9M-7) to (9M-12), particularly preferably formulas (9F-7) to (9F-9) and (9M-7) to (9M- And a group represented by formulas (9F-7) to (9F-9).
Specific examples of the repeating unit represented by the formula (6) include groups represented by the following formulas (10A-1) to (10A-7) and formulas (10B-1) to (10B-7). Groups represented by formulas (10C-1) to (10C-8), groups represented by formulas (10D-1) to (10D-5), and formulas (10E-1) to (10E-4) ), Groups represented by formulas (10F-1) to (10F-6), groups represented by formulas (10G-1) to (10G-6), and formulas (10H-1) to Examples include groups represented by (10H-6), groups represented by formulas (10I-1) to (10I-6), and groups represented by formulas (10J-1) to (10J-6). .
As the repeating unit represented by formula (6), groups represented by formulas (10A-1) to (10A-7), groups represented by formulas (10B-1) to (10B-7), and formulas Groups represented by (10C-1) to (10C-8), groups represented by formulas (10D-1) to (10D-5), and formulas (10E-1) to (10E-4). Groups represented by formulas (10F-1) to (10F-6) and groups represented by formulas (10J-1) to (10J-6) are preferred, and formulas (10A-1) to ( 10A-7), groups represented by formulas (10B-1) to (10B-7), groups represented by formulas (10C-1) to (10C-8), and formula (10D- The groups represented by the groups represented by 1) to (10D-5) and the groups represented by formulas (10E-1) to (10E-4) are more preferred, and the formulas (10D-1) to (10D) -5 In group is more preferably represented more specifically by the following formula (11A-1) ~ a group represented by (11A-5) are preferable.











(In the formula, R _A , R _a , R _b , R _c , R _d and R _e represent the same meaning as described above.)
Specific examples of the repeating unit represented by the formula (7) include groups represented by the following formulas (12A-1) to (12A-7) and formulas (12B-1) to (12B-7). Groups represented by formulas (12C-1) to (12C-8), groups represented by formulas (12D-1) to (12D-4), and formulas (12E-1) to (12E-4) ), Groups represented by formulas (12F-1) to (12F-6), groups represented by formulas (12G-1) to (12G-6), and formulas (12H-1) to Examples include groups represented by (12H-6), groups represented by formulas (12I-1) to (12I-6), and groups represented by formulas (12J-1) to (12J-6). .
The repeating unit represented by formula (7) is preferably a group represented by formula (12A-1) to (12A-7), or a group represented by formula (12B-1) to (12B-7). , Groups represented by formulas (12C-1) to (12C-8), groups represented by formulas (12F-1) to (12F-6), and formulas (12J-1) to (12J-6) More preferably, groups represented by formulas (12A-1) to (12A-7) and groups represented by formulas (12B-1) to (12B-7), More preferred are groups represented by formulas (12A-1) to (12A-7).










(In the formula, R _A , R _a , R _b , R _c , R _d and R _e represent the same meaning as described above.)
The repeating unit represented by the formula (8) is preferably —CR _a ═CR _b —, —C≡C—, —N (R _c ) —, —SO ₂ —, and — (SiR _d R _e ). _q −, more preferably —CR _a ═CR _b —, and —N (R _c ) —, and still more preferably —N (R _c ) —.
As the polyarylene of the present invention, for example,
Polyarylene a: consisting of only one type of repeating unit represented by formula (1)
Polyarylene b: one type of repeating unit represented by formula (1) and one or more types of repeating unit represented by formula (5), (6), (7) or (8) (especially one or more types and 10 types) The following),
Polyarylene b-1: One type of repeating unit represented by formula (1) and one or more types of repeating unit represented by formula (5) or (6) (in particular, one type or more and five types or less, especially 1 type or more and 3 types or less, especially 1 type or more and 2 types or less)
Polyarylene b-2: one comprising a repeating unit represented by the formula (1) and one repeating unit represented by the formula (5),
-Polyarylene b-3: comprising one type of repeating unit represented by formula (1) and one type of repeating unit represented by formula (6),
Polyarylene b-4: comprising one type of repeating unit represented by formula (1), one type of repeating unit represented by formula (5), and one type of repeating unit represented by formula (6) The polyarylene a and the polyarylene b are preferable, and the polyarylene a is more preferable. The polyarylene b is preferably a polyarylene b-1, more preferably a polyarylene b-2, a polyarylene b-3, or a polyarylene b-4, and further preferably a polyarylene b-3 or a polyarylene b. -4.
In polyarylene b, it is preferable that there are a plurality of blocks represented by the formula (BR), and there is a distribution in g in the formula (BR).
In polyarylenes b-2, b-3, and b-4, the number of blocks represented by the formula (BR) per polymer chain is preferably 3 or more. That is, it is preferable to satisfy the following formula (BR-2).

(Xn × b1 / N _Q ) ≧ 3 Formula (BR-2)

(In Formula (BR-2), N _Q represents the average number of linkages represented by Formula (A2), Xn represents the number average degree of polymerization of polyarylene b-2, b-3, or b-4. (Represented by the following formula)

Xn = Mn ′ / {(b1 × M1) + (b2 × M2) + (b3 × M3)}

(In the formula, Mn ′ represents the number average molecular weight in terms of polystyrene measured by SEC of polyarylene b-2, b-3 or b-4, and b1, b2 and b3 are polyarylene b-2, b−, respectively. The mole fraction of the repeating unit represented by formula (1) in 3 or b-4, the mole fraction of the repeating unit represented by formula (5), and the mole fraction of the repeating unit represented by formula (6) M1, M2 and M3 represent the formula weight of the repeating unit represented by the formula (1) in the polyarylene b-2, b-3 or b-4 and the repeating unit represented by the formula (5), respectively. And the formula weight of the repeating unit represented by formula (6).)

The terminal structure in the polyarylene of the present invention is not particularly limited, but is preferably a hydrogen atom and a substituent represented by Ar ¹ in formula (1), more preferably a hydrogen atom, a hydrocarbon group, a hydrocarbon oxy group, a halogen atom. And more preferably a hydrogen atom or a hydrocarbon group.

  Hereinafter, a preferred method for producing the polyarylene of the present invention will be described in detail.

  The polyarylene of the present invention can be produced by condensation polymerization using a compound represented by the following formula (A) as one of raw materials.

(Ar ^1, R ¹ in formula (A), and n Ar ^1, R ¹ in Formula (1), and represent the same meaning as n. In formula (A) Y ¹ are each independently a halogen atom, wherein Represents a sulfonate group or a methoxy group represented by (B), wherein Y ² is represented by a borate group, a boric acid group, a group represented by formula (C), or a formula (D) Or a group represented by the formula (E))

(In the formula (B), R7 represents an optionally substituted hydrocarbon group, and examples of the hydrocarbon group include the same hydrocarbon groups as those represented by R1 in the formula (1). It may be substituted with an atom, a nitro group, a cyano group, an acyl group, an amino group, a hydrocarbon oxycarbonyl group, etc. The halogen atom, acyl group, amino group, and hydrocarbon oxycarbonyl group are the same as described above. Can be mentioned.)

(In Formula (C), X _A represents a halogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.)

(In the formula (D), X _A represents a halogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.)

(In the formula (E) R ⁸ represents a hydrocarbon group which may be substituted, the same ones mentioned are. There exist a plurality of R ⁸ and hydrocarbon group represented by R ¹ in Formula (1) is the hydrocarbon groups The hydrocarbon groups may be substituted with a halogen atom, a nitro group, a cyano group, an acyl group, an amino group, a hydrocarbon oxycarbonyl group, etc. A halogen atom, an acyl group, Examples of the amino group and the hydrocarbon oxycarbonyl group are the same as described above.)

Y ¹ in the formula (A) independently represents a halogen atom, a sulfonate group represented by the formula (B), or a methoxy group.

Examples of the halogen atom for Y ¹ in the formula (A) include a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hydrocarbon group for R ⁷ in formula (B) include the same hydrocarbon groups as those represented by R ¹ in formula (1). The hydrocarbon group may be substituted with a halogen atom, nitro group, cyano group, acyl group, amino group, hydrocarbon oxycarbonyl group or the like. Examples of the halogen atom, acyl group, amino group, and hydrocarbon oxycarbonyl group are the same as those described above. Examples of the sulfonate group represented by the formula (B) include a methanesulfonate group, a trifluoromethanesulfonate group, a phenylsulfonate group, and a 4-methylphenylsulfonate group.

In the formula (A), Y ² represents a borate group, a boric acid group, a group represented by the formula (C), a group represented by the formula (D), or a group represented by the formula (E).

Examples of the borate group in Y ² in the formula (A) include groups represented by the following formula.

  As the compound represented by the formula (A), a compound synthesized and isolated in advance may be used, or it may be prepared in a reaction system and used as it is.

Y ² in formula (A) is preferably a borate group, a borate group, or a group represented by formula (C) from the viewpoint of ease of synthesis, ease of handling, toxicity, and the like. It is more preferably a group or a boric acid group.
When synthesizing a polyarylene composed of only one type of repeating unit represented by the formula (1), for example, it can be synthesized by condensation polymerization of only the monomer represented by the formula (A).
When synthesizing a polyarylene comprising a repeating unit represented by the formula (1) and a repeating unit represented by the formula (5) or (6), for example, a simple unit represented by the formula (A) is used. A monomer and a monomer represented by the following formula (F), or a monomer represented by the following formula (G) can be selected as appropriate from the necessary types and can be synthesized by condensation polymerization.

Y ³ —Ar ₂ —Y ⁴ (F)
(In the formula, Ar ₂ is as defined in the formula (5), and Y ³ and Y ⁴ each independently represent a group represented by Y ¹ or Y ² in the formula (A).)

(In the formula, Ar ₃ , Ar ₄ , X ₁ and p are each as defined in the above formula (6), and Y ⁵ and Y ⁶ are each independently as defined in the above formula (A). )

  Examples of the condensation polymerization method include a method in which the monomer represented by the formula (A) is reacted using an appropriate catalyst or an appropriate base, if necessary.

Examples of the condensation polymerization catalyst include palladium complexes such as palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, [bis (triphenylphosphine)] dichloropalladium, nickel [ Transition metal complexes such as tetrakis (triphenylphosphine)], [1,3-bis (diphenylphosphino) propane] dichloronickel, nickel complexes such as [bis (1,4-cyclooctadiene)] nickel, and Further, triphenylphosphine, tris (o-tolyl) phosphine, tris (p-tolyl) phosphine, tris (o-methoxyphenyl) phosphine, tris (p-methoxyphenyl) phosphine, tri (t-butylphosphine), tris Cyclohexylphosphine, diphe Examples thereof include catalysts comprising a ligand such as nylphosphinopropane and bipyridyl.
As this catalyst, what was synthesize | combined beforehand can also be used and what was prepared in the reaction system can also be used. In this invention, this catalyst can be used individually or in mixture of 2 or more types.
The catalyst can be used in any amount, but in general, the amount of the transition metal compound relative to the compound represented by the formula (A) is preferably 0.001 to 300 mol%, and 0.005 to 50 mol%. More preferably, 0.01-20 mol% is further more preferable.

A base may be used as necessary in the condensation polymerization. Bases include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, tripotassium phosphate, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrahydroxide hydroxide An organic base such as butylammonium may be mentioned.
Although this base can be used in arbitrary quantity, generally 0.5-20 equivalent is preferable with respect to the compound shown by Formula (A), and 1-10 equivalent is more preferable.

The condensation polymerization can be carried out in the absence of a solvent, but is usually carried out in the presence of an organic solvent.
Examples of the organic solvent to be used include tetrahydrofuran, benzene, toluene, xylene, mesitylene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide and the like. These organic solvents may be used alone or in combination of two or more.
The amount of the organic solvent used is usually such that the monomer concentration is 0.1 to 90% by weight. A preferable ratio is 1 to 50% by weight, and a more preferable ratio is 2 to 30% by weight.
The organic solvent varies depending on the compound used and the reaction, but it is generally desirable to perform a deoxygenation treatment in order to suppress side reactions.

The reaction temperature for carrying out the condensation polymerization is not particularly limited as long as the reaction medium is kept in a liquid state. A preferable temperature range is −100 ° C. to 200 ° C., more preferably −80 ° C. to 150 ° C., and further preferably 0 ° C. to 120 ° C.
Although reaction time changes with reaction conditions, such as reaction temperature, it is 1 hour or more normally, Preferably it is 2-500 hours.

It may be desirable to perform the condensation polymerization under dehydrating conditions as necessary. In particular, when Y ² in the compound represented by the formula (A) is a group represented by the formula (C), it is necessary to perform the dehydration condition.

It is possible to carry out according to. For example, the target polymer compound can be obtained by adding a reaction solution to a lower alcohol such as methanol and filtering and drying the resulting precipitate.
When the purity of the polymer compound obtained by the post-treatment is low, it can be purified by ordinary methods such as recrystallization, continuous extraction with a Soxhlet extractor, column chromatography, and the like.

  Next, the polymer light emitting device of the present invention will be described.

The polymer light emitting device 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, a hole injection layer, an electron transport layer, an electron injection layer, an interlayer 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. Further, the interlayer layer is present adjacent to the light emitting layer between the light emitting layer and the anode, and serves to isolate the light emitting layer and the anode or the light emitting layer from the hole injection layer or the hole transport layer. It is a layer that has. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. The electron injection layer and the hole injection layer are collectively referred to as a charge injection layer. Two or more light emitting layers, hole transport layers, hole injection layers, electron transport layers, and electron injection layers may be used independently.

  When the organic layer is a light emitting layer, the light emitting layer which is an organic layer may further contain a hole transporting material, an electron transporting material or a light emitting material. Here, the light-emitting material refers to a material that exhibits fluorescence and / or phosphorescence.

  When the 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 luminescent material are mixed, the mixing ratio of the luminescent material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt% with respect to the entire mixture. When the polymer compound of the present invention is mixed with a light emitting material, a hole transporting material and / or an electron transporting material, the mixing ratio of the light emitting material is 1 wt% to 50 wt% with respect to the entire mixture. , Preferably 5 wt% to 40 wt%, and the total of the hole transport material and the electron transport material is 1 wt% to 50 wt%, preferably 5 wt% to 40 wt%. Therefore, the content of the polymer compound of the present invention is 98 wt% to 1 wt%, preferably 90 wt% to 20 wt%.

As the hole-transporting material, electron-transporting material, and light-emitting material to be mixed, known low-molecular compounds, triplet light-emitting complexes, or high-molecular compounds can be used, but high-molecular compounds are preferably used.
As the hole transport material, electron transport 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, WO 95/07955, JP 2001-181618, JP 2001-123156, JP 2001-3045, JP 2000-351967, JP 2000-303066, JP 2000-299189, JP 2000-252065, JP 2000-252065, JP 2000-136379, JP 2000-104057, JP 2000-80167, JP 10-324870, JP 10-114891, JP 9-111233, JP 9-45478, and the like, and derivatives thereof And copolymers, polyarylenes, derivatives and copolymers thereof, polyarylene vinylenes, derivatives and copolymers thereof, and (co) polymers of aromatic amines and derivatives thereof.

Examples of the fluorescent material of the low molecular weight compound include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or a derivative thereof. A complex, an aromatic amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.
Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.
Examples of triplet light-emitting complexes include Ir (ppy) ₃ , Btp ₂ Ir (acac) having iridium as the central metal, PtOEP having platinum as the central metal, Eu (TTA) ₃ phen having europium as the central metal, and the like. Can be mentioned.

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

The number average molecular weight in terms of polystyrene of the polymer composition of the present invention is usually about 10 ³ to 10 ⁸ , preferably 10 ⁴ to 10 ⁶ . Moreover, the polystyrene-equivalent weight average molecular weight is usually about 10 ³ to 10 ⁸ , and preferably 1 × 10 ^{4 to} 5 × 10 ⁶ from the viewpoint of film formability and efficiency when used as an element. Here, the average molecular weight of the polymer composition refers to a value obtained by analyzing a composition obtained by mixing two or more kinds of polymer compounds by GPC.

  The film thickness of the light-emitting layer of the polymer light-emitting device of the present invention may be selected so that the optimum value varies depending on the material used and the driving voltage and the light emission efficiency are appropriate values. The thickness is preferably 2 nm to 500 nm, and 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 usually 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%, more preferably the total weight of the composition. It is 80 wt%-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. in order to prevent clogging at the time of discharge and flight bending. It is preferably in the range of ˜20 mPa · s.

The solution of the present invention may contain an additive for adjusting viscosity and / or surface tension in addition to the polymer compound of the present invention. As the additive, a high molecular weight polymer compound (thickener) for increasing the viscosity, a poor solvent, a low molecular weight compound for decreasing the viscosity, a surfactant for decreasing the surface tension, and the like are appropriately combined. Use it.
The high molecular weight polymer compound may be any compound that is soluble in the same solvent as the polymer compound of the present invention and does not inhibit light emission or charge transport. For example, high molecular weight polystyrene, polymethyl methacrylate, or a polymer compound of the present invention having a large molecular weight can be used. The weight average molecular weight is preferably 500,000 or more, more preferably 1,000,000 or more.
A poor solvent can also be used as a thickener. That is, the viscosity can be increased by adding a small amount of a poor solvent for the solid content in the solution. When a poor solvent is added for this purpose, the type and addition amount of the solvent may be selected as long as the solid content in the solution does not precipitate. Considering the stability during storage, the amount of the poor solvent is preferably 50 wt% or less, more preferably 30 wt% or less with respect to the entire solution.

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

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. Examples of the solvent include chloro solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran, dioxane and anisole, toluene, xylene and the like. Aromatic hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone , Ketone solvents such as benzophenone and acetophenone, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate and phenyl acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol Polyethyl alcohol and derivatives thereof such as noethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, methanol, ethanol, propanol, isopropanol And alcohol solvents such as cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination.
Of these, aromatic hydrocarbon solvents, ether solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents from the viewpoints of solubility of polymer compounds, uniformity during film formation, viscosity characteristics, etc. Solvents are preferred, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, s-butylbenzene, n-hexylbenzene, cyclohexylbenzene, 1-methylnaphthalene, tetralin Anisole, ethoxybenzene, cyclohexane, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, decalin, methyl benzoate, cyclohexanone, 2-propylcyclohexanone, 2- Heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone, dicyclohexyl ketone, acetophenone, benzophenone is preferable.

The number of solvents in the solution is preferably two or more, more preferably two to three, and even more preferably two from the viewpoints of film formability and device characteristics.
When two kinds of solvents are contained in the solution, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, one type of solvent is preferably a solvent having a boiling point of 180 ° C. or higher, and more preferably 200 ° C. or higher. From the viewpoint of viscosity, it is preferable that 1 wt% or more of the aromatic polymer dissolves at 60 ° C. in one of the two solvents, and one solvent out of the two solvents contains 1 wt% at 25 ° C. The above aromatic polymer is preferably dissolved.
When two or more kinds of solvents are contained in the solution, the solvent having the highest boiling point is preferably 40 to 90 wt% of the weight of the total solvent in the solution from the viewpoint of viscosity and film formability, and 50 to 90 wt%. % Is more preferable, and 65 to 85 wt% is more preferable.
The aromatic polymer of the present invention contained in the solution may be one type or two or more types, and may contain a polymer compound other than the aromatic polymer of the present invention as long as the device characteristics and the like are not impaired.
The solution of the present invention may contain water, metal and a salt thereof in the range of 1 to 1000 ppm. Specific examples of the metal include lithium, sodium, calcium, potassium, iron, copper, nickel, aluminum, zinc, chromium, manganese, cobalt, platinum, iridium and the like. Moreover, silicon, phosphorus, fluorine, chlorine, and / or bromine may be contained in a range of 1 to 1000 ppm.

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

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

  Examples of the thin film that can be produced using the solution of the present invention include a light-emitting thin film, a conductive thin film, and an organic semiconductor thin film.

The conductive thin film of the present invention preferably has a surface resistance of 1 KΩ / □ or less. The electrical conductivity can be increased by doping the thin film with a Lewis acid, an ionic compound, or the like. The surface resistance is more preferably 100Ω / □ or less, and further preferably 10Ω / □ or less.
In the organic semiconductor thin film of the present invention, the higher one of the electron mobility and the hole mobility is preferably 10 ⁻⁵ cm ² / V / second or more. More preferably, it is 10 ^<-3 > cm < ² > / V / second or more, More preferably, it is 10 ^<-1 > cm < ² > / V / second or more.
An organic transistor can be formed by forming the organic semiconductor thin film on a Si substrate on which an insulating film such as SiO ₂ and a gate electrode are formed, and forming a source electrode and a drain electrode with Au or the like.

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

The polymer light emitting device of the present invention includes a polymer light emitting device in which an electron transport layer is provided between the cathode and the light emitting layer, a polymer light emitting device in which a hole transport layer is provided between the anode and the light emitting layer, and a cathode. And a light emitting polymer layer in which an electron transport layer is provided between the anode 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.)
Further, for each of these structures, a structure in which an interlayer layer is provided adjacent to the light emitting layer between the light emitting layer and the anode is also exemplified. That is, the following structures a ′) to d ′) are exemplified.
a ′) Anode / interlayer layer / light emitting layer / cathode b ′) Anode / hole transport layer / interlayer layer / light emitting layer / cathode c ′) Anode / interlayer layer / light emitting layer / electron transport layer / cathode d ′ ) Anode / hole transport layer / interlayer layer / light emitting layer / electron transport layer / cathode When the polymer light emitting device of the present invention has a hole transport layer, the hole transport material used is polyvinylcarbazole or Derivatives thereof, polysilanes or derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, 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 a poly (2,5-thienylene vinylene) or derivatives 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, and more preferably polyvinyl carbazole or a derivative thereof A derivative, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in a 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 the polysilane or derivatives thereof include compounds described in Chem. Rev. 89, 1359 (1989), GB 2300196 published specification, and the like. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.
Since polysiloxane or a derivative thereof has almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular hole transporting material in the side chain or main chain are preferably used. Particularly, those having a hole transporting aromatic amine in the side chain or main chain are exemplified.

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

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

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

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

  When the polymer light-emitting device of the present invention has an electron transport layer, known electron transport materials can be used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinones or derivatives thereof, naphthoquinones. Or derivatives thereof, anthraquinone or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, poly Examples thereof include quinoxaline or a derivative thereof, polyfluorene or a derivative thereof.

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 for forming the electron transport layer, but for low molecular weight electron transport materials, vacuum deposition from powder or film deposition from a solution or melted state is preferred for polymer electron transport materials. Or the method by the film-forming from a molten state is illustrated, respectively. When forming a film from a solution or a molten state, the above polymer binder may be used in combination.

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

Examples of film formation methods from a solution or a molten state include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.
The 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. 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 light emitting device provided with a charge injection layer (electron injection layer, hole injection layer) is a polymer light emitting device provided with a charge injection layer adjacent to the cathode, or a charge injection adjacent to the anode. Examples thereof include a polymer light emitting device provided with a layer.
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 For each one of these structures, the light emitting layer is adjacent to the light emitting layer between the light emitting layer and the anode. A structure in which an interlayer is provided is also exemplified. In this case, the interlayer layer may also serve as a hole injection layer and / or a hole transport layer.

  Specific examples of the charge injection layer include a layer containing a conductive polymer, an intermediate between the anode material and the hole transporting material included in the hole transporting layer, provided between the anode and the hole transporting layer. A layer containing a material having an ionization potential of the value, a material provided between the cathode and the electron transport layer, and a material having an electron affinity of an intermediate value between the cathode material and the electron transport material contained in the electron transport layer Examples include layers.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ or less, and the leakage current between the light emitting pixels is reduced. In order to achieve this, 10 ⁻⁵ S / cm to 10 ² is more preferable, and 10 ⁻⁵ S / cm to 10 ¹ is more preferable.
When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less. in order to reduce the current, more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably less 10 ^-5 S / cm or more and 10 ¹ S / cm.

Usually, in order to set the electric conductivity of the conductive polymer to 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 derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, 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. The polymer light emitting device provided with an insulating layer having a thickness of 2 nm or less includes a polymer light emitting device provided with an insulating layer having a thickness of 2 nm or less adjacent to the cathode, and an insulating layer having a thickness of 2 nm or less adjacent to the anode. The provided 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 / insulating layer with a thickness of 2 nm or less / cathode ab) anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode For example, a structure in which an interlayer is provided adjacent to the light emitting layer between the light emitting layer and the anode is also exemplified. In this case, the interlayer layer may also serve as a hole injection layer and / or a hole transport layer.

Regarding the structure in which the interlayer layer is applied to the above structures a) to ab), the interlayer layer is provided between the anode and the light emitting layer, and the anode, the hole injection layer or the hole transport layer, and the light emitting layer. It is preferably composed of a material having an ionization potential intermediate to that of the polymer compound constituting
Examples of materials used for the interlayer layer include polymers containing aromatic amines such as polyvinyl carbazole or derivatives thereof, polyarylene derivatives having aromatic amines in the side chain or main chain, arylamine derivatives, and triphenyldiamine derivatives. .
Although there is no restriction | limiting in the film-forming method of an interlayer layer, For example, when using a polymeric material, the method by the film-forming from a solution is illustrated.

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

Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.
The film thickness of the interlayer layer may be selected so that the optimum value varies depending on the material used, and the drive voltage and the light emission efficiency are appropriate values. For example, it is 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the interlayer layer is provided adjacent to the light emitting layer, particularly when both layers are formed by a coating method, the materials of the two layers are mixed to adversely affect the characteristics of the device. There is. When the light emitting layer is formed by the coating method after the interlayer layer is formed by the coating method, as a method for reducing the mixing of the materials of the two layers, the interlayer layer is formed by the coating method, and then the interlayer layer is formed. A method of forming a light emitting layer after heating to insolubilize in an organic solvent used for forming a light emitting layer can be mentioned. The heating temperature is usually about 150 ° C. to 300 ° C., and the time is usually about 1 minute to 1 hour. In this case, in order to remove components that have not been insolubilized by heating, the interlayer layer can be removed by rinsing with a solvent used for forming the light emitting layer after heating and before forming the light emitting layer. When solvent insolubilization by heating is sufficiently performed, rinsing with a solvent can be omitted. In order to sufficiently insolubilize the solvent by heating, it is preferable to use a polymer compound containing at least one polymerizable group in the molecule as the polymer compound used in the interlayer layer. Furthermore, the number of polymerizable groups is preferably 5% or more with respect to the number of repeating units in the molecule.

The substrate on which the polymer light-emitting device of the present invention is formed may be any substrate that does not change when an electrode is formed and an organic layer is formed. 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 light emitting device 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, as the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used.

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.
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.

  A material for the cathode used in the polymer light-emitting device of the present invention is preferably a material having a low work function. 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, or the like Two or more of these alloys, or one or more of them and an alloy of one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, or graphite or graphite intercalation compound Etc. are 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 manufacturing 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. In addition, 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 light emitting device may be attached. In order to stably use the polymer light emitting device for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the device from the outside.
As the protective layer, a polymer compound, metal oxide, metal fluoride, metal boride and the like can be used. As the protective cover, a metal plate, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and the cover is bonded to the element substrate with a thermosetting resin or a photocurable resin and sealed. The method is preferably used. If the space is maintained by using the spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, oxidation of the cathode can be prevented, and further, a desiccant such as barium oxide is placed in the space to adsorb in the manufacturing process. It is easy to suppress damage to the element by a minute amount of moisture entering through moisture or a cured resin. Among these, it is preferable to take one or more measures.

The polymer light emitting device of the present invention can be used as a planar light source, a segment display device, a dot matrix display device, a backlight of a liquid crystal display device, and the like.
In order to obtain planar light emission using the polymer light emitting device of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic material layer of a non-light-emitting portion is formed extremely thick and substantially non- There are a method of emitting light and a method of forming either one of the anode or the cathode or both electrodes in a pattern. A segment type display element capable of displaying numbers, letters, simple symbols, etc. can be obtained by forming a pattern by any of these methods and arranging several electrodes so that they can be turned ON / OFF independently. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of polymer phosphors 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 Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
NMR measurement was performed under the following conditions.
Apparatus: Bruker Avance 600 (trade name) nuclear magnetic resonance apparatus Measurement solvent: Deuterated tetrahydrofuran Sample concentration: About 1% by weight
Measurement temperature: 30 ° C
The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were determined by SEC under the following SEC conditions 1.
<SEC condition 1>
Equipment: PL-GPC210 system (trade name) manufactured by Polymer Laboratory (RI detection)
Column: Three PLgel 10um MIXED-B (trade name) manufactured by Polymer Laboratories Mobile phase: o-dichlorobenzene Thermogravimetric measurement was performed using Rigaku's THERMOFLEX TAS200 TG8101D (trade name) under an air flow of 80 cc per minute. The weight loss rate after the temperature was raised by 10 ° C. and heated from 20 ° C. to 400 ° C. was measured.

[Comparative Example 1]
<Synthesis of Polymer Compound 1>
After dissolving 9.875 g of 5,9-Dibromo-7,7-dioctyl-7H-benzo [c] fluorene (Compound A) and 6.958 g of 2,2′-bipyridyl in 1188 mL of dehydrated tetrahydrofuran, the reaction was conducted under a nitrogen atmosphere. The temperature was raised to 60 ° C. and 12.253 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added to this solution and reacted for 3 hours. After the reaction, this reaction solution was cooled to room temperature, dropped into a mixed solution of 25% aqueous ammonia 59 ml / methanol 1188 ml / ion exchanged water 1188 ml and stirred for 30 minutes, and then the deposited precipitate was filtered and dried under reduced pressure for 2 hours. did. Subsequently, two batches of operations were performed under the same conditions as described above except that the scale was increased by 1.09 times to obtain precipitates. The precipitates obtained in a total of 3 batches were combined and dissolved in 1575 ml of toluene. After dissolution, 6.30 g of radiolite was added and stirred for 30 minutes, and the insoluble material was filtered. The obtained filtrate was purified through an alumina column. Next, after adding 3098 mL of 5.2% aqueous hydrochloric acid and stirring for 3 hours, the aqueous layer was removed. Subsequently, 3098 mL of 4% aqueous ammonia was added and stirred for 2 hours, and then the aqueous layer was removed. Further, about 3098 mL of ion exchange water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. Thereafter, the organic layer was poured into 4935 ml of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The obtained polymer (hereinafter referred to as polymer compound 1) was a polymer compound consisting only of the following (repeating unit A), and the yield was 15.460 g. Moreover, the number average molecular weight and weight average molecular weight of polystyrene conversion by SEC condition 1 were Mn = 72000 and Mw = 495000, respectively. The formula amount FW ₁ of the repeating unit of the polymer was 438.7, and the average number of connections was 164.

<Association of doublet peak of polymer compound 1>
Measurement of ¹ H detection ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) per high molecular compound 1 revealed that protons represented by H _A1 , H _B1 and H _C1 in formula (a) representing a doublet. Are 7.67 ppm, 7.39 ppm, and 7.80 ppm, respectively, and the chemical shift of carbon 13 represented by C _A1 , C _B1 , and C _C1 in formula (a) is 128.1 ppm, respectively. At 125.4 ppm and 123.9 ppm, proton-carbon 13 correlation peaks were observed for the proton-carbon pairs indicated by H _A1 and C _A1 , H _B1 and C _B1 , and H _C1 and C _C1 . On the other hand, the chemical shifts of protons represented by H _A2 , H _B2, and H _C2 in the formula (b) representing the doublet are 8.23 ppm, 7.55 ppm, and 7.78 ppm, respectively, in the formula (b) The chemical shifts of carbon 13 represented by C _A2 , C _B2 , and C _C2 are 127.8 ppm, 125.4 ppm, and 122.5 ppm, respectively, and H _A2 and C _A2 , H _B2 and C _B2 , and H _C2 A proton-carbon 13 correlation peak was observed for the proton-carbon pair denoted C _C2 .

The quantitative ratios of H _A1 and H _A2 , H _B1 and H _B2 , and H _C1 and H _C2 are determined by integrating the intensities of proton-carbon 13 correlation peaks in the HMQC spectrum, and H _A1 and H contained in one diad. _A2, showing a _{H B1, H B2, H C1} , and the results of the ratio calculated in considering the number of H _C2 diad (a) and diad (b) in Table 1.

In the ¹ H detection ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) of the polymer compound 1, the chemical shift of the proton indicated by H _D2 in the formula (c) representing the doublet and the C _D2 chemical shifts of the carbon 13 are respectively 7.79Ppm, and 125.2Ppm, protons against protons and a pair of carbon atoms represented by H _D2 and C _D2 - carbon 13 correlation peak was observed. On the other hand, the chemical shifts of carbon 13 indicated by proton chemical shifts and C _D3 represented in the formula (d) representing a diad in H _D3 are respectively 8.00Ppm, and 121.2ppm, H _D3 and C _A proton-carbon 13 correlation peak was observed for the proton-carbon pair indicated by _D3 .

The quantity ratio of H _D2 and H _D3 is obtained by integrating the intensity of the proton-carbon 13 correlation peak in the HMQC spectrum, taking into account the number of H _D2 and H _D3 contained in one biad, and the biad (c) Table 2 shows the result of calculating the ratio of the quintuplet and the doublet (d).

  Since the doublet (b) and the doublet (c) are the same, the three types of doubles constituting the polymer compound 1, that is, the doublet (a), the doublet (b) (or It was found that the ratio of the duplex (c)) and the duplex (d) was 24: 76: 25 = 19: 61: 20. The head-to-tail bond in the polymer compound 1 is a bond formed between two repeating units in the duplex (b) (or duplex (c)). , The ratio of the number of bonds formed between the head and tail to the total number of bonds formed between (repeating units A) was found to be 61%.

[Example 1]
<Synthesis of Polymer Compound 2>
2- (9-Bromo-7,7-dioctyl-7H-benzo [c] fluoren-5-yl) -4,4,5,5-tetramethyl- in a 25 ml two-necked flask connected to Dimroth under an argon atmosphere [1,3,2] dioxaborolane (Compound B) 200 mg (0.31 mmol), palladium acetate 3.5 mg (0.015 mmol), and tricyclohexylphosphine 8.7 mg (0.031 mmol) were added, and the inside of the container was replaced with argon gas. did. Thereto were added 12.4 ml of toluene, 5.9 mg (0.023 mmol) of 4-t-butyliodobenzene, and 120 μL of n-octylbenzene (internal standard substance), and the mixture was stirred at 110 ° C. for 10 minutes. To this pale yellow solution, 1.4 ml of a 20% by weight aqueous tetraethylammonium hydroxide solution was poured to start the reaction, and the reaction was continued by stirring at 110 ° C. for 17 hours. After confirming the disappearance of Compound B by high performance liquid chromatography, 10 ml of H ₂ O was added to the reaction mixture and stirred well, and the organic layer was separated from the aqueous layer. After concentration of the organic layer, 9 ml of chloroform was added, and this solution was added dropwise to 72 ml of ethanol to precipitate the polymer. The precipitate was collected by filtration and dried under reduced pressure to obtain 91.8 mg of a yellow powder. This powder was dissolved in 6.5 ml of toluene and passed through a column of silica gel and alumina. The solution eluted with 13 ml of toluene was concentrated to about 2 ml and then added dropwise to 25 ml of methanol for precipitation. The precipitate was filtered and dried to obtain 51.2 mg (yield 38%) of a polymer consisting only of the above (repeating unit A) (hereinafter referred to as polymer compound 2). Moreover, the number average molecular weight and weight average molecular weight of polystyrene conversion by SEC condition 1 were Mn = 9000 and Mw = 17000, respectively. The formula amount FW ₁ of the repeating unit of the polymer was 438.7, and the average number of connections was 21.

<Association of doublet peak of polymer compound 2>
¹ H detection ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) was measured for polymer compound 2 in the same manner as polymer compound 1, and the integrated range was obtained by integrating the same range as polymer compound 1. . Further, Table 3 shows the results obtained by calculating the ratio of the duplexes (a) and the duplexes (b) and the duplexes (c) and the duplexes (d) by the same calculation as in the polymer compound 1.

Based on the above results, the ratio of the biad (a), double (b) (or double (c)), and double (d) is calculated using the same calculation as for polymer compound 1. It was found that it was 4: 96: 0. The head-to-tail bond in the polymer compound 2 is a bond formed between two repeating units in the duplex (b) (or duplex (c)). The ratio of the number of bonds formed between the head and tail to the total number of bonds formed between (repeating units A) was found to be 96%.

[Comparative Example 2]
<Synthesis of Polymer Compound 3>
A polymer composed of only the above (repeating unit A) (hereinafter referred to as polymer compound 3) was obtained from compound A by the same method as the synthesis method of polymer compound 1. The polystyrene-equivalent number average molecular weight and weight average molecular weight according to SEC condition 1 were Mn = 17000 and Mw = 78000, respectively. The formula amount FW ₁ of the repeating unit of the polymer was 438.7, and the average number of connections was 39.

<Synthesis of Polymer Compound 4>

The compound C (5.511 g), the compound D (3.115 g), and 2,2′-bipyridyl (3.865 g) were dissolved in 1320 mL of dehydrated tetrahydrofuran, and the temperature was raised to 60 ° C. in a nitrogen atmosphere. To this solution, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (6.807 g) was added, stirred and allowed to react for 3 hours. After the reaction, the reaction solution was cooled to room temperature, dropped into a mixed solution of 25% aqueous ammonia 33 mL / methanol 1320 mL / ion-exchanged water 1320 mL, stirred for 1 hour, the deposited precipitate was filtered and dried under reduced pressure, Dissolved in 275 ml of toluene. After dissolution, 11 g of radiolite was added and stirred for 30 minutes, and the insoluble material was filtered. The obtained filtrate was purified through an alumina column. The purified solution thus obtained was added with 541 mL of 4% aqueous ammonia and stirred for 2 hours, and then the aqueous layer was removed. Subsequently, about 541 mL of ion-exchanged water was added and stirred for 1 hour, and then the aqueous layer was removed. Thereafter, the organic layer was poured into 862 ml of methanol and stirred for 0.5 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 4) was 5.48 g. Moreover, the number average molecular weight and weight average molecular weight of polystyrene conversion were Mn = 20000 and Mw = 17000, respectively.

<Creation of light-emitting element using polymer compound 3>
(Preparation of solution)
Polymer compound 3 obtained above was dissolved in toluene at a ratio of 50% by weight and polymer compound 4 at a ratio of 50% by weight to prepare a toluene solution having a polymer concentration of 2.0% by weight.
(Production of EL element)
A suspension of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) on a glass substrate with an ITO film having a thickness of 150 nm formed by a sputtering method is passed through a 0.2 μm membrane filter. A thin film having a thickness of 70 nm was formed by spin coating using the filtered liquid, and dried on a hot plate at 200 ° C. for 10 minutes. Next, the toluene solution obtained above was used to form a film at a rotational speed of 2000 rpm by spin coating. The film thickness after film formation was about 78 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then lithium fluoride was deposited by about 4 nm, calcium was deposited by about 5 nm as a cathode, and then aluminum was deposited by about 80 nm to produce an EL device. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 465 nm was obtained from this device. The EL emission color when 8.0 V is applied is C.I. I. E. In terms of color coordinate values, x = 0.157 and y = 0.220. The intensity of EL emission was almost proportional to the current density. The device started to emit light at 3.1 V, and the maximum light emission efficiency was 1.47 cd / A.
(Life measurement)
When the EL device obtained above was driven at a constant current of 150 mA / cm ^{2 and} the change in luminance with time was measured, the device had an initial luminance of 2150 cd / m ² and a luminance half time of 11.3 hours. . Assuming that the luminance-lifetime acceleration coefficient is square, this is converted to a value of initial luminance of 400 cd / m ² , and the half-life is 327 hours. The voltage required for driving was 8.64 V in the initial stage and 9.47 V after half the luminance, and the voltage change during driving was 0.83 V. The voltage increase rate calculated from this converted half life was 2.54 mV / hour.
Spectra after driving The EL element obtained above was driven at a constant current of 150 mA / cm ² for 78 hours, separately from the lifetime measurement. The luminance after driving was 10.0% of the initial luminance. When an EL spectrum was measured by applying a voltage of 8.0 V to the element thus driven, the peak wavelength was 465 nm and the EL emission color C.I. I. E. The color coordinate values were x = 0.195 and y = 0.270. Further, when the EL spectrum was compared with the EL spectrum before driving, as shown in FIG. 1, light emission having shoulder peaks at 550 nm and 590 nm was newly observed.

[Example 2]
<Synthesis of Polymer Compound 5>
Except that 4-t-butyliodobenzene was not used, a polymer consisting only of the above (repeating unit A) from compound B (hereinafter referred to as polymer compound 5) was prepared in the same manner as the synthesis method of polymer compound 2. Call). The number average molecular weight and weight average molecular weight in terms of polystyrene according to SEC condition 1 were Mn = 15000 and Mw = 31000, respectively. The formula amount FW ₁ of the repeating unit of the polymer was 438.7, and the average number of connections was 34.

<Creation of light-emitting element using polymer compound 5>
(Preparation of solution)
Polymer compound 5 obtained above was dissolved in toluene at a ratio of 50% by weight and polymer compound 4 at a ratio of 50% by weight to prepare a toluene solution having a polymer concentration of 2.0% by weight.
(Production of EL element)
A suspension of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) on a glass substrate with an ITO film having a thickness of 150 nm formed by a sputtering method is passed through a 0.2 μm membrane filter. A thin film having a thickness of 70 nm was formed by spin coating using the filtered liquid, and dried on a hot plate at 200 ° C. for 10 minutes. Next, using the toluene solution obtained above, a film was formed by spin coating at a rotational speed of 1500 rpm. The film thickness after film formation was about 74 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then lithium fluoride was deposited by about 4 nm, calcium was deposited by about 5 nm as a cathode, and then aluminum was deposited by about 80 nm to produce an EL device. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 465 nm was obtained from this device. The EL emission color when 8.0 V is applied is C.I. I. E. In terms of color coordinate values, x = 0.154 and y = 0.209. The intensity of EL emission was almost proportional to the current density. The device started to emit light from 3.0 V, and the maximum light emission efficiency was 1.51 cd / A.
(Life measurement)
When the EL device obtained above was driven at a constant current of 150 mA / cm ^{2 and} the change in luminance with time was measured, the device had an initial luminance of 2090 cd / m ² and a luminance half time of 37.4 hours. . Assuming that the luminance-lifetime acceleration coefficient is square, this is converted to a value of initial luminance of 400 cd / m ² , and the half-life is 1021 hours. The voltage required for driving was 7.81 V in the initial stage and 8.16 V after half the luminance, and the voltage change during driving was 0.35 V. When the voltage increase rate was calculated from the converted half life, it was 0.34 mV / hour.
(Spectrum after driving)
The EL element obtained above was driven at a constant current of 150 mA / cm ² for 81 hours, separately from the lifetime measurement. The luminance after the driving was 34.4% of the initial luminance. When an EL spectrum was measured by applying a voltage of 8.0 V to the element thus driven, the peak wavelength was 465 nm and the EL emission color C.I. I. E. The color coordinate values were x = 0.160 and y = 0.215. Further, when the EL spectrum was compared with the EL spectrum before driving, as shown in FIG. 2, there was almost no change in the spectrum before and after driving.
As described above, in the polymer light emitting device using the polymer compound 5 as compared with the polymer compound 3 of Comparative Example 2, the luminance half-life is long and the spectral change due to the drive is small, so that the color before and after the drive. It can be seen that the change is suppressed and the voltage increase rate during driving is small. Thus, the polymer compound according to the present invention has excellent properties as a material used for the polymer light emitting device.

[Comparative Example 3]
<Synthesis of Polymer Compound 6>
A polymer (hereinafter referred to as polymer compound 6) consisting only of the above (repeating unit A) was obtained from compound A by the same method as the synthesis method of polymer compound 1. The polystyrene-equivalent number average molecular weight and weight average molecular weight according to SEC condition 1 were Mn = 55000 and Mw = 1119,000, respectively. The formula amount FW ₁ of the repeating unit of the polymer was 438.7, and the average number of linkages was 125.

<Synthesis of Polymer Compound 7>

In a nitrogen atmosphere, 195.37 g of Compound E, 239.44 g of Compound D and 232.89 g of 2,2′-bipyridyl were dissolved in 46.26 kg of dehydrated tetrahydrofuran, and the temperature was raised to 60 ° C., and bis ( 1,5-Cyclooctadiene) nickel (0) {Ni (COD) ₂ } 410.15 g was added and reacted for 5 hours. After the reaction, this reaction solution was cooled to room temperature, dropped into a mixed solution of 25% ammonia water 8.52 kg / methanol 16.88 kg / ion-exchanged water 31.98 kg, stirred for 2 hours, and the deposited precipitate was filtered. And dried under reduced pressure. After drying, the product was dissolved in 16.22 kg of toluene. After dissolution, 830 g of radiolite was added, and the insoluble material was filtered. The obtained filtrate was purified through an alumina column, then the purified solution was added to a mixed solution of ion-exchanged water 13.52 kg / 25% ammonia water 2.04 kg, stirred for 0.5 hour, and then the aqueous layer was removed. . Further, 13.52 kg of ion-exchanged water was added to the organic layer and stirred for 0.5 hour, and then the aqueous layer was removed. A portion of the obtained organic layer was concentrated under reduced pressure, and then the organic layer was poured into 34.18 kg of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer was 234.54 g. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 12000 and Mw = 77000, respectively.
A 0.5% toluene solution of the polymer was prepared and filtered through a 0.45 μ filter. The solution obtained by filtration was repeatedly collected by SEC under the following conditions.
Column: TSKgel GMH _HR- H (TOSOH GPC column, 21.5 mm I.D. × 30 cm)
Column temperature 60 ° C
Mobile phase: Toluene Flow rate 6 ml / min.
Sample injection volume 2ml
Preparative time: 11.0-11.5 min.
The obtained fraction solution was concentrated with an evaporator and reprecipitated in methanol to obtain a high molecular weight product (hereinafter referred to as polymer compound 7). Mn = 6800 and Mw = 8900 in terms of polystyrene.

<Preparation of light-emitting element using polymer compound 6>
(Preparation of solution)
Polymer compound 6 obtained above was dissolved in toluene at a ratio of 80% by weight and polymer compound 7 at a ratio of 20% by weight to prepare a toluene solution having a polymer concentration of 2.0% by weight.
(Production of EL element)
A suspension of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) on a glass substrate with an ITO film having a thickness of 150 nm formed by a sputtering method is passed through a 0.2 μm membrane filter. A thin film having a thickness of 70 nm was formed by spin coating using the filtered liquid, and dried on a hot plate at 200 ° C. for 10 minutes. Next, using the toluene solution obtained above, a film was formed by spin coating at a rotational speed of 1500 rpm. The film thickness after film formation was about 83 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then lithium fluoride was deposited by about 4 nm, calcium was deposited by about 5 nm as a cathode, and then aluminum was deposited by about 80 nm to produce an EL device. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 470 nm was obtained from this device. The EL emission color when 8.0 V is applied is C.I. I. E. In terms of color coordinate values, x = 0.157 and y = 0.212. The intensity of EL emission was almost proportional to the current density. The device started to emit light from 3.0 V, and the maximum light emission efficiency was 1.52 cd / A.
(Life measurement)
When the EL device obtained above was driven at a constant current of 150 mA / cm ^{2 and} the change in luminance with time was measured, the device had an initial luminance of 1863 cd / m ² and a luminance half time of 6.32 hours. . Assuming that the luminance-lifetime acceleration coefficient is square, this is converted to a value of initial luminance of 400 cd / m ² , and the half-life is 137 hours. The voltage required for driving was 8.99V in the initial stage and 9.74V after half the luminance, and the voltage change during driving was 0.75V. The voltage increase rate calculated from this converted half life was 5.47 mV / hour.
Spectra after driving The EL element obtained above was driven at a constant current of 150 mA / cm ² for 81 hours, separately from the lifetime measurement. The luminance after driving was 10.7% of the initial luminance. When an EL spectrum was measured by applying a voltage of 8.0 V to the driven element thus obtained, the peak wavelength was 470 nm, and the EL emission color C.I. I. E. The color coordinate values were x = 0.230 and y = 0.310. Further, when the EL spectrum was compared with the EL spectrum before driving, emission having shoulder peaks at 550 nm and 590 nm was newly observed as shown in FIG.

[Example 3]
<Creation of light-emitting element using polymer compound 5>
(Preparation of solution)
Polymer compound 5 obtained above was dissolved in toluene at a ratio of 80% by weight and polymer compound 7 at a ratio of 20% by weight to prepare a toluene solution having a polymer concentration of 2.0% by weight.
(Production of EL element)
A suspension of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) on a glass substrate with an ITO film having a thickness of 150 nm formed by a sputtering method is passed through a 0.2 μm membrane filter. A thin film having a thickness of 70 nm was formed by spin coating using the filtered liquid, and dried on a hot plate at 200 ° C. for 10 minutes. Next, a film was formed at a rotation speed of 600 rpm by spin coating using the toluene solution obtained above. The film thickness after film formation was about 89 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then lithium fluoride was deposited by about 4 nm, calcium was deposited by about 5 nm as a cathode, and then aluminum was deposited by about 80 nm to produce an EL device. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 475 nm was obtained from this device. The EL emission color when 8.0 V is applied is C.I. I. E. In terms of color coordinate values, x = 0.159 and y = 0.224. The intensity of EL emission was almost proportional to the current density. The device started to emit light from 2.9 V, and the maximum light emission efficiency was 1.59 cd / A.
(Life measurement)
When the EL device obtained above was driven at a constant current of 150 mA / cm ^{2 and} the change in luminance with time was measured, the device had an initial luminance of 2130 cd / m ² and a luminance half time of 22.9 hours. . Assuming that the luminance-lifetime acceleration coefficient is square, this is converted to a value of initial luminance of 400 cd / m ² , and the half-life is 648 hours. The voltage required for driving was 8.64 V in the initial stage and 9.47 V after half the luminance, and the voltage change during driving was 1.03 V. The voltage increase rate calculated from this converted half life was 1.59 mV / hour.
(Spectrum after driving)
The EL element obtained above was driven at a constant current of 150 mA / cm ² for 81 hours, separately from the lifetime measurement. The luminance after the driving was 22.7% of the initial luminance. When an EL spectrum was measured by applying a voltage of 8.0 V to the element thus driven, the peak wavelength was 475 nm and the EL emission color C.I. I. E. The color coordinate values were x = 0.184 and y = 0.254. Further, when the EL spectrum was compared with the EL spectrum before driving, as shown in FIG. 4, the long wavelength component slightly increased in the region exceeding 500 nm, but almost no change was observed in the spectrum shape itself.
As described above, in the polymer light-emitting device using the polymer compound 5 as compared with the polymer compound 6 of Comparative Example 3, the luminance half-life is long and the spectral change due to driving is small, so that the color before and after driving is small. It can be seen that the change is suppressed and the voltage increase rate during driving is small. Thus, the polymer compound according to the present invention has excellent properties as a material used for the polymer light emitting device.

[Comparative Example 4]
<Thermogravimetric measurement of polymer compound 3>
When the thermogravimetric measurement of the polymer compound 3 was carried out, the weight loss rate after raising the temperature by 10 ° C. per minute and from 20 ° C. to 400 ° C. was 10.4%.

[Example 4]
<Thermogravimetric measurement of polymer compound 5>
When the thermogravimetric measurement of the polymer compound 5 was carried out, the weight loss rate after the temperature was raised from 20 ° C. to 400 ° C. by 10 ° C. per minute was 4.2%. Compared with the polymer compound 3 of Comparative Example 4, the polymer compound 5 according to the present invention has a property excellent in heat resistance.

[Comparative Example 5]
<Synthesis of Polymer Compound 8>
To a four-necked flask, 1.04 g (6.7 mmol) of 2,2′-bipyridyl and 1.19 g (3.55 mmol) of 1,4-dibromo-2-hexyloxybenzene were added, and the inside of the flask was replaced with argon gas. Then, 128 mL of dehydrated tetrahydrofuran was added. After raising the temperature to 40 ° C., bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } 1.67 g (6.06 mmol) was added, and stirring was continued at 40 ° C. for 1 hour to carry out the reaction. It was.
After the reaction, this reaction solution was cooled to room temperature, dropped into a mixed solution of 25% aqueous ammonia 12 ml / methanol 110 ml / water 110 ml and stirred for 1.5 hours, and then the deposited precipitate was filtered and dried under reduced pressure. Next, 95 mL of toluene and 6.30 g of radiolite were added to the precipitate and stirred for 40 minutes, and the insoluble material was filtered off. The obtained filtrate was purified through an alumina column, concentrated to about 60 mL, and then added dropwise to 300 mL of methanol. The deposited precipitate was filtered and dried under reduced pressure. The obtained polymer (hereinafter referred to as polymer compound 8) was a polymer compound consisting only of (repeating unit B), and the yield was 0.39 g. Moreover, the number average molecular weight and weight average molecular weight of polystyrene conversion by SEC condition 1 were Mn = 16000 and Mw = 39000, respectively. The formula amount FW ₁ of the repeating unit of the polymer was 176.27, and the average number of connections was 91.

<Determination of the ratio of head-to-tail bond of polymer compound 8>
As a result of measuring ¹ H detection ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) for polymer compound 8, the chemical shift of the proton indicated by H _E1 in formula (e) representing the triplet is 7. The chemical shift of carbon 13 shown in 30 ppm, C _E1 is 122.3 pp.
Observed at m. In the formula (f) representing the triplet, the chemical shift of proton shown in H _E2 was observed at 7.37 ppm, and the chemical shift of carbon 13 shown in C _E2 was observed at 119.6 ppm. In formula (g) representing a triplet, the chemical shift of the proton represented by H _E3 is 7.25.
The chemical shift of carbon 13 shown in ppm and C _E3 was observed at 121.3 ppm. In the formula (h) representing the triplet, the chemical shift of the proton represented by H _E4 is 7.31 ppm, C
The chemical shift of carbon 13 shown in _E4 was observed at 118.7 ppm.

The integrated value of the intensity of the proton-carbon 13 correlation peak in the HMQC spectrum is proportional to the number of H _E1 , H _E2 , H _E3 , and H _E4 described above. Table 4 shows the integrated value of the intensity of the proton-carbon 13 correlation peak.

The head-head bond, the head-tail bond, and the tail-tail bond in the polymer compound 8 are represented by formula (i).

At this time, the number of head-to-head couplings, head-to-tail couplings, and tail-to-tail couplings included in the triplets represented by formulas (e), (f), (g), and (h) , Protons H _E1 , H _E2 , H _E3 , and H _E4 , the relative number of head-head bonds, head-tail bonds, and tail-tail bonds included in polymer compound 8 is 4 is calculated as follows using the integral values (I1), (I2), (I3), and (I4) shown in FIG.

Head-head coupling = (I3 + I4) / 2

Head-tail connection = I1 + I2

Tail-tail coupling = (I2 + I4) / 2

Table 5 shows the results of calculating the ratio of the head-head bond, the head-tail bond, and the tail-tail bond included in the polymer compound 8 using the above formula.

  From the above results, the ratio of the head-to-head bond, the head-to-tail bond, and the tail-to-tail bond included in the polymer compound 8 was 9:79:12 in terms of the number ratio. From the above, in the polymer compound 8, it was found that the ratio of the number of bonds formed between the head and tail to the total number of bonds formed between the repeating units B was 79%.

[Example 5]
<Synthesis of Compound F>
Under an inert gas atmosphere, 2.0 g (6.0 mmol) of 1,4-dibromo-2-hexyloxybenzene was dissolved in 60 mL of dehydrated methyl-t-butyl ether in a 200 mL four-necked flask and cooled to -70 ° C. did. Then, a 1.6 mol / L n-butyllithium hexane solution was added dropwise at −70 ° C. over 6 minutes, and the mixture was stirred at −70 ° C. for 2 hours. Next, 1.5 mL of 2-isopropoxy-4,4,5,5, -tetramethyl-1,3,2-dioxaborolane was added dropwise at -70 ° C over 1 minute, and the mixture was stirred for 1 hour and 15 minutes. The temperature was raised to room temperature and stirring was continued for 10 hours. Next, 30 mL of water was added at 0 ° C., and the mixture was warmed to room temperature and stirred for 30 minutes. After adding ethyl acetate and stirring, the organic layer was separated from the aqueous layer. The organic layer was concentrated and allowed to stand at −5 ° C. overnight to obtain 2.3 g of a solid. Of the obtained solid, 1.1 g was dissolved in 2 mL of methanol at 40 ° C., and cooled to room temperature to precipitate crystals. The obtained crystals were filtered and dried to obtain Compound F (0.5 g, LC area percentage 99.6%).
GC-MS: [M ⁺ ] = 382

<Synthesis of Polymer Compound 9>
In a 100 ml two-necked flask connected with a Dimroth under an argon atmosphere, Compound F 300.2 mg (1.06 mmol), palladium acetate 11.9 mg (0.053 mmol), and tricyclohexylphosphine 22.9 mg (0.11 mmol). Then, the inside of the container was replaced with argon gas. To this was added 42.6 ml of toluene, and the mixture was stirred and heated to 110 ° C. Next, 5.7 mL of a 20 wt% tetraethylammonium hydroxide aqueous solution was added at 110 ° C., and the reaction was continued at 110 ° C. by continuing 18.5 hr of stirring. Subsequently, after cooling the reaction solution to room temperature, 400 mL of ethanol was added, and the precipitated solid was filtered and dried. The obtained solid was dissolved in chloroform and passed through a column filled with silica gel and alumina, and the resulting solution was concentrated to dryness to obtain a solid. Next, a solution obtained by dissolving 3 mL of chloroform in the solid was added dropwise to 50 mL of ethanol to precipitate a solid, which was filtered and dried to obtain a polymer consisting only of (repeating unit B) (hereinafter referred to as polymer compound 9). 78.4 mg). The polystyrene-equivalent number average molecular weight and weight average molecular weight according to SEC condition 1 were Mn = 3300 and Mw = 5200, respectively. The formula amount FW ₁ of the repeating unit of the polymer was 176.27, and the average number of linkages was 19.

<Determination of head-to-tail bond ratio of polymer compound 9>
¹ H detection ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) was measured for polymer compound 9 in the same manner as polymer compound 8, and the integrated range was obtained by integrating the same range as polymer compound 8. . The results are shown in Table 6.

Similar to the polymer compound 8 based on the integration results, the polymer compound 9 also calculates the ratio of the head-head bond, the head-tail bond, and the tail-tail bond contained in the polymer. Table 7 shows.

  From the above results, the ratio of the head-to-head bond, the head-to-tail bond, and the tail-to-tail bond included in the polymer compound 9 was 2: 98: 0 in number ratio. From the above, in the polymer compound 9, it was found that the ratio of the number of bonds formed between the head and tail with respect to the total number of bonds formed between the repeating B units was 98%.

[Example 6]
<Synthesis of Polymer Compound 10>
In a 200 ml three-necked flask connected with a Dimroth under an argon atmosphere, 1400.0 mg (2.17 mmol) of the compound B, 72.1 mg (0.12 mmol) of the compound A, 83.4 mg (0.12 mmol) of the following compound G And the inside of the container was replaced with argon gas. 17 ml of toluene was added and stirred, and the temperature was raised to 45 ° C. Next, 3.3 mg of [tris (dibenzylideneacetone)] dipalladium, 10.1 mg of tris (o-methoxyphenyl) phosphine and 4 mL of toluene were added and stirred for 10 minutes, and 11 mL of 30 wt% aqueous cesium carbonate solution was added to 115 ° C. The temperature was raised and stirring was carried out for 40 minutes. Next, after the reaction solution was cooled to room temperature, the aqueous layer was removed from the organic layer, the organic layer was added dropwise to 300 mL of methanol, and the precipitated solid was filtered and dried. The obtained solid was dissolved in 72 mL of toluene, passed through a column filled with silica gel and alumina, the obtained solution was dropped into 720 mL of methanol, and the precipitated solid was filtered and dried, whereby only the above repeating unit A was obtained. 864.9 mg of a polymer consisting of (hereinafter referred to as polymer compound 10) was obtained. The polystyrene-equivalent number average molecular weight and weight average molecular weight according to SEC condition 1 were Mn = 18000 and Mw = 439000, respectively. The formula amount FW ₁ of the repeating unit of the polymer was 438.7, and the average number of linkages was 410.

<Assignation of doublet peak of polymer compound 10>
Measurement of ¹ H-detected ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) per high molecular compound 10 revealed that chemical shifts of protons represented by H _B1 and H _C1 in formula (a) representing a doublet. Are 7.39 ppm and 7.81 ppm, respectively, and the chemical shifts of carbon 13 represented by C _B1 and C _C1 in formula (a) are 125.4 ppm and 123.8 ppm, respectively, and H _B1 and C _B1 , H _A proton-carbon 13 correlation peak was observed for the proton-carbon pair indicated by _C1 and _CCl . On the other hand, the chemical shifts of protons represented by H _B2 and H _C2 in the formula (b) representing the doublet are 7.54 ppm and 7.79 ppm, respectively, and are represented by C _B2 and C _C2 in the formula (b). The chemical shifts of carbon 13 were 125.2 ppm and 122.5 ppm, respectively, and proton-carbon 13 correlation peaks were observed for the proton-carbon pairs indicated by H _B2 and C _B2 and H _C2 and C _C2 . .

The quantitative ratio of H _B1 and H _B2 and H _C1 and H _C2 is determined by integrating the intensity of the proton-carbon 13 correlation peak in the HMQC spectrum, and H _B1 , H _B2 , H _C1 , and the result of taking into account the number of H _C2 calculates the ratio of diad (a) and diad (b) shown in Table 8.

In the ¹ H detection ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) of the polymer compound 10, the chemical shifts of protons represented by H _D2 and H _E2 in the formula (c) representing the doublet are 7 respectively. The chemical shifts of carbon 13 represented by C _D2 and C _E2 in formula (c) are 125.2 ppm and 129.7 ppm, respectively, and H _D2 and C _D2 , H _E2 and C _E2 A proton-carbon 13 correlation peak was observed for the proton-carbon pair indicated by On the other hand, the chemical shifts of protons represented by H _D3 and H _E3 in the formula (d) representing the doublet are 8.00 ppm and 7.96 ppm, respectively, and are represented by C _D3 and C _E3 in the formula (d). chemical shifts of carbon 13, respectively 121.2Ppm, and _126.6Ppm, protons against protons and a pair of carbon atoms represented by _{H D3} and _{C D3, H E3} and _{C E3} - carbon 13 correlation peak was observed .

The quantitative ratio of H _D2 and H _D3 , and H _E2 and H _E3 is determined by integrating the intensity of the proton-carbon 13 correlation peak in the HMQC spectrum, and H _D2 , H _D3 , H _E2 , and taking into account the number of H _E3 and diad (d) the result of the ratio calculated of diad (e) shown in Table 9.

  Since the doublet (b) and the doublet (c) are the same, the three types of doublet constituting the polymer compound 10, that is, doublet (a), doublet (b) (or It was found that the ratio of the duplex (c)) and duplex (d) was 7: 93: 6. From the above, in the polymer compound 10, it was found that the ratio of the number of bonds formed between the head and tail to the total number of bonds formed between (repeating units A) was 88%.

[Example 7]
<Synthesis of Polymer Compound 11>
In <Synthesis of Polymer Compound 10> in Example 6, Compound B (1400.0 mg, 2.17 mmol), Compound A, 72.1 mg (0.12 mmol), and Compound G, 83.4 mg (0.12 mmol) are used. Instead, 627 mg of a polymer consisting only of the above repeating unit A (hereinafter referred to as polymer compound 11) was obtained by the same formulation using only 1076 mg (1.67 mmol) of compound B. The polystyrene-equivalent number average molecular weight and weight average molecular weight according to SEC condition 1 were Mn = 109000 and Mw = 384000, respectively. The formula amount FW ₁ of the repeating unit of the polymer was 438.7, and the average number of linkages was 248.
<Assignation of doublet peak of polymer compound 11>
Measurement of ¹ H detection ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) was performed for polymer compound 11 in the same manner as polymer compound 10, and the integrated range was obtained by integrating the same range as polymer compound 10. . Further, Table 10 shows the results obtained by calculating the ratio of the duplexes (a) and the duplexes (b) and the duplexes (c) and the duplexes (d) by the same calculation as the polymer compound 10.

  Based on the above results, the ratio of the duplex (a), the duplex (b) (or the duplex (c)), and the duplex (d) is calculated by the same calculation as the polymer compound 10. It was found that it was 2: 98: 1. From the above, in the polymer compound 11, it was found that the ratio of the number of bonds formed between the head and tail to the total number of bonds formed between (repeating units A) was 98%.

[Comparative Example 6]
<Synthesis of Polymer Compound 12>
In <Synthesis of Polymer Compound 10> in Example 6, Compound B (1400.0 mg, 2.17 mmol), Compound A, 72.1 mg (0.12 mmol), and Compound G, 83.4 mg (0.12 mmol) are used. Instead, Compound B 1400.0 mg (2.17 mmol), Compound A 192.3 mg (0.32 mmol), Compound G 222.5 mg (0.32 mmol) and Compound G 222.5 mg (0.32 mmol) were used according to the same formulation and the above repeating unit A 1030 mg of a polymer consisting only of the polymer (hereinafter referred to as polymer compound 12) was obtained. The polystyrene-equivalent number average molecular weight and weight average molecular weight according to SEC condition 1 were Mn = 151000 and Mw = 388000, respectively. The formula weight of the repeating unit of the polymer was FW ₁ 438.7, and the average number of connections was 344.
<Assignation of doublet peak of polymer compound 12>
Measurement of ¹ H-detected ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) per high molecular compound 12 revealed that chemical shifts of protons represented by H _B1 and H _C1 in formula (a) representing a doublet. Are 7.39 ppm and 7.81 ppm, respectively, and the chemical shifts of carbon 13 represented by C _B1 and C _C1 in formula (a) are 125.4 ppm and 123.8 ppm, respectively, and H _B1 and C _B1 , H _A proton-carbon 13 correlation peak was observed for the proton-carbon pair indicated by _C1 and _CCl . On the other hand, the chemical shifts of protons represented by H _B2 and H _C2 in the formula (b) representing the doublet are 7.54 ppm and 7.79 ppm, respectively, and are represented by C _B2 and C _C2 in the formula (b). The chemical shifts of carbon 13 were 125.2 ppm and 122.5 ppm, respectively, and proton-carbon 13 correlation peaks were observed for the proton-carbon pairs indicated by H _B2 and C _B2 and H _C2 and C _C2 . .

The quantitative ratio of H _B1 and H _B2 and H _C1 and H _C2 is determined by integrating the intensity of the proton-carbon 13 correlation peak in the HMQC spectrum, and H _B1 , H _B2 , H _C1 , and the result of taking into account the number of H _C2 calculates the ratio of diad (a) and diad (b) shown in Table 11.

In the ¹ H detection ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) of the polymer compound 12, the chemical shifts of protons represented by H _D2 and H _E2 in the formula (c) representing the biad are 7 respectively. The chemical shifts of carbon 13 represented by C _D2 and C _E2 in formula (c) are 125.2 ppm and 129.7 ppm, respectively, and H _D2 and C _D2 , H _E2 and C _E2 A proton-carbon 13 correlation peak was observed for the proton-carbon pair indicated by On the other hand, the chemical shifts of protons represented by H _D3 and H _E3 in the formula (d) representing the doublet are 8.00 ppm and 7.96 ppm, respectively, and are represented by C _D3 and C _E3 in the formula (d). chemical shifts of carbon 13, respectively 121.2Ppm, and _126.6Ppm, protons against protons and a pair of carbon atoms represented by _{H D3} and _{C D3, H E3} and _{C E3} - carbon 13 correlation peak was observed .

The quantitative ratio of H _D2 and H _D3 , and H _E2 and H _E3 is determined by integrating the intensity of the proton-carbon 13 correlation peak in the HMQC spectrum, and H _D2 , H _D3 , H _E2 , and taking into account the number of H _E3 and diad (c) the result of the ratio calculated of diad (d) shown in Table 12.

  Since the doublet (b) and the doublet (c) are the same, the three types of doublet constituting the polymer compound 12, that is, doublet (a), doublet (b) (or It was found that the ratio of the duplex (c)) and the duplex (d) was 12: 88: 13 = 11: 78: 11. From the above, in the polymer compound 12, it was found that the ratio of the number of bonds formed between the head and tail to the total number of bonds formed between (repeating units A) was 78%.

[Comparative Example 7]
<Synthesis of Polymer Compound 13>
In <Synthesis of Polymer Compound 10> in Example 6, Compound B (1400.0 mg, 2.17 mmol), Compound A, 72.1 mg (0.12 mmol), and Compound G, 83.4 mg (0.12 mmol) are used. Instead, a polymer consisting of only the above repeating unit A (hereinafter referred to as polymer compound 13) was obtained by the same formulation using Compound A and Compound G in a molar ratio of 50:50. The polystyrene-equivalent number average molecular weight and weight average molecular weight according to SEC condition 1 were Mn = 155000 and Mw = 372000, respectively. The formula amount FW ₁ of the repeating unit of the polymer was 438.7, and the average number of connections was 353.
<Assignation of doublet peak of polymer compound 13>
The polymer compound 13 is measured for ¹ H detection ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) in the same manner as the polymer polymer compound 10, and the integrated range is obtained by integrating the same range as the polymer compound 10. It was. Further, Table 13 shows the results obtained by calculating the ratio of the duplex (a) and duplex (b) and the duplex (c) and duplex (d) by the same calculation as that of the polymer compound 13.

  Based on the above results, the ratio of the duplex (a), the duplex (b) (or the duplex (c)), and the duplex (d) is calculated by the same calculation as the polymer compound 10. It was found that it was 23:54:23. From the above, in the polymer compound 13, it was found that the ratio of the number of bonds formed between the head and tail to the total number of bonds formed between (repeating units A) was 54%.

[Example 8]
<Preparation of Light-Emitting Element Using Polymer Compound 10>
(Preparation of solution)
The polymer compound 10 obtained in Example 6 was dissolved in xylene at a concentration of 1.3% by weight.
(Production of EL element)
A suspension of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) on a glass substrate with an ITO film having a thickness of 150 nm formed by a sputtering method is passed through a 0.2 μm membrane filter. A thin film having a thickness of 70 nm was formed by spin coating using the filtered liquid, and dried on a hot plate at 200 ° C. for 10 minutes. Next, using the xylene solution of the polymer compound 10 obtained above, a film was formed by spin coating at a rotation speed of 2700 rpm. The film thickness after film formation was about 119 nm. Furthermore, after drying this at 90 ° C. for 1 hour in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less, lithium fluoride is deposited by about 4 nm, calcium is deposited by about 5 nm, and aluminum is then deposited by about 80 nm. An element was produced. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 470 nm was obtained from this device. The EL emission color at 100 cd / m ² is C.I. I. E. In terms of color coordinate values, x = 0.16 and y = 0.18. The intensity of EL emission was almost proportional to the current density. The voltage when reaching 1 cd / m 2 was 4.6 V, and the maximum luminous efficiency was 0.15 cd / A.
(Spectrum change before and after device drive)
When the EL device obtained above was driven at a constant current of 50 mA / cm ² and the EL spectrum was measured 1.5 hours later, small shoulder peaks were observed at 550 nm and 590 nm. Each emission intensity was normalized with a peak intensity of 470 nm, and the increase rate of the emission intensity at 550 nm and 590 nm was determined. As a result, the emission intensity at 550 nm was slightly increased by 3.5% and the emission intensity at 590 nm was slightly increased by 2.6%.

[Example 9]
<Preparation of Light-Emitting Element Using Polymer Compound 11>
(Preparation of solution)
The polymer compound 11 obtained in Example 7 was dissolved in xylene at a concentration ratio of 1.3% by weight.
(Production of EL element)
A suspension of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) on a glass substrate with an ITO film having a thickness of 150 nm formed by a sputtering method is passed through a 0.2 μm membrane filter. A thin film having a thickness of 70 nm was formed by spin coating using the filtered liquid, and dried on a hot plate at 200 ° C. for 10 minutes. Next, using the xylene solution of the polymer compound 11 obtained above, a film was formed by spin coating at a rotational speed of 2000 rpm. The film thickness after film formation was about 116 nm. Furthermore, after drying this at 90 ° C. for 1 hour in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less, lithium fluoride is deposited by about 4 nm, calcium is deposited by about 5 nm, and aluminum is then deposited by about 80 nm. An element was produced. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 470 nm was obtained from this device. The EL emission color at 100 cd / m 2 is C.I. I. E. In terms of color coordinate values, x = 0.16 and y = 0.18. The intensity of EL emission was almost proportional to the current density. The voltage when reaching 1 cd / m ² was 3.8 V, and the maximum luminous efficiency was 0.22 cd / A.
(Spectrum change before and after device drive)
When the EL device obtained above was driven at a constant current of 50 mA / cm ² and the EL spectrum after 1.5 hours was measured, almost no shoulder peaks were observed at 550 nm and 590 nm observed in Example 8. When the emission intensity was normalized with the peak intensity of 470 nm and the increase rate of the emission intensity at 550 nm and 590 nm was determined, the emission intensity at 550 nm was 0.1% and the emission intensity at 590 nm was an increase of 1.2%.

[Comparative Example 8]
<Creation of Light-Emitting Element Using Polymer Compound 12>
(Preparation of solution)
The polymer compound 12 obtained in Comparative Example 6 was dissolved in xylene at a concentration ratio of 1.3% by weight.
(Production of EL element)
A suspension of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) on a glass substrate with an ITO film having a thickness of 150 nm formed by a sputtering method is passed through a 0.2 μm membrane filter. A thin film having a thickness of 70 nm was formed by spin coating using the filtered liquid, and dried on a hot plate at 200 ° C. for 10 minutes. Next, using the xylene solution of the polymer compound 12 obtained above, a film was formed by spin coating at a rotational speed of 3200 rpm. The film thickness after film formation was about 119 nm. Furthermore, after drying this at 90 ° C. for 1 hour in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less, lithium fluoride is deposited by about 4 nm, calcium is deposited by about 5 nm, and aluminum is then deposited by about 80 nm. An element was produced. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 470 nm was obtained from this device. The EL emission color at 100 cd / m ² is C.I. I. E. In terms of color coordinate values, x = 0.16 and y = 0.19. The intensity of EL emission was almost proportional to the current density. The voltage when reaching 1 cd / m 2 was 5.4 V, and the maximum luminous efficiency was 0.15 cd / A.
(Spectrum change before and after device drive)
When the EL element obtained above was driven at a constant current of 50 mA / cm ² and the EL spectrum was measured after 1.5 hours, large shoulder peaks were observed at 550 nm and 590 nm. Each emission intensity was normalized with a peak intensity of 470 nm, and the increase rate of the emission intensity at 550 nm and 590 nm was determined. As a result, the emission intensity at 550 nm increased by 14% and the emission intensity at 590 nm increased by 8.9%.

[Comparative Example 9]
<Preparation of Light-Emitting Element Using Polymer Compound 13>
(Preparation of solution)
The polymer compound 13 obtained in Comparative Example 7 was dissolved in xylene at a concentration ratio of 1.3% by weight.
(Production of EL element)
A suspension of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) on a glass substrate with an ITO film having a thickness of 150 nm formed by a sputtering method is passed through a 0.2 μm membrane filter. A thin film having a thickness of 70 nm was formed by spin coating using the filtered liquid, and dried on a hot plate at 200 ° C. for 10 minutes. Next, using the xylene solution of the polymer compound 13 obtained above, a film was formed by spin coating at a rotational speed of 3200 rpm. The film thickness after film formation was about 117 nm. Furthermore, after drying this at 90 ° C. for 1 hour in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less, lithium fluoride is deposited by about 4 nm, calcium is deposited by about 5 nm, and aluminum is then deposited by about 80 nm. An element was produced. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 460 nm was obtained from this device. The EL emission color at 100 cd / m 2 is C.I. I. E. In terms of color coordinate values, x = 0.15 and y = 0.17. The intensity of EL emission was almost proportional to the current density. The voltage when reaching 1 cd / m 2 was 3.6 V, and the maximum luminous efficiency was 0.32 cd / A.
(Spectrum change before and after device drive)
When the EL element obtained above was driven at a constant current of 50 mA / cm ² and the EL spectrum was measured after 1.5 hours, large shoulder peaks were observed at 550 nm and 590 nm. Each emission intensity was normalized with a peak intensity of 460 nm, and an increase rate of the emission intensity at 550 nm and 590 nm was determined. As a result, the emission intensity at 550 nm was increased by 22% and the emission intensity at 590 nm was increased by 13%.

Table 14 shows the results of Examples 8-9 and Comparative Examples 8-9. As seen in Table 14, the polymer compound according to the present invention has little change in the EL spectrum, is excellent in chemical stability, and has excellent properties as a material used for the polymer light-emitting device.

[Comparative Example 10]
<Synthesis of Polymer Compound 14>
In <Synthesis of Polymer Compound 10> in Example 6, Compound B (1400.0 mg, 2.17 mmol), Compound A, 72.1 mg (0.12 mmol), and Compound G, 83.4 mg (0.12 mmol) are used. Instead, 2.464 g (4.12 mmol) of compound A, 3.117 g (4.50 mmol) of compound G, and 0.332 g (0.45 mmol) of compound D were used in the same manner as described below (repeating unit A). A polymer (hereinafter referred to as polymer compound 14) comprising the following (repeating unit C) was obtained. The polystyrene-equivalent number average molecular weight and weight average molecular weight according to SEC condition 1 were Mn = 62000 and Mw = 175000, respectively.

<Assignation of doublet peak of polymer compound 14>
Measurement of ¹ H-detected ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) for polymer compound 14 revealed that the chemical shift of the proton represented by H _C1 in formula (a) representing a biad is 7. The chemical shift of carbon 13 represented by C _C1 in formula (a) is 123.8 ppm, and a proton-carbon 13 correlation peak is observed for the proton-carbon pair represented by H _C1 and C _C1. It was. On the other hand, the chemical shift of the proton represented by HC ₂ in the formula (b) representing the doublet is 7.73 ppm, and the chemical shift of carbon 13 represented by C _C2 in the formula (b) is 122.4 ppm. _A proton-carbon 13 correlation peak was observed for the proton-carbon pair indicated by _C2 and _CC2 . Furthermore, the chemical shift of the proton represented by H _C4 in the formula (e) representing the doublet is 7.56 ppm, and the chemical shift of carbon 13 represented by C _C4 in the formula (e) is 122.4 ppm. _A proton-carbon 13 correlation peak was observed for the proton-carbon pair indicated by _C4 and _CC4 .

The quantitative ratio of H _C1 , H _C2 and H _C4 is obtained by integrating the intensity of the proton-carbon 13 correlation peak in the HMQC spectrum, taking into account the number of H _C1 , H _C2 and H _C4 contained in one diad. Table 15 shows the results of calculating the ratios of the doublet (a), doublet (b), and doublet (e).

In the ¹ H detection ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) of the polymer compound 14, the chemical shift of the proton indicated by H _D2 in the formula (c) representing the doublet, and C _D2 chemical shifts of the carbon 13 are respectively 7.73 ppm, and _125.2Ppm, protons against protons and a pair of carbon atoms represented by _{H D2} and _{C D2} - carbon 13 correlation peak was observed. Meanwhile, the chemical shifts of carbon 13 indicated by proton chemical shifts and _{C D3} represented in the formula (d) representing a diad in _{H D3,} respectively 7.96Ppm, and _{121.1ppm, H D3} and _{C D3} A proton-carbon 13 correlation peak was observed for the proton-carbon pair indicated by Furthermore, the chemical shifts of carbon 13 indicated by proton chemical shifts and _{C D5} represented in the formula (f) representing a diad in _{H D5,} respectively 7.71Ppm, and _{120.3ppm, H D5} and _{C D5} A proton-carbon 13 correlation peak was observed for the proton-carbon pair indicated by

The quantitative ratio of H _D2 , H _D3 , and H _D5 is obtained by integrating the intensity of the proton-carbon 13 correlation peak in the HMQC spectrum, and the number of H _D2 , H _D3 , and H _D5 contained in one diad is taken into consideration. Table 16 shows the results of calculating the ratios of the duplexes (c), duplexes (d), and duplexes (f).

  Since the doublet (b) and the doublet (c) are the same, the three types of doubles constituting the polymer compound 14, that is, the doublet (a), the doublet (b) (or It was found that the ratio of the duplex (c)) and duplex (d) was 32:66:24. From the above, it was found that in polymer compound 14, the ratio of the number of bonds formed between the head and tail to the total number of bonds formed between (repeating units A) was 54%.

<Calculation of the average number of linked (repeating unit A) in polymer compound 14>
The average number of connections (N _A ) of (repeating unit A) in the polymer compound 14 is obtained by the following formula (A2-1) by modifying the above formula (A2).

Average number of connections (N _A ) = N1 ′ / N2 ′ (A2-1)

(In the formula, N1 ′ is the ratio of the number of (repeating unit A) to the number of all diads contained per unit amount of polymer compound 14, and N2 ′ is the unit amount of polymer compound 14 This is the ratio of the number of blocks formed by (repeating unit A) to the number of all diads included, where the block formed by (repeating unit A) is represented by the following formula (BR-3). expressed.)

(In the formula, g represents an integer of 1 or more. The block is adjacent to a repeating unit or a terminal group other than the repeating unit represented by (Repeating Unit A).)

That is, in the polymer compound 14, using the number of the above-mentioned doubles,

N1 ′ = ([2 doubling (a)] + [2 doubling (b)] + [2 doubling (e)]
+ [Double continuum (c)] + [double continuum (d)] + [double continuum (f)])

N2 ′ = ([double-element (e)] + [double-element (f)])

(However, in the above two formulas, [2 continuation (a)], [2 continuation (b)], [2 continuation (e)], [2 continuation (c)], [2 continuation ( d)] and [dual (f)], respectively, are doubled (a), doubled (b), doubled ( e) Indicates the ratio of the number of doubles (c), doubles (d), and doubles (f).)
It can be expressed. Moreover, when the symbols c1, c2, c4, d2, d3, d5 described in Table 15 and Table 16 are used,

c1 = [double (a)] / ([double (a)] + [double (b)] + [double (e)])
= C [doublet (a)]

c2 = [double-element (b)] / ([double-element (a)] + [two-element (b)] + [two-element (e)])
= C [doublet (b)]

c4 = [double-element (e)] / ([double-element (a)] + [double-element (b)] + [double-element (e)])
= C [doublet (e)]

(However, in the above three formulas, C = 1 / ([2 continuum (a)] + [2 continuum (b)] + [2 continuum (e)]))

d2 = [double-element (c)] / ([double-element (c)] + [two-element (d)] + [two-element (f)])
= D [doublet (c)]

d3 = [double-element (d)] / ([double-element (c)] + [two-element (d)] + [two-element (f)])
= D [doublet (d)]

d5 = [double-element (f)] / ([double-element (c)] + [two-element (d)] + [two-element (f)])
= D [doublet (f)]

(However, in the above three formulas, D = 1 / ([2 continuum (c)] + [2 continuum (d)] + [2 continuum (f)]))

Therefore, when substituting into the above formula (A2-1), the formula (A2-1) uses c1, c2, c4, d2, d3, d5 and C, D,

N _A = N1 ′ / N2 ′
= (C1 / C + c2 / C + c4 / C + d2 / D + d3 / D + d5 / D) / (c4 / C + d5 / D)
= {C1 + c2 + c4 + (d2 + d3 + d5) · C / D} / (c4 + d5 · C / D)

... Formula (A2-2)
It can be expressed as

On the other hand, as is clear from the structure of the duplexer (b) and the structure of the duplexer (c),
[Duplicate (b)] = [Duplicate (c)]

It is. This formula uses c2, d2 and C, D,

c2 / C = d2 / D

Because it can be rewritten,

C / D = c2 / d2 (A2-3)

From formula (A2-2) and formula (A2-3),

N _A = {d2 (d1 + d2 + d4) + c2 (d2 + d3 + d5)} / (d2 · c4 + c2 · d5)
... Formula (A2-4)
Is obtained.

It was 15 when the average connection number of the high molecular compound 14 was calculated from the value of Table 15 and Table 16 using Formula (A2-4).

[Example 10]
<Synthesis of polymer compound 15>
In <Synthesis of Polymer Compound 10> in Example 6, Compound B (1400.0 mg, 2.17 mmol), Compound A, 72.1 mg (0.12 mmol), and Compound G, 83.4 mg (0.12 mmol) are used. Instead, 1000 mg (1.55 mmol) of Compound B, 30.1 mg (0.04 mmol) of Compound D, and 34.0 mg (0.04 mmol) of Compound H below were used in the same formulation and the above (Repeating Unit A) and the above A polymer composed of (repeating unit C) (hereinafter referred to as polymer compound 15) was obtained. The polystyrene-equivalent number average molecular weight and weight average molecular weight according to SEC condition 1 were Mn = 81000 and Mw = 187000, respectively.

<Assignation of doublet peak of polymer compound 15>
The HMQC spectrum of the polymer compound 15 was measured in the same manner as the polymer compound 14, and the same range as that of the polymer compound 14 was integrated to obtain the integrated intensity. Further, the calculation similar to that of the polymer compound 14 shows the ratio of the duplex (a), the duplex (b), and the duplex (e), the duplex (c), the duplex (d), and Table 17 shows the results obtained for the doublet (f).

Based on the above results, the ratio of the duplex (a), duplex (b) (or duplex (c)), and duplex (d) is calculated by the same calculation as for the polymer compound 14. It was found that it was 1: 98: 1. From the above, in the polymer compound 15, it was found that the ratio of the number of bonds formed between the head and tail to the total number of bonds formed between (repeating units A) was 98%.

<Calculation of the average number of linked (repeating unit A) in polymer compound 15>
The average number of linkages of (Repeating unit A) in polymer compound 15 is calculated from the values in Table 17 using formula (A2-4), similarly to the average number of linkages of (Repeating unit A) in polymer compound 14. , 15.

[Example 11]
<Synthesis of Polymer Compound 16>
In <Synthesis of Polymer Compound 10> in Example 6, Compound B (1400.0 mg, 2.17 mmol), Compound A, 72.1 mg (0.12 mmol), and Compound G, 83.4 mg (0.12 mmol) are used. Instead, 70.0 mg (1.08 mmol) of Compound B, 171.7 mg (0.23 mmol) of Compound D, and 193.5 mg (0.23 mmol) of Compound H described below were used in the same manner as described above (repeating unit A). And a polymer comprising the above (repeating unit C) (hereinafter referred to as polymer compound 16). The number-average molecular weight and weight-average molecular weight in terms of polystyrene according to SEC condition 1 were Mn = 45000 and Mw = 99000, respectively.
<Assignation of doublet peak of polymer compound 16>
The HMQC spectrum of the polymer compound 16 was measured in the same manner as the polymer compound 14, and the same range as that of the polymer compound 14 was integrated to obtain the integrated intensity. Further, the calculation similar to that of the polymer compound 14 shows the ratio of the duplex (a), the duplex (b), and the duplex (e), the duplex (c), the duplex (d), and Table 18 shows the results obtained for the doublet (f).

Based on the above results, the ratio of the duplex (a), duplex (b) (or duplex (c)), and duplex (d) is calculated by the same calculation as for the polymer compound 14. It was found that it was 0: 100: 0. From the above, in the polymer compound 16, it was found that the ratio of the number of bonds formed between the head and tail to the total number of bonds formed between (repeating units A) was 100%.

<Calculation of the average number of linked (repeating unit A) in polymer compound 16>
The average number of (repeating unit A) linkages in polymer compound 16 is calculated from the values in Table 18 using formula (A2-4) in the same manner as the average number of (repeating unit A) linkages in polymer compound 14. 4.

[Comparative Example 11]
<Synthesis of Polymer Compound 17>
In <Synthesis of Polymer Compound 10> in Example 6, Compound B (1400.0 mg, 2.17 mmol), Compound A, 72.1 mg (0.12 mmol), and Compound G, 83.4 mg (0.12 mmol) are used. Instead, Compound A 500.0 mg (0.84 mmol), Compound G 578.6 mg (0.84 mmol), Compound D 16.2 mg (0.02 mmol), Compound H 18.3 mg (0.02 mmol) In the same manner using 10.4 mg (0.02 mmol) of the following compound I and 12.5 mg (0.02 mmol) of the following compound J, the above (repeat unit A), the above (repeat unit C) and the following (repeat unit) A polymer comprising D) (hereinafter referred to as polymer compound 17) was obtained. The polystyrene-reduced number average molecular weight and weight average molecular weight according to SEC condition 1 were Mn = 77000 and Mw = 420,000, respectively.

<Assignation of doublet peak of polymer compound 17>
When the HMQC spectrum of the polymer compound 17 was measured, the chemical shift of the proton represented by H _C1 in the formula (a) representing the doublet was 7.81 ppm, and represented by C _C1 in the formula (a). The chemical shift of carbon 13 was 123.9 ppm, and a proton-carbon 13 correlation peak was observed for the proton-carbon pair indicated by H _C1 and C _C1 . On the other hand, the chemical shift of the proton represented by H _C2 in the formula (b) representing the doublet is 7.77 ppm, and the chemical shift of carbon 13 represented by C _C2 in the formula (b) is 122.5 ppm. _A proton-carbon 13 correlation peak was observed for the proton-carbon pair indicated by _C2 and _CC2 . Furthermore, the chemical shift between the proton represented by H _C4 in the formula (e) representing the biad and the proton represented by H _C6 in the formula (g) representing the biad is 7.60 ppm, and the formula (e The chemical shift of carbon 13 represented by C _C4 in formula (c) and carbon 13 represented by C _C6 in formula (g) is 122.3 ppm, both of proton and carbon represented by H _C4 and C _C4 and H _C6 and C _C6 . A proton-carbon 13 correlation peak was observed for the pair.

The amount ratio of the sum of H _C1 , H _C2 , and the sum of H _C4 and H _C6 is determined by integrating the intensity of the proton-carbon 13 correlation peak in the HMQC spectrum, and H _C1 , H _C2 , H _C4 contained in one doublet and taking into account the number of _{H C6} diad (a), diad (b), and diad (e) and 2 sum of diad (g) (hereinafter, diad (e) + ( The results of calculating the ratio of g) are shown in Table 19.

In HMQC spectrum of the polymer compound 17, chemical shifts of proton indicated by _{H D2} formula (c) representing a diad, and chemical shifts of carbon 13 indicated by _{C D2,} respectively 7.79ppm and 125 a _.3Ppm, protons against protons and a pair of carbon atoms represented by _{H D2} and _{C D2} - carbon 13 correlation peak was observed. Meanwhile, the chemical shifts of carbon 13 indicated by proton chemical shifts and _{C D3} represented in the formula (d) representing a diad in _{H D3,} respectively 7.99Ppm, and _{121.2ppm, H D3} and _{C D3} A proton-carbon 13 correlation peak was observed for the proton-carbon pair indicated by Furthermore, the chemical shifts of proton indicated by _{H D7} in the formula (h) representing the protons and diads represented by _{H D5} in the formula (f) representing a diad are both 7.78Ppm, a diad represents the chemical shifts of carbon 13 indicated by _{C D7} in the formula (h) representing the carbon 13 and diad represented by _{C D5} in the formula (f) are both _120.4Ppm, and _{H D5} and _{C D5} and _{H D7} carbon 13 correlation peak was observed - protons against protons and a pair of carbon atoms represented by C _D7.

The amount ratio of H _D2 , H _D3 , and the sum of H _D5 and H _D7 is obtained by integration of the intensity of the proton-carbon 13 correlation peak in the HMQC spectrum, and H _D2 , H _D3 , H _D5 contained in one _doublet. And _HD7 , taking into account the number of doubles (c), doubles (d), and the sum of doubles (f) and doubles (h) (hereinafter, doubles (f) + ( Table 20 shows the result of calculating the ratio of h).

  Since the doublet (b) and the doublet (c) are the same, the three types of doublet constituting the polymer compound 17, that is, doublet (a), doublet (b) (or It was found that the ratio of the doublet (c)) and the doublet (d) was 34:69:24. From the above, it was found that in polymer compound 17, the ratio of the number of bonds formed between the head and tail to the total number of bonds formed between (repeating units A) was 54%.

<Calculation of the average number of linked (repeating unit A) in polymer compound 17>
The average number of linkages (N _B ) of (repeating unit A) in the polymer compound 17 is obtained by the following formula (A2-5) by modifying the above formula (A2).

Average number of connections (N _B ) = N1 ″ / N2 ″ (A2-5)

(Where N1 ″ is the ratio of the number of (repeating unit A) to the number of all diads contained per unit amount of polymer compound 17, and N2 ″ is the unit amount of polymer compound 17) This is the ratio of the number of blocks formed by (repeating unit A) to the number of all diads included in the vicinity, where the block formed by (repeating unit A) is the above formula (BR-3). )

That is, in the polymer compound 17, using the number of the above-mentioned doubles,

N _B = ([Dual (a)] + [Dual (b)] + [Dual (e) + (g)]
+ [Double-term (c)] + [double-term (d)] + [double-term (f) + (h)])
/ ([Duplicate (e) + (g)] + [Duplicate (f) + (h)])
. . . . (A2-6)

(However, in the above two formulas, [2 doubling (a)], [2 doubling (b)], [2 doubling (e) + (g)], [2 doubling (c)], [ [2 doubling (d)] and [2 doubling (f) + (h)] are respectively 2 doublings (a) and 2 doublings with respect to the number of all doublings included in the polymer compound 17. (B) Indicates the number of doubles (e) + (g), doubles (c), doubles (d), and doubles (f) + (h))
It can be expressed. Moreover, when the symbols c1, c2, c4_6, d2, d3, d5_7 described in Table 19 and Table 20 are used,

c1 = [2 continuation (a)] / ([2 continuation (a)] + [2 continuation (b)] + [2 continuation (e) + (g)])
= C '[2 continuum (a)]

c2 = [2 continuation (b)] / ([2 continuation (a)] + [2 continuation (b)] + [2 continuation (e) + (g)])
= C '[doublet (b)]

c4 — 6 = [double-element (e) + (g)] / ([two-element (a)] + [two-element (b)] + [two-element (e) + (g)])
= C '[doublet (e) + (g)]

(However, in the above three formulas, C ′ = 1 / ([2 continuum (a)] + [2 continuum (b)] + [2 continuum (e) + (g)]))

d2 = [2 continuum (c)] / ([2 continuum (c)] + [2 continuum (d)] + [2 continuum (f) + (h)])
= D '[doublet (c)]

d3 = [double-element (d)] / ([double-element (c)] + [double-element (d)] + [double-element (f) + (h)])
= D '[doublet (d)]

d5_7 = [double-element (f) + (h)] / ([double-element (c)] + [two-element (d)] + [two-element (f) + (h)])
= D '[doublet (f) + (h)]

(However, in the above three formulas, D ′ = 1 / ([2 continuum (c)] + [2 continuum (d)] + [2 continuum (f) + (h)]))

Therefore, when substituting into the above formula (A2-6), formula (A2-6) uses c1, c2, c4_6, d2, d3, d5_7 and C, D,

N _B = (c1 / C ′ + c2 / C ′ + c4 — 6 / C ′ + d2 / D ′ + d3 / D ′
+ D5_7 / D ') / (c4_6 / C' + d5_7 / D ')
= {C1 + c2 + c4_6 + (d2 + d3 + d5_7) · C ′ / D ′}
/ (C4_6 + d5_7 · C ′ / D ′)
... Formula (A2-7)
It can be expressed as

On the other hand, as is clear from the structure of the duplexer (b) and the structure of the duplexer (c),
[Duplicate (b)] = [Duplicate (c)]

It is. This formula uses c2, d2 and C ', D',

c2 / C '= d2 / D'

Because it can be rewritten,

C ′ / D ′ = c2 / d2
... Formula (A2-8)

From formula (A2-7) and formula (A2-8),

N _B = {d2 (d1 + d2 + d4_6) + c2 (d2 + d3 + d5_7)}
/ (D2 · c4_6 + c2 · d5_7)
... Formula (A2-9)
Is obtained.

  It was 17 when the average connection number of the high molecular compound 17 was calculated from the value of Table 19 and Table 20 using Formula (A2-9).

[Example 12]
<Synthesis of Polymer Compound 18>
In <Synthesis of Polymer Compound 10> in Example 6, Compound B (1400.0 mg, 2.17 mmol), Compound A, 72.1 mg (0.12 mmol), and Compound G, 83.4 mg (0.12 mmol) are used. Instead, Compound B 1050.0 mg (1.63 mmol), Compound D 15.8 mg (0.02 mmol), Compound H 17.8 mg (0.02 mmol), Compound I 10.1 mg (0.02 mmol), A polymer comprising the above (repeating unit A), the above (repeating unit C) and the above (repeating unit D) in a similar formulation using 12.1 mg (0.02 mmol) of compound J (hereinafter referred to as polymer compound 18) Call). The polystyrene-equivalent number average molecular weight and weight average molecular weight according to SEC condition 1 were Mn = 65000 and Mw = 457000, respectively.

<Assignation of doublet peak of polymer compound 18>
The HMQC spectrum of the polymer compound 18 was measured in the same manner as the polymer compound 17, and the same range as that of the polymer compound 17 was integrated to obtain the integrated intensity. Further, the calculation similar to that of the polymer compound 17 is performed, and the ratio of the duplex (a), the duplex (b) and the duplex (e) + (g), and the duplex (c) and the duplex (d) ) And the ratio of doublet (f) + (h) are shown in Table 21.

Based on the above results, the ratio of the duplex (a), duplex (b) (or duplex (c)), and duplex (d) is calculated by the same calculation as for the polymer compound 17. It was found that the ratio was 2: 98: 0. From the above, in the polymer compound 18, it was found that the ratio of the number of bonds formed between the head and tail to the total number of bonds formed between (repeating units A) was 98%.

<Calculation of the average number of linked (repeating unit A) in polymer compound 18>
The average number of linkages of (Repeating unit A) in polymer compound 18 is calculated from the values in Table 22 using formula (A2-9), similarly to the average number of linkages of (Repeating unit A) in polymer compound 17. , 12.

[Comparative Example 12]
<Preparation of Light-Emitting Element Using Polymer Compound 17>
(Preparation of solution)
The polymer compound 17 obtained in Comparative Example 11 was dissolved in xylene at a concentration ratio of 1.0% by weight.
(Production of EL element)
A suspension of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083 (trade name)) on a glass substrate on which an ITO film having a thickness of 150 nm was formed by a sputtering method was 0. A thin film having a thickness of 70 nm was formed by spin coating using the liquid filtered through a 2 μm membrane filter, and dried on a hot plate at 200 ° C. for 10 minutes. Next, a film was formed at a rotational speed of 2500 rpm by spin coating using the xylene solution of polymer compound 17 obtained above. The film thickness after film formation was about 101 nm. Furthermore, after drying this at 90 ° C. for 1 hour in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less, lithium fluoride is deposited by about 4 nm, calcium is deposited by about 5 nm, and aluminum is then deposited by about 80 nm. An element was produced. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 470 nm was obtained from this device. The EL emission color at 100 cd / m 2 is C.I. I. E. In terms of color coordinate values, x = 0.15 and y = 0.25. The intensity of EL emission was almost proportional to the current density. The voltage at the time of reaching 1 cd / m 2 was 5.4 V, and the maximum luminous efficiency was 2.74 cd / A.
(Spectrum change before and after device drive)
When the EL element obtained above was driven at a constant current of 50 mA / cm ² and the EL spectrum was measured after 5 hours, shoulder peaks were observed at 550 nm and 590 nm. Each emission intensity was normalized with a peak intensity of 470 nm, and the increase rate of the emission intensity at 550 nm and 590 nm was determined. As a result, the emission intensity at 550 nm was increased by 8.6%, and the emission intensity at 590 nm was increased by 5.3%.

[Example 13]
<Creation of Light-Emitting Element Using Polymer Compound 18>
(Preparation of solution)
The polymer compound 18 obtained in Example 12 was dissolved in xylene at a polymer concentration ratio of 1.0% by weight.
(Production of EL element)
A suspension of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) on a glass substrate with an ITO film having a thickness of 150 nm formed by a sputtering method is passed through a 0.2 μm membrane filter. A thin film having a thickness of 70 nm was formed by spin coating using the filtered liquid, and dried on a hot plate at 200 ° C. for 10 minutes. Next, using the xylene solution of the polymer compound 18 obtained above, a film was formed by spin coating at a rotational speed of 2500 rpm. The film thickness after film formation was about 111 nm. Furthermore, after drying this at 90 ° C. for 1 hour in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less, lithium fluoride is deposited by about 4 nm, calcium is deposited by about 5 nm, and aluminum is then deposited by about 80 nm. An element was produced. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
(EL element performance)
By applying voltage to the resulting device, EL light emission having a peak at 470 nm was obtained from this device. The EL emission color at 100 cd / m 2 is C.I. I. E. In terms of color coordinate values, x = 0.15 and y = 0.28. The intensity of EL emission was almost proportional to the current density. The voltage when reaching 1 cd / m 2 was 5.8 V, and the maximum luminous efficiency was 2.74 cd / A.
(Spectrum change before and after device drive)
When the EL device obtained above was driven at a constant current of 50 mA / cm ² and the EL spectrum was measured after 5 hours, almost no shoulder peaks were observed at 550 nm and 590 nm. Each emission intensity was normalized with a peak intensity of 475 nm, and the increase rate of the emission intensity at 550 nm and 590 nm was determined. As a result, the emission intensity at 550 nm was increased by 0.1% and the emission intensity at 590 nm was increased by 0.7%.
As described above, compared with Comparative Example 12, the polymer compound according to the present invention has a small change in EL spectrum after driving and is excellent in chemical stability.

[Reference Example 1]
<Substituent stability test>
In a 200 mL four-necked flask, 102.1 mg (0.76 mmol) of n-butylbenzene, 115.9 mg (0.77 mmol) of n-butyloxybenzene, 124.8 mg (0.76 mmol) of n-butyloxymethylbenzene, and 162.6 mg (0.77 mmol) of benzyl benzoate was added, and the inside of the flask was replaced with argon gas. Then, 42 mL of tetrahydrofuran, 15 mL (15 mmol) of 1.0 N lithium aluminum hydride in tetrahydrofuran, and 102.1 mg of n-octylbenzene as an internal standard substance were added. The temperature was raised to 70 ° C. and the mixture was stirred for 10 hours. Further, 15 mL (15 mmol) of 1.0 N lithium aluminum hydride in tetrahydrofuran was added, and the mixture was stirred at 70 ° C. for 8 hours. When the ratio of the amount not decomposed to the charged amount) was measured, the results shown in Table 22 were obtained.

From the above results, it was found that the alkoxymethyl group and the acyloxymethyl group are easily decomposed in a reducing atmosphere, and are not preferable as the substituent of polyarylene in the present invention.

  The polymer compound (polyarylene) of the present invention is excellent in stability such as thermal stability and chemical stability, and is useful as a light emitting material and a charge transporting material, and is a laser dye, an organic solar cell material, and an organic transistor. It can be used as materials for electrically conductive thin films such as organic semiconductors, conductive thin films, organic semiconductor thin films, and polymer electrolyte materials such as polymer electrolyte membranes such as metal ion and proton conductive membranes.

The EL spectrum before and behind the drive of the EL element obtained by the comparative example 2. FIG. The EL spectrum before and behind the drive of the EL element obtained in Example 2. FIG. 6 shows EL spectra before and after driving the EL element obtained in Comparative Example 3. 7 shows EL spectra before and after driving the EL element obtained in Example 3. FIG. 10 shows an EL spectrum before and after driving the EL element obtained in Example 8. 10 shows an EL spectrum before and after driving the EL element obtained in Example 9. 10 shows EL spectra before and after driving of the EL element obtained in Comparative Example 8. 10 shows EL spectra before and after driving of the EL element obtained in Comparative Example 9.

Claims (28)

Including a chain composed only of repeating units represented by the following formula (1), the average value of the number of repeating units forming the chain is 15 or more, and among all the bonds formed between the repeating units A polymer compound characterized in that the proportion of bonds formed between the head and tail is 85% or more.

(In the formula (1), Ar ¹ is










A divalent aromatic group selected from the group consisting of: and the aromatic ring is an aromatic hydrocarbon ring. R ¹ represents a substituent on Ar ¹ and each independently represents a hydrocarbon group, a hydrocarbon oxy group, a hydrocarbon thio group, a trialkylsilyl group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a mercapto group, Represents an acyl group, formyl group, carboxyl group, hydrocarbon oxycarbonyl group, amino group, aminocarbonyl group, imidoyl group, azo group, acyloxy group, phosphonic acid group or sulfonic acid group. In Ar ¹ , R ³ and R ⁴ each represent the same substituent as the substituent represented by R ¹ in Formula (1) . When a plurality of R ³ are present in one repeating unit, R ³ may be the same as or different from each other. If R ³ and R ⁴ coexist within one repeating unit R ³ and R ⁴ each represent a different substituent. n represents an integer of 0 to 30. When n represents an integer of 2 or more, a plurality of R ¹ may be the same or different. When the number of carbon atoms is given by the IUPAC organic chemical nomenclature using the repeating unit represented by formula (1) as a divalent group, the carbon having the smaller number among the two carbon atoms having free valences. Let the atom be the head and the higher carbon atom be the tail. The repeating unit represented by the formula (1) does not have a 2-fold symmetry axis perpendicular to the straight line at the midpoint of the straight line connecting the head and the tail. )   The polymer compound according to claim 1, wherein an average value of the number of repeating units forming the chain is 20 or more.   The polymer compound according to claim 1, comprising only one type of repeating unit represented by the formula (1). The repeating unit comprising one type of repeating unit represented by the formula (1) and one or more repeating units represented by the following formula (5), (6), (7) or (8): 2. The polymer compound according to 2.

(In the formula, Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. X ₁ , X ₂ and X ₃ Each independently represents —CR _a ═CR _b —, —C≡C—, —N (R _c ) —, —O—, —S—, —SO—, —SO ₂ —, or — (SiR _d R). _e ) _q— R _a and R _b each independently represent a hydrogen atom, a monovalent hydrocarbon group, a monovalent heterocyclic group, a carboxyl group, a hydrocarbon oxycarbonyl group, or a cyano group. R _c , R _d and R _e each independently represent a hydrogen atom, a monovalent hydrocarbon group or a monovalent heterocyclic group, p represents 1 or 2, q represents an integer of 1 to 12. When there are a plurality of R _a , R _b , R _c , R _d and R _e , they may be the same or different.)   5. The polymer compound according to claim 4, comprising one type of repeating unit represented by the formula (1) and one or more types of repeating units represented by the formula (5) or (6). .   The ratio of the bonds formed between the head and the tail among all the bonds formed between the repeating units represented by the formula (1) is 90% or more. The polymer compound according to item.   The ratio of the bond formed between the head and the tail among all the bonds formed between the repeating units represented by the formula (1) is 95% or more. The polymer compound according to item. The method for producing a polymer compound according to any one of claims 1 to 7, wherein the condensation polymerization is performed using a compound represented by the following formula (A) as one of raw materials.

(Formula (Ar ¹ at A), R ^1, and n have the same meanings as Ar ^1, R ^1, and n in Formula (1).
In Formula (A), Y ¹ each independently represents a halogen atom, a sulfonate group represented by Formula (B), or a methoxy group. In the formula (A), Y ² represents a borate group, a boric acid group, a group represented by the formula (C), a group represented by the formula (D), or a group represented by the formula (E). )

(In the formula (B), R ⁷ represents an optionally substituted hydrocarbon group.)

(In the formula (C), X _A represents a halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom.)

(In the formula (D), X _A represents a halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom.)

(In the formula (E), R ⁸ represents a hydrocarbon group which may be substituted. A plurality of R ⁸ may be the same or different.)   A high composition comprising at least one material selected from the group consisting of a hole transport material, an electron transport material, and a light emitting material, and the polymer compound according to any one of claims 1 to 7. Molecular composition.   A solution comprising the polymer compound according to claim 1.   A solution comprising the polymer composition according to claim 9.   The solution according to claim 10 or 11, comprising two or more kinds of organic solvents.   The solution according to any one of claims 10 to 12, which has a viscosity of 1 to 20 mPa · s at 25 ° C.   A light-emitting thin film containing the polymer compound according to any one of claims 1 to 7, or the polymer composition according to claim 9.   The luminescent thin film according to claim 14, wherein the quantum yield of fluorescence is 50% or more.   The electroconductive thin film containing the polymer compound as described in any one of Claims 1-7, or the polymer composition of Claim 9.   The organic-semiconductor thin film containing the polymer compound as described in any one of Claims 1-7, or the polymer composition of Claim 9.   An organic transistor comprising the organic semiconductor thin film according to claim 17.   The method for forming a thin film according to any one of claims 14 to 17, wherein an inkjet method is used.   It has an organic layer between the electrodes which consist of an anode and a cathode, and this organic layer contains the polymer compound as described in any one of Claims 1-7, or the polymer composition as described in Claim 9. A polymer light emitting device characterized by the above.   The polymer light emitting device according to claim 20, wherein the organic layer is a light emitting layer.   The polymer light emitting device according to claim 21, wherein the light emitting layer further contains a hole transport material, an electron transport material or a light emitting material.   It has a light emitting layer and a charge transport layer between the electrodes which consist of an anode and a cathode, and this charge transport layer is the high molecular compound as described in any one of Claims 1-7, or high. The polymer light-emitting device according to claim 20, comprising a molecular composition.   A light emitting layer and a charge transport layer are provided between an electrode composed of an anode and a cathode, a charge injection layer is provided between the charge transport layer and the electrode, and the charge injection layer is any one of claims 1 to 7. The polymer light-emitting device according to claim 20, comprising the polymer compound according to claim 1 or the polymer composition according to claim 9.   A planar light source comprising the polymer light emitting device according to any one of claims 20 to 24.   A segment display device using the polymer light emitting device according to any one of claims 20 to 24.   A dot matrix display using the polymer light emitting device according to any one of claims 20 to 24.   25. A liquid crystal display device comprising the polymer light-emitting element according to claim 20 as a backlight.