JP2007016228A - Method for producing polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polymer, by which the polymer having aromatic rings in the main chain and having complicated structure substituents on the side chains of the aromatic rings can simply be produced. <P>SOLUTION: This method for producing the polymer is characterized by comprising the following step (A) and step (B). (A) The step in which a polymer having repeating units represented by the general formula (1):-Ar<SP>1</SP>-(wherein Ar<SP>1</SP>represents an arylene, a divalent heterocyclic group, or a divalent aromatic amine group) is used as a raw material, and one or more of the C-H bond(s) on the aromatic ring are converted to produce a polymer having repeating units which have one or more characteristic groups X and are represented by the general formula (2), and (B) the step in which the characteristic group X-having polymer produced in the step (A) is reacted with the compound having a characteristic group Y reacting with the characteristic group X to produce a bond. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a polymer compound. The polymer compound produced by the present invention can be used for electronic devices such as a polymer light emitting device (polymer LED).

Since the polymer compound having an aromatic ring in the main chain exhibits specific properties such as electronic properties such as charge transporting property, light emitting property, and mechanical properties such as rigidity and thermal stability, Its application is being actively promoted in the fields of electronic materials, chemistry, energy materials, medicine, and the like (for example, see Non-Patent Document 1).
In particular, various applications for electronic devices have been studied. For example, polyarylene polymers such as polyfluorene and polyparaphenylene derivatives are used as high molecular weight light emitting materials (polymer phosphors). Compounds and polyarylene vinylene polymer compounds are known (see, for example, Non-Patent Document 2). In order to improve the properties of these polymer compounds, various introductions of substituents to aromatic ring side chains of the polymer compounds have been studied (for example, see Patent Documents 1 and 2). In order to produce a polymer compound having a substituent on the side chain of the aromatic ring, it was a normal production method to synthesize a monomer having the substituent and polymerize the monomer. In addition, in recent years, after producing a polymer as a main chain having the characteristic group by a method characterized in that a monomer having the characteristic group is polymerized under a condition that the characteristic group is not lost, the characteristic is obtained. A method for producing a polymer compound having a relatively complicated side chain by further reacting a compound having a characteristic group capable of reacting with a group has been proposed (Patent Document 3). Further, a method of synthesizing a polymer having a branch point by copolymerizing a polyfunctional monomer that can be a branch point is known (Patent Document 4).

Journal of Polymer Science Part A (Volume 39), page 1533 (2001) Progress in Polymer Science 28, 875 (2003) Japanese Patent Laid-Open No. 2003-155476 WO98 / 27136 published specification Japanese Patent Laid-Open No. 2003-253001 Japanese Patent Laid-Open No. 2001-342459

However, among the conventional production methods described above, in the method of copolymerizing a monomer that can be a branching point, the main chain and the side chain are not distinguished from each other, so that a polymer compound having a complicated structure in the aromatic ring side chain is produced. It was difficult. In addition, in order to produce a polymer compound having a substituent having a complex structure on the aromatic ring side chain, it is necessary to produce a monomer having a complex substituent on the aromatic ring side chain, which is complicated to produce. Met. Also, depending on the type of substituent, polymerization of the monomer may be difficult. Further, in the method for producing a polymer having a main chain having a characteristic group by polymerization, it is required that the characteristic group does not react when the main chain is polymerized. There was a difficulty that the characteristic group was limited. Further, depending on the type of the characteristic group, there is a possibility that the reactivity may be lowered during the production of the main chain polymer.
An object of the present invention is to provide a method capable of easily producing a polymer compound having an aromatic ring in the main chain and having a substituent having a complex structure in the side chain of the aromatic ring.

  As a result of intensive studies to solve the above problems, the present inventors have converted a CH bond on an aromatic ring from a polymer compound containing a repeating unit represented by the following general formula (1) as a raw material. A polymer compound containing a repeating unit having a characteristic group X represented by the following general formula (2) (hereinafter also referred to as a polymer compound having a characteristic group X), and a polymer compound having the characteristic group X: By reacting with a compound having a characteristic group Y that reacts with the characteristic group X to form a bond, the main chain has an aromatic ring, and a side chain of the aromatic ring has a complex structure substituent. The inventors have found that molecular compounds can be easily produced, and have completed the present invention.

That is, this invention relates to the manufacturing method of the high molecular compound characterized by including the following process (A) and process (B).
(A) General formula (1)
-Ar ^1- (1)
(In the formula, Ar ¹ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group having at least one C—H bond on the aromatic ring.)
A polymer compound containing a repeating unit represented by formula (2) is used as a raw material, and the C—H bond on the aromatic ring is converted to give a general formula (2)

(In the formula, X represents a characteristic group, Ar ² represents an n + 2 valent arylene group in which n of C—H bonds on the aromatic ring of Ar ¹ are converted to C—X bonds, and an n + 2 valent heterocyclic ring. A group, or an n + 2 valent aromatic amine group, wherein n represents an integer of 1 to 4.
(B) A step of reacting the polymer compound having the characteristic group X produced in step A with the compound having the characteristic group Y that reacts with the characteristic group X to form a bond.

  According to the production method of the present invention, a polymer compound having an aromatic ring in the main chain and having a substituent having a complicated structure in the side chain of the aromatic ring can be easily produced. In addition, the polymer compound produced by the production method of the present invention is expected as a polymer material useful for the creation of various highly functional materials in the fields of electronic materials, chemistry, energy materials, medicine, and the like. . In particular, when the polymer compound according to the production method of the present invention is used in the field of electronic materials, a functional substituent that improves the charge injection / transport property is added to the charge transportable main chain composed of a conjugated polymer. Thus, it is possible to realize high functionality such as improvement of charge injection / transport properties and adjustment of emission wavelength by adding functional substituents including fluorescent or phosphorescent dyes. For example, by adding an electron injection / transport side chain to the electron injection / transport main chain, the electron injection / transport property of the polymer compound can be improved, or the hole injection / transport main chain can be added to the main chain. By imparting a hole injection / transport side chain, the hole injection / transport property of the polymer compound can be improved. Also, by adding a hole injection / transport side chain to the electron injection / transport main chain, or by adding an electron injection / transport side chain to the hole injection / transport main chain In addition, the injection / transport properties of both electrons and holes can be improved in the polymer compound. Thus, the polymer compound according to the production method of the present invention is used as a light emitting material or charge transport material for polymer LED, a dye for laser, a material for organic solar cell, an organic semiconductor for organic transistor, a material for conductive thin film, etc. Can be used.

  In the production method of the present invention, the step (A) is performed by converting a C—H bond on the aromatic ring using a polymer compound containing the repeating unit represented by the general formula (1) as a raw material. This is a step of producing a polymer compound containing a repeating unit having the characteristic group X represented by 2).

In the repeating unit of the formula (1) used in the present invention, Ar ¹ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group. The Ar ¹ has at least one C—H bond on the aromatic ring. The Ar ¹ may have a substituent.

  An arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, having a condensed ring, two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene Also included. The arylene group may have a substituent. Carbon number of the part except the substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. Moreover, the total carbon number including the substituent of an arylene group is about 6-100 normally. Examples of the arylene group include formulas 1A-1 to 1A-20 shown below.

In Ar ¹ represented by the above formulas 1A-1 to 1A-20, R represents a hydrogen atom, a bond, or a substituent. Any two of a plurality of Rs represent a bond, and any one or more of them represent a hydrogen atom. When a plurality of substituents represented by R are present, they may be the same or different. Ra represents a hydrogen atom or a substituent. When a plurality of substituents represented by Ra are present, they may be the same or different. When two Ra are present on the same atom, they may be combined to form an oxo group or a thioxo group, or may be bonded to each other to form a ring.

  In addition, the substituent represented by R is a 5- to 7-membered aliphatic ring which may include heteroatoms such as an oxygen atom, a sulfur atom and a nitrogen atom among the substituents on adjacent atoms, Alternatively, a 5- to 7-membered aromatic ring may be formed.

As the arylene group represented by Ar ¹ , among the above formulas 1A-1 to 1A-14, a phenylene group (formula 1A-1), a naphthalene-diyl group (formula 1A-2), a dihydrophenanthrene-diyl group (formula 1A-10), fluorene-diyl group (formula 1A-13), benzofluorene-diyl group (formula 1A-14), biphenylene group (formula 1A-15), terphenylene group (formula 1A-16 to 1A-18) , A stilbene-diyl group (1A-19) and a distilbene-diyl group (1A-20) are preferable, a phenylene group (formula 1A-1), a naphthalene-diyl group (formula 1A-2), a dihydrophenanthrene-diyl group (formula 1A-10), fluorene-diyl group (formula 1A-13), benzofluorene-diyl group (formula 1A-14), biphenylene group (formula 1A-15), turf Nylene groups (Formulas 1A-16 to 1A-18) are more preferred, among which phenylene groups (Formula 1A-1), naphthalene-diyl groups (Formula 1A-2), fluorene-diyl groups (Formula 1A-13), benzo More preferred is a fluorene-diyl group (Formula 1A-14).

A divalent heterocyclic group is a remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound, having a condensed ring, an independent monocyclic heterocyclic compound, or two or more condensed rings directly Or the thing couple | bonded through groups, such as vinylene, is also contained. Moreover, what combined the heterocyclic compound and aromatic hydrocarbon is also contained. The divalent heterocyclic group may have a substituent. Carbon number of the part except the substituent in a bivalent heterocyclic group is about 4-60 normally, Preferably it is 2-20.
Moreover, the total carbon number including the substituent of a bivalent heterocyclic group is about 2-100 normally. Here, a heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, and boron in the ring. Say. Examples of the divalent heterocyclic group include formulas 2A-1 to 2A-53 and 2A-101 to 2A-116 shown below.

In Ar ¹ represented by the above formulas 2A-1 to 2A-53 and 2A-101 to 2A-116, R represents a hydrogen atom, a bond, or a substituent. Any two of a plurality of Rs represent a bond, and any one or more of them represent a hydrogen atom. When a plurality of substituents represented by R are present, they may be the same or different. Ra represents a hydrogen atom or a substituent. When a plurality of substituents represented by Ra are present, they may be the same or different. When two Ra are present on the same atom, they may be combined to form an oxo group or a thioxo group, or may be bonded to each other to form a ring. ]

  The substituent represented by R is a substituent on adjacent atoms, a 5- to 7-membered aliphatic ring containing a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom, or an oxygen atom A 5- to 7-membered aromatic ring which may contain a heteroatom such as sulfur atom or nitrogen atom may be formed.

Examples of the divalent heterocyclic group represented by Ar ¹ include pyridine-diyl group (formula 2A-1) and quinoline-diyl among the formulas 2A-1 to 2A-53 and 2A-101 to 2A-116. Group (formula 2A-6), isoquinoline-diyl group (formula 2A-7), quinoxaline-diyl group (formula 2A-8), phenanthroline-diyl group (2A-18), thiophene-diyl group (formula 2A-22) , An imidazole-diyl group (2A-24), an oxazole-diyl group (formula 2A-26), a thiazole-diyl group (2A-27), containing nitrogen, sulfur, or oxygen as a heteroatom, and a condensed benzene ring 5-membered ring heterocyclic groups (formulas 2A-30 to 2A-32 and 2A-34 to 2A-40), heterocyclic groups having a fluorene-like skeleton containing silicon, nitrogen, oxygen, or sulfur as a hetero atom ( 2A-41 to 2A-44 and 2A-46 to 2A-47), a heterocyclic group having a condensed ring structure represented by the formula (2A-48 to 2A-53), a diazaphenylene group (formula 2A-101) ), A compound group in which a phenyl group or a thienyl group is bonded to the 2,5-position of a 5-membered heterocyclic group containing nitrogen, oxygen or sulfur as a hetero atom (formula 2A-103, 2A-105 to 2A-106, And 2A-108 to 2A-110), a compound group (formula 2A-111) containing nitrogen, oxygen, or sulfur as a hetero atom, and a phenyl group or a thienyl group bonded to a 5-membered heterocyclic group condensed with a benzene ring. To 2A-116), pyridine-diyl group (formula 2A-1), quinoline-diyl group (formula 2A-6), isoquinoline-diyl group (formula 2A-7), quinoxaline-diyl group (formula 2A-8) ), Phenant Phosphorus-diyl group (2A-18), heterocyclic groups having a fluorene-like skeleton containing silicon, nitrogen, oxygen, or sulfur as a hetero atom (Formulas 2A-41 to 2A-44 and 2A-46 to 2A-47) , A heterocyclic group having a condensed ring structure represented by the formula (2A-48 to 2A-53), a diazaphenylene group (formula 2A-101), a 5-membered ring heterocyclic ring containing nitrogen, oxygen or sulfur as a hetero atom Compound groups (formula 2A-103, 2A-105 to 2A-106, and 2A-108 to 2A-110) having a phenyl group bonded at the 2,5-position of the group, containing nitrogen, oxygen, or sulfur as a hetero atom And a compound group (formula 2A-111-2A-116) in which a phenyl group is bonded to a 5-membered heterocyclic group having a condensed benzene ring, and fluorine containing silicon, nitrogen, oxygen or sulfur as a hetero atom. Heterocyclic groups having a similar skeleton (formulas 2A-41 to 2A-44 and 2A-46 to 2A-47), heterocyclic groups having a condensed ring structure represented by formula (2A-48 to 2A-53), Compound groups in which a phenyl group is bonded at the 2,5-position of a 5-membered heterocyclic group containing nitrogen, oxygen or sulfur as a hetero atom (formulas 2A-103, 2A-105 to 2A-106, and 2A-108 to 2A-110), a compound group (formula 2A-111-2A-116) containing nitrogen, oxygen, or sulfur as a heteroatom and having a phenyl group bonded to a 5-membered heterocyclic group condensed with a benzene ring .

  The divalent aromatic amine group is a remaining atomic group obtained by removing two hydrogen atoms from an aromatic amine. The divalent aromatic amine group may have a substituent. The carbon number of the part except the substituent in a bivalent aromatic amine group is about 4-60 normally. As a bivalent aromatic amine group, group shown by the following general formula (1-2) is mentioned, for example.

(In the formula, Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ each independently represent an arylene group or a divalent heterocyclic group. Ar ⁷ , Ar ⁸ and Ar ⁹ each independently represent an aryl group or a monovalent group. Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ and Ar ⁹ may have a substituent, r and rr each independently represent 0 or 1 .)

  Specific examples of the divalent aromatic amine group include groups represented by the following formulas 3A-1 to 3A-8.

In Ar ¹ represented by the above formulas 3A-1 to 3A-8, R represents a hydrogen atom, a bond, or a substituent. Any two of a plurality of Rs represent a bond, and any one or more of them represent a hydrogen atom. When a plurality of substituents represented by R are present, they may be the same or different.

The divalent aromatic amine group represented by Ar ¹ is preferably a divalent aromatic amine group represented by the formulas 3A-1 to 3A-4 among the formulas 3A-1 to 3A-8. The divalent aromatic amine group represented by 3A-1 to 3A-3 is more preferred, and the groups represented by Formulas 3A-2 and 3A-3 are more preferred.

  The substituent represented by R is a substituent on adjacent atoms, a 5- to 7-membered aliphatic ring containing a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom, or an oxygen atom A 5- to 7-membered aromatic ring which may contain a heteroatom such as sulfur atom or nitrogen atom may be formed.

Of the arylene group, divalent heterocyclic group, and divalent aromatic amine group, the group represented by Ar ¹ is preferably an arylene group or a divalent heterocyclic group, and more preferably an arylene group.

  The substituent represented by R or Ra is not particularly limited as long as it does not substantially inhibit the reaction in the step A and step B of the present invention, but an alkyl group, an aryl group, an aralkyl group, a monovalent group. Heterocyclic group, arylalkenyl group, arylalkynyl group, alkoxy group, aryloxy group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, substituted amino group, substituted silyl group, sulfonic acid group, phosphono group, cyano group And a nitro group.

The alkyl group represented by R or Ra may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include methyl group, ethyl group Group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl Group, decyl group, 3,7-dimethyloctyl group, dodecyl group, octadecyl group and the like.
From the standpoint of solubility in organic solvents, ease of synthesis, or the balance between device characteristics and heat resistance when the polymer compound obtained by the production method of the present invention is used in a polymer LED, methyl Group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, cyclohexyl group, heptyl group, cyclohexylmethyl group, octyl group 2-ethylhexyl group, 2-cyclohexylethyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, and dodecyl group are preferable, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, cyclohexyl group, heptyl group, o A til group, 2-ethylhexyl group, nonyl group, decyl group, and 3,7-dimethyloctyl group are more preferable, and propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group More preferred are isopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, and 3,7-dimethyloctyl group.

The aryl group is an atomic group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, and includes those having a condensed ring. The aryl group usually about 6 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include a phenyl _group, C 1 _{-C 12} alkylphenyl group _(C 1 _{-C 12} is 1 to carbon atoms The same applies to the following.), 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group and the like.
From the viewpoint of solubility in organic solvent, ease of synthesis, etc., or from the balance between device characteristics and heat resistance when the polymer compound obtained by the production method of the present invention is used for polymer LED, C ₁ -C ₁₂ alkylphenyl group are preferred.
Specific examples C ₁ -C ₁₂ alkylphenyl group include a methylphenyl group, ethylphenyl group, dimethylphenyl group, dimethyl -t- butylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, n-butylphenyl group, isobutylphenyl group, s-butylphenyl group, t-butylphenyl group, pentylphenyl group, isopentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group 3,7-dimethyloctylphenyl group, dodecylphenyl group and the like are exemplified. Dimethylphenyl group, dimethyl-t-butylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, n-butylphenyl group Base , Isobutylphenyl group, s-butylphenyl group, t-butylphenyl group, pentylphenyl group, isopentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, 3,7- A dimethyloctylphenyl group and a dodecylphenyl group are preferred.

Aralkyl groups, usually about 7 to 60 carbon atoms, preferably 7 to 48, and examples thereof include phenyl _-C 1 _{-C 12} alkyl _group, C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} Examples include an alkyl group, a 1-naphthyl-C ₁ -C ₁₂ alkyl group, a 2-naphthyl-C ₁ -C ₁₂ alkyl group, and the like.
From the standpoints of solubility in organic solvents, ease of synthesis, and the balance between device characteristics and heat resistance when the polymer compound obtained by the production method of the present invention is used in a polymer LED, C ₁ -C ₁₂ alkylphenyl _-C 1 _{-C 12} alkyl group are preferable.

The monovalent heterocyclic group is a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms, preferably 4 to 20 carbon atoms. The carbon number of the heterocyclic group does not include the carbon number of the substituent. Here, a heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, etc. in the ring. To tell. Specific examples include a thienyl group, a C _{1 to} C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a C _{1 to} C ₁₂ alkyl pyridyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group.
From the standpoints of solubility in organic solvents, ease of synthesis, etc., or from the balance between device characteristics and heat resistance when the polymer compound obtained by the production method of the present invention is used in a polymer LED, thienyl _group, C 1 _{-C 12} alkyl thienyl group, a pyridyl group, and _C 1 _{-C 12} alkyl pyridyl group are preferable.

The arylalkenyl group has a carbon number of usually about 8 to 60, specifically, a phenyl _-C 2 _{-C 12} alkenyl _group, C 1 _{-C 12} alkylphenyl _-C 2 _{-C 12} alkenyl group, 1- Examples thereof include a naphthyl-C ₂ -C ₁₂ alkenyl group and a 2-naphthyl-C ₂ -C ₁₂ alkenyl group.
From the viewpoint of solubility in organic solvent, ease of synthesis, etc., or from the balance between device characteristics and heat resistance when the polymer compound obtained by the production method of the present invention is used for polymer LED, C ₁ -C ₁₂ alkylphenyl _-C 2 _{-C 12} alkenyl groups are preferred.

The arylalkynyl group has a carbon number of usually about 8 to 60, specifically, a phenyl _-C 2 _{-C 12} alkynyl _group, C 1 _{-C 12} alkylphenyl _-C 2 _{-C 12} alkynyl group, 1- naphthyl _-C 2 _{-C 12} alkynyl group, 2-naphthyl _-C 2 _{-C 12} alkynyl groups.
From the standpoints of solubility in organic solvents, ease of synthesis, and the balance between device characteristics and heat resistance when the polymer compound obtained by the production method of the present invention is used in a polymer LED, C ₁ -C ₁₂ alkylphenyl _-C 2 _{-C 12} alkynyl group are preferable.

The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, and a propyloxy group. , Isopropyloxy group, n-butoxy group, isobutoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, dodecyloxy group and the like can be mentioned.
From the viewpoint of solubility in an organic solvent, ease of synthesis, etc., or from the balance between device characteristics and heat resistance when the polymer compound obtained by the production method of the present invention is used in a polymer LED, pentyl An oxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, and a 3,7-dimethyloctyloxy group are preferred.

The aryloxy group is usually about 6 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include a phenoxy _group, C 1 _{-C 12} alkylphenoxy group, 1-naphthyloxy group, 2-naphthyl An oxy group etc. are illustrated.
From the standpoints of solubility in organic solvents, ease of synthesis, and the balance between device characteristics and heat resistance when the polymer compound obtained by the production method of the present invention is used in a polymer LED, C _{A 1 to} C ₁₂ alkylphenoxy group is preferred.
Specific examples C ₁ -C ₁₂ alkylphenoxy group, methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, isopropylphenoxy radical, n -Butylphenoxy group, isobutylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isopentylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group, dodecylphenoxy group, etc. Is done.

The aralkyloxy group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenylmethoxy group, a phenylethoxy group, a phenyl-n-butoxy group, and a phenylpentyloxy group. , phenylhexyloxy group, phenyl heptyloxy group, phenyl _-C 1 _{-C 12} alkoxy groups such as a phenyl octyl _group, C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkoxy groups, 1-naphthyl _-C 1 ~ C ₁₂ alkoxy groups, 2-naphthyl _-C 1 _{-C 12} alkoxy groups.
From the viewpoint of solubility in organic solvent, ease of synthesis, etc., or from the balance between device characteristics and heat resistance when the polymer compound obtained by the production method of the present invention is used for polymer LED, C ₁ -C ₁₂ alkylphenyl _-C 1 _{-C 12} alkoxy group are preferable.

The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, a propylthio group, Isopropylthio group, n-butylthio group, isobutylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7- Examples thereof include dimethyloctylthio group and dodecylthio group.
From the viewpoint of solubility in organic solvents, ease of synthesis, or from the balance between device characteristics and heat resistance when the polymer compound obtained by the production method of the present invention is used in a polymer LED, pentylthio Group, hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group and 3,7-dimethyloctylthio group are preferred.

The arylthio group has a carbon number of usually about 3 to 60, and specific examples thereof include a phenylthio _group, C 1 _{-C 12} alkyl phenylthio group, 1-naphthylthio group and 2-naphthylthio groups.
From the viewpoint of solubility in an organic solvent, easiness of synthesis, or the balance between device characteristics and heat resistance when the polymer compound obtained by the production method of the present invention is used in a polymer LED, C _{A 1 to} C ₁₂ alkylphenylthio group is preferred.

The aralkylthio group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkylthio group and a C ₁ -C ₁₂ alkylphenyl-C. Examples thereof include a _{1 to} C ₁₂ alkylthio group, a 1-naphthyl-C _{1 to} C ₁₂ alkylthio group, and a 2-naphthyl-C _{1 to} C ₁₂ alkylthio group.
From the standpoints of solubility in organic solvents, ease of synthesis, and the balance between device characteristics and heat resistance when the polymer compound obtained by the production method of the present invention is used in a polymer LED, C ₁ -C ₁₂ alkylphenyl _-C 1 _{-C 12} alkylthio group are preferable.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group, and usually has about 1 to 60 carbon atoms, Preferably it is C2-C48.
Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, n-butylamino group, isobutylamino group, t-butyl Amino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, dodecylamino group, cyclopentylamino group, cyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, diphenylamino _group, (C 1 _{-C 12} alkylphenyl) amino group, di _(C 1 _{-C 12} alkylphenyl) amino , 1-naphthylamino group, 2-naphthylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, triazyl amino group, phenyl _-C 1 _{-C 12} alkylamino _group, C 1 _{-C 12} Alkylphenyl-C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) amino group, 1-naphthyl-C ₁ -C ₁₂ alkylamino group, 2-naphthyl-C Examples are _{1 to} C ₁₂ alkylamino groups.
From the viewpoint of solubility in an organic solvent, ease of synthesis, or the balance between device characteristics and heat resistance when the polymer compound obtained by the production method of the present invention is used in a polymer LED, dimethyl A di-substituted amino group such as an amino group, a diethylamino group, a diphenylamino group, or a di (C ₁ -C ₁₂ alkylphenyl) amino group is preferred, and a diaryl such as a diphenylamino group or a di (C ₁ -C ₁₂ alkylphenyl) amino group An amino group is more preferable.

Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. The substituted silyl group usually has about 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms.
Specifically, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, dimethylisopropylpropylsilyl group, diethylisopropylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group , Heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, dodecyldimethylsilyl group, phenyl-C _1- C ₁₂ alkylsilyl _group, C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkylsilyl group, 1-naphthyl _-C 1 _{-C 12} alkylsilyl group, 2-naphthyl _-C 1 _{-C 12} alkylsilyl group, phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- methylphenyl silyl group, tribenzylsilyl group, diphenylmethylsilyl group, t- butyl diphenyl silyl group, dimethyl phenyl silyl groups.

When the substituent represented by R or Ra contains an aryl group or a monovalent heterocyclic group, the hydrogen atom on the aryl group or monovalent heterocyclic group is an aryl group, an aralkyl group, 1 Valent heterocyclic group, arylalkenyl group, arylalkynyl group, alkoxy group, aryloxy group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, substituted amino group, substituted silyl group, sulfonic acid group, phosphono group, It may be substituted with a cyano group or a nitro group. Among them, aryl groups, aralkyl groups, monovalent heterocyclic groups, alkoxy groups, aryloxy groups, aralkyloxy groups, alkylthio groups, arylthio groups, aralkylthio groups, substituted amino groups, substituted silyl groups, sulfonic acid groups, phosphono groups, A cyano group and a nitro group are preferred, and an alkyl group, aryl group, aralkyl group, monovalent heterocyclic group, alkoxy group, aryloxy group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, and substituted amino group Are more preferable, and an alkoxy group and an alkylthio group are more preferable.
Specifically, for example, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl _-C 2 _{-C 12} alkynyl _groups, C 1 _{-C 12} alkoxyphenoxy _groups, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkoxy _groups, C 1 _{-C 12} alkoxyphenyl-thio groups, C ₁ -C ₁₂ alkoxyphenyl _-C 1 _{-C 12} alkylthio _group, C 1 _{-C 12} alkoxyphenyl amino group, di _(C 1 _{-C 12} alkoxyphenyl) amino _groups, C 1 _{-C 12} alkoxyphenyl _-C 1 -C ₁₂ alkylamino groups, di _(C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkyl) amino _Group, and a group having a _C 1 _{-C 12} alkoxy substituents such as C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkylsilyl groups. Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, isopropyloxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy , 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, dodecyloxy and the like.

In addition, when the substituent represented by R or Ra includes an alkylene chain, the arbitrary —CH ₂ — group in the alkylene chain includes a divalent heteroatom such as oxygen, sulfur, or nitrogen, or a heteroatom. It may be substituted with a divalent group or a divalent group in which two or more of them are combined. Examples of the divalent group containing a divalent hetero atom or hetero atom include groups represented by the following formulas r-1 to r-9.

(In the formula, R ″ represents a substituent selected from a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms.)

  Examples of the divalent group in which two or more divalent groups containing a divalent hetero atom or a hetero atom are combined include groups represented by the following formulas rr-1 to rr-4. .

(In the formula, R ″ represents the same meaning as described above.)
Among the formulas r-1 to r-9 and rr-1 to rr-4, groups represented by the formulas r-1, r-2, r-3, r-5, and r-6 are preferable, Groups represented by formulas r-1 and r-2 are more preferred, and groups represented by formula r-1 are more preferred. Specific examples include a methoxymethyloxy group and a 2-methoxyethyloxy group.

Examples of the substituent represented by R in the group represented by Ar ¹ include an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, an arylthio group, and an aralkyl group. Thio group, substituted amino group, substituted silyl group, sulfonic acid group, phosphono group, cyano group, nitro group are preferred, alkyl group, aryl group, aralkyl group, monovalent heterocyclic group, alkoxy group, aryloxy group, aralkyl group An oxy group, an alkylthio group, an arylthio group, an aralkylthio group, and a substituted amino group are more preferable, an alkyl group, an alkoxy group, and an alkylthio group are more preferable, and an alkyl group is most preferable.

Examples of the substituent represented by Ra in the group represented by Ar ¹ include an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, an arylthio group, and an aralkyl group. A thio group, a substituted amino group, a substituted silyl group, an oxo group and a thioxo group are preferred, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an oxo group and a thioxo group are more preferred, and an alkyl group and an alkoxy group are preferred. Even more preferred is an alkyl group.

  Next, the polymer unit containing the repeating unit represented by the above formula (1) is used as a raw material, and the repeating unit having the characteristic group X represented by the above formula (2) is obtained by converting the C—H bond on the aromatic ring. A process for producing a polymer compound containing s.

In the repeating unit represented by the formula (2) in the present invention, Ar ² represents an n + 2 valent arylene group, an n + 2 valent heterocyclic group, or an n + 2 valent aromatic amine group. The Ar ² has n characteristic groups X on the aromatic ring. The Ar ² may have a substituent.

  In the formula (2), n represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1.

Examples of the n + 2-valent arylene group represented by Ar ² include the arylene groups represented by the above formulas 1A-1 to 1A-20.
In Ar ² represented by the above formulas 1A-1 to 1A-20, R represents a hydrogen atom, a characteristic group X, a bond, or a substituent. Any two of a plurality of Rs represent a bond, and any one or more and n or less represent a characteristic group X. When a plurality of substituents represented by R are present, they may be the same or different. Ra represents a hydrogen atom or a substituent. When a plurality of substituents represented by Ra are present, they may be the same or different. When two Ra are present on the same atom, they may be combined to form an oxo group or a thioxo group, or may be bonded to each other to form a ring.

Examples of the n + 2-valent heterocyclic group represented by Ar ² include the heterocyclic groups represented by the above formulas 2A-1 to 2A-53 and 2A-101 to 2A-116.
In Ar ² represented by the above formulas 2A-1 to 2A-53 and 2A-101 to 2A-116, R represents a hydrogen atom, a characteristic group X, a bond or a substituent. Any two of a plurality of Rs represent a bond, and any one or more and n or less represent a characteristic group X. When a plurality of substituents represented by R are present, they may be the same or different. Ra represents a hydrogen atom or a substituent. When a plurality of substituents represented by Ra are present, they may be the same or different. When two Ra are present on the same atom, they may be combined to form an oxo group or a thioxo group, or may be bonded to each other to form a ring.

Examples of the n + 2-valent aromatic amine group represented by Ar ² include aromatic amine groups represented by the above formulas 3A-1 to 3A-8.
In Ar ² represented by the above formulas 3A-1 to 3A-8, R represents a hydrogen atom, a characteristic group X, a bond, or a substituent. Any two of a plurality of Rs represent a bond, and any one or more and n or less represent a characteristic group X. When a plurality of substituents represented by R are present, they may be the same or different.

  The substituent represented by R is a substituent on adjacent atoms, a 5- to 7-membered aliphatic ring containing a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom, or an oxygen atom A 5- to 7-membered aromatic ring which may contain a heteroatom such as sulfur atom or nitrogen atom may be formed.

The substituent represented by R or Ra is not particularly limited as long as it does not substantially inhibit the reaction in the step A and the step B of the present invention, but the repeating unit represented by Ar ¹ in the formula (1) The same group as the substituent which may have is illustrated.

  The conversion reaction of the C—H bond on the aromatic ring is not particularly limited as long as it is a conversion reaction in which the polymer compound containing the repeating unit represented by the above formula (1) does not substantially decompose during the conversion reaction. Examples thereof include an aromatic electrophilic substitution reaction, an aromatic oxidation reaction, and the like. Among them, the aromatic electrophilic substitution reaction is preferable because of the high degree of freedom of the characteristic group to be introduced. More preferable examples of the conversion reaction of the C—H bond on the aromatic ring include those described in Table 1 below.

  The reaction conditions will be described more specifically. In the halogenation reaction, a halogenating agent such as bromine, chlorine, iodine, iodine monochloride, N-chlorosuccinimide, N-bromosuccinimide, or the like, in an excess amount of 10 equivalents or less, is used. Depending on the reactivity, 0.01 to 50 equivalents of an acid such as acetic acid, sulfuric acid, trifluoroacetic acid, trifluoromethanesulfonic acid may be added and reacted. As the solvent, an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, N, N-dimethylformamide, tetrahydrofuran or the like is preferably used, but an acid such as acetic acid or sulfuric acid may be used as the solvent. The reaction can usually proceed at a temperature of about 0 to 100 ° C. The reaction time is, for example, 5 minutes to 100 hours, but may be a time for which the reaction proceeds sufficiently, and since it is not necessary to leave for a long time after the reaction is completed, it is preferably 10 minutes to 50 hours. . If the concentration during the reaction is too dilute, the efficiency of the reaction is poor, and if it is too thick, it becomes difficult to control the reaction due to the precipitation of the polymer compound. It is usually in the range of 0.1 wt% to 30 wt%. The halogenation method is described in, for example, Polymer, Volume 30, page 1137 (1989), Japanese Patent Application Laid-Open No. 2002-241493, and the like.

  The nitration reaction is appropriately performed using a nitration reagent such as mixed acid, concentrated nitric acid, concentrated nitric acid-acetic acid at a temperature of 0 ° C. or higher and a boiling point or lower.

Friedel-Crafts alkylation, halomethylation, and Friedel-Crafts acylation reactions include alkyl halides, terminal alkenes, alkylating reagents such as alcohols, halomethylating reagents such as formaldehyde and hydrogen chloride, acid chlorides, acid anhydrides, An acylating reagent such as carboxylic acid is appropriately performed at a temperature of about room temperature to about 200 ° C. in the presence of an acid catalyst such as AlCl ₃ , FeCl ₃ , BF ₃ , ZnCl ₂ . For example, these reactions are described in Organic Reactions, Volume 2, page 114, (1944).

In the Gattermann aldehyde synthesis, formylation is performed by allowing hydrogen chloride, etc. to react with hydrogen cyanide, Zn (CN) ₂ , triazine or the like in the presence of a Lewis acid such as AlCl ₃ . For example, this reaction is described in Organic Reactions, Vol. 9, page 37, (1957), Chemical Review, Vol. 63, page 526 (1963).

In the Vilsmeier formylation reaction, formylation can be performed by appropriately reacting 1 to 5 equivalents of POCl ₃ in N, N-dimethylformamide at about −20 ° C. to 40 ° C. For example, this reaction is described in New Experimental Chemistry Course, Vol. 14, 688 (1977).

  In the step (A), a reaction that further induces the group introduced by the above various reactions to various characteristic groups by various reactions is included. Further, as the reaction to be induced, various known functional group conversion reactions can be used, and examples thereof include known reactions shown in Table 2 below.

  The conversion reaction of the C—H bond on the aromatic ring is preferably a halogenation reaction from the viewpoint of easy control of reactivity and introduction amount.

  After completion of the reaction, the reaction solution may be used for the next reaction as it is, but after completion of the reaction, the obtained polymer compound may be subjected to acid washing, alkali washing, neutralization, water washing, organic solvent washing, if necessary. It may be subjected to conventional separation operations such as reprecipitation, centrifugation, extraction, column chromatography, purification operations, drying and other operations. From the viewpoint of improving the yield of the next reaction, it is preferable to perform a separation operation, a purification operation, and drying.

In the repeating unit represented by the formula (2) in the step A in the production method of the present invention, the characteristic group represented by X includes a halogen atom, —OSO ₂ Q ¹ , —B (OQ ² ) ₂ , —Sn. (Q ³ ) ₃ , Z ¹ (Z ² ) m, —OH, —CH ₂ Z ³ , —CHQ ⁴ —P ⁺ (Q ⁵ ) ₃ Z ⁴ , —CHQ ⁶ —P (═O) (OQ ⁷ ) ₂ , groups such as —C (═O) Q ⁸ are exemplified.
Q ¹ is a hydrocarbon group, Q ² is a hydrogen atom or a hydrocarbon group, and two Q ² may be the same or different, and may be bonded to each other to form a ring. Q ³ is a hydrocarbon group, and the three Q ³ may be the same or different. Q ⁴ is a hydrogen atom or a hydrocarbon group, Q ⁵ is a hydrocarbon group, and three Q ^{5 s} may be the same or different from each other. Q ⁶ is a hydrogen atom or a hydrocarbon group, Q ⁷ is a hydrocarbon group, and two Q ⁷ may be the same or different from each other. Q ⁸ is a hydrogen atom or a hydrocarbon group. Z ¹ is a metal atom or a metal ion, Z ² represents a counter anion, m represents an integer of 0 or more. Z ³ represents a halogen atom or a cyano group. Z ⁴ represents a monovalent counter anion.

The reactions in Table 2 will be described more specifically.
It is known that a —NO ₂ group can be reduced to a —NH ₂ group by allowing a metal such as zinc, iron, or tin to react with an acid such as hydrochloric acid.
It is known that the —NH ₂ group can be diazotized with a nitrous acid purified by reacting an acid such as NaNO ₂ and hydrochloric acid to be a diazonium salt.
It is known that a diazonium salt can be converted into a halogen atom by a Sandmeyer reaction or the like, for example, by reacting hydrochloric acid, hydrobromic acid or the like in the presence of copper (I) halide. For example, Organic Synthesis, Collective Volume, Vol. 3, 185 (1955), Organic Synthesis, Collective Volume, Vol. 73, 133 It is described in. In addition, it is known that diazonium salts can be converted to —OH groups by heating in the presence of water under acidic conditions.

As a conversion reaction of a halogen atom to a -Z ¹ (Z ² ) m group, it is known that it can be lithiated by a lithiation reagent such as n-alkyllithium, and metal magnesium, zinc, etc. It is known that the compound can be converted to a magnesium halide group, a zinc halide group, or the like by a Grignard exchange reaction with isopropyl (i-Pr) MgCl or the like by reacting with. For example, this reaction is described in Angew. Chem. Int. Ed. Vol. 37, p. 1701 (1998). The Grignard reaction is described, for example, in Bulletin of Chemical Society of Japan, Vol. 51, p. 2091 (1978), Chemistry Letters, p. ing.
In addition, it is known that a halogen atom can be converted into a group represented by —Sn (Q ³ ) ₃ by allowing hexaalkyldistannane to act in the presence of a palladium catalyst. For example, this reaction is described in Angew. Chem. Int. Ed. Vol. 25, p. 508 (1986).

A group represented by —Z ¹ (Z ² ) m such as —Li, —MgCl, —MgBr, etc. can be derived into a —B (OH) ₂ group by hydrolysis with, for example, trimethoxyborane. It is also known that it can be derived into a boronic ester group by the action of isopropoxypinacol borane. For example, this reaction can be performed as described in Journal of American Chemical Society Vol. 126, p. 7041 (2004).
A group represented by —Z ¹ (Z ² ) m such as —Li, —MgCl, and —MgBr is derived, for example, from —OH group by oxidative decomposition with hydrogen peroxide after acting a trialkoxyborane. It is known that you can.
It is known that a group represented by —Z ¹ (Z ² ) m such as —Li, —MgCl, and —MgBr can be converted to a —CHO group by acting, for example, DMF or N-formylpiperidine. Yes. For example, this reaction is described in Synthesis, p. 228 (1984).

It is known that a methyl group can be converted into a halomethyl group such as —CH ₂ Cl and —CH ₂ Br by the action of SOCl ₂ , SOBr ₂ and the like. Moreover, it is known that a halomethyl group can be derived into a group represented by -CHQ ⁴ -P ⁺ (Q ⁵ ) ₃ Z ⁴ by the action of triphenylphosphine, and phosphorous acid by Arbuzov reaction. by the action of such ^trialkyl, it can be guided to the group represented by -CHQ 6 -P (= O) ( OQ 7) 2.

  In the repeating unit represented by the above formula (2), among the characteristic groups represented by X, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom, a bromine atom, and an iodine atom Are preferable, a chlorine atom and a bromine atom are more preferable, and a bromine atom is still more preferable.

In the above formula, the hydrocarbon group in the group represented by Q ¹ , Q ² , Q ³ , Q ⁴ , Q ⁵ , Q ⁶ , Q ⁷ , and Q ⁸ includes, for example, a methyl group, an ethyl group, a propyl group An alkyl group having about 1 to 50 carbon atoms such as isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, nonyl group, dodecyl group, pentadecyl group, octadecyl group, docosyl group; A cyclic saturated hydrocarbon group having about 3 to 50 carbon atoms such as propyl group, cyclobutyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group, norbornyl group, adamantyl group; ethenyl group, propenyl group, C2-C5 such as 3-butenyl group, 2-butenyl group, 2-pentenyl group, 2-hexenyl group, 2-nonenyl group, 2-dodecenyl group, etc. About alkenyl group; phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4- Having about 6 to 50 carbon atoms such as isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-adamantylphenyl group, 4-phenylphenyl group, etc. Aryl group; phenylmethyl group, 1-phenyleneethyl 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 group, 1-phenyl-6-hexyl group, etc. Aralkyl group of about 7 to 50 carbon atoms. As this hydrocarbon group, a C1-C20 hydrocarbon group is preferable, More preferably, it is a C1-C12 hydrocarbon group, More preferably, it is a C1-C8 hydrocarbon group. The hydrocarbon group may have a substituent.

^{Q 1} in -OSO ₂ Q ¹ is a hydrocarbon group which may have a substituent include a hydrocarbon group.
Examples of the group represented by —OSO ₂ Q ¹ include an alkyl sulfonate group, an aryl sulfonate group, and an aryl alkyl sulfonate group. Examples of the alkyl sulfonate group include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group. Examples of the aryl sulfonate group include a benzene sulfonate group, a p-toluene sulfonate group, a p-nitrobenzene sulfonate group, and an o-nitrobenzene sulfonate group. Examples of the aryl alkyl sulfonate group include a benzyl sulfonate group. Preferable examples include a trifluoromethanesulfonate group, a benzenesulfonate group, a p-toluenesulfonate group, and a p-nitrobenzenesulfonate group, and more preferable examples include a trifluoromethanesulfonate group.

-B (OQ ²⁾ Q ² in ₂ is a hydrogen atom, or an optionally substituted hydrocarbon group, forming two Q ² is may be the same or different and bonded to each other to form a ring You may do it. Examples of the hydrocarbon group include the hydrocarbon groups described above, and an alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, a hexyl group, and a nonyl group are preferable. More preferred are a methyl group, an ethyl group, a propyl group, an n-butyl group, a pentyl group, and a hexyl group. In the case of forming a ring, as the bifunctional hydrocarbon group composed of two Q ² , 1,2-ethylene group, 1,1,2,2-tetramethyl-1,2-ethylene group, 1, A 3-propylene group, a 2,2-dimethyl-1,3-propylene group, and a 1,2-phenylene group are preferred. Examples of the substituent include an amino group.
Examples of the group represented by —B (OQ ² ) ₂ include groups represented by the following formulae.

-Sn (Q ³⁾ Q ³ in ₃ is a hydrocarbon group which may have a substituent, three Q ³ are may be the same or different. Examples of the hydrocarbon group include the hydrocarbon groups described above, and an alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, a hexyl group, and a nonyl group are preferable. More preferred are a methyl group, an ethyl group, a propyl group, an n-butyl group, a pentyl group, and a hexyl group. Examples of the substituent include an amino group and an alkoxy group.
Examples of the group represented by —Sn (Q ³ ) ₃ include a tri (n-butyl) tin group and a triphenyltin group.

^{Z 1} (Z 2) Z ¹ in m is a metal atom or metal ion, ^{Z 2} is a counter anion, m is an integer of 0 or more. The Z ^1, Li Examples, Na, K, Rb, Cs , Be, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Pb, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ag, Cd, La, Ce, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Atoms or ions such as Hg can be mentioned. Preferred are Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Pb, Sc, Ti, Cu, Zn, Y, Zr, Ag, and Hg. More preferably Li, Na, K, Rb, Cs, Be, Mg, Ca, In, Tl, Pb, Cu, Zn, Zr, Ag, and Hg, and more preferably Li, Na, K, Mg, Ca, Cu, and Zn.

As Z ² , a conjugate base of Bronsted acid is usually used. Specific examples include fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, perchlorate ion. , Tetrafluoroborate ion, hexafluorophosphate ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, hydroxide ion, oxidation A product ion, a methoxide ion, an ethoxide ion and the like. Preferably chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, And benzoate ion, more preferably chloride ion, bromide ion, iodide ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate Acid ions, and more preferably chloride ions, bromide ions, iodide ions, methanesulfonate ions, trifluoromethanesulfonate ions, acetate ions, and trifluoroacetate ions.

m is determined so as to be electrically neutral as the aromatic compound represented by the general formula (I). When the characteristic group represented by X is Z ¹ (Z ² ) m, that is, when the repeating unit represented by the general formula (2) is represented by the following formula (2-2),

Z ^{1 (Z} 2) m portion as a +1 valence, the following general formula (2-3)

It is preferable that the part represented by the formula ( ¹ ) is regarded as -n valence, and the Z ¹ (Z ² ) m part and the remaining part are regarded as being ionically bonded.
Examples of the atomic group represented by Z ¹ (Z ² ) m include a zinc halide group, an alkali metal atom, and a halogenated alkaline earth metal group. Examples of the zinc halide group include a zinc chloride group, a zinc bromide group, and a zinc iodide group, and a zinc chloride group and a zinc bromide group are preferable. Examples of the alkali metal atom include lithium, sodium, potassium and the like, preferably lithium and sodium. Examples of the alkaline earth metal halide group include a magnesium chloride group, a magnesium bromide group, a magnesium iodide group, a calcium chloride group, a calcium bromide group, and a calcium iodide group. Preferably, a magnesium chloride group, a magnesium bromide group, and a magnesium iodide group are mentioned.

^{Z 3} in -CH ₂ Z ³ represents a halogen atom or a cyano group. Examples of the halogen atom represented by Z ³ include a chlorine atom, a bromine atom, and an iodine atom, and among them, a chlorine atom and a bromine atom are preferable.

_{^{-CHQ 4 -P + (Q 5)}} Q 4 in 3 ^{Z 4} is a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include the above-described hydrocarbon groups, and a methyl group, an ethyl group, a propyl group, an n-butyl group, a hexyl group, an octyl group, and the like are preferable. Q ⁵ is a hydrocarbon group which may have a substituent, and three Q ³ may be the same or different. Examples of the hydrocarbon group include the hydrocarbon groups described above, and a methyl group, an ethyl group, a propyl group, an n-butyl group, and a phenyl group are preferable. Z ⁴ represents a monovalent counter anion. As the monovalent counter anion represented by Z ⁴ , a conjugate base of Bronsted acid is usually used, and specific examples include fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitric acid. Ion, carbonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoic acid Acid ions, hydroxide ions, oxide ions, methoxide ions, ethoxide ions and the like can be mentioned. Preferred are chloride ion, bromide ion, iodide ion, tetrafluoroborate ion, and trifluoromethanesulfonate ion, and more preferred are chloride ion and bromide ion. Examples of the group represented by —CHQ ⁴ —P ⁺ (Q ⁵ ) ₃ Z ⁴ include the following groups.

^{-CHQ 6 -P (= O) Q} 6 in ^(OQ _{7) 2} is a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include the above-described hydrocarbon groups, and a methyl group, an ethyl group, a propyl group, an n-butyl group, a hexyl group, an octyl group, and the like are preferable. Q ⁷ is a hydrocarbon group which may have a substituent, and two Q ³ may be the same or different. Examples of the hydrocarbon group include the above-described hydrocarbon groups, and a methyl group, an ethyl group, a propyl group, an n-butyl group, and a phenyl group are preferable.

^{Q 8} in -C (= O) ^{Q 8} is a hydrogen atom, or a hydrocarbon group. Examples of the hydrocarbon group include the above-described hydrocarbon groups, and a methyl group, ethyl group, propyl group, n-butyl group, hexyl group, octyl group, phenyl group, benzyl group and the like are preferable. Examples of the group represented by —C (═O) Q ⁸ include a formyl group, an acetyl group, a benzoyl group, and a benzylcarbonyl group, and a formyl group and a benzoyl group are preferable.

The characteristic group X of the polymer compound containing the repeating unit having the characteristic group X produced in the step (A) of the production method of the present invention is not particularly limited as long as it reacts with the characteristic group Y in the step (B). However, from the viewpoint of ease of synthesis, a halogen atom, —OSO ₂ Q ¹ , —B (OQ ² ) ₂ , Z ¹ (Z ² ) m, —CH ₂ Z ³ , —CHQ ⁴ —P ⁺ (Q ⁵ ) ₃ Z ⁴ , —CHQ ⁶ —P (═O) (OQ ⁷ ) ₂ , and —C (═O) Q ⁸ are preferred. From the viewpoint of reactivity during introduction and ease of control of the amount introduced, a halogen atom , and a group derived from a halogen ^{_{atom, -OSO 2 Q 1, -B (}} OQ 2) 2, -Sn (Q 3) 3, Z 1 (Z 2) m, -OH, -C (= O ) A group such as Q ⁸ is preferable, and from the viewpoint of reactivity in Step B, a halogen atom, —OSO ₂ Q ¹ , —B (OQ ² ) ₂ , —Sn (Q ³ ) ₃ , Z ¹ (Z ² ) m, and —CHO are even more preferable, and among them, a halogen atom is most preferable.

Although the molecular weight of the polymer compound containing the repeating unit having the characteristic group X produced in the step (A) of the present invention is not particularly limited, it is typically from the viewpoint of solubility in an organic solvent during the reaction. has a number average molecular weight in terms of polystyrene is preferably a Mn ⁼ 10 3 ~10 ^8, more preferably 5x10 ³ ~5x10 ^7.

  About the high molecular compound containing the repeating unit which has the characteristic group X manufactured at the process (A) of the manufacturing method of this invention, the sum total of the repeating unit shown by Formula (2) is 0.5 mol of all the repeating units. % To 100 mol%, more preferably 2 mol% to 100 mol%.

  About the high molecular compound containing the repeating unit which has the characteristic group X manufactured at the process (A) of the manufacturing method of this invention, the sum total of the repeating unit shown by Formula (2) and the repeating unit shown by Formula (1) Is 50 mol% or more of all repeating units of the polymer compound, and the total of the repeating units represented by the formula (2) and the formula (1) is represented by the formula (2) The repeating unit shown is preferably 2 mol% or more and 90 mol% or less.

  The polymer compound containing the repeating unit having the characteristic group X produced in the step (A) of the production method of the present invention is other than the repeating unit represented by the formula (2) and the repeating unit represented by the formula (1). The repeating unit may be included. Moreover, the repeating unit may be connected with vinylene or a non-conjugated part, or the vinylene or non-conjugated part may be contained in the repeating unit. Examples of the bonding structure containing the non-conjugated moiety include those shown below in formulas X-1 to X-15, those in which formulas X-1 to X-15 shown below are combined with vinylene groups, and those shown below. The thing etc. which combined 2 or more are illustrated. Here, R ″ and Ar have the same meaning as described above.

  Among the linking groups containing a non-conjugated moiety represented by the formulas X-1 to X-15, the linking groups represented by the formulas X-3, X-5, X-6, and X-12 to X-15 are Preferably, a linking group represented by the formulas X-3, X-5, X-6, and X-12 to X-14 is more preferred, and a linking group represented by the formulas X-3, X-5, and X-6. Is more preferable.

  The polymer compound containing the repeating unit having the characteristic group X produced in the step (A) of the production method of the present invention contains other than the repeating unit represented by the formula (2) and the repeating unit represented by the formula (1). The ratio of the total number of linking groups containing vinylene and non-conjugated moieties is preferably 30% or less, more preferably 20% or less, and more preferably 10% with respect to the total number of all repeating units. The following is more preferable, and it is most preferable that vinylene and a linking group containing the non-conjugated moiety are not included.

  Further, the polymer compound containing the repeating unit having the characteristic group X produced in the step (A) of the production method of the present invention may be a random, block or graft copolymer, or an intermediate between them. It may be a polymer having a structure, for example, a random copolymer having a block property. A case in which the main chain is branched and there are three or more terminal portions and dendrimers are also included.

Next, the process (B) in the manufacturing method of this invention is demonstrated.
Step (B) in the production method of the present invention comprises a polymer compound having the characteristic group X produced in the step (A), and a compound having the characteristic group Y that reacts with the characteristic group X to form a bond. Is a step of reacting.

In the step (B), examples of the compound having the characteristic group Y include low molecular weight compounds, oligomers, polymers, dendrimers, and compounds having a metal complex structure. Preferably, compounds represented by the following formulas (3), (4) and (5) are mentioned.
Y-GA ¹ (3)
(Wherein, Y represents the same meaning as above, G may have a direct bond or a linear or branched structure, represents an C ₁ -C ₂₀ alkyl chains contain a cyclic structure, A ¹ is Represents a monovalent organic group and does not have a characteristic group that reacts with the characteristic groups X and Y to form a bond in the organic group.)
^{Y-G-A 2 -X 2} (4)
(In the formula, Y and G each have the same meaning as described above, X ² represents a characteristic group that reacts with the characteristic group Y to form a bond, and the definition is the same as the definition of X. X and X ² may be the same or different, and A ² represents a divalent organic group having a characteristic group that reacts with the characteristic groups X, Y, and X ² to form a bond. (Represents what is not.)
Y-GA ³ -G-Y (5)
(In the formula, Y and G each independently represent the same meaning as described above, A ³ represents a divalent organic group, and reacts substantially with the characteristic groups X and Y to form a bond in the organic group. Represents those that do not have the characteristic group

In the above formula (3), the monovalent organic group represented by A ¹ may have an aryl group, a monovalent heterocyclic group, a monovalent aromatic amine group, a linear or branched structure. Examples thereof include a monovalent aromatic oligomer group, a monovalent aromatic polymer group which may have a linear or branched structure, and an aromatic dendrimer group.

In the above formulas (4) and (5), the divalent organic group represented by A ² and A ³ includes an arylene group, a divalent heterocyclic group, a divalent aromatic amine group, a straight chain or a branched group. Examples thereof include a divalent aromatic oligomer group that may have a structure and a divalent aromatic polymer group that may have a linear or branched structure.

G is independently a direct bond, or may have a linear or branched structure, represents an C ₁ -C ₂₀ alkyl chains contain a cyclic structure. Examples of the C ₁ -C ₂₀ alkyl chain include a methylene group, an ethylene group, a propyl-1,3-diyl group, a butyl-1,4-diyl group, a pentyl-1,5-diyl group, and a hexyl-1,6-diyl group. Group, octyl-1,8-diyl group, decyl-1,10-diyl group, octadecyl-1,18-diyl group, butyl-2,3-diyl group, 3,7-dimethyloctyl-1,8-diyl Group, cyclohexyl-1,4-diyl group, cyclohexyl-1,4-dimethyl-1 ′, 1 ″ -diyl group, etc. When G represents an alkyl chain, the alkyl chain contains a heteroatom. The hetero atom may be interrupted by an oxygen atom, a sulfur atom, a nitrogen atom, etc. Examples of the group containing a hetero atom include the formulas X-1 to X-10. The group shown by It is done.

  The group containing a hetero atom that interrupts the alkyl chain is preferably a group represented by the formulas X-1 to X-5, more preferably groups represented by the formulas X-1 to X-3 and X-5, Even more preferred are groups of formula X-1 and X-2.

Directly as the G bonds, or may have a linear or branched structure, but represents an C ₁ -C ₂₀ alkyl chains contain a cyclic structure, a direct bond, more preferably a linear alkyl chain, is a direct bond Further preferred.

In the divalent organic group represented by A ² and A ³ , the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, having an condensed ring, an independent benzene ring or condensed A ring in which two or more rings are bonded directly or via a group such as vinylene is also included. The arylene group may have a substituent. Examples of the substituent that the arylene group may have include an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, an arylalkenyl group, an arylalkynyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an alkylthio group. And arylthio group, aralkylthio group, arylamino group, hydrocarbon silyl group, cyano group, nitro group and the like. Carbon number of the part except the substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. Moreover, the total carbon number including the substituent of an arylene group is about 6-100 normally. Examples of the arylene group include structures represented by the formulas 1A-1 to 1A-20. Here, as the arylene group represented by A ² and A ³ , R in the formulas 1A-1 to 1A-20 represents a hydrogen atom, a bond, or a substituent. Any two of a plurality of Rs represent a bond. When there are a plurality of substituents represented by R, they may be the same or different, and the substituents on adjacent atoms may include heteroatoms such as oxygen, sulfur, and nitrogen atoms. A good 5- to 7-membered aliphatic ring or a 5- to 7-membered aromatic ring may be formed. Ra represents a hydrogen atom or a substituent. When a plurality of substituents represented by Ra are present, they may be the same or different. When two Ra are present on the same atom, they may be combined to form an oxo group or a thioxo group, or may be bonded to each other to form a ring.

The arylene group represented by A ^1, of the formula 1A-1~1A-14, a phenylene group (formula 1A-1), naphthalene - diyl group (formula 1A-2), fluorene - diyl group (formula 1A -13), benzofluorene-diyl group (formula 1A-14), biphenylene group (formula 1A-15), terphenylene group (formula 1A-16 to 1A-18), stilbene-diyl group (1A-19), distilbene -Diyl group (1A-20) is preferred, among which phenylene group (Formula 1A-1), naphthalene-diyl group (Formula 1A-2), fluorene-diyl group (Formula 1A-13), benzofluorene-diyl group ( Formula 1A-14) is more preferred.

In the divalent organic group represented by A ² and A ³ , the divalent heterocyclic group is a remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound, and has a condensed ring. In addition, an independent monocyclic heterocyclic compound or a compound in which two or more condensed rings are bonded directly or via a group such as vinylene is also included. In addition, a combination of a heterocyclic compound and an aromatic hydrocarbon is also included. The divalent heterocyclic group may have a substituent. Examples of the substituent that the divalent heterocyclic group may have include an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, an arylalkenyl group, an arylalkynyl group, an alkoxy group, an aryloxy group, and an aralkyloxy group. Groups, alkylthio groups, arylthio groups, aralkylthio groups, arylamino groups, hydrocarbon silyl groups, cyano groups, nitro groups and the like. Carbon number of the part except the substituent in a bivalent heterocyclic group is about 4-60 normally, Preferably it is 2-20. Moreover, the total carbon number including the substituent of a bivalent heterocyclic group is about 2-100 normally. Here, the heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. Say. Examples of the divalent heterocyclic group include structures represented by the above formulas 2A-1 to 2A-68 and structures represented by the following formulas 4A-1 to 4A-4.

Here, as the monovalent heterocyclic group represented by A ² and A ³ , in the formulas 2A-1 to 2A-68, R represents a hydrogen atom, a bond, or a substituent. Any two of a plurality of Rs represent a bond. When there are a plurality of substituents represented by R, they may be the same or different, and the substituents on adjacent atoms include heteroatoms such as an oxygen atom, a sulfur atom, and a nitrogen atom. A 7-membered aliphatic ring or a 5- to 7-membered aromatic ring that may contain a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom may be formed. When two Ra are present on the same atom, they may be combined to form an oxo group or a thioxo group, or may be bonded to each other to form a ring. Ra represents a hydrogen atom or a substituent. When a plurality of substituents represented by Ra are present, they may be the same or different.

In the divalent organic group represented by A ² and A ³ , the divalent aromatic amine group is the remaining atomic group obtained by removing two hydrogen atoms from the aromatic amine. The divalent aromatic amine group may have a substituent. Examples of the substituent that the divalent aromatic amine group may have include an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, an arylalkenyl group, an arylalkynyl group, an alkoxy group, an aryloxy group, and an aralkyl group. Examples include an oxy group, an alkylthio group, an arylthio group, an aralkylthio group, an arylamino group, a hydrocarbon silyl group, a cyano group, and a nitro group. Carbon number of the part except the substituent in a bivalent aromatic amine group is about 4-60 normally. Examples of the divalent aromatic amine group include groups represented by the general formula (1-2), and specific examples include groups represented by the formulas 3A-1 to 3A-8. . Here, in A ² and A ³ represented by formulas 3A-1 to 3A-8, R represents a hydrogen atom, a bond, or a substituent. Any two of a plurality of Rs represent a bond. When there are a plurality of substituents represented by R, they may be the same or different, and the substituents on adjacent atoms include heteroatoms such as an oxygen atom, a sulfur atom, and a nitrogen atom. A 7-membered aliphatic ring or a 5- to 7-membered aromatic ring that may contain a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom may be formed.

The divalent organic group represented by A ² and A ³ may have a divalent aromatic oligomer group that may have a linear or branched structure, and a linear or branched structure. The divalent aromatic polymer group includes an arylene group, a divalent heterocyclic group, or two or more divalent aromatic amine groups directly or between a divalent linking group and a p-valent branch group. And those having a bond.
Here, k represents an integer of 3 to 6.

Here, as the divalent linking group, a C ₁ -C ₂₀ alkyl chain represented by G, which may have a linear or branched structure and may contain a cyclic structure, the above formulas X-1 to X -15, a combination of the formulas X-1 to X-15 and a vinylene group, a combination of two or more of the formulas X-1 to X-15, and the like Is done. Here, R ″ and Ar have the same meaning as described above.

As the divalent linking group, a C ₁ -C ₂₀ alkyl chain which may have a linear or branched structure represented by G and may contain a cyclic structure is preferable, and a linear alkyl chain is more preferable. A straight chain C ₁ -C ₈ alkyl chain is more preferred.

  Here, as the p-valent branching group, R in the formulas 1A-1 to 1A-20, 2A-1 to 2A-68, and 3A-1 to 3A-8 represents a hydrogen atom, a bond or a substituent. An example is shown in which an arbitrary p of a plurality of Rs represent a bond. As a p-valent branching group, when there are a plurality of substituents represented by R, they may be the same or different, and the substituents on adjacent atoms are oxygen atoms, sulfur atoms, nitrogen atoms, etc. A 5- to 7-membered aliphatic ring containing a heteroatom or a 5- to 7-membered aromatic ring that may contain a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Ra represents a hydrogen atom or a substituent. When a plurality of substituents represented by Ra are present, they may be the same or different. When two Ra are present on the same atom, they may be combined to form an oxo group or a thioxo group, or may be bonded to each other to form a ring.

In the divalent organic group represented by A ² and A ³ , a divalent aromatic oligomer group that may have a linear or branched structure, and a divalent that may have a linear or branched structure As the aromatic polymer group, those in which two or more arylene groups, divalent heterocyclic groups, and divalent aromatic amine groups are directly bonded are preferable.

The definition and specific examples of the monovalent organic group represented by A ¹ are defined and exemplified as one hydrogen atom bonded to the divalent organic group represented by A ² and A ³ .

  The compound having the characteristic group Y represented by the above formulas (3), (4) and (5) may be used alone or independently of one of the compounds represented by any formula. One or more selected compounds may be used. Moreover, when using the compound shown by the said Formula (4), it is preferable to use together the compound shown by the said Formula (3).

From the viewpoint of producing a polymer compound having a more complicated structure, when a compound having the characteristic group Y represented by the above formula (5) is used, a compound represented by the following formula (6) may be used in combination. .
X ³ -A ⁴ -X ⁴ (6)
(In the formula, X ³ and X ⁴ represent a characteristic group that reacts with the characteristic group Y to form a bond, and the definition is the same as the definition of X. X, X ³ and X ⁴ are the same or different from each other. A ⁴ represents a divalent organic group and does not have a characteristic group that reacts with the characteristic groups X, Y, X ³ and X ⁴ to form a bond in the organic group. Represents.)

The definition and specific examples of the divalent organic group represented by A ⁴ in Formula (6) are defined and exemplified in the same manner as the divalent organic group represented by A ² and A ³ .

  From the viewpoint of suppressing gelation due to the formation of a crosslinked structure, in the case where a compound having a characteristic group Y represented by the above formula (5) is used, in addition to the compound represented by the above formula (6), the above formula ( The compound represented by 3) may be used in combination.

From the viewpoint of synthesizing a side chain having a branched structure, in addition to the compounds represented by the above formulas (3), (4), (5) and (6), it is further represented by the following general formula (7). A compound may be used.

Wherein Y and G have the same meanings as described above, X ⁵ represents a characteristic group that reacts with the characteristic group Y to form a bond, A ⁵ represents a (k + 1) -valent organic group, The group having no characteristic group that reacts with the characteristic groups X, Y, X ¹ , X ² , X ³ , X ⁴ and X ⁵ to form a bond is represented by k. To express.)

As a definition and a specific example of the k + divalent organic group represented by A ⁴ in Formula (7), k hydrogen atoms or substituents are removed from the divalent organic group represented by A ² and A ^3. The remaining atomic groups are defined and exemplified.

  In order to suppress the gelation of the polymer compound due to the formation of a crosslinked structure, the compounds represented by the above formulas (3) and (4) are preferable. In order to more highly control the side chain structure, the above formula ( The compound represented by 3) is preferred.

The characteristic group Y is not particularly limited as long as it reacts with the characteristic group X to form a bond, and is a halogen atom, —OSO ₂ Q ¹ , —B (OQ ² ) ₂ , —Sn (Q ³ ) ₃ , Z. ¹ (Z ² ) m, —OH, —CH ₂ Z ³ , —CHQ ⁴ —P ⁺ (Q ⁵ ) ₃ Z ⁴ , —CHQ ⁶ —P (═O) (OQ ⁷ ) ₂ , —C (═O ) Q ⁸ , —CHQ ⁹ ═CHQ ¹⁰ , —C≡CH, —NHQ ¹¹ , and —SH groups.
(Q ¹ , Q ² , Q ³ , Q ⁴ , Q ⁵ , Q ⁶ , Q ⁷ , Q ⁸ , Z ¹ , Z ² , Z ³ , Z ⁴ , and m
Represents the same meaning as described above. Q ⁹ , Q ¹⁰ , and Q ¹¹ are a hydrogen atom or a hydrocarbon group. )
Examples of combinations and reaction methods of the characteristic groups X and Y include those shown in Table 3 below.

  The reaction method used for the reaction of the characteristic groups X and Y includes aryl-aryl coupling reaction using a zerovalent nickel complex, reaction by Wittig reaction, reaction by Horner-Wadsworth-Emmons method, reaction by Knoevenagel reaction, Suzuki coupling Reaction, Grignard coupling reaction, Negishi coupling reaction, Stille coupling reaction is preferable in terms of high reactivity. Among them, the reaction by Wittig reaction, the reaction by Horner-Wadsworth-Emmons method, the Knoevenagel reaction The method of reacting by reaction, Suzuki coupling reaction, and Grignard coupling reaction is preferable because the structure can be easily controlled.

  In the production method of the present invention, the type of bond generated by the reaction of the characteristic groups X and Y is not particularly limited, and examples thereof include a covalent bond, an ionic bond, and a coordination bond. Examples of ionic bonds include, for example, when a polymer compound containing a repeating unit having a characteristic group X has a carboxyl group, a sulfonic acid group, a phosphoric acid residue, etc. as the reactive group Y, the group and an organic amine Can be combined by ionic bonding to form a salt. Moreover, as an example of the coordination bond, a method by generation of a metal complex is exemplified. For example, when a polymer compound including a repeating unit having the characteristic group X has a ligand group as the characteristic group X, the group and the metal compound can be bonded by a coordinate bond. Examples of the covalent bond include a direct bond, a single bond, a double bond, a triple bond, an ester bond, an amide bond, and the like. Aryl-carbon single bond, carbon-carbon double bond, carbon-carbon triple bond, aryl-aryl A direct bond or the like is preferable, and an aryl-carbon single bond or an aryl-aryl direct bond is more preferable.

^{Q 9} and ^{Q 10} in -CHQ ⁹ = ^{CHQ 10} are each a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include the above-described hydrocarbon groups, and a methyl group, an ethyl group, a propyl group, an n-butyl group, a hexyl group, an octyl group, a phenyl group, and the like are preferable.

-NHQ ^{Q 11} in ¹¹ is a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include the above-described hydrocarbon groups, and a methyl group, an ethyl group, a propyl group, an n-butyl group, a hexyl group, an octyl group, a phenyl group, and the like are preferable.

  When the polymer compound produced in the step (B) of the present invention has a characteristic group, the polymer compound may be further reacted with a compound having a characteristic group that reacts with the characteristic group.

  In the production method of the present invention, the polymer compound containing the repeating unit having the characteristic group X represented by the formula (2) and the compound having the characteristic group represented by the formulas (3) to (7) are mixed together. You may make it react and you may divide and mix as needed. If necessary, the compound having these characteristic groups can be dissolved in an organic solvent and reacted, for example, with an alkali or an appropriate catalyst at a temperature not lower than the melting point of the organic solvent and not higher than the boiling point. The organic solvent varies depending on the compound and reaction to be used, but it is generally preferable that the solvent to be used is sufficiently deoxygenated and the reaction proceeds in an inert atmosphere in order to suppress side reactions. Similarly, it is preferable to perform a dehydration treatment (however, this is not the case in the case of a two-phase reaction with water such as the Suzuki coupling reaction). In order to make it react, an alkali and a suitable catalyst are added suitably. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. As a method of mixing the alkali or catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or conversely, slowly add the reaction solution to the alkali or catalyst solution. And the method of adding.

  More specifically, the reaction conditions will be described. In the case of Wittig reaction, Horner reaction, Knoevengel reaction, etc., the reaction is carried out using an alkali equivalent to or more, preferably 1 to 3 equivalents of the functional group of the compound. Examples of the alkali include, but are not limited to, metal alcoholates such as potassium tert-butoxide, sodium tert-butoxide, sodium ethylate and lithium methylate, hydride reagents such as sodium hydride, and amides such as sodium amide. Etc. can be used. As the solvent, N, N-dimethylformamide, tetrahydrofuran, dioxane, toluene and the like are used. The reaction can be allowed to proceed at a reaction temperature of usually from room temperature to about 150 ° C. The reaction time is, for example, 5 minutes to 40 hours, but may be any time that allows sufficient polymerization to proceed, and it is not necessary to leave the reaction for a long time after the reaction is completed. is there. If the reaction concentration is too dilute, the reaction efficiency is poor. If the concentration is too high, it becomes difficult to control the reaction. Therefore, the concentration may be appropriately selected within the range of about 0.01 wt% to the maximum concentration to be dissolved. The range is from 1 wt% to 30 wt%. The Wittig reaction is described in “Organic Reactions”, Vol. 14, pages 270-490, John Wiley & Sons, Inc., 1965, and the like. Knoevenagel, Wittig, and dehydrohalogenation reactions are described in Macromolecular Chemistry Macromolecular Symposium (Macromol. Chem., Macromol. Symp.), Vol. 12, 229 (1987).

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

  In the case of the Suzuki reaction, for example, palladium [tetrakis (triphenylphosphine)], palladium acetates, etc. are used as a catalyst. If necessary, a phosphine ligand such as triphenylphosphine or tricyclohexylphosphine is added and potassium carbonate is added. In addition, an inorganic base such as sodium carbonate and barium hydroxide, an organic base such as triethylamine and tetraethylammonium hydroxide, and an inorganic salt such as cesium fluoride are added in an amount of not less than an equivalent amount, and preferably 1 to 10 equivalents. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. By using an organic base or an inorganic salt as an aqueous solution, the reaction may be performed under conditions that form a two-phase system with the solvent. Although depending on the solvent, a temperature of about 50 to 160 ° C. is preferably used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours. Regarding the Suzuki reaction, for example, Chemical Review (Chem. Rev.), 95, 2457 (1995), Journal of Organometallic Chemistry (J. Organomet. Chem.), 576, 147 (1999). ) Etc.

  The case where a zerovalent nickel complex is used will be described. As the nickel complex, there are a method in which zero-valent nickel is used as it is, and a method in which a nickel salt is reacted in the presence of a reducing agent to generate zero-valent nickel in the system and react. Examples of the zero-valent nickel complex include bis (1,5-cyclooctadiene) nickel (0), (ethylene) bis (triphenylphosphine) nickel (0), tetrakis (triphenylphosphine) nickel, Bis (1,5-cyclooctadiene) nickel (0) is preferred from the viewpoint of versatility and low cost. Moreover, it is preferable from a viewpoint of a yield improvement to add a neutral ligand. Here, the neutral ligand is a ligand having no anion or cation, and 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N′-tetramethylethylenediamine. Nitrogen-containing ligands such as triphenylphosphine, tolylphosphine, tributylphosphine, triphenoxyphosphine, and the like, and nitrogen-containing ligands are preferred in terms of versatility and low cost. 2,2′-bipyridyl is particularly preferable in terms of high reactivity and high yield. In particular, from the viewpoint of improving the yield of the polymer, a system in which 2,2'-bipyridyl is added as a neutral ligand to a system containing bis (1,5-cyclooctadiene) nickel (0) is preferable. In the method of reacting zero-valent nickel in the system, nickel salts such as nickel chloride and nickel acetate can be used. Examples of the reducing agent include zinc, sodium hydride, hydrazine and derivatives thereof, lithium aluminum hydride, and the like, and ammonium iodide, lithium iodide, potassium iodide, and the like are used as additives. The polymerization solvent is not particularly limited as long as it does not inhibit the polymerization, and examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, aromatic hydrocarbon solvents, ether solvents and the like. Here, the aromatic hydrocarbon solvent is a solvent composed of an aromatic hydrocarbon compound, and examples thereof include benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, butylbenzene, naphthalene, tetralin, and the like. Xylene, tetralin and tetramethylbenzene are preferred. The ether solvent is a solvent composed of a compound in which a hydrocarbon group is bonded with an oxygen atom, such as diisopropyl ether, tetrahydrofuran, 1,4-dioxane, diphenyl ether, ethylene glycol dimethyl ether, tert-butyl methyl ether, and the like. Preferred are tetrahydrofuran, 1,4-dioxane and the like, which are good solvents for the polymer compound. These may be used as a mixture. For example, the polymerization reaction is usually performed in an inert gas atmosphere such as argon or nitrogen in a tetrahydrofuran solvent at a temperature of 60 ° C. in the presence of a zero-valent nickel complex or a neutral ligand. The polymerization time is usually about 0.5 to 100 hours, but is preferably within 10 hours from the viewpoint of production cost. The polymerization temperature is usually about 0 to 200 ° C, but 20 to 100 ° C is preferable from the viewpoint of high yield and low heating cost. The case of using a nickel catalyst is described in, for example, Progressive Polymer Science (Prog. Polym. Sci.), Vol. 17, pp. 1153-1205, 1992.

  In the case of the Grignard reaction, for example, dichloronickel (bisdiphenylphosphinopropane), dichloronickel (bisdiphenylphosphinoethane), nickel (2,2′-bipyridyl) dichloride or the like is used as a catalyst, and toluene, dimethoxyethane, tetrahydrofuran The method of making it react in solvents, such as, is illustrated. Although depending on the solvent, a temperature of about -20 to 160 ° C is preferably used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 0.1 to 200 hours. The Grignard reaction is described, for example, in Bulletin of Chemical Society of Japan, Vol. 51, p. 2091 (1978), Chemistry Letters, p. ing.

The polymer compound produced by the production method of the present invention usually has fluorescence in a solid state, and typically has a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ , preferably 5 × 10 ^3.
~ 5x10 ⁷

  When the polymer compound produced by the production method of the present invention is used in the field of electronic materials such as polymer LEDs, the polymer compound containing the repeating unit represented by the formula (1) is a conjugated polymer compound. It is preferable that the repeating unit may be linked with vinylene or a non-conjugated part within a range not impairing the fluorescence property or the charge transport property, and the repeating unit contains such vinylene or non-conjugated part. May be. Examples of the bonding structure including the non-conjugated moiety include two or more of the following formulas X-1 to X-15, combinations of the formulas X-1 to X-15 and vinylene groups, and those shown below. A combination of these is exemplified. Here, R ″ and Ar have the same meaning as described above.

  Among the linking groups containing a non-conjugated moiety represented by the formulas X-1 to X-15, the linking groups represented by the formulas X-3, X-5, X-6, and X-12 to X-15 are Preferably, a linking group represented by the formulas X-3, X-5, X-6, and X-12 to X-14 is more preferred, and a linking group represented by the formulas X-3, X-5, and X-6. Is more preferable.

  The polymer compound produced by the production method of the present invention contains, in addition to repeating units, the proportion of the total number of vinylenes and linking groups containing the non-conjugated moiety is 30% with respect to the total number of all repeating units. It is preferably not more than 20%, more preferably not more than 20%, still more preferably not more than 10%, and most preferably not containing vinylene and a linking group containing the non-conjugated moiety.

  Further, the polymer compound produced by the production method of the present invention may be a random, block or graft copolymer, or a polymer having an intermediate structure thereof, such as a random copolymer having a block property. It may be a polymer. From the viewpoint of obtaining a polymeric fluorescent substance having a high fluorescence quantum yield, a random copolymer having a block property and a block or graft copolymer are preferable to a complete random copolymer. A case in which the main chain is branched and there are three or more terminal portions and dendrimers are also included.

  When the polymer compound obtained by the production method of the present invention is used as a light emitting material (polymer fluorescent substance) of a polymer LED, the purity affects the light emission characteristics, and therefore, separation and purification are sufficiently performed, unreacted monomers, It is preferable to sufficiently remove by-products and catalyst residues. In the case of drying, it is sufficient that the remaining solvent is sufficiently removed. In order to prevent deterioration of the polymer compound, it is preferable to dry it while shielding light in an inert atmosphere. Moreover, it is preferable to dry at a temperature at which the polymer compound is not thermally denatured.

  In addition, the terminal group of the polymer compound produced by the method of the present invention may be protected with a stable group because if the characteristic group remains as it is, there is a possibility that the light emission characteristics and lifetime of the device will be reduced. May be. Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and for example, a structure bonded to an aryl group or a heterocyclic group via a vinylene group may be used. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478. Examples of the good solvent for the polymer compound include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, decalin, n-butylbenzene, dioxane and the like. Although depending on the structure and molecular weight of the polymer compound, it can usually be dissolved in these solvents in an amount of 0.1% by weight or more.

  The polymer compound produced by the method of the present invention can be suitably used for, for example, a polymer light emitting device (polymer LED). The polymer LED has a light emitting layer between electrodes composed of a pair of an anode and a cathode, at least one of which is transparent or translucent, and the polymer compound obtained by the production method of the present invention comprises: It is contained in the light emitting layer.

  As the polymer LED, a polymer LED in which an electron transport layer is provided between the cathode and the light emitting layer, a polymer LED in which a hole transport layer is provided between the anode and the light emitting layer, a cathode and the light emitting layer, Examples of the polymer LED include an electron transport layer provided between them and a hole transport layer 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.)

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

  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.

Polymer LED provided with a charge injection layer (electron injection layer, hole injection layer) includes a polymer LED provided with a charge injection layer adjacent to the cathode, and a polymer provided with a charge injection layer adjacent to the anode. LED is mentioned. For example, the following structures e) to p) are specifically mentioned.
e) Anode / charge injection layer / light emitting layer / cathode f) Anode / light emitting layer / charge injection layer / cathode g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode h) Anode / charge injection layer / hole Transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / charge injection layer / cathode j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode k) anode / charge Injection layer / light emitting layer / electron transport layer / cathode l) anode / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode n) anode / Charge injection layer / hole transport layer / light emitting layer / electron transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) anode / charge injection layer / hole transport Layer / light emitting layer / electron transport layer / charge injection layer / cathode Specific examples of the charge injection layer include a layer containing a conductive polymer, an anode and a hole transport layer. A layer containing a material having an ionization potential of an intermediate value between the anode material and the hole transport material included in the hole transport layer, provided between the cathode and the electron transport layer. Examples include a layer containing a material having an electron affinity with an intermediate value between the cathode material and the electron transport material contained in the electron transport layer.

In the case where 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 S / cm 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. As the polymer LED provided with the insulating layer having a thickness of 2 nm or less, the polymer LED provided with the insulating layer having a thickness of 2 nm or less adjacent to the cathode, or the insulating layer having a thickness of 2 nm or less provided adjacent to the anode. Polymer LED is mentioned.

Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode u) Anode / hole transporting layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode w) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode x) anode / Light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode y) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode z) anode / film Insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode aa) anode / hole transport layer / light emitting layer / electron transport Layer / thickness 2nm or less of the insulating layer / cathode ab) anode / thickness 2nm or less of the insulating layer / hole transport layer / light emitting layer / electron transporting layer / thickness 2nm or less of the insulating layer / cathode

  When forming a film from a solution by using these organic solvent-soluble polymer compounds obtained by the production method of the present invention when producing a polymer LED, the solvent is removed by drying after coating the solution. In addition, the same technique can be applied even when a charge transport material or a light emitting material is mixed, which is very advantageous in manufacturing. 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.

  The film thickness of the light emitting layer varies depending on the material used, and may be selected so that the driving voltage and the light emission efficiency are appropriate values. For example, the thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. Preferably it is 5 nm-200 nm.

  In the polymer LED, a light emitting material other than the polymer compound obtained by the production method of the present invention may be mixed and used in the light emitting layer. In the polymer LED of the present invention, a light emitting layer containing a light emitting material other than the polymer compound may be laminated with a light emitting layer containing the polymer compound. As the light emitting material, known materials can be used. Examples of low molecular weight compounds include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or metal complexes of derivatives thereof, aromatic amines, and the like. , 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.

  When the polymer LED has a hole transport layer, the hole transport material used includes polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, and a pyrazoline derivative. , Arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thienylene vinylene) Or the derivative | guide_body etc. are illustrated. Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

  Among these, as a hole transport 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, polyaniline or a derivative thereof, Preferred is a polymer hole transport material such as polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or poly (2,5-thienylene vinylene) or a derivative thereof, more preferably polyvinyl carbazole or a derivative thereof, Polysilane or a derivative thereof, or a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder. 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, In the low molecular hole transport material, the method by the film-forming from a mixed solution with a polymer binder is illustrated. In the case of a polymer hole transport material, a method of film formation from a solution is exemplified.

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

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

  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. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

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

  When the polymer LED has an electron transport layer, known electron transport materials can be used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones. Or a derivative thereof, tetracyanoanthraquinodimethane or a derivative thereof, a fluorenone derivative, diphenyldicyanoethylene or a derivative thereof, a diphenoquinone derivative, or a metal complex of 8-hydroxyquinoline or a derivative thereof, a polyquinoline or a derivative thereof, a polyquinoxaline or a derivative thereof, And 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, and polyfluorene or derivatives thereof are preferable. 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferred.

  There are no particular restrictions on the method of forming the electron transport layer, but in the case of a low molecular electron transport material, a vacuum deposition method from powder or a method by film formation from a solution or a molten state is used. Each method is exemplified by film formation from a molten state. When forming a film from a solution or a molten state, a polymer binder may be used in combination.

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

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

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those not strongly absorbing 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, or polysiloxane.

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

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

  In the polymer LED, the anode side is preferably transparent or translucent, but 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.

  As a material for the cathode used in the polymer LED, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, 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 producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression-bonded, or the like is used. Further, a layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material or the like having an average film thickness of 2 nm or less may be provided between the cathode and the organic material layer. A protective layer for protecting the polymer LED may be attached.
In order to stably use the polymer LED for a long period of time, it is preferable to attach a protective layer and / or protective cover in order to protect the element from the outside.

  As the protective layer, a polymer compound, metal oxide, metal fluoride, metal boride and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing the cover by bonding it to the element substrate with a heat effect resin or a photo-curing resin is preferable. Used for. If 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, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It is easy to suppress damage to the element. Among these, it is preferable to take any one or more measures.

  In order to obtain planar light emission using the polymer LED, 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 will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

(Number average molecular weight and weight average molecular weight)
Here, regarding the number average molecular weight (Mn), the weight average molecular weight (Mw), and the peak top molecular weight (Mp), the number average molecular weight (Mn), the weight average molecular weight (Mw), and the peak top molecular weight (Mp) converted to polystyrene by GPC. )
<GPC measurement method A> By GPC (manufactured by Shimadzu Corporation: LC-10Avp (trade name)), two TSKgel SuperHM-H (trade name) manufactured by Tosoh Corporation and one TSKgel SuperH2000 (trade name, manufactured by Tosoh Corporation) are connected in series. Using a connected column, tetrahydrofuran was used as a developing solvent, and flowed at a flow rate of 0.6 mL / min, and measurement was performed at 40 ° C. A differential refractive index detector (manufactured by Shimadzu Corporation: RID-10A (trade name)) was used as the detector.
<GPC measurement method B> By using PL-GPC210 system (trade name) (RI detection) manufactured by Polymer Laboratories, three PLgel 10um MIXED-B (trade name) manufactured by Polymer Laboratories were used as columns, and o-dichlorobenzene (2, 6-di-t-butyl-4-methylphenol (containing 0.01% w / v) was used as a developing solvent, and the measurement was performed at 70 ° C.
<GPC measurement method C>
Using a column in which three TSKgel SuperHM-H (trade name, manufactured by Tosoh Corp.) are directly connected by an HLC-8220 GPC system (trade name) (RI detection) manufactured by Tosoh Corporation, 0.5 mL / The measurement was conducted at 40 ° C. with a flow rate of min. A suggested refractive index detector was used as the detector.

(NMR measurement)
The NMR measurement was performed at room temperature using an INOVA300 nuclear magnetic resonance apparatus manufactured by Varian as a deuterated tetrahydrofuran solution.

Synthesis example 1
<N- (4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) phenyl) -N- (4-t-butyl-2,6-dimethylphenyl) -Synthesis of N-phenylamine and Compound N>
(Synthesis of 4-t-butyl-2,6-dimethylbromobenzene)

Under an inert atmosphere, 225 g of acetic acid was placed in a 500 ml three-necked flask, and 24.3 g of 5-t-butyl-m-xylene was added. Then, after adding 31.2 g of bromine, it was made to react at 15-20 degreeC for 3 hours.
The reaction solution was added to 500 ml of water, and the deposited precipitate was filtered. This was washed twice with 250 ml of water to obtain 34.2 g of a white solid.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ (ppm) = 1.3 [s, 9H], 2.4 [s, 6H], 7.1 [s, 2H]
MS (FD ⁺ ) M ⁺ 241

(Synthesis of N, N-diphenyl-N- (4-t-butyl-2,6-dimethylphenyl) -amine)

Under an inert atmosphere, 100 ml of degassed dehydrated toluene was placed in a 300 ml three-necked flask, and 16.9 g of diphenylamine and 25.3 g of 4-t-butyl-2,6-dimethylbromobenzene were added. Subsequently, 0.92 g of tris (dibenzylideneacetone) dipalladium and 12.0 g of t-butoxy sodium were added, and then 1.01 g of tri (t-butyl) phosphine was added. Then, it was made to react at 100 degreeC for 7 hours.
The reaction solution was poured into saturated brine and extracted with 100 ml of toluene. The toluene layer was washed with dilute hydrochloric acid and saturated brine, and then the solvent was distilled off to obtain a black solid. This was separated and purified by silica gel column chromatography (hexane / chloroform 9/1) to obtain 30.1 g of a white solid.
¹ H-NMR (300 MHz / CDCl ₃ ): δ (ppm) = 1.3 [s, 9H], 2.0 [s, 6H], 6.8 to 7.3 [m, 10H]

(Synthesis of N- (4-bromophenyl) -N- (4-t-butyl-2,6-dimethylphenyl) -N-phenylamine)

A dry three-necked flask was charged with 3.0 g (9.1 mmol) of N, N-diphenyl-N- (4-t-butyl-2,6-dimethylphenyl) -amine, and the inside of the container was replaced with argon gas. Using a syringe, 105 mL of dehydrated dimethylformamide was added to make uniform. The reaction solution was cooled to 0 to 5 ° C. in an ice bath, and a solution consisting of 1.5 g (0.9 equivalent) of N-bromosuccinimide and 5.2 mL of dehydrated dimethylformamide was added dropwise over 30 minutes, and the mixture was stirred as it was for 30 minutes. did. Next, after removing the ice bath and returning to room temperature, the mixture was stirred for 5 hours. Next, 130 mL of distilled water and 150 mL of chloroform were added to the reaction solution and stirred sufficiently to separate the organic layer and the aqueous layer. The organic layer was dried over anhydrous magnesium sulfate and concentrated to dryness. Subsequently, it was dissolved in 200 mL of toluene and passed through a silica gel column, and the solution was concentrated to dryness. Purified by silica gel column chromatography using chloroform and cyclohexane as developing solution, concentrated to dryness, and N- (4-bromophenyl) -N- (4-tert-butyl-2,6-dimethylphenyl) -N-phenylamine. 2.0 g was obtained as a white solid (LC area percentage 99.7%, yield 53.3%).
¹ H-NMR (300 MHz, CDCl 3): δ 1.32 (s, 9H), 2.00 (s, 6H), 6.81-6.98 (m, 5H), 7.09 (s, 2H), 7.16-7.27 (m, 4H)
LC / MS (APPI (+)): M ⁺ 407

(N- (4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) phenyl) -N- (4-t-butyl-2,6-dimethylphenyl) Synthesis of -N-phenylamine)

7.78 g (19.1 mmol) of N- (4-bromophenyl) -N- (4-tert-butyl-2,6-dimethylphenyl) -N-phenylamine was charged into a dry three-necked flask, Was replaced with argon gas, and 76 mL of dehydrated tetrahydrofuran and 191 mL of dehydrated diethyl ether were added and dissolved by stirring. The reaction solution was cooled to −76 ° C., and 13.61 mL (21.0 mmol) of a 1.54 mol / L n-butyllithium n-hexane solution was added dropwise over 30 minutes, followed by stirring for 0.5 hours. Then, 5.83 mL (28.6 mmol) of 2-isopropyloxy-4,4,5,5-tetramethyl- [1,3,2] dioxaborolane was added dropwise at −76 ° C. over 20 minutes and left for 1 hour. After stirring, the mixture was warmed to room temperature and stirred for 2 hours. The reaction solution was added dropwise to 200 mL of 0.2N hydrochloric acid cooled to 0 ° C. over 15 minutes and stirred at room temperature for 15 minutes, and then the organic layer and the aqueous layer were separated. The aqueous layer was extracted with diethyl ether, and the organic layers were combined, then washed sequentially with distilled water, 5% aqueous sodium hydrogen carbonate solution, and distilled water. The obtained organic layer was dried over anhydrous sodium sulfate and then concentrated to dryness. As a result, 9.0 g of a crude product was obtained as a light pink solid. 8.6 g of this crude product was dissolved by heating in 17.1 g of tetrahydrofuran at 50 ° C., and crystallized by slowly adding 85.6 g of methanol, filtered and dried under reduced pressure to give N- (4- (4 , 4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) phenyl) -N- (4-t-butyl-2,6-dimethylphenyl) -N-phenylamine 7.6 g Was obtained as a white solid. (LC area percentage 98.5%, yield 86.7%). As an impurity, N, N-diphenyl-N- (4-t-butyl-2,6-dimethylphenyl) -amine was contained in an LC surface percentage of 1.5%.
¹ H-NMR (300 MHz, CDCl 3): δ 1.32 (s, 9H), 1.32 (s, 12H), 2.00 (s, 6H), 6.81-6.98 (m, 3H), 7.01 (d, 2H), 7.09 (s, 2H), 7.15-7.27 (m, 2H), 7.62 (d, 2H),
LC / MS (APPI (+)): [M + H] ⁺ 456

(Synthesis of N, N-bis (4-bromophenyl) -N- (4-t-butyl-2,6-dimethylphenyl) -amine)

Under an inert atmosphere, 333 ml of dehydrated N, N-dimethylformamide and 166 ml of hexane were placed in a 1000 ml three-necked flask, and N, N-diphenyl-N- (4-t-butyl) synthesized in the same manner as above. After dissolving 29.7 g of -2,6-dimethylphenyl) -amine, 33.6 g of N-bromosuccinimide / 100 ml of N, N-dimethylformamide solution was added dropwise under a light-shielded and ice bath, and allowed to react for a whole day and night.
The reaction solution was concentrated under reduced pressure to 200 ml, added to 1000 ml of water, and the deposited precipitate was filtered. The obtained crystals were recrystallized twice with DMF / ethanol to obtain 23.4 g of a white solid.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ (ppm) = 1.3 [s, 9H], 2.0 [s, 6H], 6.8 [d, 2H], 7.1 [s, 2H], 7.3 [d, 2H],
MS (APCI (+)): M ⁺ 488

<Synthesis of Compound N>

Compound N
(4-Bromophenyl)-(4-tert-butyl-2,6-dimethylphenyl)-[4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) Synthesis of -phenyl] amine 91.89 g (188.58 mmol) of bis- (4-bromophenyl)-(4-tert-butyl-2,6-dimethylphenyl) amine was added to a dried four-necked flask under an argon atmosphere. The mixture was charged and homogenized with 2750 mL of dehydrated tetrahydrofuran. The reaction solution was cooled to −70 ° C., and 98 mL (150.9 mmol) of a 1.54M n-butyllithium n-hexane solution was added dropwise over 78 minutes, and the mixture was stirred as it was for 65 minutes. Next, 35.1 g (188.65 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl- [1,3,2] dioxaborolane was added dropwise at −70 ° C. over 60 minutes and stirred for 1 hour. Then, the temperature was raised to 15 to 20 ° C. and the mixture was stirred for 2 hours. After adding 1 L of water at room temperature and stirring for 1 hour, tetrahydrofuran was distilled off by concentration under reduced pressure. 2 L of toluene was added to the concentrated suspension and stirred, and then the oil layer was separated from the aqueous layer. The oil layers obtained by the above three liquid separation operations were combined, and anhydrous sodium sulfate was added and stirred. Anhydrous sodium sulfate was filtered off, and the resulting filtrate was concentrated under reduced pressure to obtain 113.54 g of a white solid. This white solid was purified by silica gel column chromatography using toluene and n-hexane as a developing solution and concentrated to dryness to obtain 45.5 g of a yellowish white solid. This yellowish white was dissolved in 800 mL of tetrahydrofuran, 800 mL of distilled water was added dropwise at 25 ° C. over 3 hours, crystals were precipitated, stirred for 1 hour, and then filtered 7 times, and the obtained crystals were dried under reduced pressure, Desired (4-bromophenyl)-(4-tert-butyl-2,6-dimethylphenyl)-[4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolane-2 -Il) -phenyl] amine was obtained as a white solid (yield 40.2 g, yield 37.8%, LC area percentage 98.0%).
^{1 H-NMR: 1.32 (s} , 9H), 1.32 (s, 12H), 1.98 (s, 6H), 6.87 (d, 2H), 6.90 (d, 2H), 7.09 (s, 2H), 7.28 (d, 2H), 7.63 (d, 2H)
LC-MS: 535.1 (M + H)

Synthesis example 2
<Synthesis of Compounds F and G>
(Synthesis of Compound A)

Under an inert atmosphere, in a 300 ml three-necked flask, 5.00 g (29 mmol) of 1-naphthaleneboronic acid, 6.46 g (35 mmol) of 2-bromobenzaldehyde, 10.0 g (73 mmol) of potassium carbonate, 36 ml of toluene, and ion-exchanged water 36 ml was added, and argon was bubbled for 20 minutes while stirring at room temperature. Subsequently, 16.8 mg (0.15 mmol) of tetrakis (triphenylphosphine) palladium was added, and argon was bubbled for 10 minutes while stirring at room temperature. The temperature was raised to 100 ° C. and reacted for 25 hours. After cooling to room temperature, the organic layer was extracted with toluene, dried over sodium sulfate, and the solvent was distilled off. By producing with a silica gel column using toluene: cyclohexane = 1: 2 mixed solvent as a developing solvent, 5.18 g (yield 86%) of Compound A was obtained as white crystals.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.39-7.62 (m, 5H), 7.70 (m, 2H), 7.94 (d, 2H), 8.12 (dd, 2H), 9.63 (s, 1H)
MS (APCI (+)): (M + H) ^<+> 233

(Synthesis of Compound B)

Under an inert atmosphere, 8.00 g (34.4 mmol) of Compound A and 46 ml of dehydrated THF were placed in a 300 ml three-necked flask and cooled to -78 ° C. Subsequently, 52 ml of n-octylmagnesium bromide (1.0 mol / l THF solution) was added dropwise over 30 minutes. After completion of dropping, the temperature was raised to 0 ° C., stirred for 1 hour, then warmed to room temperature and stirred for 45 minutes. The reaction was terminated by adding 20 ml of 1N hydrochloric acid in an ice bath, and the organic layer was extracted with ethyl acetate and dried over sodium sulfate. After distilling off the solvent, the residue was purified by a silica gel column using a mixed solvent of toluene: hexane = 10: 1 as a developing solvent to obtain 7.64 g (yield: 64%) of Compound B as a pale yellow oil. Although two peaks were observed in the HPLC measurement, they were determined to be a mixture of isomers because they were the same mass number in the LC-MS measurement.

(Synthesis of Compound C)

Under an inert atmosphere, 5.00 g (14.4 mmol) of Compound B (mixture of isomers) and 74 ml of dehydrated dichloromethane were placed in a 500 ml three-necked flask and stirred and dissolved at room temperature.
Subsequently, an etherate complex of boron trifluoride was added dropwise at room temperature over 1 hour, and after completion of the addition, the mixture was stirred at room temperature for 4 hours. While stirring, 125 ml of ethanol was slowly added. When the exotherm subsided, the organic layer was extracted with chloroform, washed twice with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was purified by a silica gel column using hexane as a developing solvent to obtain 3.22 g (yield 68%) of Compound C as a colorless oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 3H), 1.03-1.26 (m, 14H), 2.13 (m, 2H), 4.05 (t, 1H), 7.35 (dd, 1H), 7 .46-7.50 (m, 2H), 7.59-7.65 (m, 3H), 7.82 (d, 1H), 7.94 (d, 1H), 8.35 (d, 1H) ), 8.75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 329

(Synthesis of Compound D)

Under an inert atmosphere, 20 ml of ion-exchanged water was placed in a 200 ml three-necked flask, and 18.9 g (0.47 mol) of sodium hydroxide was added little by little with stirring to dissolve. After the aqueous solution was cooled to room temperature, 20 ml of toluene, 5.17 g (15.7 mmol) of Compound C and 1.52 g (4.72 mmol) of tributylammonium bromide were added, and the temperature was raised to 50 ° C.
N-Octyl bromide was added dropwise, and after completion of the addition, the mixture was reacted at 50 ° C. for 9 hours. After completion of the reaction, the organic layer was extracted with toluene, washed twice with water, and dried over sodium sulfate. Purification by a silica gel column using hexane as a developing solvent gave 5.13 g (yield 74%) of Compound D as a yellow oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.52 (m, 2H), 0.79 (t, 6H), 1.00-1.20 (m, 22H), 2.05 (t, 4H), 7.34 (d, 1H), 7 40 to 7.53 (m, 2H), 7.63 (m, 3H), 7.83 (d, 1H), 7.94 (d, 1H), 8.31 (d, 1H), 8. 75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 441

(Synthesis of Compound E)

Under an air atmosphere, 4.00 g (9.08 mmol) of Compound D and 57 ml of a mixed solvent of acetic acid: dichloromethane = 1: 1 were placed in a 50 ml three-necked flask, and the mixture was stirred and dissolved at room temperature. Subsequently, while adding 7.79 g (20.0 mmol) of benzyltrimethylammonium tribromide and stirring, zinc chloride was added until benzyltrimethylammonium tribromide was completely dissolved. After stirring at room temperature for 20 hours, the reaction was stopped by adding 10 ml of 5% aqueous sodium bisulfite solution, and the organic layer was extracted with chloroform, washed twice with aqueous potassium carbonate solution, and dried over sodium sulfate. After purification twice with a flash column using hexane as a developing solvent, 4.13 g (yield 76%) of Compound E was obtained as white crystals by recrystallization with ethanol: hexane = 1: 1, followed by a 10: 1 mixed solvent. Got as.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.60 (m, 4H), 0.91 (t, 6H), 1.01-1.38 (m, 20H), 2.09 (t, 4H), 7.62-7.75 (m, 4H), 7.89 (s, 1H), 8.20 (d, 1H), 8.47 (d, 1H), 8.72 (d, 1H)
MS (APPI (+)): M ⁺ 596

<Synthesis of Compound F>

In an argon gas atmosphere, 11.97 g (20.0 mmol) of compound E, 200 mL of commercially available dehydrated tetrahydrofuran, and 200 mL of commercially available dehydrated diethyl ether were charged into a 500 mL three-necked flask and dissolved by stirring at room temperature. While cooling, 12.99 mL (20.0 mmol) of a hexane solution (1.54 mol / L) of n-butyllithium was slowly added dropwise over 30 minutes. After stirring at −78 ° C. for 50 minutes, 4.90 mL (24.0 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl- [1,3,2] dioxaborolane was added dropwise over 15 minutes. After stirring at −78 ° C. for 1 hour, the temperature was raised to room temperature over 1.5 hours, and the reaction mass was dropped into 200 mL of 2N hydrochloric acid at room temperature. After stirring at room temperature for 30 minutes, the oil layer is separated, extracted and separated from the aqueous layer with 40 mL of diethyl ether, and the obtained oil layer is combined, and then distilled water, 5% aqueous sodium hydrogen carbonate solution, distilled water After washing sequentially with, dried over anhydrous sodium sulfate and concentrated to obtain a crude product as a pale yellow oil (15.3 g). The operation of dissolving the obtained oil in tetrahydrofuran and crystallizing it dropwise by adding methanol was repeated three times to obtain 11.0 g (yield 85%) of Compound F as white crystals.
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.40 to 0.60 (m, 4H), 0.80 (t, 6H), 0.90 to 1.20 (m, 20H), 1.45 (s, 12H), 1.94 to 2. 17 (m, 4H), 7.54 to 7.64 (m, 4H), 8.03 (s, 1H), 8.19 (d, 1H), 8.66 (d, 1H), 8.92 (D, 1H)
MS (APPI (+)): M ⁺ 644

<Synthesis of Compound G>

After replacing the 100 mL 4-neck round bottom flask with argon gas, compound E (3.2 g, 5.3 mmol) synthesized in the same manner as in Synthesis Example 2, bispinacolato diboron (3.8 g, 14.8 mmol), PdCl ₂ (dppf ) (0.39 g, 0.45 mmol), bis (diphenylphosphino) ferrocene (0.27 g, 0.45 mmol), potassium acetate (3.1 g, 32 mmol), and 45 ml of dehydrated dioxane were added. In an argon atmosphere, the temperature was raised to 100 ° C. and reacted for 36 hours. After standing to cool, 2 g of Celite was filtered with a precoat and concentrated to obtain a black liquid. Dissolved in 50 g of hexane to remove colored components with activated carbon to obtain 37 g of a pale yellow liquid (Radiolite (made by Showa Kagaku Kogyo Co., Ltd.) 5 g pre-coating was performed during filtration).
6 g of ethyl acetate, 12 g of dehydrated methanol and 2 g of hexane were added and immersed in a dry ice-methanol bath to obtain 2.1 g of colorless crystals of compound G.

Synthesis example 3
<Synthesis of Polymer 1>

Under an argon atmosphere, 10.0 g (15.5 mmol) of compound F, 173.9 mg of palladium acetate, and 435.1 mg of tricyclohexylphosphine were added to a 1 L three-necked flask connected to a Dimroth, and the inside of the container was replaced with argon gas. . To this, 620 ml of toluene and 8.6 g of n-octylbenzene (internal standard substance) were added and stirred at 110 ° C. for 10 minutes. To this monomer solution, 80 ml of a 20 wt% tetraethylammonium hydroxide aqueous solution was added, and the mixture was stirred at 110 ° C. for 16 hours. After confirming the disappearance of Compound F by liquid chromatography, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer. The organic layer was concentrated to about 200 mL, and then added to 1.8 L of ethanol to precipitate the polymer. The precipitate was filtered and dried under reduced pressure to obtain a powder. This powder was dissolved in toluene, passed through a column of silica gel and alumina, and the solution was dried to obtain a powder. This powder was dissolved in chloroform (130 mL) and added dropwise to ethanol (1.5 L) to precipitate a polymer. The precipitate was filtered and dried to obtain 6.4 g of a polymer (hereinafter referred to as polymer 1) (yield 94.1). %)Obtained. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 1.5 × 10 ⁴ and Mw = 3.1 × 10 ⁴ (GPC measurement method B), respectively.
^{1 H-NMR (300MHz / CDCl} 3): δ 0.83 (bs), 1.16 (bs)
2.19 (bs), 7.3 to 9.1 (m), and the integration ratio was (proton derived from alkyl group) / (proton derived from aryl group) = 4.19.

Example 1
<Synthesis of Polymer Compound 1: Step A>

In a 50 mL flask under an argon gas atmosphere, Polymer 1 (400 mg, 0.912 mmol in terms of benzofluorene repeat unit) and 20 mL of chloroform were charged and dissolved by stirring at room temperature, then 1.40 mL of trifluoroacetic acid, bromine 19.6 μL (0.38 mmol, 42 mol% with respect to the benzofluorene unit) was sequentially added and stirred for 16 hours under light shielding. The reaction mass was precipitated by dropwise addition to 200 mL of methanol with stirring. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 405 mg of a polymer. The resulting polymer is referred to as polymer compound 1. The obtained polymer compound 1 has a polystyrene-equivalent number average molecular weight of Mn = 1.5 × 10 ⁴ , a weight average molecular weight of Mw = 3.2 × 10 ⁴ , and a peak top molecular weight of Mp = 3.3 ×. 10 ⁴ , the degree of dispersion was Mw / Mn = 2.1 (GPC measurement method B).
As a result of elemental analysis, the ratio of the repeating unit formula (P-2) having a Br group to the repeating unit formula (P-1) not containing a Br group is (P-1) / (P-2) = 62/38. Yes, (total benzofluorene repeating unit) / Br group = 73/27.
Elemental analysis measurements: C 84.33%, H 8.82%, N <0.3%, Br 6.49%
Elemental analysis calculated values: C 84.55%, H 8.96%, N 0%, Br 6.49% (calculated value at (P-1) / (P-2) = 62/38)
As a result of ¹ H-NMR measurement, the peak derived from the proton of the alkyl group on the high magnetic field side did not change, and the peak derived from the proton of the aryl group on the low magnetic field side changed, and further the alkyl of the aryl group proton A decrease in the integration ratio with respect to the group proton was observed, and it was found that the Br group was introduced into the aromatic ring portion of benzofluorene.
¹ H-NMR (300 MHz / CDCl ₃ ): δ 0.83 (bs), 1.16 (bs), 2.19 (bs), 7.3 to 9.3 (m), integral ratio is (alkyl group (Proton derived from) / (proton derived from aryl group) = 4.40.

<Synthesis of Polymer Compound 2: Step B>

Polymer compound 1 (150 mg, 0.322 mmol in terms of benzofluorene repeating unit), N- (4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) phenyl) -N- (4-t-butyl-2,6-dimethylphenyl) -N-phenylamine (100 mg, 0.22 mmol), palladium (II) acetate (1.23 mg, 0.005 mmol), and tricyclohexylphosphine ( 3.07 mg, 0.011 mmol) was charged into a 50 mL flask and replaced with argon gas, and then 18.6 mL of commercially available dehydrated toluene was charged and dissolved by stirring at room temperature. After heating up to 110 degreeC, the tetraethylammonium hydroxide aqueous solution (1.4 mol / L, 0.49 mL, 0.68 mmol) was prepared, and it stirred at 110 degreeC for 2.5 hours. After cooling to room temperature, 7.5 mL of distilled water was added for washing, and the organic layer was concentrated, dissolved in chloroform, and precipitated by dropping into acetone. The obtained precipitate was filtered, washed with acetone, and dried under reduced pressure to obtain 160 mg of a crude polymer. The number average molecular weight in terms of polystyrene of the obtained crude polymer is Mn = 2.2 × 10 ⁴ , the weight average molecular weight is Mw = 3.8 × 10 ⁴ , and the peak top molecular weight is Mp = 3.7 × 10 ^4. The dispersity was Mw / Mn = 1.8 (GPC measurement method B).
146 mg of the above crude polymer was dissolved in 30 mL of toluene at room temperature, and the solution was passed through a silica gel column and an alumina column through which toluene had been passed in advance. It was re-precipitated by dropping. The precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 145 mg of a polymer. The resulting polymer is referred to as polymer compound 2. The obtained polymer compound 2 has a polystyrene-equivalent number average molecular weight of Mn = 2.0 × 10 ⁴ , a weight average molecular weight of Mw = 3.7 × 10 ⁴ , and a peak top molecular weight of Mp = 3.5 ×. The dispersion degree was 10 ⁴ and Mw / Mn = 1.8 (GPC measurement method B).
As a result of elemental analysis, the ratio of the repeating unit formula (P-1), the repeating unit formula (P-2) having a Br group, and the repeating unit (P-3) having a side chain is (P-1) / (P- 2) / (P-3) = 75/0/25, and the ratio of the benzofluorene repeating unit to the side chain was found to be benzofluorene / side chain = 80/20.
Elemental measurement: C 89.86%, H 9.22%, N 0.68%, Br <0.1%
Calculated value of elemental analysis: C 89.97%, H 9.35%, N 0.68%, Br 0% ((P-1) / (P-2) / (P-3) = 75/0/25 Calculated value at

Synthesis example 4
<Synthesis of polymer 2: condensation polymerization of 2,7-dibromo-9,9-di-n-octylfluorene and 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene>
2,6.3 g of 2,7-dibromo-9,9-di-n-octylfluorene, 5.6 g of 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene and 22 g of 2,2′-bipyridyl were dehydrated. After dissolving in 1600 mL of the resulting tetrahydrofuran, the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (40.66 g) was added to this solution, the temperature was raised to 60 ° C., and the mixture was stirred for 8 hours. Reacted. After the reaction, this reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 1200 mL / methanol 1200 mL / ion-exchanged water 1200 mL, and stirred for 0.5 hour, and then the deposited precipitate was filtered. And then dried under reduced pressure for 2 hours, and then dissolved in 1110 mL of toluene, followed by filtration. Toluene was added to the filtrate to make a solution of about 2800 mL, and then 1 ml of 1N hydrochloric acid was used for 1 hour with 4% aqueous ammonia. The organic layer was washed with 2200 mL for 1 hour, ion-exchanged water 1000 mL for 10 minutes, and ion-exchanged water 1000 mL for 10 minutes. The organic layer was concentrated under reduced pressure to 592 g at 50 ° C., then dropped into 3330 mL of methanol and stirred for 0.5 hour, the deposited precipitate was filtered, washed twice with 500 mL of methanol, And dried under reduced pressure for 5 hours. The yield of the obtained copolymer was 12.6 g. This copolymer is referred to as polymer 2. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 8.4 × 10 ⁴ and Mw = 1.6 × 10 ⁵ (GPC measurement method C), respectively. In the polymer 5, the ratio of the repeating units of 9,9-di-n-octylfluorene and 9,9-bis (3-methylbutyl) fluorene is 80:20.

Example 2
<Synthesis of Polymer Compound 3: Step A>
In an argon gas atmosphere, a 200 mL flask was charged with Polymer 2 (2.00 g, 5.38 mmol in terms of fluorene repeat unit) and 100 mL of chloroform and dissolved by stirring at room temperature. Then, 8.3 mL of trifluoroacetic acid, Bromine 104 μL (2.05 mmol, 38 mol% with respect to the fluorene repeating unit) was sequentially added, and the mixture was stirred for 20 hours in the dark. The reaction mass was precipitated by dropwise addition to 500 mL of methanol with stirring. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 2.17 g of a polymer. The resulting polymer is referred to as polymer compound 3. The number average molecular weight in terms of polystyrene is Mn = 9.2 × 10 ⁴ , the weight average molecular weight is Mw = 1.7 × 10 ⁵ , the peak top molecular weight is Mp = 1.4 × 10 ⁵ , and the dispersity is Mw /Mn=1.90 (GPC measurement method C).
As a result of elemental analysis, the ratio of the combination of repeating units having a Br group (formula P-7) and the combination of repeating units not containing a Br group (formula P-6) is (P-6) / (P-7) = 63/37, and it was found that (total fluorene repeating unit) / Br group = 73/27.
Elemental analysis measured values: C 82.48%, H 9.25%, N <0.3%, Br 7.44%
Elemental analysis calculated values: C 83.21%, H 9.35%, N 0%, Br 7.44% (calculated values at (P-6) / (P-7) = 63/37)

<Synthesis of Polymer Compound 4: Step B>
Polymer Compound 3 300 mg, N- (4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) phenyl) -N- (4-t-butyl-2, 6-Dimethylphenyl) -N-phenylamine 62.0 mg, palladium acetate (II) 0.65 mg, tricyclohexylphosphine 1.58 mg were charged into a 100 mL flask, purged with argon gas, and then 72 mL of commercially available dehydrated toluene was charged at room temperature. And dissolved by stirring. A tetraethylammonium hydroxide aqueous solution (1.4 M) (1.00 mL) was charged, the temperature was raised to 110 ° C., and the mixture was stirred at 110 ° C. for 3 hours. Once heating was stopped, 196.3 mg of 4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) butyltoluene, 0.63 mg of palladium (II) acetate, 1.62 mg of cyclohexylphosphine and 1.00 mL of tetraethylammonium hydroxide aqueous solution (1.4 M) were charged, the temperature was raised again to 110 ° C., and the mixture was stirred for 3 hours. After cooling to room temperature, diluting with 15 mL of toluene, separating the solution, washing twice with 20 mL of 15% brine, and filtering the organic layer obtained with 3 g of radiolite (Showa Kagaku Kogyo Co., Ltd.) And washed with 20 mL of toluene. After concentrating the obtained organic layer, it was precipitated by dripping into acetone. The resulting precipitate was filtered, washed with acetone, and dried under reduced pressure to obtain 278 mg of a crude polymer.
277 mg of the above crude polymer was dissolved in 60 mL of toluene at room temperature, and the solution was passed through a silica gel column and an alumina column that had been preliminarily passed with toluene, and further washed with toluene, followed by washing twice with 3% ammonia water and distilled water. The solution concentrated under reduced pressure was reprecipitated by dropping it into methanol. The precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 259 mg of a polymer.
The resulting polymer is referred to as polymer compound 4. The number average molecular weight in terms of polystyrene is Mn = 9.2 × 10 ⁴ , the weight average molecular weight is Mw = 1.7 × 10 ⁵ , the peak top molecular weight is Mp = 1.4 × 10 ⁵ , and the dispersity is Mw /Mn=1.9 (GPC measurement method C).
The aromatic polymer 5 includes a combination of repeating units represented by the formula (P-6) and a combination of repeating units represented by the formula (P-8), and the ratio thereof is (P-6) / (P- 8) = 94/6.
Elemental analysis measured values: C 89.36%, H 9.92%, N 0.24%, Br <0.1%
Elemental analysis calculated values: C88.71%, H11.05%, N0.24%, Br0% (calculated value at (P-6) / (P-8) = 94/6)

Synthesis example 5
<Synthesis of Polymer 3>
In an argon atmosphere, to a 200 mL flask connected with a Dimroth, 37.7 g (63 mmol) of compound E synthesized in the same manner as in Synthesis Example 2 and 43.6 g (63 mmol) of compound G synthesized in the same manner as in Synthesis Example 6 were added. After dissolving in 70 mL of toluene, degassing was performed by bubbling argon gas. Thereto, 42 mg of palladium acetate and 266 mg of tris (o-methoxyphenyl) phosphine were added, and 283.4 mL of a bis (tetraethylammonium) carbonate aqueous solution (33 wt%) was added dropwise while heating, and the mixture was refluxed for 24 hours. 10.8 g of bromobenzene was added and the mixture was further refluxed for 1 hour, after which 8.9 g of phenylboronic acid was added and the mixture was further refluxed for 1 hour. The oil layer was washed twice with 2N aqueous hydrochloric acid, twice with 10% aqueous acetic acid and twice with water, filtered through Celite, and concentrated under reduced pressure to cause precipitation by dropping into methanol. The obtained solid was collected by filtration, dried under reduced pressure, then dissolved again in toluene, reprecipitated in methanol, and dried under reduced pressure twice to obtain 22.4 g of a polymer (hereinafter referred to as polymer 3). Got. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 7.3 × 10 ⁴ and Mw = 1.8 × 10 ⁵ (GPC measurement method C).

Example 3
<Synthesis of Polymer Compound 5: Step A>
In a 500 mL flask under an argon gas atmosphere, Polymer 3 (5.00 g, 11.4 mmol in terms of benzofluorene repeating unit) and 150 mL of chloroform were charged and dissolved by stirring at room temperature, and then 17.6 mL of trifluoroacetic acid. Then, 236 μL of bromine (4.6 mmol, 40 mol% with respect to the benzofluorene unit) was sequentially added and stirred for 24 hours under light shielding. The reaction mass was precipitated by dropwise addition to 1250 mL of methanol with stirring. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 5.29 g of a polymer. The resulting polymer is referred to as polymer compound 5. The number average molecular weight in terms of polystyrene is Mn = 7.5 × 10 ⁴ , the weight average molecular weight is Mw = 1.6 × 10 ⁵ , the peak top molecular weight is Mp = 1.2 × 10 ⁵ , and the dispersity is Mw /Mn=2.1 (GPC measurement method C).
As a result of elemental analysis, the ratio of the repeating unit having a Br group (formula P-2) to the repeating unit not containing a Br group (formula P-1) is (P-1) / (P-2) = 61/39. Yes, (total benzofluorene repeating unit) / Br group = 72/28.
Elemental analysis measured values: C 84.93%, H 9.06%, N <0.3%, Br 6.57%
Elemental analysis calculated values: C84.48%, H8.94%, N0%, Br6.57% (calculated value at (P-1) / (P-2) = 61/39)

<Synthesis of Polymer Compound 6: Step B>
Polymer Compound 5 600 mg, N- (4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) phenyl) -N- (4-t-butyl-2, 6-dimethylphenyl) -N-phenylamine 147 mg, palladium (II) acetate 0.96 mg, tricyclohexylphosphine 2.40 mg were charged into a 100 mL flask, and replaced with argon gas, and then commercially available dehydrated toluene 72 mL was charged at room temperature. Stir to dissolve. After raising the temperature to 110 ° C., 1.55 mL of an aqueous tetraethylammonium hydroxide solution (1.4 M) was added, and the mixture was stirred at 110 ° C. for 3 hours. Once the heating was stopped, 336 mg of 4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) butylbenzene, 1.00 mg of palladium (II) acetate, tricyclohexylphosphine 2.43 mg and an aqueous tetraethylammonium hydroxide solution (1.4 M) (1.55 mL) were charged, the temperature was raised to 110 ° C., and the mixture was stirred for 3 hours. After cooling to room temperature, diluting with 30 mL of toluene, separating the solution, washing twice with 36 mL of 15% brine, and filtering the organic layer with 6 g of radiolite (Showa Kagaku Kogyo Co., Ltd.) And washed with 36 mL of toluene. After concentrating the obtained organic layer, it was precipitated by dripping into acetone. The resulting precipitate was filtered, washed with acetone, and dried under reduced pressure to obtain 630 mg of a crude polymer.
630 mg of the above crude polymer was dissolved in 130 mL of toluene at room temperature, and the solution was passed through a silica gel column and an alumina column that had been previously passed through toluene, and further washed out with toluene, followed by washing twice with 3% ammonia water and distilled water. The solution concentrated under reduced pressure was dropped into methanol to reprecipitate. The precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 627 mg of a polymer.
The resulting polymer is referred to as polymer compound 6. The number average molecular weight in terms of polystyrene is Mn = 8.3 × 10 ⁴ , the weight average molecular weight is Mw = 1.6 × 10 ⁵ , the peak top molecular weight is Mp = 1.3 × 10 ⁵ , and the dispersity is Mw /Mn=1.9 (GPC measurement method C).
As a result of elemental analysis, the ratio of the repeating unit (formula P-1), the repeating unit having a Br group (formula P-2), and the repeating unit having a substituent (P-3) is (P-1) / (P- 2) / (P-3) = 82/0/18, and the ratio of the benzofluorene repeating unit to the substituent was found to be benzofluorene / side chain = 85/15.
Elemental analysis measured values: C 90.46%, H 9.18%, N 0.49%, Br <0.1%
Elemental analysis calculated values: C90.08%, H9.43%, N0.49%, Br0% ((P-1) / (P-2) / (P-3) = calculated value at 82/0/18) )

Synthesis Example 6
<Synthesis of Compound I>
(Synthesis of Compound H)
Under an argon gas atmosphere, 9H-carbazole 6.63 g (40.0 mmol), palladium (II) acetate 0.09 g (0.4 mmol), potassium carbonate 16.5 g (119 mmol), 4-trimethylsilylbromobenzene 10.0 g (43 6 mmol), the temperature was raised to 120 ° C., and the mixture was stirred for 12 hours. On the way, at 3, 6, and 9 hours, 1.0 g of 4-trimethylsilylbromobenzene was additionally charged. The reaction mass was diluted with xylene, washed with distilled water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, recrystallized from chloroform-methanol, recrystallized from ethyl acetate-methanol, and 5.25 g of compound H ( Yield 41%) was obtained as light gray crystals.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm) 0.35 (s, 9H), 7.23-7.29 (m, 2H), 7.35-7.45 (m, 4H), 7 .53 (d, J = 8.0Hz, 2H), 7.72 (d, J = 8.0Hz, 2H), 8.12 (d, J = 7.7Hz, 2H)

(Synthesis of Compound I)
Under an argon gas atmosphere, a solution obtained by dissolving 5.00 g (15.9 mmol) of Compound H in 100 mL of dichloromethane was cooled to 0 ° C., and 32.0 mL of boron tribromide in dichloromethane (1.0 M) was added over 20 minutes. And dripped. After stirring at 0 ° C. for 3.5 hours, the solvent was distilled off under reduced pressure. After adding 160 mL of ethyl acetate and 6.74 g of pinacol and stirring for 1 hour at room temperature, the mixture was washed with distilled water, 5% aqueous sodium hydrogen carbonate solution and distilled water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. In addition, a solid was precipitated, collected by filtration, and dried under reduced pressure to obtain 5.0 g of Compound I.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm) 1.39 (s, 12H), 7.24-7.30 (m, 2H), 7.36-7.46 (m, 4H), 7 58 (d, J = 8.2Hz, 2H), 8.05 (d, J = 8.2Hz, 2H), 8.12 (d, J = 7.8Hz, 2H)

Example 4
<Synthesis of Polymer Compound 7: Step B>
Polymer compound 5 300 mg, Compound I 55.5 mg, Palladium (II) acetate 0.55 mg, Tricyclohexylphosphine 1.38 mg were charged into a 100 mL flask and purged with argon gas, and then commercial dehydrated toluene 36 mL was charged at room temperature. Stir to dissolve. After raising the temperature to 110 ° C., 0.88 mL of an aqueous tetraethylammonium hydroxide solution (1.4 M) was added, and the mixture was stirred at 110 ° C. for 3 hours. Once the heating was stopped, 167 mg of 4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) butylbenzene, 0.55 mg of palladium (II) acetate, tricyclohexylphosphine 1.40 mg and tetraethylammonium hydroxide aqueous solution (1.4 M) 0.88 mL were charged, the temperature was raised to 110 ° C., and the mixture was stirred for 3 hours. After cooling to room temperature, diluting with 15 mL of toluene, separating the solution, washing twice with 20 mL of 15% brine, and filtering the organic layer obtained with 3 g of radiolite (Showa Kagaku Kogyo Co., Ltd.) And washed with 20 mL of toluene. After concentrating the obtained organic layer, it was precipitated by dripping into acetone. The resulting precipitate was filtered, washed with acetone, and dried under reduced pressure to obtain 309 mg of a crude polymer.
309 mg of the above crude polymer was dissolved in 60 mL of toluene at room temperature, and the solution was passed through a silica gel column and an alumina column that had been preliminarily passed with toluene, and further washed with toluene, and then washed twice with 3% ammonia water and distilled water. The solution concentrated under reduced pressure was reprecipitated by dropping it into methanol. The precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 293 mg of a polymer.
The resulting polymer is referred to as polymer compound 7. The number average molecular weight in terms of polystyrene is Mn = 8.7 × 10 ⁴ , the weight average molecular weight is Mw = 1.8 × 10 ⁵ , the peak top molecular weight is Mp = 1.4 × 10 ⁵ , and the dispersity is Mw /Mn=2.1 (GPC measurement method C).
As a result of elemental analysis, the ratio of the repeating unit (formula P-1), the repeating unit having a Br group (formula P-2), and the repeating unit having a substituent (P-4) is (P-1) / (P- 2) / (P-4) = 83/0/17, and the ratio of the benzofluorene repeating unit to the substituent was found to be benzofluorene / side chain = 86/14.
Elemental analysis measured values: C 89.49%, H 9.00%, N 0.50%, Br <0.1%
Elemental analysis calculated values: C90.28%, H9.22%, N0.50%, Br0% ((P-1) / (P-2) / (P-4) = calculated value at 83/0/17) )

Example 5
<Synthesis of Polymer Compound 8: Step B>
Polymer compound 5 300 mg, Compound N 791 mg, Palladium (II) acetate 3.9 mg, Tricyclohexylphosphine 9.8 mg were charged into a 100 mL flask, purged with argon gas, charged with 36 mL of commercially available dehydrated toluene, and stirred at room temperature. And dissolved. An aqueous solution of tetraethylammonium hydroxide (1.4 M) (6.2 mL) was charged, the temperature was raised to 110 ° C., and the mixture was stirred at 110 ° C. for 3 hours. Once the heating was stopped, 4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) butylbenzene 166 mg, palladium (II) acetate 3.88 mg, tricyclohexylphosphine 9.69 mg and tetraethylammonium hydroxide aqueous solution (1.4 M) 1.2 mL were charged, the temperature was raised again to 110 ° C., and the mixture was stirred for 3 hours. After cooling to room temperature, diluting with 15 mL of toluene, separating the solution, washing twice with 15 mL of 15% saline, and filtering the organic layer obtained with 3 g of radiolite (Showa Kagaku Kogyo Co., Ltd.) And washed with 18 mL of toluene. After concentrating the obtained organic layer, it was precipitated by dripping into acetone. The resulting precipitate was filtered, washed with acetone, and dried under reduced pressure to obtain 730 mg of a crude polymer.
Dissolve 728 mg of the above crude polymer in 140 mL of toluene at room temperature, pass the solution through a silica gel column and an alumina column previously passed through toluene, wash out with toluene, and then drop the solution concentrated under reduced pressure into acetone. Re-sinked. The precipitate was filtered, washed with acetone, and dried under reduced pressure to obtain 705 mg of a polymer.
The resulting polymer is referred to as polymer compound 8. The number average molecular weight in terms of polystyrene is Mn = 4.2 × 10 ⁴ , the weight average molecular weight is Mw = 1.8 × 10 ⁵ , the peak top molecular weight is Mp = 1.6 × 10 ⁵ , and the dispersity is Mw /Mn=4.4 (GPC measurement method C).
From the results of elemental analysis, the polymer compound 8 is composed of a repeating unit (formula P-1) and a repeating unit having a side chain (P-5), and the side chain length thereof is a triphenylamine derivative repeating unit (the following formula (P -5) is equivalent to a 4.1-mer, and the ratio is (P-1) / (P-5) = 61/39, and the benzofluorene repeating unit and the triphenylamine derivative repeating unit The ratio was found to be benzofluorene / side chain = 38/62.
Elemental analysis measured values: C88.57%, H8.57%, N2.32%, Br <0.1%
Elemental analysis calculated values: C 88.94%, H 8.74%, N 2.32%, Br 0% (calculated value at (P-1) / (P-5) = 61/39)

Synthesis example 7
<Synthesis of Compound L>
(Synthesis of Compound L-1)

Compound L-1
Benzofuran (23.2 g, 137.9 mmol) and acetic acid (232 g) were placed in a 1 l three-necked flask under an inert atmosphere, stirred and dissolved at room temperature, and then heated to 75 ° C. After heating, broth (92.6 g, 579.3 mmol) diluted with acetic acid (54 g) was added dropwise. After completion of the dropwise addition, the mixture was stirred for 3 hours while maintaining the temperature and allowed to cool. After confirming disappearance of the raw material by TLC, sodium thiosulfate water was added to terminate the reaction, and the mixture was stirred at room temperature for 1 hour. After stirring, the mixture was filtered to separate the cake, further washed with aqueous sodium thiosulfate and water, and dried. The obtained crude product was recrystallized from hexane to obtain the desired product. (Yield: 21.8 g, Yield: 49%)
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.44 (d, 2H), 7.57 (d, 2H), 8.03 (s, 2H)

(Synthesis of Compound L-2)

Compound L-2
Under an inert atmosphere, Compound L-1 (16.6 g, 50.9 mmol) and tetrahydrofuran (293 g) were placed in a 500 ml four-necked flask and cooled to -78 ° C. n-Butyllithium (80 ml <1.6 molar hexane solution>, 127.3 mmol) was added dropwise, and the mixture was stirred for 1 hour while maintaining the temperature. This reaction solution was added dropwise to a 1000 ml four-necked flask in an inert atmosphere with trimethoxyboronic acid (31.7 g, 305.5 mmol) and tetrahydrofuran (250 ml) cooled to -78 ° C. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and after stirring at room temperature for 2 hours, disappearance of the raw material was confirmed by TLC. The reaction completed mass was poured into a 2000 ml beaker containing concentrated sulfuric acid (30 g) and water (600 ml) to terminate the reaction. Toluene (300 ml) was added, the organic layer was extracted, and further washed with water. After distilling off the solvent, 8 g of the mixture and ethyl acetate (160 ml) were placed in a 300 ml four-necked flask, followed by addition of 30% aqueous hydrogen peroxide (7.09 g) and stirring at 40 ° C. for 2 hours. This reaction solution was poured into an aqueous solution of ammonium iron (II) sulfate (71 g) and water (500 ml) in a 1000 ml beaker. After stirring, the organic layer was extracted, and the organic layer was washed with water. By removing the solvent, 6.72 g of a crude compound L-2 was obtained.
MS spectrum: M ⁺ 20.0.

(Synthesis of Compound L-3)

Compound L-3
Compound L-2 (2.28 g, 11.4 mmol) synthesized in the same manner as above and N, N-dimethylformamide (23 g) were placed in a 200 ml four-necked flask under an inert atmosphere and stirred at room temperature. After dissolution, potassium carbonate (9.45 g, 68.3 mmol) was added and the temperature was raised to 60 ° C. After heating, n-octyl bromide (6.60 g, 34.2 mmol) diluted with N, N-dimethylformamide (11 g) was added dropwise. After completion of the dropwise addition, the temperature was raised to 60 ° C., and the mixture was stirred for 2 hours while maintaining the temperature. Water (20 ml) was added to terminate the reaction, followed by addition of toluene (20 ml) to extract the organic layer, and the organic layer was washed twice with water. After drying over anhydrous sodium sulfate, the solvent was distilled off. The obtained crude product was purified by a silica gel column to obtain the desired product. (Yield: 1.84 g, Yield: 38%)
MS spectrum: M ⁺ 425.3.

(Synthesis of Compound L)

Compound L
Compound L-3 (7.50 g, 17.7 mmol) synthesized in the same manner as described above and N, N-dimethylformamide were placed in a 500 ml four-necked flask under an inert atmosphere, and the mixture was stirred and dissolved at room temperature. Cooled in bath. After cooling, a solution prepared by diluting N-bromosuccinimide (6.38 g, 35.9 mmol) with N, N-dimethylformamide (225 ml) was added dropwise. After completion of the dropwise addition, the mixture was heated to 40 ° C. for 1 hour in an ice bath, 18.5 hours at room temperature, stirred for 6.5 hours while maintaining the temperature, and disappearance of the raw materials was confirmed by liquid chromatography. The solvent was removed, toluene (75 ml) was added and dissolved, and the organic layer was washed 3 times with water. After drying over anhydrous sodium sulfate, the solvent was distilled off. About half of the resulting crude product was purified by silica gel column and liquid chromatography fractionation to obtain the desired product. (Yield: 0.326g)
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.95 (m, 24H), 4.11 (t, 4H), 7.34 (s, 2H), 7.74 (s, 2H)
MS spectrum: M ⁺ 582.1.

Synthesis example 8
<Synthesis of Polymer 4>
Under a nitrogen atmosphere, 0.18 g of 3,8-dibromodibenzofuran, 0.719 g of compound L, and 0.578 g of 2,2′-bipyridyl were dissolved in 30 g of dehydrated tetrahydrofuran, and the temperature was raised to 60 ° C. To this solution, 1.040 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added and reacted at 60 ° C. for 3 hours. After the reaction, this reaction solution was cooled to room temperature, dropped into a mixed solution of 25 g ammonia water 9 g / methanol 95 g / ion exchanged water 50 g and stirred for 30 minutes, and then the deposited precipitate was filtered and dried under reduced pressure for 2 hours. And dissolved in 30 ml of toluene. After adding 30 g of 1N hydrochloric acid and stirring for 3 hours, the aqueous layer was removed. Next, 30 g of 4% aqueous ammonia was added to the organic layer and stirred for 3 hours, and then the aqueous layer was removed. Subsequently, the organic layer was dropped into 200 mL of methanol and stirred for 30 minutes, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 30 mL of toluene. Then, it refine | purified through the alumina column (alumina amount 10g), and the collect | recovered toluene solution was dripped at methanol 200mL, it stirred for 30 minutes, the depositing precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained polymer was 0.456 g. This polymer is referred to as polymer 4. The number average molecular weight in terms of polystyrene was Mn = 1.3 × 10 ⁵ , and the weight average molecular weight was Mw = 4.6 × 10 ⁵ (GPC measurement method A).
Polymer 4 contains dibenzofuran repeating units represented by formulas (P-9) and (P-10), and the ratio estimated from the charging ratio is (P-9) / (P-10) = 80/20 is there.

Example 6
<Synthesis of Polymer Compound 9: Step A>
In a 20 mL flask under argon gas atmosphere, Polymer 7 (150 mg, 0.404 mmol in terms of dibenzofuran repeating unit) and 8 mL of chloroform were charged, dissolved by stirring at room temperature, and then 0.6 mL of trifluoroacetic acid and 1 mL of chloroform. Then, a solution diluted with 5.2 μL of bromine (0.10 mmol, 25 mol% with respect to the dibenzofuran repeating unit) was sequentially added and stirred for 20 hours in the dark. The reaction mass was precipitated by dropwise addition to 38 mL of methanol with stirring. The resulting precipitate was filtered, washed with methanol, dried under reduced pressure for 2 hours, and then dissolved in 25 mL of toluene. The solution was passed through a silica gel column and an alumina column through which toluene was passed in advance, and after washing with toluene, the solution concentrated under reduced pressure was dropped into methanol to reprecipitate. The precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 152 mg of a polymer. This polymer is called synthesis of polymer compound 9. The number average molecular weight in terms of polystyrene is Mn = 1.5 × 10 ⁵ , the weight average molecular weight is Mw = 3.8 × 10 ⁵ , the peak top molecular weight is Mp = 3.7 × 10 ⁵ , and the dispersity is Mw /Mn=2.6 (GPC measurement method C).
The polymer compound 9 is considered to contain dibenzofuran repeating units represented by the formulas (P-9), (P-10), (P-9b), and (P-11).
Of the repeating unit having the Br group (formula P-9b), (formula P-11) and the repeating unit not containing the Br group (formula P-9), (formula P-10), which is inferred from the results of elemental analysis The ratio is {(formula P-9) + (formula P-10)} / {(formula P-9b) + (formula P-11)} = 77/23, (all dibenzofuran repeating units) / Br group = It corresponds to 81/19.
Elemental measurement: C75.46%, H7.93%, N <0.3%, Br4.67%
Elemental analysis calculated values: C76.52%, H8.12%, N0%, Br4.67% ({(Formula P-9) + (Formula P-10)} / {(Formula P-9b) + (Formula P) −11)} = calculated value at 77/23)

<Synthesis of Polymer Compound 10: Step B>
Aliquot 336 40 mg, polymer compound 980 mg, compound I 15.3 mg were charged into a 25 mL flask and purged with argon gas. Then, 36 mL of commercially available dehydrated toluene was charged and dissolved by stirring at room temperature. After degassing by bubbling argon gas into the solution, the temperature was raised to 80 ° C. Palladium (II) acetate (0.30 mg) and tris (o-methoxyphenyl) phosphine (1.91 mg) were added, and further sodium carbonate aqueous solution (17.5 wt%) (0.41 mL) was added. It heated up to 105 degreeC and stirred for 3 hours. Once the heating was stopped, 42 mg of 4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) butyltoluene was charged, and the temperature was raised to 105 ° C. again for 2 hours. Stir. The aqueous layer was separated and removed, and then washed twice with ion-exchanged water, twice with 3% aqueous acetic acid and twice with ion-exchanged water, and precipitated by dropping into methanol. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 93 mg of a crude polymer.
90 mg of the above crude polymer was dissolved in 6 mL of toluene at room temperature, and the solution was passed through a silica gel column and an alumina column through which toluene was passed in advance. The solution was further washed out with toluene, and then reprecipitated by dropping into methanol. The precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 63 mg of a polymer.
The resulting polymer is referred to as polymer compound 10. The number average molecular weight in terms of polystyrene is Mn = 1.5 × 10 ⁵ , the weight average molecular weight is Mw = 4.7 × 10 ⁵ , the peak top molecular weight is Mp = 3.7 × 10 ⁵ , and the dispersity is Mw /Mn=3.1 (GPC measurement method C).
The polymer compound 10 is considered to contain dibenzofuran repeating units represented by the formulas (P-9), (P-10), (P-9c), and (P-12).
From the results of elemental analysis, the ratio of the repeating units (Formula P-9) and (Formula P-10) to the repeating units having a substituent (Formula P-9c) and (Formula P-12) is {(Formula P-9). ) + (Formula P-10)} / {(Formula P-9c) + (Formula P-12)} = 92/8, which corresponds to (all dibenzofuran repeating units) / carbazole substituent = 93/7.
Elemental analysis measured values: C 78.90%, H 7.90%, N 0.27%
Elemental analysis calculated values: C80.64%, H8.41%, N0.27% ({(Formula P-9) + (Formula P-10)} / {(Formula P-9c) + (Formula P-12)) } = Calculated value at 92/8)

Reference example 1
Preparation of Solution The polymer compound 2 obtained above was dissolved in toluene to prepare a toluene solution having a polymer concentration of 2.0% by weight.
Fabrication of an electronic single element A layer of about 500 nm of aluminum was formed by vapor deposition on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering. In addition, aluminum was made into the electrode pattern shape with the vapor deposition mask. In a nitrogen gas atmosphere, a film was formed on the obtained aluminum electrode substrate at a rotational speed of 2600 rpm by spin coating using the toluene solution obtained above. 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 electronic single device. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
Production of a single hole element A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) is placed on a glass substrate on which an ITO film is formed with a thickness of 150 nm by sputtering. 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, using the toluene solution obtained above, a film was formed by spin coating at a rotational speed of 2600 rpm. The film thickness after film formation was about 78 nm. Furthermore, after drying this at 80 degreeC under pressure reduction for 1 hour, gold | metal | money was vapor-deposited 200 nm and the hall | hole single element was produced. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
Voltage-current characteristic measurement About the electronic single element and the hall single element obtained above, using a Hewlett-Packard Picoampere meter and a DC power supply (model number: 4140B), in the range of 0V to 12V, 0.2V step. A voltage was applied, and the current value flowing through the device at that time was recorded. Note that, in each of these carrier single elements, in the relatively low voltage region, the electrons are substantially independent from the relative relationship between the work function of the metal used for the anode and cathode of each element and the HOMO and LUMO of the light emitting material. The element may be regarded as electrons only, and the hole-only element may be regarded as only holes flowing in the element. The measurement results are shown in FIG.

Reference example 2
Preparation of Solution The polymer compound 2 obtained above was dissolved in toluene 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) is 0.2 μm on a glass substrate on which an ITO film is formed with a thickness of 150 nm by sputtering. A thin film having a thickness of 70 nm was formed by spin coating using the liquid filtered through a membrane filter, 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 2600 rpm. 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 device performance By applying a voltage to the obtained device, EL light emission having a peak at 460 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 = 0.217 and y = 0.324. The intensity of EL emission was almost proportional to the current density. The device started to emit light from 4.2 V, and the maximum light emission efficiency was 0.29 cd / A. The voltage (V) -current (I) characteristics obtained by the measurement are shown in FIG.

The measurement result of the voltage-current characteristic of an electronic single element, a hole single element, and an EL element is shown.

Claims (14)

The manufacturing method of the high molecular compound characterized by including the following process (A) and process (B).
(A) General formula (1)
-Ar ^1- (1)
(In the formula, Ar ¹ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group having at least one C—H bond on the aromatic ring.)
A polymer compound containing a repeating unit represented by formula (2) is used as a raw material, and the C—H bond on the aromatic ring is converted to give a general formula (2)

(In the formula, X represents a characteristic group, Ar ² represents an n + 2 valent arylene group in which n of C—H bonds on the aromatic ring of Ar ¹ are converted to C—X bonds, and an n + 2 valent heterocyclic ring. Group or an n + 2-valent aromatic amine group, and n represents an integer of 1 to 4.)
The process of manufacturing the high molecular compound (henceforth the high molecular compound which has the characteristic group X) containing the repeating unit which has the characteristic group X shown by these.
(B) A step of reacting the polymer compound having the characteristic group X produced in the step (A) with a compound having the characteristic group Y that reacts with the characteristic group X to form a bond.   In the step (A), the C—H bond conversion reaction on the aromatic ring is an aromatic electrophilic substitution reaction, and the characteristic group X is introduced from the aromatic electrophilic substitution reaction or derived therefrom. The method according to claim 1, which is a characteristic group.   In the step (A), the conversion reaction of the C—H bond on the aromatic ring is carried out by halogenation, nitration, Friedel-Crafts alkylation, halomethylation, Friedel-Crafts acylation, Guttermann aldehyde synthesis, and Vilsmeier. The method according to claim 1 or 2, which is an aromatic electrophilic substitution reaction selected from the group consisting of formylation. The characteristic group X is a halogen atom, —OSO ₂ Q ¹ , —B (OQ ² ) ₂ , —Sn (Q ³ ) ₃ , Z ¹ (Z) m, —OH, —CH ₂ Z ³ , —CHQ ^4. A characteristic group selected from the group consisting of —P ⁺ (Q ⁵ ) ₃ Z ⁴ , —CHQ ⁶ —P (═O) (OQ ⁷ ) ₂ , and —C (═O) Q ⁸ (wherein Q ¹ is a hydrocarbon group, Q ² is a hydrogen atom, or a hydrocarbon group, two Q ² is may be the same or different and may .Q ³ be bonded to each other to form a ring carbide Three Q ³ may be the same or different, Q ⁴ is a hydrogen atom or a hydrocarbon group, Q ⁵ is a hydrocarbon group, and three Q ⁵ are the same or different from each other. Q ⁶ is a hydrogen atom or a hydrocarbon group, Q ⁷ is a hydrocarbon group, and two Q ⁷ are the same Q ⁸ is a hydrogen atom or a hydrocarbon group, Z ¹ is a metal atom or a metal ion, Z ² is a counter anion, and m is an integer of 0 or more. The method according to any one of claims 1 to 3, wherein Z ³ represents a halogen atom or a cyano group, and Z ⁴ represents a monovalent counter anion.   The method according to claim 1, wherein in the step (A), the conversion reaction of the C—H bond on the aromatic ring is a halogenation reaction. The characteristic group X is selected from the group consisting of a halogen atom, —OSO ₂ Q ¹ , —B (OQ ² ) ₂ , —Sn (Q ³ ) ₃ , Z ¹ (Z ² ) m, and —CHO. The method according to claim ¹ , wherein Q ¹ , Q ² , Q ³ , Z ¹ , Z ² , and m have the same meaning as described above. In the said process (B), 1 or more types chosen from the compound represented by the following general formula (3) and (4) are used as a compound which has the characteristic group Y, Any one of Claims 1-6. The method described in 1.
Y-GA ¹ (3)
(In the formula, Y represents the same meaning as described above, G represents a C _{1 to} C ₂₀ alkyl chain which may have a direct bond or a linear or branched structure and may contain a cyclic structure, and A ¹ represents Represents a monovalent organic group and does not have a characteristic group that reacts with the characteristic groups X and Y to form a bond in the organic group.)
^{Y-G-A 2 -X 2} (4)
(Wherein Y and G each have the same meaning as described above, X ² represents a characteristic group that reacts with the characteristic group Y to form a bond, and the definition is the same as the definition of X. X and X ² may be the same or different, A ² represents a divalent organic group, and a characteristic group that reacts substantially with the characteristic groups X, Y, and X ² to form a bond in the organic group. (Represents something you do not have.)   In the said process (B), 1 or more types of compounds represented by said Formula (4) are used, and also 1 or more types of compounds represented by said Formula (3) are used. The method according to item. The characteristic group Y is a halogen _{^{atom, -OSO 2 Q 1, -B (}} OQ 2) 2, -Sn (Q 3) 3, Z 1 (Z 2) m, -OH, -CH 2 Z 3, -CHQ _{^{4 -P + (Q 5) 3}} Z 4, -CHQ 6 -P (= O) (OQ 7) 2, -C (= O) Q 8, -CHQ 9 = CHQ 10, -C≡CH, -NHQ ¹¹ and a group selected from the group consisting of —SH (Q ¹ , Q ² , Q ³ , Q ⁴ , Q ⁵ , Q ⁶ , Q ⁷ , Q ⁸ , Z ¹ , Z ² , Z ³ , Z ⁴ , The method according to claim 1, wherein m represents the same meaning as described above, and Q ⁹ , Q ¹⁰ , and Q ¹¹ are a hydrogen atom or a hydrocarbon group. The characteristic group Y is a halogen atom, —OSO ₂ Q ¹ , —B (OQ ² ) ₂ , —Sn (Q ³ ) ₃ , Z ¹ (Z ² ) m, —OH, —CHQ ⁴ —P ⁺ (Q _{^{5) 3 Z 4, -CHQ 6}} -P (= O) (OQ 7) 2, -CHQ 9 = CHQ 10, -C≡CH, characteristic group selected from the group consisting of -NHQ ^11, and -SH (Q ¹ , Q ² , Q ³ , Q ⁴ , Q ⁵ , Q ⁶ , Q ⁷ , Q ⁹ , Q ¹⁰ , Q ¹¹ , Z ¹ , Z ² , Z ³ , Z ⁴ , and m have the same meaning as described above. 10. The method according to any one of claims 1 to 9, wherein The characteristic group Y is a characteristic group (Q ¹ selected from the group consisting of a halogen atom, —OSO ₂ Q ¹ , —B (OQ ² ) ₂ , —Sn (Q ³ ) ₃ , and Z ¹ (Z ² ) m. , Q ² , Q ³ , Z ¹ , Z ² , and m have the same meanings as described above.) The method according to claim 1. In the step (B), the combination of the characteristic groups X and characteristic group Y is a halogen atom and _{^{-B (OQ 2) 2 (Q}} 2 represents. As defined above) is a combination of, claims 1 to 11 The method according to any one of the above.   The production method according to any one of claims 1 to 12, wherein the polymer compound containing the repeating unit represented by the formula (1) is a conjugated polymer compound. The process according to any one of conjugated claims 1 to 13 number average molecular weight in terms of polystyrene of the polymer compound is 10 ³ to 10 ⁸ in claim 13.