JP2007211237A - Block copolymer - Google Patents

Abstract

（式（1）において、Ａｒは共役系の二価の基を表し、同一ブロック内では同じ二価の基を表し、ｍは１つのブロックに存在するＡｒの数平均重合度を表し１以上の数を表す。）
該共重合体に複数存在するｍのうち少なくとも２つは５以上の数を表し、該共重合体の、隣り合う２つのブロックにおけるＡｒは互いに異なり、該共重合体は、前記式（１）で表されるブロック２つからなる場合は二種類のＡｒを有し、前記式（１）で表されるブロック３つからなる場合は二種類以上のＡｒを有し、前記式（１）で表されるブロック４つ以上からなる場合は四種類以上のＡｒを有することを特徴とするブロック共重合体。
【選択図】なしA copolymer capable of providing an electronic device having excellent device performance when used as a material for an electronic device.
A block copolymer comprising two or more blocks represented by the following formula (1):

(In the formula (1), Ar represents a conjugated divalent group, represents the same divalent group in the same block, m represents the number average degree of polymerization of Ar present in one block, Represents a number.)
At least two of m present in the copolymer represent a number of 5 or more, Ar in two adjacent blocks of the copolymer are different from each other, and the copolymer is represented by the formula (1) In the case of consisting of two blocks represented by the formula (1), two types of Ar are contained. A block copolymer comprising four or more types of Ar when the block consists of four or more blocks.
[Selection figure] None

Description

  The present invention relates to a block copolymer.

Various studies have been made on high-molecular-weight light-emitting materials and charge transport materials that are soluble in a solvent because an organic layer in a light-emitting element can be formed by a coating method. For example, random copolymers such as polyfluorenes are known as polymer compounds that can be used as light emitting materials and charge transport materials in electronic devices such as polymer light emitting devices (polymer LEDs). (Patent Document 1, Non-Patent Document 1).
JP2001-151868 Monthly Display, 2000, September, 26-32 pages

However, the device performance of the device using the random copolymer as a light emitting material, a charge transporting material or the like has not yet been practically satisfactory.
An object of the present invention is to provide a copolymer capable of providing an electronic device having excellent device performance when used as a material for an electronic device.

（式（1）において、Ａｒは共役系の二価の基を表し、同一ブロック内では同じ二価の基を表し、ｍは１つのブロックに存在するＡｒの数平均重合度を表し１以上の数を表す。）
該共重合体に複数存在するｍのうち少なくとも２つは５以上の数を表し、該共重合体の、隣り合う２つのブロックにおけるＡｒは互いに異なり、該共重合体は、前記式（１）で表されるブロック２つからなる場合は二種類のＡｒを有し、前記式（１）で表されるブロック３つからなる場合は二種類以上のＡｒを有し、前記式（１）で表されるブロック４つ以上からなる場合は四種類以上のＡｒを有することを特徴とするブロック共重合体を提供するものである。 That is, the present invention is a block copolymer comprising two or more blocks represented by the following formula (1),

(In the formula (1), Ar represents a conjugated divalent group, represents the same divalent group in the same block, m represents the number average degree of polymerization of Ar present in one block, Represents a number.)
At least two of m present in the copolymer represent a number of 5 or more, Ar in two adjacent blocks of the copolymer are different from each other, and the copolymer is represented by the formula (1) In the case of consisting of two blocks represented by the formula (1), two types of Ar are contained. In the case of comprising three blocks of the formula (1), two or more types of Ar are contained, and in the formula (1), In the case of comprising four or more represented blocks, the present invention provides a block copolymer characterized by having four or more types of Ar.

The block copolymer of the present invention is useful as a light emitting material and a charge transport material, and is excellent in device performance. Therefore, the polymer LED containing the block copolymer of the present invention can be used for a curved or flat light source, a segment type display element, a dot matrix flat panel display, etc. for backlight or illumination of a liquid crystal display. . Moreover, it can also be used as a photoelectric conversion material such as a polymer electrolyte membrane for fuel cells and a solar cell.

The block copolymer of the present invention comprises two or more blocks represented by the formula (1).

In the formula (1), each Ar independently represents a conjugated divalent group. Ar represents a structural unit in one block.

The conjugated divalent group is a divalent group in which electrons of a bond in the molecule are delocalized, and specifically, a group represented by the following formula (2) is preferable.

（２）

（式（２）において、Ａ¹，Ａ²，Ａ³，Ａ⁴およびＡ⁵はそれぞれ独立に置換されていてもよいアリーレン基または二価の複素環基を表す。Ｂ¹, Ｂ²,Ｂ³およびＢ⁴はそれぞれ独立に、−ＢＲ¹−、−ＮＲ²−、−ＳｉＲ³Ｒ⁴−、−ＰＲ⁵−、−Ｃ≡Ｃ−、−ＣＲ^b＝ＮＲ^b−または置換基を有していてもよいビニレン基を表す。Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ^bはそれぞれ独立に水素原子または置換基を表す。ａ¹, ａ², ａ³, ａ⁴およびａ⁵はそれぞれ独立に０から３の整数を表し、かつ１≦ａ¹＋ａ²＋ａ³＋ａ⁴＋ａ⁵≦１５を満たす整数を表す。ｂ¹, ｂ²,ｂ³およびｂ⁴はそれぞれ独立に０または１を表す。）

(2)

(In the formula (2), A ¹ , A ² , A ³ , A ⁴ and A ⁵ each independently represent an arylene group or a divalent heterocyclic group which may be substituted. B ¹ , B ² , B ³ and B ⁴ are each ^{independently, -BR 1 -, - NR 2} -, - SiR 3 R 4 -, - PR 5 -, - C≡C -, - have a or a substituent - CR ^b = NR ^b R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^b each independently represents a hydrogen atom or a substituent, a ¹ , a ² , a ³ , a ⁴ and a ⁵ independently represents an integer of 0 to 3, and 1 ≦ a ¹ + a ² + a ³ + a ⁴ + a ⁵ ≦ 15, and b ¹ , b ² , b ³ and b ⁴ each independently Represents 0 or 1)

In the formula (2), A ¹ , A ² , A ³ and A ⁴ each independently represent an arylene group or a divalent heterocyclic group which may be substituted.

Here, the arylene group is a group formed by elimination of two hydrogen atoms bonded to an aromatic hydrocarbon ring. The arylene group generally has about 6 to 60 carbon atoms, preferably 6 to 48 carbon atoms, more preferably 6 to 30 carbon atoms, still more preferably 6 to 25 carbon atoms, and particularly preferably 6 to 20 carbon atoms. The carbon number does not include the carbon number of the substituent.

Specific examples of the arylene group include those represented by the following formulas (A-1) to (A-49), preferably formulas (A-1) to (A-12) and (A-19) to (A -49), more preferably an arylene group represented by (A-1) to (A-4) and (A-19) to (A-49), and even more preferably. Is an arylene group represented by (A-1) to (A-4) and (A-22) to (A-49), more preferably (A-1) to (A-3) and (A -22) to (A-30), more preferably an arylene group represented by (A-1) to (A-3) and (A-22), particularly preferably Is an arylene group represented by (A-1) and (A-22). Hereinafter, the bond in the aromatic hydrocarbon ring represents that it can take any position.

A divalent heterocyclic group is a group formed by elimination of two hydrogen atoms bonded to an aromatic ring of an aromatic compound having a heterocyclic ring. The divalent heterocyclic group generally has about 2 to 60 carbon atoms, preferably 3 to 48, more preferably 5 to 30, still more preferably 6 to 25, and particularly preferably 10 to 20 carbon atoms. It is. The carbon number does not include the carbon number of the substituent. Specific examples of the divalent heterocyclic group include heterocyclic groups represented by the following formulas (B-1) to (B-49), preferably (B-4) to (B-49). It is a heterocyclic group represented, More preferably, it is a heterocyclic group represented by (B-8)-(B-49), More preferably, it is represented by (B-11)-(B-49). More preferably, it is a heterocyclic group represented by (B-11) to (B-37), and still more preferably represented by (B-11) to (B-29). And particularly preferably a heterocyclic group represented by (B-14) to (B-25). In the following, the bond in the aromatic ring represents that it can take any carbon atom position.

In the above formula, R ^a represents a hydrogen atom or a substituent, and from the viewpoints of stability of the copolymer and ease of synthesis, a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a monovalent heterocyclic ring It is preferably a group, more preferably an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, still more preferably an alkyl group or an aryl group.

Here, the alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. Are methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl Group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, 1-adamantyl group, 2-adamantyl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, per group Fluorooctyl group and the like. From the viewpoint of device characteristics, easiness of synthesis, etc., methyl group, ethyl group, propyl group, i-propyl group, etc. Propyl group, butyl group, i- butyl, t- butyl group, a pentyl group, an isoamyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, decyl group, 3,7-dimethyl octyl group are preferable. When there are a plurality of R ^{a s} , two alkyl groups may be bonded to form a ring.

An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and has a condensed ring, or two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene. Also included. The aryl group generally has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, pentafluorophenyl group, and the like. May have a substituent such as a group, an alkyloxycarbonyl group, and a substituted amino group. From the viewpoint of solubility in these organic solvents, device characteristics, easiness of synthesis, etc., an alkyl group having 1 to 12 carbon atoms and / or an alkoxy group having 1 to 12 carbon atoms and / or an alkyloxycarbonyl group is used. A phenyl group having one or more substituents is preferred, and specific examples thereof include 3-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4-propylphenyl group, mesityl group, 4-i -Propylphenyl group, 4-butylphenyl group, 4-i-butylphenyl group, 4-t-butylphenyl group, 4-pentylphenyl group, 4-isoamylphenyl group, 4-hexylphenyl group, 2,6-dimethyl -4-t-butylphenyl group, 4-heptylphenyl group, 4-octylphenyl group, 4-nonylphenyl group, 4-decylphenyl group, -Dodecylphenyl group, 3-methyloxyphenyl group, 4-methyloxyphenyl group, 3,5-dimethyloxyphenyl group, 4-propyloxyphenyl group, 4-i-propyloxyphenyl group, 4-butyloxyphenyl group 4-i-butyloxyphenyl group, 4-t-butyloxyphenyl group, 4-hexyloxyphenyl group, 3,5-dihexyloxyphenyl group, 4-heptyloxyphenyl group, 4-octyloxyphenyl group, 4 -Nonyloxyphenyl group, 4- (methoxymethoxy) phenyl group, 3- (methoxymethoxy) phenyl group, 4- (2-ethoxy-ethoxy) phenyl group, 3- (2-ethoxy-ethoxy) phenyl group, 3, 5-bis (2-ethoxy-ethoxy) phenyl group, 3-methoxycarbonylphenyl group, 4- Toxicarbonylphenyl group, 3,5-dimethoxycarbonylphenyl group, 3-ethoxycarbonylphenyl group, 4-ethoxycarbonylphenyl group, 3-ethyloxycarbonyl-4-methoxyphenyl group, 3-ethyloxycarbonyl-4-ethoxyphenyl Group, 3-ethyloxycarbonyl-4-hexyloxyphenyl group, 4-diphenylaminophenyl group and the like.

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

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

In the formula (2), when A ¹ , A ² , A ³ and A ⁴ have a substituent, the substituent is an alkyl from the viewpoint of solubility in an organic solvent, device characteristics, ease of synthesis, and the like. Group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group Selected from groups, halogen atoms, acyl groups, acyloxy groups, imine residues, amide groups, acid imide groups, monovalent heterocyclic groups, carboxyl groups, substituted carboxyl groups, substituted phosphino groups, sulfonic acid groups and cyano groups It is preferable that More preferably, it is selected from an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, a substituted silyl group, an acyl group, a substituted carboxyl group, and a cyano group. Preferably, it is selected from alkyl groups, alkoxy groups, aryl groups, aryloxy groups, arylalkyl groups, arylalkoxy groups and substituted carboxyl groups, more preferably selected from alkyl groups, alkoxy groups, and aryl groups. And particularly preferably an alkyl group.

Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, acyl group , Acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, substituted carboxyl group and substituted phosphino group are each independently the above alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group. Group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue Base Amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, a substituted phosphino group, may be substituted with a sulfonic acid group and a cyano group.

Here, the alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. Is methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl Group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, 1-adamantyl group, 2-adamantyl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, per group Fluorooctyl group and the like. From the viewpoint of device characteristics, easiness of synthesis, etc., methyl group, ethyl group, propyl group, i-propyl group, etc. Propyl group, butyl group, i- butyl, t- butyl group, a pentyl group, an isoamyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, decyl group, 3,7-dimethyl octyl group are preferable. When a plurality of alkyl groups are present, two alkyl groups may be bonded to form a ring.

The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group , 2-ethoxyethyloxy group, etc. From the viewpoints of solubility in solvents, device characteristics, ease of synthesis, etc., pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, 3,7-dimethyloctyloxy group preferable.

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

An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and has a condensed ring, or two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene. Also included. The aryl group generally has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a pentafluorophenyl group, and the like. And may have a substituent such as an alkyloxycarbonyl group. From the viewpoint of solubility in these organic solvents, device characteristics, easiness of synthesis, etc., an alkyl group having 1 to 12 carbon atoms and / or an alkoxy group having 1 to 12 carbon atoms and / or an alkyloxycarbonyl group is used. A phenyl group having one or more substituents is preferred, and specific examples thereof include 3-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4-propylphenyl group, mesityl group, 4-i -Propylphenyl group, 4-butylphenyl group, 4-i-butylphenyl group, 4-t-butylphenyl group, 4-pentylphenyl group, 4-isoamylphenyl group, 4-hexylphenyl group, 2,6-dimethyl -4-t-butylphenyl group, 4-heptylphenyl group, 4-octylphenyl group, 4-nonylphenyl group, 4-decylphenyl group, -Dodecylphenyl group, 3-methyloxyphenyl group, 4-methyloxyphenyl group, 3,5-dimethyloxyphenyl group, 4-propyloxyphenyl group, 4-i-propyloxyphenyl group, 4-butyloxyphenyl group 4-i-butyloxyphenyl group, 4-t-butyloxyphenyl group, 4-hexyloxyphenyl group, 3,5-dihexyloxyphenyl group, 4-heptyloxyphenyl group, 4-octyloxyphenyl group, 4 -Nonyloxyphenyl group, 4- (methoxymethoxy) phenyl group, 3- (methoxymethoxy) phenyl group, 4- (2-ethoxy-ethoxy) phenyl group, 3- (2-ethoxy-ethoxy) phenyl group, 3, 5-bis (2-ethoxy-ethoxy) phenyl group, 3-methoxycarbonylphenyl group, 4- Toxicarbonylphenyl group, 3,5-dimethoxycarbonylphenyl group, 3-ethoxycarbonylphenyl group, 4-ethoxycarbonylphenyl group, 3-ethyloxycarbonyl-4-methoxyphenyl group, 3-ethyloxycarbonyl-4-ethoxyphenyl Group, 3-ethyloxycarbonyl-4-hexyloxyphenyl group and the like.

The aryloxy group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenoxy group, a C _{1 to} C ₁₂ alkoxyphenoxy group (C _{1 to} C ₁₂ have 1 carbon atom). And the same applies to the following.), C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group, etc. From the viewpoints of solubility, device characteristics, ease of synthesis, etc., a C ₁ -C ₁₂ alkoxyphenoxy group and a C ₁ -C ₁₂ alkylphenoxy group are preferred.
Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkylphenoxy such as methyl phenoxy groups as group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, i- propyl phenoxy group, Examples include butylphenoxy, i-butylphenoxy, t-butylphenoxy, pentylphenoxy, isoamylphenoxy, hexylphenoxy, heptylphenoxy, octylphenoxy, nonylphenoxy, decylphenoxy, dodecylphenoxy Is done.

Arylthio group has a carbon number of usually about 3 to 60, and specific examples thereof include a phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2 - naphthylthio group, are exemplified such as pentafluorophenyl thio group, solubility in organic solvents, device properties, from the standpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ An alkylphenylthio group is preferred.

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

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

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

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

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

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

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

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

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

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

The imine residue has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include groups represented by the following structural formulas.

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

The acid imide group includes a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, and has about 4 to 20 carbon atoms. Specific examples include the groups shown below. .

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

  Examples of the substituted carboxyl group include a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and usually has about 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms. Specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group. Cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycal Nyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group, etc. Is mentioned.

Examples of the substituted phosphino group include a phosphino group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and usually has about 2 to 60 carbon atoms, preferably 9 to 48 carbon atoms. Specific examples thereof include dimethylphosphino group, diethylphosphino group, dibutylphosphino group, bis (t-butyl) phosphino group, dicyclohexylphosphino group, diphenylphosphino group, bis (1-naphthyl) phosphino group, Bis (2-methylphenyl) phosphino group, bis (4-methylphenyl) phosphino group, bis (2-methoxyphenyl) phosphino group, bis (4-methoxyphenyl) phosphino group, bis (4-fluorophenyl) phosphino group, And dibenzylphosphino group.

In the formula (2), B ¹ , B ² , B ³ and B ⁴ are each independently —BR ¹ —, —NR ² —, —SiR ³ R ⁴ —, —PR ⁵ —, —C≡C—. , -CR ^b = N- or a vinylene group optionally having a substituent. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^b represent a hydrogen atom or a substituent. B ¹ , B ² , B ³ and B ^{4 in} formula (2) preferably have —NR ² —, —SiR ³ R ⁴ —, —C≡C—, —CR ^b ═N— and a substituent. It is selected from vinylene groups which may be substituted, more preferably —NR ² —, which is selected from vinylene groups which may have a substituent, and further preferably —NR ² —.

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a monovalent complex or the like from the viewpoints of stability of the copolymer and ease of synthesis. It is preferably a cyclic group, more preferably an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and still more preferably an alkyl group or an aryl group. Specific examples of the alkyl group, aryl group, arylalkyl group, and monovalent heterocyclic group are alkyl groups in which A ¹ , A ² , A ^3, and A ⁴ in the formula (2) each have a substituent, Specific examples are the same as those of the aryl group, arylalkyl group and monovalent heterocyclic group.

-CR ^b = N- represented by B ¹ , B ² , B ³ and B ⁴ in the formula (2) is specifically represented by the following formula (3) or (4).

（式（３）においてＲ^bはそれぞれ独立に水素原子または置換基を表す。）

(In formula (3), each R ^b independently represents a hydrogen atom or a substituent.)

（式（４）においてＲ^bはそれぞれ独立に水素原子または置換基を表す。）

(In formula (4), each R ^b independently represents a hydrogen atom or a substituent.)

R ^b in formula (3) and formula (4) is an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group from the viewpoints of solubility in an organic solvent, device characteristics, ease of synthesis, and the like. , Arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue Amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group and cyano group are preferred. More preferably, it is selected from an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, a substituted silyl group, an acyl group, a substituted carboxyl group, and a cyano group. Preferably, it is selected from alkyl groups, alkoxy groups, aryl groups, aryloxy groups, arylalkyl groups, arylalkoxy groups and substituted carboxyl groups, more preferably selected from alkyl groups, alkoxy groups, and aryl groups. Particularly preferred are those selected from alkyl groups and aryl groups. Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, Specific examples of the acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group and substituted carboxyl group are A ¹ , A ² , A ³ and A in the formula (2), respectively. ^{When 4} has a substituent, an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group , Substituted silyl groups, halogen atoms, Specific examples are the same as those described above for a ru group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group and a substituted carboxyl group.

Specific examples of the vinylene group which may have a substituent include vinylene groups represented by the following formulas (3 ′) and (4 ′).

（式（３’）においてＲ^bはそれぞれ独立に水素原子または置換基を表す。）

(In formula (3 ′), each R ^b independently represents a hydrogen atom or a substituent.)

（式（４’）においてＲ^bはそれぞれ独立に水素原子または置換基を表す。）

(In formula (4 ′), each R ^b independently represents a hydrogen atom or a substituent.)

Preferred examples of R ^b in formula (3 ′) and formula (4 ′) are the same as the preferred examples of R ^b in formula (3).

In the formula (2), a ¹ , a ² , a ³ , a ⁴ and a ⁵ each independently represents an integer of 0 to 3, and 1 ≦ a ¹ + a ² + a ³ + a ⁴ + a ⁵ ≦ 15 Represents. a ¹ , a ² , a ³ , a ⁴ and a ⁵ are preferably integers satisfying 1 ≦ a ¹ + a ² + a ³ + a ⁴ + a ⁵ ≦ 10, more preferably 1 ≦ a ¹ + a ² + a ³ + a ⁴ + a ⁵ ≦ 7, more preferably 1 ≦ a ¹ + a ² + a ³ + a ⁴ + a ⁵ ≦ 5, more preferably 1 ≦ a ¹ + a ² + a ³ + a ⁴ + a ⁵ An integer satisfying ≦ 4, and particularly preferably an integer satisfying 1 ≦ a ¹ + a ² + a ³ + a ⁴ + a ⁵ ≦ 3.

In the formula (2), b ¹ , b ² , b ³ and b ⁴ each independently represents 0 or 1. b ¹ , b ² , b ³ and b ⁴ are preferably integers satisfying 0 ≦ b ¹ + b ² + b ³ + b ⁴ ≦ 3, more preferably integers satisfying 0 ≦ b ¹ + b ² + b ³ + b ⁴ ≦ 2. It is.

From the viewpoint of element characteristics, in the formula (2), when a ¹ = 1 and a ² = a ³ = a ⁴ = a ⁵ = b ¹ = b ² = b ³ = b ⁴ = 0, or a ¹ = a ³ = b ¹ = b ² = 1 and 1 ≦ a ² ≦ 2 and a ⁴ = a ⁵ = b ¹ = b ² = 0 or a ¹ = a ² = 1 and b ¹ = 1 and a ³ = It is preferable that a ⁴ = a ⁵ = b ² = b ³ = b ⁴ = 0

Specific examples of the group represented by the formula (2) include the following formulas (C-1) to (C-22), (D-1) to (D-24), and (E- 1) to (E-26), (F-1) to (F-13), (G-1) to (G-14), (H-1) to (H-12) or (J-1) To (J-22) are preferable, and (C-1) to (C-22), (D-1) to (D-24), and (E-1) to (E-) are more preferable. 26), (F-1) to (F-13), (G-1) to (G-14) or a group represented by (J-1) to (J-22), more preferably (C-1) to (C-22), (D-1) to (D-24), (E-1) to (E-26), (F-1) to (F-13), (G -1) to (G-14) or (J-20) to (J-22). Preferably, (C-1) to (C-22), (D-1) to (D-2), (D-4) to (D-24), (E-1) to (E-16) , (E-19) to (E-26), (F-9) to (F-13), (G-1) to (G-14) or (J-20) to (J-22) And more preferably (C-1) to (C-22), (D-9) to (D-24), (E-1) to (E-16), (E-19). ) To (E-26), (F-9) to (F-13), (G-1) to (G-14) or (J-20) to (J-22). Particularly preferably (C-1), (C-11) to (C-22), (D-9) to (D-24), (E-1) to (E-16), (E-19) ) To (E-26), (F-9) to (F-13), (G-1) to (G-14) or ( -20) is a group represented by ~ (J-22). Among these, (C-11) to (C-22), (D-9) to (D-24), (E-1) to (E-16), (E-19) to (E-26) are preferable. ), (F-9) to (F-13) or (G-1) to (G-14), more preferably (C-11) to (C-22), (D -9) to (D-24), (E-1) to (E-16), (E-19) to (E-26) or a group represented by (G-1) to (G-14) And more preferably (C-11) to (C-22), (D-9) to (D-24), (E-1) to (E-16) or (G-1) to (G G-14), more preferably (C-11) to (C-22), (D-9) to (D-24), or (G-1) to (G-14). And more preferably (C-11). It is a group represented by (C-15) to (C-22), (D-9) to (D-24) or (G-1) to (G-14), particularly preferably (C-11). ), (C-15) to (C-22), (D-10-1) or (G-1) to (G-14). Among them, a group represented by (C-11), (C-15) to (C-22), (D-10-1) or (G-1) to (G-4) is preferable. , More preferably a group represented by (C-11), (C-15), (D-10-1) or (G-1) to (G-4), and more preferably (C-11). ), (C-15), (D-10-1) or (G-1).
Here, each of wherein R ^a independently represents the same meaning as R ^a in formula (B-12), R ^b each independently represents the same meaning as R ^b in the formula (3). In the formula, each R ^c independently represents a hydrogen atom or a substituent, and the substituent is the same as the preferable substituent when A ¹ , A ² , A ³ and A ⁴ in the formula (2) have a substituent. Represents. In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group, an aryl group, an aryl from the viewpoint of the stability of the copolymer and the ease of synthesis. An alkyl group and a monovalent heterocyclic group are preferable, an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group are more preferable, and an alkyl group and an aryl group are more preferable. Specific examples of the alkyl group, aryl group, arylalkyl group, and monovalent heterocyclic group are alkyl groups in which A ¹ , A ² , A ^3, and A ⁴ in the formula (2) each have a substituent, Specific examples are the same as those of the aryl group, arylalkyl group and monovalent heterocyclic group.

Ar in the formula (1) represents the same group in the same block, and two Ars in two adjacent blocks represent different groups.

The block copolymer of the present invention has two types of Ar when it consists of two blocks represented by the above formula (1), and two when it consists of three blocks represented by the above formula (1). When it has more than one kind of Ar and consists of four or more blocks represented by the formula (1), it has four or more kinds of Ar. Preferably, Ar in different blocks all represent different divalent groups.

The number average molecular weight (Mn) in terms of polystyrene of the block copolymer of the present invention is usually about 1 × 10 ³ to 1 × 10 ⁸ , preferably 1 × 10 ³ to 1 × 10 ⁷ , more preferably. 2 × 10 ³ to 1 × 10 ⁶ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁵ , still more preferably 1 × 10 ^{4 to} 5 × 10 ⁵ , and particularly preferably 2 × 10 ^4. it is ~5 × 10 ^5. In addition, the polystyrene-equivalent weight average molecular weight (Mw) is usually about 2 × 10 ³ to 1 × 10 ⁸ , and preferably 4 × 10 ³ to 4 × 10 ³ from the viewpoint of film formability and efficiency in the case of an element. 2 × 10 ⁷ , more preferably 1 × 10 ^{4 to} 5 × 10 ⁶ , still more preferably 2 × 10 ⁴ to 1 × 10 ⁶ , and even more preferably 4 × 10 ^{4 to} 5 × 10 ^5. It is. Mn and Mw can be measured by size exclusion chromatography (hereinafter referred to as SEC).

In formula (1), m represents the number average degree of polymerization of the structural unit Ar present in one block, and each independently represents a number of 1 or more. At least two of m's present in the block copolymer of the present invention represent a number of 5 or more. Preferably at least two are numbers from 5 to 5 × 10 ⁴ , more preferably at least two are numbers from 5 to 5 × 10 ³ , even more preferably at least two are numbers from 10 to 1 × 10 ³ More preferably, at least two are numbers of 15 to 5 × 10 ² , and particularly preferably at least two are numbers of ^{20 to 5} × 10 ² .

The number average degree of polymerization represented by m in one block is the number average molecular weight of the block copolymer of the present invention Mn, the total of the structural units Ar of the block relative to all the structural units contained in the block copolymer of the present invention. When the molar fraction is Qa and the chemical formula amount of the structural unit Ar in the block is Ma, it is represented by the following formula (a-1). Here, the chemical formula amount is the sum of the relative atomic masses of atoms contained in the chemical formula (first edition, Tokyo Kagaku Dojin, 1994) as described in page 253, when expressed in the composition formula. is there.

m = (Mn × Qa) / Ma (a-1)

The block copolymer of the present invention may have a terminal group. The terminal group is a monovalent group present at both terminals of the block copolymer, and m in the block adjacent to the terminal group represents a number of 2 or more. The block copolymer of the present invention may have two or more types of terminal groups.

The terminal group of the block copolymer of the present invention is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group. , Arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, It is preferably selected from a carboxyl group, a substituted carboxyl group, a substituted phosphino group, a hydroxyl group, a sulfonic acid group, and a cyano group. Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, Specific examples of the acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, substituted carboxyl group and substituted phosphino group are respectively A ¹ , A ² , An alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group when A ³ and A ⁴ have a substituent Substituted amino group, substituted silyl group, Specific examples are the same as the halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, substituted carboxyl group and substituted phosphino group.

The terminal group of the block copolymer of the present invention is preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, a substituted group from the viewpoint of device characteristics and the like. It is selected from silyl group, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group and substituted phosphino group, more preferably alkyl group, alkoxy group, aryl group, aryl It is selected from an oxy group, an arylalkyl group, an arylalkoxy group and a substituted phosphino group, more preferably selected from an alkyl group, an alkoxy group, an aryl group and a substituted phosphino group, particularly preferably an alkyl group and an alkoxy group. Group and an aryl group.

The block copolymer of the present invention may form a cyclic structure by forming a single bond between both ends.

The block copolymer of the present invention may contain impurities such as a homopolymer that does not deteriorate the device characteristics.

  The block copolymer of the present invention comprises two or more blocks represented by the formula (1). From the viewpoint of device characteristics, easiness of synthesis, etc., preferably 2-100 blocks, more preferably 2-50 blocks, still more preferably 2-30 blocks, and even more preferably blocks. It consists of 2 to 20, more preferably 2 to 10 blocks, and particularly preferably 2 to 5 blocks. Among them, it is preferably composed of 2 to 4 blocks, more preferably composed of 2 to 3 blocks, and further preferably composed of 2 blocks.

（５）

（式（５）において、Ａｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴、Ａｒ⁵、Ａｒ⁶、Ａｒ⁷、Ａｒ⁸、Ａｒ⁹およびＡｒ¹⁰はそれぞれ独立に共役系の二価の基を表し、同一ブロック内では同じ基を表し、隣り合う２つのブロックにおいては互いに異なる基を表す。Ｒ^XおよびＲ^Yはそれぞれ独立に末端基を表すか、またはＲ^XおよびＲ^Yで一つの単結合を形成しブロック共重合体の二つの末端どうしで結合して環状構造をとる。ｍ¹、ｍ²、ｍ³、ｍ⁴、ｍ⁵、ｍ⁶、ｍ⁷、ｍ⁸、ｍ⁹およびｍ¹⁰はそれぞれＡｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴、Ａｒ⁵、Ａｒ⁶、Ａｒ⁷、Ａｒ⁸、Ａｒ⁹およびＡｒ¹⁰の数平均重合度を表し、それぞれ独立に０以上の数を表し、ｍ¹、ｍ²、ｍ³、ｍ⁴、ｍ⁵、ｍ⁶、ｍ⁷、ｍ⁸、ｍ⁹およびｍ¹⁰のうち少なくとも２つは５以上の数を表す。ｍ¹≧５かつｍ²≧５かつｍ³＝ｍ⁴＝ｍ⁵＝ｍ⁶＝ｍ⁷＝ｍ⁸＝ｍ⁹＝ｍ¹⁰＝０の場合はＡｒ¹およびＡｒ²は互いに異なる基を表す。ｍ¹、ｍ²、ｍ³がそれぞれ１以上の数であり、かつｍ¹、ｍ²、ｍ³のうち少なくとも２つが５以上の数であり、かつｍ⁴＝ｍ⁵＝ｍ⁶＝ｍ⁷＝ｍ⁸＝ｍ⁹＝ｍ¹⁰＝０の場合は、Ａｒ¹およびＡｒ²は互いに異なる基を表し、Ａｒ²およびＡｒ³は互いに異なる二価の基を表し、Ａｒ¹およびＡｒ³は互いに同一でも異なっていてもよい。ｍ¹、ｍ²、ｍ³、ｍ⁴、ｍ⁵、ｍ⁶、ｍ⁷、ｍ⁸、ｍ⁹およびｍ¹⁰のうち少なくとも４つが１以上の数を表し、かつ少なくとも２つが５以上の数を表す場合、Ａｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴、Ａｒ⁵、Ａｒ⁶、Ａｒ⁷、Ａｒ⁸、Ａｒ⁹およびＡｒ¹⁰が表す二価の基は四種類以上である。） When it is composed of 2 to 10 blocks represented by the formula (1), which is a preferred form of the block copolymer of the present invention, the copolymer is represented by the following formula (5), for example.

(5)

(In the formula (5), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ and Ar ¹⁰ each independently represents a conjugated divalent group; In the same block, the same group is represented, and two adjacent blocks represent different groups, R ^X and R ^Y each independently represent a terminal group, or R ^X and R ^Y form a single bond. The two ends of the block copolymer are bonded to form a cyclic structure, where m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , m ⁷ , m ⁸ , m ⁹ and m ¹⁰ are respectively Represents the number average degree of polymerization of Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ and Ar ¹⁰ , each independently representing a number of 0 or more, m ¹ , At least ^{two of} m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , m ⁷ , m ⁸ , m ⁹ and m ¹⁰ are 5 or more. When m ¹ ≧ 5 and m ² ≧ 5 and m ³ = m ⁴ = m ⁵ = m ⁶ = m ⁷ = m ⁸ = m ⁹ = m ¹⁰ = 0, Ar ¹ and Ar ² are Each represents a group different from each other, and m ¹ , m ² , and m ³ are each a number of 1 or more, and at least two of m ¹ , m ² , and m ³ are a number of 5 or more, and m ⁴ = m ⁵ = M ⁶ = m ⁷ = m ⁸ = m ⁹ = m ¹⁰ = 0, Ar ¹ and Ar ² represent different groups, Ar ² and Ar ³ represent different divalent groups, Ar ¹ And Ar ³ may be the same or different from each other, and at least four of m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , m ⁷ , m ⁸ , m ⁹ and m ¹⁰ are one or more. represents a number, and if that represents a number of at least two 5 or ^{more, Ar 1, Ar 2, Ar} 3, Ar 4, Ar 5, Ar 6, Ar 7, Ar 8, Ar 9 and Ar ¹⁰ are Be divalent groups are four types or more.)

In Formula (5), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ and Ar ¹⁰ each independently represent a conjugated divalent group, and are preferable. Examples are the same as preferred examples of Ar.

In the formula (5), R ^X and R ^Y each independently represent a terminal group, or R ^X and R ^Y form a single bond and are bonded at two ends of the block copolymer to form a cyclic structure Take. Examples of the terminal group include those described above. Two or more types of terminal groups represented by R ^X and R ^Y may exist.

In the formula (5), m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , m ⁷ , m ⁸ , m ⁹ and m ¹⁰ are Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar, respectively. ⁵ represents the number average degree of polymerization of Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ and Ar ¹⁰ , each independently represents a number of 0 or more, m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ^6, at least two of m ^7, m ^8, m ⁹ and m ¹⁰ represents a number of 5 or more. When R ^X and R ^Y represent a terminal group, the number average degree of polymerization of the block next to R ^X and R ^Y is 2 or more.

The number average degree of polymerization represented by m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , m ⁷ , m ⁸ , m ⁹ and m ¹⁰ is the number average molecular weight of the block copolymer of the present invention. And the chemical formula weights of Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ and Ar ¹⁰ are respectively Mn ¹ , Mn ² , Mn ³ , Mn ⁴ , Mn ^5. , Mn ⁶ , Mn ⁷ , Mn ⁸ , Mn ⁹ and Mn ^10, and the sum of Ar ¹ , the sum of Ar ² , the sum of Ar ³ , the sum of Ar ⁴ with respect to all the structural units contained in the block copolymer of the present invention, The total molar fraction of Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ , and Ar ¹⁰ is defined as Q ¹ , Q ² , Q ³ , Q ⁴ , Q ⁵ , Assuming Q ⁶ , Q ⁷ , Q ⁸ , Q ⁹ and Q ¹⁰ , they are represented by the following formula (a-2).

m ⁱ = (Mn × Q ⁱ ) / Mn ⁱ (a-2)
(In the formula (a-2), i represents 1,2,3,4,5,6,7,8,9 or 10)

At ^{least two of} m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , m ⁷ , m ⁸ , m ⁹ and m ¹⁰ represent a number of 5 or more, preferably at least 2 is 5 to 5 × 10 ⁴ , more preferably at least two are 5 to 5 × 10 ³ , even more preferably at least two are 10 to 1 × 10 ³ , and even more preferably at least two are 15 It is a number of ˜5 × 10 ² , particularly preferably at least two are numbers of ^{20 to} 5 × 10 ² .

m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , m ⁷ , m ⁸ , m ⁹ and m ¹⁰ represent at least 4 and at least 2 represent 5 or more. In the case of expression, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ and Ar ¹⁰ represent four or more types of divalent groups. Preferably, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ and Ar ¹⁰ represent seven or more types, more preferably ten types. It is.

（５−Ａ）

（式（５−Ａ）において、Ａｒ¹、Ａｒ²、Ａｒ³およびＡｒ⁴はそれぞれ独立に置換基を有していてもよい共役系の二価の基を表し、互いに異なる二価の基を表す。Ｒ^XおよびＲ^Yはそれぞれ独立に末端基を表すか、またはＲ^XおよびＲ^Yで一つの単結合を形成しブロック共重合体の二つの末端どうしで結合して環状構造をとる。ｍ¹、ｍ²、ｍ³およびｍ⁴はそれぞれＡｒ¹、Ａｒ²、Ａｒ³およびＡｒ⁴の数平均重合度を表し、それぞれ独立に１以上の数を表し、ｍ¹、ｍ²、ｍ³およびｍ⁴のうち少なくとも２つは５以上の数を表す。） In the case where the block copolymer is composed of four blocks represented by the formula (1), which is one of the preferred forms of the block copolymer of the present invention, in the formula (5), m ¹ , m ² , m ³ and m ⁴ is independently a number of 1 or more, and at least two of m ¹ , m ² , m ³ and m ⁴ are 5 or more, and m ⁵ = m ⁶ = m ⁷ = m ⁸ = m ^This is a case where ⁹ = m ¹⁰ = 0 and is a block copolymer represented by the following formula (5-A).

(5-A)

(In the formula (5-A), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represents a conjugated divalent group which may have a substituent, and each represents a divalent group different from each other. R ^X and R ^Y each independently represent a terminal group, or R ^X and R ^Y form a single bond and are bonded at two ends of the block copolymer to form a cyclic structure. ¹ , m ² , m ³ and m ⁴ each represent the number average degree of polymerization of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ , each independently representing a number of 1 or more, m ¹ , m ² , m ³ and (At least two of m ⁴ represent a number of 5 or more.)

In the formula (5-A), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent the same divalent group as the divalent group represented by Ar in the formula (1), and a preferred example is Ar. This is the same example. However, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent different divalent groups.

Preferably, at least ^one of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ is a divalent group represented by the above formula (C-11) or (C-15) and Ar ¹ , Ar ² , Ar One or more of ³ and Ar ⁴ are represented by the formula (D-10-1), (D-16), (G-1), (G-2), (G-3) or (G-4) More preferably, Ar ¹ and Ar ² are each independently a divalent group represented by the above formula (C-11) or (C-15), and Ar ³ and Ar ⁴ are each independently represented by the above formula (D-10-1), (D-16), (G-1), (G-2), (G-3) or (G-4). divalent there is a group, divalent group and more preferably is a divalent group Ar ¹ is represented by formula (C-15) and the Ar ² is represented by formula (C-11) that Enabled with Ar3 is when a divalent group wherein a divalent group represented by (G-1) and Ar4 is represented by the formula (D-10-1).

In Formula (5-A), R ^X and R ^Y each independently represent a terminal group, or R ^X and R ^Y form a single bond and are bonded to each other at the two ends of the block copolymer. It takes a ring structure. Examples of the terminal group include those described above. Two or more types of terminal groups represented by R ^X and R ^Y may exist.

In formula (5-A), m ¹ , m ² , m ³ and m ⁴ each represent the number average degree of polymerization of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ , each independently representing a number of 1 or more, At least two of m ¹ , m ² , m ³ and m ⁴ represent a number of 5 or more. m ¹ , m ² , m ³ and m ⁴ can be obtained in the same manner depending on the case where i represents 1, 2, 3 or 4 in the formula (a-2).

At least two of m ¹ , m ² , m ³ and m ⁴ represent a number of 5 or more, preferably at least two are 5 to 5 × 10 ⁴ , more preferably at least two are 5 to 5 ×. 10 ³ , even more preferably at least 2 is a number from 10 to 1 × 10 ³ , more preferably at least 2 is a number from 15 to 5 × 10 ² , particularly preferably at least 2 is from 20 to The number is 5 × 10 ² .

In the formula (5-A), when R ^X and R ^Y represent a terminal group, the number average degree of polymerization of the block next to R ^X and R ^Y is 2 or more.

（式（６）において、Ａｒ¹、Ａｒ²およびＡｒ³はそれぞれ独立に共役系の二価の基を表し、Ａｒ¹およびＡｒ²は互いに異なり、Ａｒ²およびＡｒ³は互いに異なり、Ａｒ¹およびＡｒ³は互いに同一でも異なっていてもよい。Ｒ^XおよびＲ^Yはそれぞれ独立に末端基を表すか、またはＲ^XおよびＲ^Yで一つの単結合を形成しブロック共重合体の二つの末端どうしで結合して環状構造をとる。ｍ¹、ｍ²およびｍ³はそれぞれＡｒ¹、Ａｒ²およびＡｒ³の数平均重合度を表し、それぞれ独立に１以上の数を表し、ｍ¹、ｍ²およびｍ³のうち少なくとも２つは５以上の数を表す。） In the case where the block copolymer of the present invention is constituted by three blocks represented by the formula (1), which is one of the preferred forms, m ¹ , m ² and m ³ in the formula (5) are respectively It is independently a number of 1 or more, and at least two of m ¹ , m ² and m ³ are 5 or more, and m ⁴ = m ⁵ = m ⁶ = m ⁷ = m ⁸ = m ⁹ = m ^This is a case of ¹⁰ = 0, which is a block copolymer represented by the following formula (6).

(In the formula (6), Ar ¹ , Ar ² and Ar ³ each independently represent a conjugated divalent group, Ar ¹ and Ar ² are different from each other, Ar ² and Ar ³ are different from each other, Ar ¹ and Ar ³ may be the same as or different from each other, R ^X and R ^Y each independently represent a terminal group, or R ^X and R ^Y form a single bond between the two ends of the block copolymer. And m ¹ , m ² and m ³ each represent the number average degree of polymerization of Ar ¹ , Ar ² and Ar ³ , each independently represents a number of 1 or more, m ¹ , m ² And at least two of m ³ represent a number of 5 or more.)

In Formula (6), Ar ¹ , Ar ² and Ar ³ each independently represent the same divalent group as the divalent group represented by Ar in Formula (1), and preferred examples are the same as the preferred examples of Ar. is there.

In formula (6), Ar ¹ and Ar ² represent different divalent groups, Ar ² and Ar ³ represent different divalent groups, and Ar ¹ and Ar ³ may be the same or different from each other. . In a preferred case, Ar ¹ and Ar ³ represent different divalent groups.

Preferably, at least ^one of Ar ¹ , Ar ² and Ar ³ is a divalent group represented by the above formula (C-11) or (C-15) and Ar ¹ , Ar ² and Ar ³ One or more of the divalent compounds represented by the above formula (D-10-1), (D-16), (G-1), (G-2), (G-3) or (G-4) More preferably, Ar ¹ is a divalent group represented by the above formula (C-11) or (C-15) and Ar ³ is the above formula (D-10-1), It may be a divalent group represented by (D-16), (G-1), (G-2), (G-3) or (G-4), and more preferably Ar ¹ is represented by the formula ( A divalent group represented by C-15) and Ar ² is a divalent group represented by formula (C-11) and Ar ³ is represented by formula (G-1). This is the case of

In Formula (6), R ^X and R ^Y each independently represent a terminal group, or R ^X and R ^Y form a single bond and are bonded to each other at the two ends of the block copolymer to form a cyclic structure Take. Examples of the terminal group include those described above. Two or more types of terminal groups represented by R ^X and R ^Y may exist.

In Formula (6), m ¹ , m ² and m ³ each represent the number average degree of polymerization of Ar ¹ , Ar ² and Ar ³ , each independently represents a number of 1 or more, m ¹ , m ² and m ³ At least two of these represent numbers of 5 or more. m ¹ , m ² or m ³ can be obtained in the same manner depending on the case where i represents ¹ , ² or ³ in the formula (a-2).

At least two of m ¹ , m ² and m ³ represent a number of 5 or more, preferably at least two are 5 to 5 × 10 ⁴ , more preferably at least two are 5 to 5 × 10 ³ . And more preferably at least two are numbers from 10 to 1 × 10 ³ , more preferably at least two are numbers from 15 to 5 × 10 ² , particularly preferably at least two are from 20 to 5 × 10 3. It is a number of ^two .

In the formula (6), when R ^X and R ^Y represent a terminal group, the number average polymerization degree of the block adjacent to R ^X and R ^Y is 2 or more.

（式（７）において、Ａｒ¹およびＡｒ²はそれぞれ独立に共役系の二価の基を表し、Ａｒ¹およびＡｒ²は互いに異なり、Ｒ^XおよびＲ^Yはそれぞれ独立に末端基を表すか、またはＲ^XおよびＲ^Yで一つの単結合を形成しブロック共重合体の二つの末端どうしで結合して環状構造をとる。ｍ¹およびｍ²はそれぞれＡｒ¹およびＡｒ²の数平均重合度を表し、それぞれ独立に５以上の数を表す。） In the case where the block copolymer of the present invention is a more preferable form and is composed of two blocks represented by the formula (1), in the formula (5), m ¹ ≧ 5 and m ² ≧ 5 and m ³ = M ⁴ = m ⁵ = m ⁶ = m ⁷ = m ⁸ = m ⁹ = m ¹⁰ = 0 and is a block copolymer represented by the following formula (7).

(In Formula (7), Ar ¹ and Ar ² each independently represent a conjugated divalent group, Ar ¹ and Ar ² are different from each other, and R ^X and R ^Y each independently represent a terminal group, Alternatively, R ^X and R ^Y form a single bond and are bonded to each other at two ends of the block copolymer to form a cyclic structure, where m ¹ and m ² are the number average degree of polymerization of Ar ¹ and Ar ² , respectively. And each independently represents a number of 5 or more.)

In Formula (7), Ar ¹ and Ar ² each independently represent the same divalent group as the divalent group represented by Ar in Formula (1), and preferred examples are the same as the preferred examples of Ar.

In the formula (7), Ar ¹ and Ar ² represent different divalent groups.

Preferably, Ar ¹ is a divalent group represented by the above formula (C-11) or (C-15), and Ar ² is the above formula (D-10-1), (D-16), (G -1), (G-2), (G-3) or (G-4), more preferably Ar ¹ is represented by formula (C-11) or (C- 15), and Ar ² is a divalent group represented by the formula (D-10-1) or (G-1).

In the formula (7), R ^X and R ^Y each independently represent a terminal group, or R ^X and R ^Y form a single bond and are bonded at two ends of the block copolymer to form a cyclic structure Take. Examples of the terminal group include those described above. Two or more types of terminal groups represented by R ^X and R ^Y may exist.

In Formula (7), m ¹ and m ² each represent the number average degree of polymerization of Ar ¹ and Ar ² , and each independently represents a number of 5 or more. m ¹ and m ² can be similarly determined depending on the case where i represents 1 or 2 in the formula (a-2).

m ¹ and m ² each independently represents a number of 5 or more, preferably each is a number of 5 to 5 × 10 ⁴ , more preferably each is a number of 5 to 5 × 10 ³ , and still more preferably Are each a number of 10 to 1 × 10 ³ , more preferably a number of 15 to 5 × 10 ² , and particularly preferably a number of ^{20 to 5} × 10 ² .
Among the block copolymers of the present invention, block copolymers produced by condensation polymerization using two or more monomers represented by the following general formula (b) as raw materials are preferred.

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

（式（ｂ）においてＡｒは前記式（１）におけるＡｒが表す二価の基と同じ二価の基を表す。Ｘ¹はハロゲン原子、式（ｃ）で表されるスルホネート基、またはメトキシ基を表す。Ｍ¹はホウ酸エステル基、ホウ酸基、式（ｄ）で表される基、式（ｅ）で表される基、または式（ｆ）で表される基を表す。） The block copolymer of the present invention can be produced by condensation polymerization using two or more monomers represented by the following general formula (b) as raw materials.

(In the formula (b), Ar represents the same divalent group as the divalent group represented by Ar in the formula (1). X ¹ represents a halogen atom, a sulfonate group represented by the formula (c), or a methoxy group. M ¹ represents a borate group, a boric acid group, a group represented by the formula (d), a group represented by the formula (e), or a group represented by the formula (f).

（式（ｃ）、（ｄ）においてＸ_Aは、塩素原子、臭素原子、及びヨウ素原子からなる群から選ばれるハロゲン原子を表す。）

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

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

（式（ｆ）においてＲ^Q、Ｒ^RおよびＲ^Sはそれぞれ独立にアルキル基またはアリール基を表す。）

(In the formula (f), R ^Q , R ^R and R ^S each independently represents an alkyl group or an aryl group.)

X ¹ in the formula (b) independently represents a halogen atom, a sulfonate group represented by the formula (c), or a methoxy group.

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

The alkyl group or aryl group which may be substituted in R ^P in the formula (c) is an alkyl group in the case where A ¹ , A ² , A ³ and A ⁴ in the formula (2) have a substituent, respectively. And the same specific examples as the aryl group. Examples of the sulfonate group represented by the formula (c) include a methanesulfonate group, a trifluoromethanesulfonate group, a phenylsulfonate group, and a 4-methylphenylsulfonate group.

In formula (b), M ¹ represents a borate group, a borate group (—B (OH) ₂ ), a group represented by formula (d), a group represented by formula (e), or formula (f) Represents a group represented by

Examples of the borate group in M ¹ in the formula (b) include groups represented by the following formula.

R ^Q , R ^R and R ^{S in} formula (f) each independently represents an alkyl group or an aryl group. Specific examples thereof include the same specific examples as the alkyl group and aryl group in the case where A ¹ , A ² , A ³ and A ⁴ in the formula (2) have a substituent.

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

M ¹ in the formula (b) is a boric acid ester group, a boric acid group (—B (OH) ₂ ), or a group represented by the formula (d) from the viewpoint of ease of synthesis, ease of handling, toxicity, and the like. Preferably there is.

As a method of condensation polymerization, the monomer represented by the formula (b) can be dissolved in an organic solvent as necessary, and an alkali or a suitable catalyst can be used at a melting point or higher and a boiling point or lower of the organic solvent. For example, a method of polymerizing from a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by Stille coupling, a method of polymerizing by Negishi coupling, and the like are exemplified.

Of these, the polymerization method by Suzuki coupling reaction and the polymerization method by Grignard reaction are preferable because the structure can be easily controlled. Among these, a method of polymerizing by a Suzuki coupling reaction is preferable.
The Suzuki coupling reaction can be performed, for example, under the reaction conditions described in Synthetic Communications, 1981, 11 (7), 513.

（式中、Ar、X¹およびM¹は式（ｂ）におけるAr、X¹およびM¹と同じ意味を表す。）
例えば、Ｒ^X−Ｘ¹などのＸ¹のみを有する化合物を１モルと、Ｍ¹−Ａｒ¹−Ｘ¹をｍ¹モルを縮合重合することによって、Ｒ^X−（Ａｒ¹）ｍ¹−Ｘ¹のようなＸ¹のみを有する高分子化合物が生成する。該高分子化合物にさらに Ｍ¹−Ａｒ²−Ｘ¹ をｍ²モル縮合重合させることにより、Ｒ^X−（Ａｒ¹）ｍ¹−（Ａｒ²）ｍ²−Ｘ¹のようなＡｒ¹からなるブロックとＡｒ²からなるブロックの２つのブロックからなる高分子化合物を合成することができる。３つ以上のブロックからなる高分子化合物も同様にして合成可能であり、ブロックが並ぶ順序も適宜変更できる。ここで、Ａｒ¹、Ａｒ²、ｍ¹、ｍ²およびＲ^X はそれぞれ式（５）におけるＡｒ¹、Ａｒ²、ｍ¹、ｍ²およびＲ^Xと同じ意味を表し、Ｍ¹およびＸ¹はそれぞれ式（ｂ）におけるＭ¹およびＸ¹と同じ意味を表す。 By using an appropriate catalyst, in the monomer represented by formula (b), the carbon atom on Ar to which X ^{1 of} one molecule is bonded is bonded to M ^{1 of} another molecule. It forms a bond with a carbon atom on Ar. For example, when two molecules of the monomer of formula (b) are reacted, the reaction formula is as shown below.

(Wherein, Ar, X ¹ and M ¹ are as defined Ar, and X ¹ and M ¹ in formula (b).)
For example, R ^X -X ¹ compounds having only X ^1, such as 1 mole, by the M ¹ -Ar ¹ -X ¹ condensation polymerization of m ^{1 mole, R X - (Ar 1)} m 1 -X a polymer compound having only X ^1, such as ¹ to produce. M ¹ -Ar ² -X ¹ is further subjected to m ² molar condensation polymerization to the polymer compound, thereby comprising Ar ¹ such as R ^X- (Ar ¹ ) m ^1- (Ar ² ) m ² -X ^1. A polymer compound composed of two blocks of a block and a block composed of Ar ² can be synthesized. A polymer compound composed of three or more blocks can be synthesized in the same manner, and the order in which the blocks are arranged can be appropriately changed. ^{Here, Ar 1, Ar 2, m} 1, m 2 and R ^X are as defined ^{Ar 1, Ar 2, m 1} , m 2 and R ^X in each formula (5), M ¹ and X ¹ Each represents the same meaning as M ¹ and X ¹ in formula (b).

Therefore, a block copolymer like Formula (5) can be manufactured as follows, for example.
1) and M ¹ -Ar ¹ -X ¹ terminating agent and m ¹ mole of such R ^X -X ¹ are reacted in the presence of a catalyst R ^x - were synthesized (Ar ¹⁾ _m1 -X ^{1,
2) R x - (Ar 1} ) m1 -X 1 with respect to 1 mol of M ¹ -Ar ² -X ¹ in m ² moles are reacted in the presence of a catalyst _{^{R x - (Ar 1) m1}} - (Ar ²⁾ was synthesized _m2 -X ^{1,
3) R x - (Ar 1} ) m1 - (Ar 2) m2 relative -X ¹ 1 mol of M ¹ -Ar ³ -X ¹ in m ³ moles are reacted in the presence of a catalyst R ^x - (Ar _{^{1) m1 - (Ar 2)}} m2 - (Ar 3) was synthesized _m3 -X ^1,
4) R ⁴ —M ¹ —Ar ⁴ —X ¹ is reacted in the presence of a catalyst with ¹ mol of R ^x — (Ar ¹ ) _{m 1} — (Ar ² ) _m ² — (Ar ³ ) _{m 3} —X ^{1. _{(Ar 1) m1 - - (}} Ar 2) m2 - (Ar 3) m3 - (Ar 4) were synthesized _m4 -X ^1, R ^x Te
^{5) R x - (Ar 1} ) m1 - and (Ar ⁴⁾ with respect to _m4 -X ¹ 1 mole, m ⁵ moles of ^{M 1 -Ar 5 -X 1 - (} Ar 2) m2 - (Ar 3) m3 are reacted in the presence of a catalyst _{^{R x - (Ar 1) m1}} - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) were synthesized _m5 -X ^{1,
6) R x - (Ar 1} ) m1 - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 -X 1 with respect to 1 mole, m ⁶ moles of M ¹ - the Ar ⁶ -X ¹ are reacted in the presence of a catalyst _{^{R x - (Ar 1) m1}} - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 - (Ar 6) combining the _m6 -X ^{1,
7) R x - (Ar 1} ) m1 - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 - (Ar 6) m6 -X 1 with respect to 1 mole, m ⁷ mol of M ¹ -Ar ⁷ -X ¹ was reacted in the presence of a catalyst to produce R ^x- (Ar ¹ ) _m ^1- (Ar ² ) _m ^2- (Ar ³ ) _m ^3- (Ar ⁴ ) _{m 4-} (Ar ⁵ ). _{^{m5 - (Ar 6) m6 -}} (Ar 7) was synthesized _m7 -X ^{1,
8) R x - (Ar 1} ) m1 - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 -X 1 1 M ⁸ mol of M ¹ -Ar ⁸ -X ¹ is reacted in the presence of a catalyst with respect to mol, and R ^x- (Ar ¹ ) _m ^1- (Ar ² ) _m ^2- (Ar ³ ) _m ^3- (Ar ⁴ ) _{^{m4 - (Ar 5) m5 -}} (Ar 6) m6 - (Ar 7) m7 - (Ar 8) was synthesized _m8 -X ^{1,
9) R x - (Ar 1} ) m1 - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 - (Ar 8 ) relative to _m8 -X ¹ 1 mol of M ¹ -Ar ⁹ -X ¹ in m ⁹ moles are reacted in the presence of a catalyst _{^{R x - (Ar 1) m1}} - (Ar 2) m2 - (Ar 3) _{^{m3 - (Ar 4) m4 -}} (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 - (Ar 8) m8 - (Ar 9) was synthesized _m9 -X ^{1,
10) R x - (Ar 1} ) m1 - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 - (Ar 8 _{^{) m8 - (Ar 9) m9}} -X 1 with respect to 1 mol of M ¹ -Ar ¹⁰ -X ¹ in m ¹⁰ moles are reacted in the presence of a catalyst _{^{R x - (Ar 1) m1}} - (Ar 2) _{^{m2 - (Ar 3) m3 -}} (Ar 4) m4 - (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 - (Ar 8) m8 - (Ar 9) m9 - (Ar 10) m10 - by combining the X ^{1,
11) R x - (Ar 1} ) m1 - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 - (Ar 8 _{^{) m8 - (Ar 9) m9}} - ( relative to _{^{Ar 10) m10 -X 1, R}} Y -M 1 a chain terminator, such as by reacting the presence of a catalyst _{^{R x - (Ar 1) m1}} - (Ar 2 _{^{) m2 - (Ar 3) m3}} - (Ar 4) m4 - (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 - (Ar 8) m8 - (Ar 9) m9 - (Ar 10) m10 -R ^Y is synthesized,
An example is given.
Here, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ , Ar ¹⁰ , m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , M ⁷ , m ⁸ , m ⁹ , m ¹⁰ , R ^X and R ^Y are Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar in the formula (5), respectively. ⁹ , Ar ¹⁰ , m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , m ⁷ , m ⁸ , m ⁹ , m ¹⁰ , R ^X and R ^Y have the same meaning, M ¹ and X ¹ represents the same meaning as M ¹ and X ¹ in formula (b), respectively.

Further, as another example of synthesizing a block copolymer such as the formula (5),
1) and M ¹ -Ar ¹ -X ¹ terminating agent and m ¹ mole of such R ^X -M ¹ are reacted in the presence of a catalyst R ^x - were synthesized (Ar ¹⁾ _m1 -M ^{1,
2) R x - (Ar 1} ) with respect to _m1 -M ¹ 1 mol of M ¹ -Ar ² -X ¹ in m ² moles are reacted in the presence of a catalyst _{^{R x - (Ar 1) m1}} - (Ar ²⁾ synthesizing the _{m @ 2} -M ^1,
3) R ^x- (Ar ¹ ) _m1- (Ar ² ) _m2 -M ¹ is reacted with 1 mol of m ³ mol of M ¹ -Ar ³ -X ¹ in the presence of a catalyst to produce R ^x- ( Ar ¹ ) _m1- (Ar ² ) _m2- (Ar ³ ) _m3 -M ¹ ,
4) R ^x- (Ar ¹ ) _m ^1- (Ar ² ) _m ^2- (Ar ³ ) _{m 3} -M ^{1 is} reacted with m ⁴ mol of M ¹ -Ar ⁴ -X ¹ in the presence of a catalyst. _{^{(Ar 1) m1 - - (}} Ar 2) m2 - (Ar 3) m3 - (Ar 4) were synthesized _m4 -M ^1, R ^x Te
^{5) R x - (Ar 1} ) m1 - and (Ar ⁴⁾ with respect to _m4 -M ¹ 1 mole, m ⁵ moles of ^{M 1 -Ar 5 -X 1 - (} Ar 2) m2 - (Ar 3) m3 are reacted in the presence of a catalyst _{^{R x - (Ar 1) m1}} - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) were synthesized _m5 -M ^{1,
6) R x - (Ar 1} ) m1 - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 -M 1 with respect to 1 mole, m ⁶ moles of M ¹ - the Ar ⁶ -X ¹ are reacted in the presence of a catalyst _{^{R x - (Ar 1) m1}} - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 - (Ar 6) combining the _m6 -M ^{1,
7) R x - (Ar 1} ) m1 - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 - (Ar 6) with respect to _m6 -M ¹ 1 mole, m ⁷ mol of M ¹ -Ar ⁷ -X ¹ was reacted in the presence of a catalyst to produce R ^x- (Ar ¹ ) _m ^1- (Ar ² ) _m ^2- (Ar ³ ) _m ^3- (Ar ⁴ ) _{m 4-} (Ar ⁵ ). _{^{m5 - (Ar 6) m6 -}} (Ar 7) was synthesized _m7 -M ^{1,
_{R x - (Ar 1) m1}} - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 -M 1 1 mole On the other hand, m ⁸ mol of M ¹ -Ar ⁸ -X ¹ was reacted in the presence of a catalyst to produce R ^x- (Ar ¹ ) _m1- (Ar ² ) _m ^2- (Ar ³ ) _m ^3- (Ar ⁴ ) _{m4- ^{(Ar 5) m5 - (Ar}} 6) m6 - (Ar 7) m7 - (Ar 8) was synthesized _m8 -M ^{1,
9) R x - (Ar 1} ) m1 - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 - (Ar 8 ) M ⁹ mol of M ¹ -Ar ⁹ -X ¹ is reacted with ¹ mol of m ₈ -M ^{1 in} the presence of a catalyst to produce R ^x- (Ar ¹ ) _m ^1- (Ar ² ) _m ^2- (Ar ³ ). _{^{m3 - (Ar 4) m4 -}} (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 - (Ar 8) m8 - (Ar 9) was synthesized _m9 -M ^{1,
10) R x - (Ar 1} ) m1 - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 - (Ar 8 ) _M8- (Ar ⁹ ) _m9- M ^{1 per} 1 mol, m ¹⁰ mol of M ¹ -Ar ¹⁰ -X ¹ is reacted in the presence of a catalyst to produce R ^x- (Ar ¹ ) _m1- (Ar ² ). _{^{m2 - (Ar 3) m3 -}} (Ar 4) m4 - (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 - (Ar 8) m8 - (Ar 9) m9 - (Ar 10) m10 - Synthesize M ^{1
11) R x - (Ar 1} ) m1 - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) m4 - (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 - (Ar 8 _{^{) m8 - (Ar 9) m9}} - (Ar 10) to _m10 -M ¹ R ^Y -X ¹ a chain terminator, such as by reacting the presence of a catalyst _{^{R x - (Ar 1) m1}} - (Ar 2) m2 - _{^{(Ar 3) m3 - (Ar}} 4) m4 - (Ar 5) m5 - (Ar 6) m6 - (Ar 7) m7 - (Ar 8) m8 - (Ar 9) m9 - (Ar 10) m10 -R Y Synthesize
An example is given. Here, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ , Ar ¹⁰ , m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , M ⁷ , m ⁸ , m ⁹ , m ¹⁰ , R ^X and R ^Y are Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar in the formula (5), respectively. ⁹ , Ar ¹⁰ , m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , m ⁷ , m ⁸ , m ⁹ , m ¹⁰ , R ^X and R ^Y have the same meaning, M ¹ and X ¹ represents the same meaning as M ¹ and X ¹ in formula (b), respectively.

Similarly, a block copolymer represented by the formula (5-A) can be produced, for example, as follows.
1) and M ¹ -Ar ¹ -X ¹ terminating agent and m ¹ mole of such R ^X -X ¹ are reacted in the presence of a catalyst R ^x - were synthesized (Ar ¹⁾ _m1 -X ^{1,
2) R x - (Ar 1} ) m1 -X 1 with respect to 1 mol of M ¹ -Ar ² -X ¹ in m ² moles are reacted in the presence of a catalyst _{^{R x - (Ar 1) m1}} - (Ar ²⁾ was synthesized _m2 -X ^{1,
3) R x - (Ar 1} ) m1 - (Ar 2) m2 relative -X ¹ 1 mol of M ¹ -Ar ³ -X ¹ in m ³ moles are reacted in the presence of a catalyst R ^x - (Ar _{^{1) m1 - (Ar 2)}} m2 - (Ar 3) was synthesized _m3 -X ^1,
4) R ⁴ —M ¹ —Ar ⁴ —X ¹ is reacted with ¹ mol of R ^x — (Ar ¹ ) _{m 1} — (Ar ² ) _m ² — (Ar ³ ) _{m 3} —X ^{1 in} the presence of a catalyst. _{^{(Ar 1) m1 - - (}} Ar 2) m2 - (Ar 3) m3 - (Ar 4) were synthesized _m4 -X ^1, R ^x Te
^{5) R x - (Ar 1} ) m1 - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) with respect to _m4 -X ^1, the presence of a catalyst a terminating agent such as R ^Y -M ¹ It reacted _{^{R x - (Ar 1) m1}} - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) synthesizing _m4 -R ^Y,
An example is given.
Here, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , m ¹ , m ² , m ³ , m ⁴ , R ^X and R ^Y are respectively Ar ¹ , Ar ² , Ar ³ , Ar ⁴ in the formula (5). ^{, m 1, m 2, m} 3, m 4, the same meanings as R ^X and R ^Y, M ¹ and X ¹ have the same meanings as M ¹ and X ¹ in each formula (b).

Another example of synthesizing a block copolymer such as formula (5-A) is as follows:
1) and M ¹ -Ar ¹ -X ¹ terminating agent and m ¹ mole of such R ^X -M ¹ are reacted in the presence of a catalyst R ^x - were synthesized (Ar ¹⁾ _m1 -M ^{1,
2) R x - (Ar 1} ) with respect to _m1 -M ¹ 1 mol of M ¹ -Ar ² -X ¹ in m ² moles are reacted in the presence of a catalyst _{^{R x - (Ar 1) m1}} - (Ar ²⁾ synthesizing the _{m @ 2} -M ^1,
3) R ^x- (Ar ¹ ) _m1- (Ar ² ) _m2 -M ¹ is reacted with 1 mol of m ³ mol of M ¹ -Ar ³ -X ¹ in the presence of a catalyst to produce R ^x- ( Ar ¹ ) _m1- (Ar ² ) _m2- (Ar ³ ) _m3 -M ¹ ,
4) R ^x- (Ar ¹ ) _m ^1- (Ar ² ) _m ^2- (Ar ³ ) _{m 3} -M ^{1 is} reacted with m ⁴ mol of M ¹ -Ar ⁴ -X ¹ in the presence of a catalyst. _{^{(Ar 1) m1 - - (}} Ar 2) m2 - (Ar 3) m3 - (Ar 4) were synthesized _m4 -M ^1, R ^x Te
^{5) R x - (Ar 1} ) m1 - (Ar 2) m2 - (Ar 3) m3 - (Ar 4) to _m4 -M ¹ a terminating agent such as R ^Y -X ¹ is reacted presence of a catalyst R _{^{x - (Ar 1) m1 -}} (Ar 2) m2 - (Ar 3) m3 - (Ar 4) synthesizing _m4 -R ^Y,
An example is given. Here, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , m ¹ , m ² , m ³ , m ⁴ , R ^X and R ^Y are Ar ¹ , Ar ² , Ar ³ , Ar ⁴ in formula (5), respectively. ^{, m 1, m 2, m} 3, m 4, the same meanings as R ^X and R ^Y, M ¹ and X ¹ have the same meanings as M ¹ and X ¹ in each formula (b).

Similarly, as an example of synthesizing a block copolymer like the formula (6),
1) and M ¹ -Ar ¹ -X ¹ terminating agent and m ¹ mole of such R ^X -X ¹ are reacted in the presence of a catalyst R ^x - were synthesized (Ar ¹⁾ _m1 -X ^1,
2) With respect to 1 mol of R ^x- (Ar ¹ ) _m1 -X ¹ , m ² mol of M ¹ -Ar ² -X ¹ was reacted in the presence of a catalyst to produce R ^x- (Ar ¹ ) _m1- (Ar ²⁾ was synthesized _m2 -X ^{1,
3) R x - (Ar 1} ) m1 - (Ar 2) m2 relative -X ¹ 1 mol of M ¹ -Ar ³ -X ¹ in m ³ moles are reacted in the presence of a catalyst R ^x - (Ar _{^{1) m1 - (Ar 2)}} m2 - (Ar 3) was synthesized _m3 -X ^1,
4) R ^x- (Ar ¹ ) _m ^1- (Ar ² ) _m ^2- (Ar ³ ) _{m 3} -X ¹ is reacted with a terminal terminator such as R ^Y -M ^{1 in} the presence of a catalyst to produce R ^x- (Ar ¹ ). _{^{m1 - (Ar 2) m2 -}} (Ar 3) synthesizing _m3 -R ^Y,
An example is given. Here, Ar ¹ , Ar ² , Ar ³ , m ¹ , m ² , m ³ , R ^X and R ^Y are Ar ¹ , Ar ² , Ar ³ , m ¹ , m ² , m ³ in the formula (5), respectively. represent the same meanings as R ^X and R ^Y, M ¹ and X ¹ have the same meanings as M ¹ and X ¹ in each formula (b).

As another example of synthesizing a block copolymer such as the formula (6),
1) and M ¹ -Ar ¹ -X ¹ terminating agent and m ¹ mole of such R ^X -M ¹ are reacted in the presence of a catalyst R ^x - were synthesized (Ar ¹⁾ _m1 -M ^1,
2) With respect to 1 mol of R ^x- (Ar ¹ ) _m1 -M ¹ , m ² mol of M ¹ -Ar ² -X ¹ was reacted in the presence of a catalyst to produce R ^x- (Ar ¹ ) _m1- (Ar ²⁾ synthesizing the _{m @ 2} -M ^1,
3) R ^x- (Ar ¹ ) _m ^1- (Ar ² ) _m ² -M ^{1 is} reacted with m ³ mol of M ¹ -Ar ³ -X ¹ in the presence of a catalyst to react with R ^x- (Ar _{^{1) m1 - (Ar 2)}} m2 - (Ar 3) was synthesized _m3 -M ^1,
4) R ^x- (Ar ¹ ) _m ^1- (Ar ² ) _m ^2- (Ar ³ ) _{m 3} -M ¹ is reacted with a terminal terminator such as R ^Y -X ^{1 in} the presence of a catalyst to produce R ^x- (Ar ¹ ). _{^{m1 - (Ar 2) m2 -}} (Ar 3) synthesizing _m3 -R ^Y,
An example is given. Here, Ar ¹ , Ar ² , Ar ³ , m ¹ , m ² , m ³ , R ^X and R ^Y are Ar ¹ , Ar ² , Ar ³ , m ¹ , m ² , m ³ in formula (5), respectively. represent the same meanings as R ^X and R ^Y, M ¹ and X ¹ have the same meanings as M ¹ and X ¹ in each formula (b).

Similarly, as an example of synthesizing a block copolymer like the formula (7),
1) and M ¹ -Ar ¹ -X ¹ terminating agent and m ¹ mole of such R ^X -X ¹ are reacted in the presence of a catalyst R ^x - were synthesized (Ar ¹⁾ _m1 -X ^1,
2) With respect to 1 mol of R ^x- (Ar ¹ ) _m1 -X ¹ , m ² mol of M ¹ -Ar ² -X ¹ was reacted in the presence of a catalyst to produce R ^x- (Ar ¹ ) _m1- (Ar ²⁾ was synthesized _m2 -X ^1,
3) R ^x- (Ar ¹ ) _m ^1- (Ar ² ) _m ² -X ¹ is reacted with a terminal terminator such as R ^Y -M ^{1 in} the presence of a catalyst to produce R ^x- (Ar ¹ ) _m ^1- (Ar ² ). synthesize _m2- ^RY
An example is given. ^{Here, Ar 1, Ar 2, m} 1, m 2, R X and R ^Y are Ar ¹ in each formula ^{(5), Ar 2, m} 1, m 2, the same meanings as R ^X and R ^Y, M ¹ and X ¹ represent the same meaning as M ¹ and X ¹ in the formula (b), respectively.

As another example of synthesizing a block copolymer such as the formula (7),
1) and M ¹ -Ar ¹ -X ¹ terminating agent and m ¹ mole of such R ^X -M ¹ are reacted in the presence of a catalyst R ^x - were synthesized (Ar ¹⁾ _m1 -M ^1,
2) With respect to 1 mol of R ^x- (Ar ¹ ) _m1 -M ¹ , m ² mol of M ¹ -Ar ² -X ¹ was reacted in the presence of a catalyst to produce R ^x- (Ar ¹ ) _m1- (Ar ²⁾ synthesizing the _{m @ 2} -M ^1,
3) R ^x- (Ar ¹ ) _m1- (Ar ² ) _m ² -M ¹ is reacted with a terminal terminator such as R ^Y -X ^{1 in} the presence of a catalyst to produce R ^x- (Ar ¹ ) _m1- (Ar ² ). synthesize _m2- ^RY
An example is given. ^{Here, Ar 1, Ar 2, m} 1, m 2, R X and R ^Y are Ar ¹ in each formula ^{(5), Ar 2, m} 1, m 2, the same meanings as R ^X and R ^Y, M ¹ and X ¹ represent the same meaning as M ¹ and X ¹ in the formula (b), respectively.

  Examples of condensation polymerization catalysts include palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, bis (diphenylphosphinopropane) nickel, bis (cyclooctadiene) nickel, etc. Transition metal complexes and, if necessary, triphenylphosphine, tri-t-butylphosphine, tricyclohexylphosphine, tris (2-methylphenyl) phosphine, tris (2-methoxyphenyl) phosphine, diphenylphosphinopropane, bipyridyl A catalyst comprising a ligand such as

It is represented by the formula (b), X ¹ is selected from a halogen atom, a sulfonate group represented by the formula (c), or a methoxy group, and M ¹ is the borate group or —B (OH) When the monomer selected from two groups is subjected to condensation polymerization by Suzuki coupling reaction, palladium [tetrakis (triphenylphosphine)], palladium dichloro [bis (triphenylphosphine)], [tris (di Benzylideneacetone)] dipalladium, palladium acetate and the like, and if necessary, triarylphosphine such as triphenylphosphine, tris (2-methylphenyl) phosphine, tris (2-methoxyphenyl) phosphine, tri-t -Butylphosphine, tricyclohexylphosphine, etc. Use a catalyst comprising a ligand such as a dialkylmonoarylphosphine such as a realkylphosphine, di-t-butyl-o-biphenylphosphine, a monoalkyldiarylphosphine such as t-butyldiphenylphosphine, or a carbene type ligand. Is preferred.

  From the standpoint of increasing reactivity and suppressing side reactions, a catalyst combining [tris (dibenzylideneacetone)] dipalladium or palladium acetate as a palladium complex and triarylphosphine as a ligand is preferable. It is more possible to use a catalyst prepared by combining [tris (dibenzylideneacetone)] dipalladium or palladium acetate as a ligand and tris (2-methylphenyl) phosphine or tris (2-methoxyphenyl) phosphine as a ligand. It is preferable to use a catalyst prepared by combining [tris (dibenzylideneacetone)] dipalladium tris and (2-methoxyphenyl) phosphine.

As this catalyst, what was synthesize | combined beforehand can also be used and what was prepared in the reaction system can also be used. In this invention, this catalyst can be used individually or in mixture of 2 or more types.
The catalyst can be used in any amount, but in general, the amount of the transition metal compound relative to the compound represented by the formula (b) is preferably 0.001 to 300 mol%, and 0.005 to 50 mol%. More preferably, 0.01-20 mol% is further more preferable.

  A base may be used as necessary in the condensation polymerization. Examples of the base include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, and tripotassium phosphate, and aqueous solutions thereof, tetrabutylammonium fluoride, tetrabutylammonium chloride, and tetrabutylammonium bromide. And organic bases such as tetrabutylammonium hydroxide and aqueous solutions thereof. From the viewpoint of increasing reactivity and suppressing side reactions, an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, an aqueous cesium carbonate solution or an aqueous tetrabutylammonium hydroxide solution is preferred, an aqueous sodium carbonate solution or an aqueous cesium carbonate solution is more preferred, and cesium carbonate is preferred. An aqueous solution is more preferred.

  Although this base can be used in arbitrary quantity, generally 0.5-20 equivalent is preferable with respect to the compound shown by Formula (b), and 1-10 equivalent is more preferable.

The condensation polymerization can be carried out in the absence of a solvent, but is usually carried out in the presence of an organic solvent.
Examples of the organic solvent used include tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide and the like. These organic solvents may be used alone or in combination of two or more.

  The amount of the organic solvent used is usually such that the monomer concentration is 0.1 to 90% by weight. A preferable ratio is 1 to 50% by weight, and a more preferable ratio is 2 to 30% by weight.

  The organic solvent varies depending on the compound used and the reaction, but it is generally desirable to perform a deoxygenation treatment in order to suppress side reactions.

In the condensation polymerization, water may be used in combination so as not to inhibit the reaction.

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

It may be desirable to perform the condensation polymerization under dehydrating conditions as necessary. In particular, when M ¹ in the compound represented by the formula (b) is a group represented by the formula (d), it is necessary to perform the dehydration condition.

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

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

The polymer light emitting device of the present invention has an organic layer between electrodes composed of an anode and a cathode, and the organic layer contains the block copolymer of the present invention.
The organic layer may be any of a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, an interlayer layer, and the like, but the organic layer is preferably a light emitting layer.
Here, the light emitting layer refers to a layer having a function of emitting light, the hole transport layer refers to a layer having a function of transporting holes, and the electron transport layer is a layer having a function of transporting electrons. Say. The interlayer layer is present adjacent to the light emitting layer between the light emitting layer and the anode, and serves to isolate the light emitting layer and the anode or the light emitting layer from the hole injection layer or the hole transport layer. It is a layer that has. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. The electron injection layer and the hole injection layer are collectively referred to as a charge injection layer. Two or more light emitting layers, hole transport layers, hole injection layers, electron transport layers, and electron injection layers may be used independently.

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

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

As the hole-transporting material, electron-transporting material, and light-emitting material to be mixed, known low-molecular compounds, triplet light-emitting complexes, or polymer compounds can be used, but polymer compounds are preferably used.
As the hole transport material, electron transport material and light emitting material of the polymer compound, WO99 / 13692, WO99 / 48160, GB2340304A, WO00 / 53656, WO01 / 19834, WO00 / 55927, GB23448316, WO00 / 46321, WO00 / 06665, WO99 / 54943, WO99 / 54385, US5777070, WO98 / 06773, WO97 / 05184, WO00 / 35987, WO00 / 53655, WO01 / 34722, WO99 / 24526, WO00 / 22027, WO00 / 22026, WO98 / 27136, US573636 , WO98 / 21262, US5741921, WO97 / 09394, WO96 / 29356, WO96 / 10617, EP07070. 0, WO 95/07955, JP 2001-181618, JP 2001-123156, JP 2001-3045, JP 2000-351967, JP 2000-303066, JP 2000-299189, JP 2000-252065, JP 2000-252065, JP 2000-136379, JP 2000-104057, JP 2000-80167, JP 10-324870, JP 10-114891, JP 9-111233, JP 9-45478, and the like, and derivatives thereof And copolymers, polyarylenes, derivatives and copolymers thereof, polyarylene vinylenes, derivatives and copolymers thereof, and (co) polymers of aromatic amines and derivatives thereof.

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

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

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

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

  The film thickness of the light-emitting layer of the polymer light-emitting device of the present invention may be selected so that the optimum value varies depending on the material used and the driving voltage and the light emission efficiency are appropriate values, for example, 1 nm to 1 μm. The thickness is preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

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

The ink composition used in the printing method or the like only needs to contain at least one type of the block copolymer of the present invention. In addition to the block copolymer of the present invention, a hole transport material, an electron transport material, a light emission Additives such as materials, solvents and stabilizers may be included.
The proportion of the block copolymer of the present invention in the ink composition is usually 20 wt% to 100 wt%, preferably 40 wt% to 100 wt%, based on the total weight of the composition excluding the solvent.
When the ink composition contains a solvent, the ratio of the solvent is 1 wt% to 99.9 wt%, preferably 60 wt% to 99.5 wt%, more preferably the total weight of the composition. It is 80 wt%-99.0 wt%.
The viscosity of the ink composition varies depending on the printing method. However, when the ink composition passes through a discharge device, such as an ink jet printing method, the viscosity is 1 at 25 ° C. to prevent clogging and flight bending at the time of discharge. It is preferably in the range of ˜20 mPa · s.

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

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

Although there is no restriction | limiting in particular as a solvent used as an ink composition, The thing which can melt | dissolve or disperse | distribute materials other than the solvent which comprises this ink composition is preferable. Examples of the solvent include chloro solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran, dioxane and anisole, toluene, xylene and the like. Aromatic hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone , Ketone solvents such as benzophenone and acetophenone, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate and phenyl acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol Polyethyl alcohol and its derivatives such as noethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, methanol, ethanol, propanol, isopropanol And alcohol solvents such as cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination.
Of these, aromatic hydrocarbon solvents, ether solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents from the viewpoints of solubility of polymer compounds, uniformity during film formation, viscosity characteristics, etc. Solvents are preferred, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, s-butylbenzene, n-hexylbenzene, cyclohexylbenzene, 1-methylnaphthalene, tetralin , Anisole, ethoxybenzene, cyclohexane, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, decalin, methyl benzoate, cyclohexanone, 2-propylcyclohexanone, 2- Heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone, dicyclohexyl ketone, acetophenone, benzophenone is preferable.

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

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

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

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

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

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

The polymer light emitting device of the present invention includes a polymer light emitting device in which an electron transport layer is provided between the cathode and the light emitting layer, a polymer light emitting device in which a hole transport layer is provided between the anode and the light emitting layer, and a cathode. And a light emitting polymer layer in which an electron transport layer is provided between the anode and the light emitting layer, and a hole transport layer is provided between the anode and the light emitting layer.
For example, the following structures a) to d) are specifically exemplified.
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)
Further, for each of these structures, a structure in which an interlayer layer is provided adjacent to the light emitting layer between the light emitting layer and the anode is also exemplified. That is, the following structures a ′) to d ′) are exemplified.
a ′) Anode / interlayer layer / light emitting layer / cathode b ′) Anode / hole transport layer / interlayer layer / light emitting layer / cathode c ′) Anode / interlayer layer / light emitting layer / electron transport layer / cathode d ′ ) Anode / hole transport layer / interlayer layer / light emitting layer / electron transport layer / cathode When the polymer light emitting device of the present invention has a hole transport layer, the hole transport material used is polyvinylcarbazole or Derivatives thereof, polysilanes or derivatives thereof, polysiloxane derivatives having an aromatic amine in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or Derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof Or a poly (2,5-thienylene vinylene) or derivatives thereof.

Specifically, as the hole transporting material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2-209988 are disclosed. Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.
Among these, as a hole transporting material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, a polyaniline or a derivative thereof , Polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or a polymer hole transporting material such as poly (2,5-thienylene vinylene) or a derivative thereof, and more preferably polyvinyl carbazole or a derivative thereof A derivative, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in a side chain or main chain.

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

As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those 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, polysiloxane and the like.
Polyvinylcarbazole or a derivative thereof is obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.
Examples of the polysilane or derivatives thereof include compounds described in Chem. Rev. 89, 1359 (1989), GB 2300196 published specification, and the like. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.
Since polysiloxane or derivatives thereof have almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular hole transporting material in the side chain or main chain are preferably used. Particularly, those having a hole transporting aromatic amine in the side chain or main chain are exemplified.

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

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

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

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

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

Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, The thing etc. which are described in the same 3-152184 gazette are illustrated.
Of these, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

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

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

Examples of film formation methods from a solution or a molten state include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.
The film thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

Further, among the charge transport layers provided adjacent to the electrodes, those having a function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers). , An electron injection layer).
Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be improved. In order to prevent mixing, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.
The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

In the present invention, a polymer light emitting device provided with a charge injection layer (electron injection layer, hole injection layer) is a polymer light emitting device provided with a charge injection layer adjacent to the cathode, or a charge injection adjacent to the anode. Examples thereof include a polymer light emitting device provided with a layer.
For example, the following structures e) to p) are specifically mentioned.
e) Anode / charge injection layer / light emitting layer / cathode f) Anode / light emitting layer / charge injection layer / cathode g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode h) Anode / charge injection layer / hole Transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / charge injection layer / cathode j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode k) anode / charge Injection layer / light emitting layer / electron transport layer / cathode l) anode / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode n) anode / Charge injection layer / hole transport layer / light emitting layer / electron transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) anode / charge injection layer / hole transport Layer / light emitting layer / electron transport layer / charge injection layer / cathode For each one of these structures, the light emitting layer is adjacent to the light emitting layer between the light emitting layer and the anode. A structure in which an interlayer is provided is also exemplified. In this case, the interlayer layer may also serve as a hole injection layer and / or a hole transport layer.

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

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

Usually, in order to make the electric conductivity of the conductive polymer 10 ⁻⁵ S / cm or more and 10 ³ or less, the conductive polymer is doped with an appropriate amount of ions.
The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions, and the like.

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

  The material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer. Polyaniline and 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. A polymer light emitting device provided with an insulating layer having a thickness of 2 nm or less includes a polymer light emitting device provided with an insulating layer having a thickness of 2 nm or less adjacent to the cathode, and an insulating layer having a thickness of 2 nm or less adjacent to the anode. The provided polymer LED is mentioned.
Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode u) Anode / hole transporting layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode w) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode x) anode / Light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode y) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode z) anode / film Insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode aa) anode / hole transport layer / light emitting layer / electron transport Layer / insulating layer having a thickness of 2 nm or less / cathode ab) anode / insulating layer having a thickness of 2 nm or less / hole transporting layer / light emitting layer / electron transporting layer / insulating layer having a thickness of 2 nm or less / cathode Is also exemplified by a structure in which an interlayer is provided adjacent to the light emitting layer between the light emitting layer and the anode. In this case, the interlayer layer may also serve as a hole injection layer and / or a hole transport layer.

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

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

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

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

The substrate on which the polymer light-emitting device of the present invention is formed may be any substrate that does not change when an electrode is formed and an organic layer is formed. Examples thereof include glass, plastic, polymer film, and silicon substrate. . In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.
Usually, at least one of the anode and the cathode of the polymer light emitting device of the present invention is transparent or translucent. The anode side is preferably transparent or translucent.

  As the material of the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Further, as the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used.

The film thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there.
In order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

  A material for the cathode used in the polymer light-emitting device of the present invention is preferably a material having a low work function. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, or the like Two or more of these alloys, or one or more of them and an alloy of one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, or graphite or graphite intercalation compound Etc. are used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The cathode may have a laminated structure of two or more layers.

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

As a method for 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 light emitting device may be attached. In order to stably use the polymer light emitting device for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the device from the outside.
As the protective layer, a polymer compound, metal oxide, metal fluoride, metal boride and the like can be used. Further, as the protective cover, a metal plate, a glass plate, a plastic plate having a surface subjected to low water permeability treatment, or the like can be used. The method is preferably used. If the space is maintained by using the spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, oxidation of the cathode can be prevented, and further, a desiccant such as barium oxide is adsorbed in the manufacturing process by installing in the space. It becomes easy to suppress the minute amount of moisture entering through moisture or the cured resin from damaging the element. Among these, it is preferable to take any one or more measures.

The polymer light emitting device of the present invention can be used as a planar light source, a segment display device, a dot matrix display device, a backlight of a liquid crystal display device, and the like.
In order to obtain planar light emission using the polymer light emitting device of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic layer of a non-light-emitting portion is formed extremely thick and substantially non-light-emitting. There are a method of emitting light and a method of forming either one of the anode or the cathode or both electrodes in a pattern. By forming a pattern by any of these methods and arranging several electrodes so that they can be turned on and off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of polymeric fluorescent substances having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively or may be driven actively in combination with TFTs. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.
Furthermore, the planar light emitting element is a self-luminous thin type, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

The block copolymer of the present invention can also be used for polymer electrolyte membranes, photoelectric conversion materials, thermoelectric conversion materials and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
The NMR measurement of the monomer was performed under the following conditions.
Apparatus: INOVA300 nuclear magnetic resonance apparatus manufactured by Varian Inc. Measurement solvent: Deuterated chloroform Sample concentration: Approximately 1% by weight
Measurement temperature: 25 ° C
NMR measurement of the block copolymer of the present invention was performed under the following conditions.
Apparatus: Bruker Avance 600 nuclear magnetic resonance apparatus Measurement solvent: Deuterated tetrahydrofuran Sample concentration: About 1% by weight
Measurement temperature: 30 ° C
The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were determined by size exclusion chromatography (SEC) under the following conditions.
Equipment: Tosoh HLC-8220GPC
Column: 1 TSKguard column SuperH-H (manufactured by Tosoh) 2 TSKgel SuperHM-H (manufactured by Tosoh) 1 TSKgel SuperH2000 (manufactured by Tosoh) The above four were connected in series.
Mobile phase: Tetrahydrofuran detector: Differential refractive index detector

不活性ガス雰囲気下、５，９−ジブロモ−７，７−ジオクチル−７H−ベンゾ[ｃ]フルオレン（化合物２）７０．０ｇ（０．１２ｍｏｌ）を脱水テトラヒドロフラン１１７０ｍＬおよび脱水ジエチルエーテル１１７０ｍＬに溶解し、−６５℃に冷却した。１．６ｍｏｌ/Ｌヘキサン溶液のｎ−ブチルリチウム７３．１ｍＬ（０．１２ｍｏｌ）を−６５〜−７０℃にて３０分かけて滴下し、−７０℃にて約１時間攪拌した。次いで、２−イソプロポキシ−４，４，５，５−テトラメチル―１，３，２−ジオキサボロラン２８．６ｍL（０．１４ｍｏｌ）を−７０℃にて１０分かけて滴下し、−７０℃で約１時間攪拌し、さらに室温にて一晩攪拌した。次いで、水９３６ｍＬ、濃塩酸２３４ｍＬからなる混合液に、反応溶液を室温にて１５分かけて滴下し、さらに１５分攪拌した後、油層を水層と分離した。該油層を蒸留水、５％ＮａＨＣＯ３水溶液、蒸留水の順で洗浄、分液した後、濃縮し油状の粗生成物７７ｇ得た。該粗生成物をテトラヒドロフラン３１ｍＬに溶解し、メタノール３０６ｍＬを滴下し結晶を析出させ、濾過、洗浄、減圧乾燥をして、固体を得た。上記固体をさらにテトラヒドロフランとメタノールから再結晶を２回実施し、化合物１を５７．７ｇ（純度９９．９％、収率７６％）得た。
¹Ｈ−ＮＭＲ：０．５０（ｂｒ,４Ｈ）、０．８０（ｔ,６Ｈ）、０．９２〜１．２６（ｍ,２０Ｈ）、１．４６（ｓ,１２Ｈ）、２．０５（ｍ,４Ｈ）、７．５７〜７．５１（ｍ,４Ｈ）、８．１９（ｄ,１Ｈ）、８．６６（ｄ,１Ｈ）、８．９２（ｄ,１Ｈ）
ＬＣ−ＭＳ：６４４（Ｍ⁺）

[Synthesis Example 1]
<2- (9-Bromo-7,7-dioctyl-7H-benzo [c] fluoren-5-yl) -4,4,5,5-tetramethyl- [1,3,2] dioxaborolane (Compound 1) Synthesis>

Under an inert gas atmosphere, 70.0 g (0.12 mol) of 5,9-dibromo-7,7-dioctyl-7H-benzo [c] fluorene (compound 2) was dissolved in 1170 mL of dehydrated tetrahydrofuran and 1170 mL of dehydrated diethyl ether, Cooled to -65 ° C. A 1.6 mol / L hexane solution of n-butyllithium 73.1 mL (0.12 mol) was added dropwise at −65 to −70 ° C. over 30 minutes, and the mixture was stirred at −70 ° C. for about 1 hour. Then, 28.6 mL (0.14 mol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise at −70 ° C. over 10 minutes, and at −70 ° C. The mixture was stirred for about 1 hour, and further stirred overnight at room temperature. Next, the reaction solution was dropped into a mixed solution consisting of 936 mL of water and 234 mL of concentrated hydrochloric acid over 15 minutes at room temperature, and further stirred for 15 minutes, and then the oil layer was separated from the aqueous layer. The oil layer was washed with distilled water, 5% NaHCO 3 aqueous solution and distilled water in this order, separated, and concentrated to obtain 77 g of an oily crude product. The crude product was dissolved in 31 mL of tetrahydrofuran, 306 mL of methanol was added dropwise to precipitate crystals, filtered, washed and dried under reduced pressure to obtain a solid. The solid was further recrystallized twice from tetrahydrofuran and methanol to obtain 57.7 g of compound 1 (purity 99.9%, yield 76%).
¹ H-NMR: 0.50 (br, 4H), 0.80 (t, 6H), 0.92-1.26 (m, 20H), 1.46 (s, 12H), 2.05 (m , 4H), 7.57 to 7.51 (m, 4H), 8.19 (d, 1H), 8.66 (d, 1H), 8.92 (d, 1H)
LC-MS: 644 (M ^<+> )

乾燥した四つ口フラスコにアルゴン雰囲気下、ビス−(４−ブロモ−フェニル)−(４−tert−ブチル−２，６−ジメチル−フェニル)アミン ９１．８９ｇ (１８８．５８ｍｍｏｌ)を仕込み、脱水テトラヒドロフラン２７５０ｍＬを加えて均一にした。反応溶液を−７０℃に冷却し、１．５４Ｍのｎ−ブチルリチウムのｎ−ヘキサン溶液９８ｍＬ (１５０．９ｍｍｏｌ)を７８分かけて滴下し、そのまま６５分間攪拌した。次いで、２−イソプロポキシ−４，４，５，５−テトラメチル―１，３，２−ジオキサボロラン３５．１ｇ (１８８．６５ｍｍｏｌ)を−７０℃で６０分かけて滴下しそのまま１時間攪拌し、その後１５〜２０℃に昇温し２時間攪拌した。室温で水１Lを仕込み１時間攪拌した後、減圧濃縮によってテトラヒドロフランを留去した。濃縮した懸濁液にトルエン２Ｌを加え攪拌した後、油層を水層と分液した。上記３回の分液操作で得られた油層を合一し、無水硫酸ナトリウムを加え攪拌した。無水硫酸ナトリウムを濾別し、得られた濾液を減圧濃縮し白色固体１１３．５４ｇを得た。この白色固体をトルエン、ｎ−ヘキサンを展開液とするシリカゲルカラムクロマトグラフィーによって精製し濃縮乾固し、黄白色固体４５．５ｇを得た。この黄白色をテトラヒドロフラン８００ｍＬに溶解し、２５℃にて蒸留水８００ｍＬを３時間かけて滴下し結晶を析出させ１時間攪拌後ろ過するという操作を７回繰り返し、得られた結晶を減圧乾燥し、化合物３を白色固体として得た（収量４０．２ｇ、収率３７．８%、ＬＣ面百値９８．０%）。
１Ｈ−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]
<(4-Bromo-phenyl)-(4-tert-butyl-2,6-dimethyl-phenyl)-[4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolane-2 Synthesis of -yl) -phenyl] -amine (Compound 3)>

A dry four-necked flask was charged with 91.89 g (188.58 mmol) of bis- (4-bromo-phenyl)-(4-tert-butyl-2,6-dimethyl-phenyl) amine under an argon atmosphere, and dehydrated tetrahydrofuran. 2750 mL was added to make uniform. The reaction solution was cooled to −70 ° C., and 98 mL (150.9 mmol) of 1.54 M n-butyllithium in n-hexane 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 the mixture was stirred as it was for 1 hour. Thereafter, the temperature was raised to 15 to 20 ° C. and 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, Compound 3 was obtained as a white solid (yield 40.2 g, yield 37.8%, LC area percentage 98.0%).
1H-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 3]
<Synthesis of Random Copolymer 1>
Under an inert gas atmosphere, 0.70 g (1.2 mmol) of Compound 2 and 0.24 g (0 of bis- (4-bromo-phenyl)-(4-tert-butyl-2,6-dimethyl-phenyl) amine were obtained. .50 mmol), 0.63 g (4.0 mmol) of 2,2′-bipyridyl, 1.10 g (4.0 mmol) of bis (1,5-cyclooctadiene) nickel (0), and 50 mL of dehydrated tetrahydrofuran were added. And stirred at 60 ° C. for 5 hours. After the reaction, this reaction solution was cooled to room temperature, dropped into a mixed solution of 25% aqueous ammonia 5 ml / methanol 50 ml / ion exchanged water 50 ml and stirred, and then the deposited precipitate was filtered and dried under reduced pressure. Subsequently, it melt | dissolved in toluene 50mL, the radiolite was added and stirred, and the insoluble matter was filtered. The obtained filtrate was purified through an alumina column. Next, 5.2% aqueous hydrochloric acid was added and stirred, the aqueous layer was removed, 4% aqueous ammonia was added to the organic layer and stirred, the aqueous layer was removed, and ion-exchanged water was further added to the organic layer and stirred. The layer was removed. Thereafter, the organic layer was poured into methanol and stirred, and the deposited precipitate was filtered and dried under reduced pressure to obtain Random Copolymer 1. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 3.5 × 10 ⁴ and Mw = 1.0 × 10 ⁵ , respectively. The molar ratio of the following divalent group 1 and divalent group 2 of the random copolymer was 70:30.

[Synthesis Example 4]
<Synthesis of Random Copolymer 2>
Under an inert gas atmosphere, 0.80 g (1.3 mmol) of Compound 2 and 0.65 g of bis- (4-bromo-phenyl)-(4-tert-butyl-2,6-dimethyl-phenyl) amine (1 .3 mmol), 1.00 g (6.4 mmol) of 2,2′-bipyridyl, 1.8 g (6.4 mmol) of bis (1,5-cyclooctadiene) nickel (0), and 150 mL of dehydrated tetrahydrofuran were added. And stirred at 60 ° C. for 4 hours. After the reaction, this reaction solution was cooled to room temperature, dropped into a mixed solution of 25% ammonia water 15 ml / methanol 150 ml / ion-exchanged water 150 ml and stirred, and then the deposited precipitate was filtered and dried under reduced pressure. Subsequently, it melt | dissolved in 150 mL of toluene, the radiolite was added and stirred, and the insoluble matter was filtered. The obtained filtrate was purified through an alumina column. Next, 5.2% aqueous hydrochloric acid was added and stirred, the aqueous layer was removed, 4% aqueous ammonia was added to the organic layer and stirred, the aqueous layer was removed, and ion-exchanged water was further added to the organic layer and stirred. The layer was removed. Thereafter, the organic layer was poured into methanol and stirred, and the deposited precipitate was filtered and dried under reduced pressure to obtain Random Copolymer 2. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 1.9 × 10 ⁴ and Mw = 6.5 × 10 ⁴ , respectively. The molar ratio of the divalent group 1 to the divalent group 2 of the random copolymer was 50:50.

[Example 1]
<Synthesis of Block Copolymer 1>
A 200 mL three-necked flask was charged with 1.00 g (1.5 mmol) of Compound 1, and the inside of the flask was replaced with argon gas. Next, 6.6 mg (0.03 mmol) of 4-t-butylbromobenzene and 34 mL of toluene were added and stirred at 45 ° C. for 5 minutes. Next, 2.2 mg (0.002 mmol) of tris (dibenzylideneacetone) dipalladium and 6.6 mg (0.019 mmol) of tris (2-methoxyphenyl) phosphine were added, and the mixture was stirred at 45 ° C. for 10 minutes. 7.0 mL of an aqueous cesium solution was added and stirred at 45 ° C. for 7 minutes. Next, the mixture was stirred at 110 ° C. for 3 hours, and disappearance of Compound 1 was confirmed by high performance liquid chromatography. The molecular weight of the peak top in SEC of the polymer compound at this time was confirmed to be 7.1 × 10 ⁴ . . Next, 0.82 g (1.5 mmol) of Compound 3 and 10 mL of toluene were added, and the mixture was stirred at 110 ° C. for 21 hr, and disappearance of Compound 3 was confirmed by high performance liquid chromatography. It was confirmed that the top molecular weight was 8.9 × 10 ⁴ and the molecular weight was increased by copolymerization. Next, 0.17 g (0.78 mmol) of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene and 2 mL of toluene were added, and the mixture was stirred at 110 ° C. for 3 hours. did. After cooling to room temperature, the reaction solution was added dropwise to 500 mL of ethanol, and the resulting precipitate was filtered and dried to obtain a yellow solid. The yellow solid was dissolved in 65 mL of toluene, subjected to silica gel and activated alumina column chromatography, and concentrated to dryness. A solution obtained by dissolving the obtained solid in chloroform was added dropwise to ethanol, and the deposited precipitate was filtered and dried to obtain 0.82 g of a solid. 0.73 g of the solid was dissolved in tetrahydrofuran, and the precipitate obtained by dropping the solution into acetone was filtered and dried four times. Thus, 0.40 g of the target block copolymer 1 was obtained. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 7.2 × 10 ⁴ and Mw = 1.1 × 10 ⁵ , respectively. From the result of elemental analysis of the block copolymer, the molar ratio of the divalent group 1 to the divalent group 2 was 73:27. Accordingly, the block copolymer 1 comprises a block having a divalent group 1 as a constituent unit and two blocks having a divalent group 2 as a constituent unit. The chemical formula weight of the divalent group 1 and the divalent group 2 Are 438.7 and 327.4, respectively, so that the number average degree of polymerization of a block having a divalent group 1 as a constituent unit is 120, and the number average degree of polymerization of a block having a divalent group 2 as a constituent unit is Was 59.

<Fractionation of block copolymer 1 by SEC>
200.2 mg of block copolymer 1 was weighed and dissolved in 40 ml of toluene, and 200 μl each was injected into the SEC column to separate the high molecular weight component of block copolymer 1. The SEC column is a Tosoh TSKgel GMH _HR- 3000 column and one TSKgel GMH _HR- 4000 column connected in series, and the chromatographic apparatus is Shimadzu LC-10Avp, with tetrahydrofuran as the mobile phase at 60 ° C. SEC was performed. The flow rate was 1.0 ml / min and the eluent was collected at 30 second intervals. Among the fractions, the fraction after 10.5 minutes to 11 minutes before injection (fr. 2) and the fraction after 11 minutes before 11.5 minutes (fr. 3) are collectively removed to remove the solvent, and the block copolymer 1A was obtained. The fr. 2 and fr. The polystyrene-converted Mn and Mw of 3 were as follows.

<NMR measurement of block copolymer 1A>
The block copolymer 1A was made into a tetrahydrofuran-d ₈ solution, and the TOCSY spectrum was measured at 30 ° C. The NMR apparatus was an Avance 600 nuclear magnetic resonance apparatus manufactured by Bruker.

（Ｚ１）
（ただし、式（Ｚ１）においてＲはＣ₈Ｈ₁₇基を表す。） In the TOCSY spectrum, at the positions of (F1 axis, F2 axis) = (7.11 ppm, 7.67 ppm) and (F1 axis, F2 axis) = (7.67 ppm, 7.11 ppm), the formula (Z1) _A cross peak between protons indicated by H _A and H _B was clearly observed in FIG. This means that in the block copolymer 1A, a block having a divalent group 1 as a constituent unit and a block having a divalent group 2 as a constituent unit are bonded by a chemical bond.

(Z1)
(In the formula (Z1), R represents a C ₈ H ₁₇ group.)

（Ｚ２）
（ただし、式（Ｚ２）においてＲはＣ₈Ｈ₁₇基を表す。） On the other hand, the said TOCSY spectrum, the appearance position of the cross peaks between protons represented by H _C and H _D in formula (Z2), namely (F1 axis, F2 axis) = (7.97ppm, 8.60ppm), and No peak was observed at (F1 axis, F2 axis) = (8.60 ppm, 7.97 ppm).

(Z2)
(In the formula (Z2), R represents a C ₈ H ₁₇ group.)

（Ｚ３）
（ただし、式（Ｚ３）においてＲはＣ₈Ｈ₁₇基を表す。） Furthermore, the appearance position of the cross peak between protons represented by H _E and H _F in the formula (Z3), that is, (F1 axis, F2 axis) = (7.38 ppm, 7.67 ppm), and (F1 axis, F2 axis) ) = (7.67 ppm, 7.38 ppm), no peak was observed.

(Z3)
(In the formula (Z3), R represents a C ₈ H ₁₇ group.)

（Ｚ４）
（ただし、式（Ｚ４）においてＲはＣ₈Ｈ₁₇基を表す。） Furthermore, in the formula (Z4), the appearance positions of cross peaks between protons represented by H _G and H _H , that is, (F1 axis, F2 axis) = (7.43 ppm, 7.18 ppm), and (F1 axis, F2 No peak was observed at (axis) = (7.18 ppm, 7.43 ppm).

(Z4)
(In the formula (Z4), R represents a C ₈ H ₁₇ group.)

By summing up these findings, the block having the divalent group 1 of the block copolymer 1A as a structural unit is a head-head bond represented by the formula (Z3) or a tail-tail bond represented by the formula (Z2). Is so high that the head-tail regularity cannot be detected on the NMR spectrum. On the other hand, it is clear from the reaction using the model compound that even in the block having the divalent group 2 as a structural unit, the reaction in which two Br groups of the monomer of the compound 3 are eliminated and coupled does not occur. Thus, in the block copolymer 1A, the structure of the reaction point of the block having the divalent group 1 as the structural unit and the block having the divalent group 2 as the structural unit is represented by the formula (Z1). It is shown that there is only one kind of such structure, and there is only one such structure per molecule of the block copolymer 1A. Accordingly, it was confirmed that the block copolymer 1A was composed of a block having a divalent group 1 as a structural unit and two blocks having a divalent group 2 as a structural unit.

[Example 2]
<Synthesis of Block Copolymer 2>
A 300 mL three-necked flask was charged with 1.00 g (1.5 mmol) of Compound 1, and the inside of the flask was replaced with argon gas. Next, 6.6 mg (0.03 mmol) of 4-t-butylbromobenzene and 34 mL of toluene were added and stirred at 45 ° C. for 5 minutes. Next, 2.1 mg (0.002 mmol) of tris (dibenzylideneacetone) dipalladium and 6.5 mg (0.018 mmol) of tris (2-methoxyphenyl) phosphine were added, and the mixture was stirred at 45 ° C. for 10 minutes. 7.0 mL of a cesium aqueous solution was added and stirred at 45 ° C. for 5 minutes. Next, the mixture was stirred at 110 ° C. for 2.5 hours, and disappearance of Compound 1 was confirmed by high performance liquid chromatography. The molecular weight at the peak top in SEC of the polymer compound at this time was 5.2 × 10 ^4. confirmed. Then, 2.23 g (4.2 mmol) of compound 3, 5.7 mg (0.006 mmol) of tris (dibenzylideneacetone) dipalladium, 17.4 mg (0.049 mmol) of tris (2-methoxyphenyl) phosphine, 33 19 mL of a weight% aqueous cesium carbonate solution and 9 mL of toluene were added and stirred at 110 ° C. for 17 hours, and disappearance of compound 3 was confirmed by high performance liquid chromatography. The molecular weight of the peak top in SEC of the polymer compound at this time was 8.1. × a 10 ^4, a molecular weight was confirmed to have increased by copolymerization. Next, 0.46 g (2.1 mmol) of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene and 2 mL of toluene were added, and the mixture was stirred at 110 ° C. for 3 hours. did. The same purification operation as in Example 1 was performed to obtain 1.1 g of the target block copolymer 2. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 5.1 × 10 ⁴ and Mw = 8.1 × 10 ⁴ , respectively. From the result of elemental analysis of the block copolymer, the molar ratio of the divalent group 1 to the divalent group 2 was 42:58. Accordingly, the block copolymer 2 comprises a block having a divalent group 1 as a constituent unit and two blocks having a divalent group 2 as a constituent unit, and the chemical formula weight of the divalent group 1 and the divalent group 2 Are 438.7 and 327.4, respectively, so that the number average degree of polymerization of the block having the divalent group 1 as the structural unit is 49, and the number average degree of polymerization of the block having the divalent group 2 as the structural unit. Was 90.

[Example 3]
<Synthesis of Block Copolymer 3>
A 300 mL three-necked flask was charged with 1.00 g (1.5 mmol) of Compound 1, and the inside of the flask was replaced with argon gas. Next, 6.6 mg (0.03 mmol) of 4-t-butylbromobenzene and 34 mL of toluene were added and stirred at 45 ° C. for 5 minutes. Next, 2.1 mg (0.002 mmol) of tris (dibenzylideneacetone) dipalladium and 6.6 mg (0.018 mmol) of tris (2-methoxyphenyl) phosphine were added and stirred at 45 ° C. for 10 minutes. 7.0 mL of a cesium aqueous solution was added and stirred at 45 ° C. for 5 minutes. Next, the mixture was stirred at 110 ° C. for 4 hours, and disappearance of Compound 1 was confirmed by high performance liquid chromatography. The molecular weight of the peak top in SEC of the polymer compound at this time was confirmed to be 5.6 × 10 ⁴ . . Then, 5.12 g (9.6 mmol) of compound 3, 13.2 mg (0.014 mmol) of tris (dibenzylideneacetone) dipalladium, 40.6 mg (0.115 mmol) of tris (2-methoxyphenyl) phosphine, 33 44 mL of a weight% aqueous cesium carbonate solution and 10 mL of toluene were added, and the mixture was stirred at 110 ° C. for 14.5 hr. The disappearance of compound 3 was confirmed by high performance liquid chromatography. It was 0.0 × 10 ⁵ , and it was confirmed that the molecular weight was increased by copolymerization. Next, 1.05 g (4.8 mmol) of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene and 2 mL of toluene were added, and the mixture was stirred at 110 ° C. for 3 hours. did. The same purification operation as in Example 1 was performed to obtain 2.5 g of the target block copolymer 3. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 7.2 × 10 ⁴ and Mw = 1.2 × 10 ⁵ , respectively. From the result of elemental analysis of the block copolymer, the molar ratio of the divalent group 1 to the divalent group 2 was 24:76. Therefore, the block copolymer 3 comprises a block having a divalent group 1 as a constituent unit and two blocks having a divalent group 2 as a constituent unit. The chemical formula weight of the divalent group 1 and the divalent group 2 Are 438.7 and 327.4, respectively. Therefore, the number average degree of polymerization of the block having the divalent group 1 as the structural unit is 39, and the number average degree of polymerization of the block having the divalent group 2 as the structural unit. Was 167.

[Comparative Example 1]
<Creation of a light-emitting element using random copolymer 1>
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, Bytron P AI4083) was spin-coated to a glass substrate with an ITO film having a thickness of 150 nm formed by sputtering. Then, the film was formed on a hot plate and dried at 200 ° C. for 10 minutes. Next, the random copolymer 1 obtained in Synthesis Example 3 was dissolved in toluene. At this time, it prepared so that the density | concentration of solid content might be 1.6 wt%. A film was formed at 2800 rpm by spin coating using this toluene solution. Then, after drying at 90 ° C. for 1 hour at a vacuum of 5 × 10 ⁻³ Pa or less, lithium fluoride was deposited as a cathode at about 4 nm, then calcium was deposited at 5 nm, and finally aluminum was deposited at about 100 nm to obtain an organic EL device. Produced. The element configuration is ITO / Baytron P (80 nm) / Random Copolymer 1 (80 nm) / LiF / Ca / Al. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.
When voltage was applied to the resulting device, blue light emission with a peak wavelength of 460 nm derived from random copolymer 1 was exhibited. The maximum luminous efficiency of this device was 0.60 cd / A.

[Example 4]
<Creation of light-emitting element using block copolymer 1>
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, Bytron P AI4083) was spin-coated to a glass substrate with an ITO film having a thickness of 150 nm formed by sputtering. Then, the film was formed on a hot plate and dried at 200 ° C. for 10 minutes. Next, the block copolymer 1 obtained in Example 1 was dissolved in toluene. At this time, it prepared so that the density | concentration of solid content might be 1.6 wt%. A film was formed at 2800 rpm by spin coating using this toluene solution. Then, after drying at 90 ° C. for 1 hour at a vacuum of 5 × 10 ⁻³ Pa or less, lithium fluoride was deposited as a cathode at about 4 nm, then calcium was deposited at 5 nm, and finally aluminum was deposited at about 100 nm to obtain an organic EL device. Produced. The element configuration is
ITO / Baytron P (80 nm) / Block copolymer 1 (80 nm) / LiF / Ca / Al. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.
When voltage was applied to the resulting device, blue light emission having a peak wavelength of 460 nm derived from the block copolymer 1 was exhibited. The maximum luminous efficiency of this device was 1.36 cd / A.
As described above, the block copolymer according to the present invention exhibits higher luminous efficiency than the random copolymer of Comparative Example 1, and has excellent properties as a material used for the polymer light emitting device.

[Comparative Example 2]
<Creation of a light-emitting element using the random copolymer 2>
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, Bytron P AI4083) was spin-coated to a glass substrate with an ITO film having a thickness of 150 nm formed by sputtering. Then, the film was formed on a hot plate and dried at 200 ° C. for 10 minutes. Next, the random copolymer 2 obtained in Synthesis Example 4 was dissolved in toluene. At this time, it prepared so that the density | concentration of solid content might be 1.8 wt%. A film was formed at 1200 rpm by spin coating using this toluene solution. Then, after drying at 90 ° C. for 1 hour at a vacuum of 5 × 10 ⁻³ Pa or less, lithium fluoride was deposited as a cathode at about 4 nm, then calcium was deposited at 5 nm, and finally aluminum was deposited at about 100 nm to obtain an organic EL device. Produced. The element configuration is
ITO / Baytron P (80 nm) / random copolymer 2 (80 nm) / LiF / Ca / Al. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.
When voltage was applied to the resulting device, blue light emission with a peak wavelength of 460 nm derived from random copolymer 2 was exhibited. The maximum luminous efficiency of this device was 0.08 cd / A.

[Example 5]
<Creation of light-emitting element using block copolymer 2>
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, Bytron P AI4083) was spin-coated to a glass substrate with an ITO film having a thickness of 150 nm formed by sputtering. Then, the film was formed on a hot plate and dried at 200 ° C. for 10 minutes. Next, the block copolymer 2 obtained in Example 2 was dissolved in toluene. At this time, it prepared so that the density | concentration of solid content might be 1.8 wt%. A film was formed at 1200 rpm by spin coating using this toluene solution. Then, after drying at 90 ° C. for 1 hour at a vacuum of 5 × 10 ⁻³ Pa or less, lithium fluoride was deposited as a cathode at about 4 nm, then calcium was deposited at 5 nm, and finally aluminum was deposited at about 100 nm to obtain an organic EL device. Produced. The element configuration is
ITO / Baytron P (80 nm) / Block copolymer 2 (80 nm) / LiF / Ca / Al. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.
When voltage was applied to the resulting device, blue light emission having a peak wavelength of 460 nm derived from the block copolymer 2 was exhibited. The maximum luminous efficiency of this device was 0.61 cd / A.
As described above, the block copolymer according to the present invention exhibits higher luminous efficiency than the random copolymer of Comparative Example 2, and has excellent properties as a material used for the polymer light emitting device.

（化合物４）
[Synthesis Example 5]
<Synthesis of alternating copolymer 1>
In a 200 mL three-necked flask, 0.703 g (1.02 mmol) of the following compound 4 and 0.491 g of bis- (4-bromo-phenyl)-(4-tert-butyl-2,6-dimethyl-phenyl) amine (1. 01 mmol) was charged, and the inside of the flask was replaced with argon gas. Next, 21.5 mL of toluene was charged and stirred at 45 ° C. for 5 minutes. Next, 2.70 mg (0.0029 mmol) of tris (dibenzylideneacetone) dipalladium, 8.22 mg (0.023 mmol) of tris (2-methoxyphenyl) phosphine and 4.0 mL of toluene were added, and the mixture was stirred at 45 ° C. for 10 minutes. Then, 9.1 mL of 33 wt% aqueous cesium carbonate solution was added, and the mixture was stirred at 114 ° C. for 2 hours and 10 minutes. Next, 2.75 mg (0.0030 mmol) of tris (dibenzylideneacetone) dipalladium, 8.56 mg (0.024 mmol) of tris (2-methoxyphenyl) phosphine, and 4.0 mL of toluene were added. Subsequently, the mixture was stirred at 114 ° C. for 2 hours and 20 minutes, and the disappearance of compound 4 and bis- (4-bromo-phenyl)-(4-tert-butyl-2,6-dimethyl-phenyl) amine was confirmed by high performance liquid chromatography. confirmed. Next, 42.6 mg (0.20 mmol) of 4-t-butylbromobenzene and 2.0 mL of toluene were added, and 0.87 mg (0.001 mmol) of tris (dibenzylideneacetone) dipalladium and tris (2-methoxy) were added. Phenyl) phosphine 2.57 mg (0.0073 mmol), toluene 1.0 mL, 33 wt% cesium carbonate aqueous solution 2.7 mL were added. Next, the mixture was stirred at 114 ° C. for 2 hours and 25 minutes, and then 0.090 g (0.41 mmol) of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene. Then, 2.0 mL of toluene was added, and the mixture was stirred at 114 ° C. for 2 hours.
After cooling to room temperature, the organic layer of the reaction solution was added dropwise to 165 mL of methanol, and the resulting precipitate was filtered and dried to obtain a yellow solid. The yellow solid was dissolved in 71 mL of toluene, subjected to silica gel and activated alumina column chromatography, concentrated and dried to obtain 0.59 g of a solid. The solid obtained by dissolving 0.59 g of the solid in tetrahydrofuran and dropping the solution into acetone was filtered and dried three times. Further, the solid was dissolved in toluene, and the solution was dropped into methanol to precipitate. Was filtered and dried to obtain 0.52 g of the intended alternating copolymer 1. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 6.5 × 10 ⁴ and Mw = 1.1 × 10 ⁵ , respectively. From the result of elemental analysis of the alternating copolymer, the molar ratio of the divalent group 1 to the divalent group 2 was 54:46.

(Compound 4)

（化合物８）

（化合物９）
[Synthesis Example 9]
<Synthesis of hole transporting polymer 1>
Under an inert gas atmosphere, 1.59 g (3.0 mmol) of the following compound 8 in the reaction vessel, 1.38 g (3.0 mmol) of the following compound 9, palladium acetate (2.0 mg), tris (2-methoxyphenyl) Phosphine (22.2 mg), Aliquat 336 (0.39 g, manufactured by Aldrich) and toluene (30 ml) were mixed and heated to 105 ° C. To this reaction solution, 2M Na ₂ CO ₃ aqueous solution (8.2 ml) was added dropwise and refluxed for 2 hours. After the reaction, phenylboric acid (37 mg) was added, and the mixture was further refluxed for 2 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, it was washed twice with water (40 ml), twice with 3% aqueous acetic acid (40 ml) and twice with water (40 ml), and the resulting solution was added dropwise to methanol (465 mL) and precipitated by filtration. I got a thing. The precipitate was dissolved in toluene (93 mL) and purified by passing through an alumina column and a silica gel column. The obtained toluene solution was added dropwise to methanol (465 ml) and stirred, and then the resulting precipitate was collected by filtration and dried. The yield of the obtained hole transporting polymer 1 was 1.4 g. The hole-transporting polymer 1 had a polystyrene-equivalent number average molecular weight of 1.1 × 10 ⁵ and a polystyrene-equivalent weight average molecular weight of 2.8 × 10 ⁵ .

(Compound 8)

(Compound 9)

[Example 6]
<Creation of light-emitting element using block copolymer 2>
Preparation of Solution The block copolymer 2 obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.8% by weight.
Preparation of EL element A suspension of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (manufactured by Bayer, BaytronP CH8000) on a glass substrate on which an ITO film is formed to a thickness of 150 nm by sputtering is used. A thin film having a thickness of 60 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 xylene solution (concentration 0.5 wt%) of the hole transporting polymer compound 1 obtained above, a thin film having a thickness of 10 nm was formed by spin coating at a rotational speed of 3000 rpm. Thereafter, heat treatment was performed at 180 ° C. for 15 minutes on a hot plate in a nitrogen atmosphere.
On the layer of the hole transporting polymer compound 1 thus formed, a film was formed by spin coating at a rotational speed of 3200 rpm using the xylene solution of the block copolymer 2 obtained above. The film thickness after film formation was about 80 nm. Further, this was dried on a hot plate at 130 ° C. for 20 minutes under a nitrogen atmosphere, and then barium was deposited as a cathode at about 5 nm and then aluminum was deposited at about 83 nm to produce an EL device. The degree of vacuum metal vapor deposition was initiated after reaching below 1 × 10 ^-4 Pa.
EL device performance By applying a voltage to the obtained device, EL light emission having a peak at 450 nm was obtained from this device. The EL emission color at a luminance of 100 cd / m 2 is represented by C.I. I. E. In terms of color coordinate values, x = 0.150 and y = 0.126. The intensity of EL emission was almost proportional to the current density. The driving voltage at 100 cd / m 2 was 7.8V. The device started to emit light from 4.9 V, and the maximum light emission efficiency was 0.07 cd / A.

[Comparative Example 3]
<Creation of light-emitting element using alternating copolymer 1>
Preparation of Solution The alternating copolymer 1 obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.8% by weight.
Production of EL device An EL device was produced in the same manner as in Example 6 except that the xylene solution of the alternating copolymer 1 obtained above was used instead of the xylene solution of the block copolymer 2. The rotation speed during spin coating was 2000 rpm, and the film thickness after film formation was about 82 nm.
EL device performance By applying a voltage to the obtained device, EL light emission having a peak at 455 nm was obtained from this device. The EL emission color at a luminance of 100 cd / m 2 is represented by C.I. I. E. In terms of color coordinate values, x = 0.186 and y = 0.206. The intensity of EL emission was almost proportional to the current density. The driving voltage at 100 cd / m 2 was 9.8V. The device started to emit light at 5.8 V, and the maximum light emission efficiency was 0.01 cd / A.
FIG. 1 shows the voltage-current characteristics and FIG. 2 shows the voltage-luminance characteristics of the element of the block copolymer 2 in Example 6 and the element of the alternating copolymer 1 in Comparative Example 3. (In the figure, ◯ indicates the block copolymer 2 and □ indicates the alternating copolymer 1.) As can be seen from the figure, the block copolymer 2 has a current density at the same voltage as that of the alternating copolymer 1. It can also be seen that the luminance is large. Further, since the block copolymer 2 has a lower emission starting voltage and higher luminous efficiency than the alternating copolymer 1, it can be said that the block copolymer 2 is a more suitable material for use in an electroluminescent device.

（化合物５）


[Synthesis Example 6]
<Synthesis of Compound 5>
Under an inert atmosphere, 31.26 g (57.0 mmol) of 2,7-dibromo-9,9-dioctylfluorene and 390 mL of t-butyl methyl ether were added to the reaction vessel, and 1 of n-butyl lithium was added at -70 ° C. A 6M hexane solution was added dropwise over 30 minutes, the mixture was stirred at -20 ° C for 2 hours, and stirred at 0 ° C for 2 hours. Next, 17.5 mL (76.1 mmol) of triisopropoxyborane was added dropwise at −70 ° C. over 20 minutes, stirred at the same temperature for 1 hour, and stirred at room temperature for 16 hours. Subsequently, 88 mL of 5% hydrochloric acid aqueous solution was dripped over 20 minutes at -20 degreeC, and it stirred at room temperature for 30 minutes. The operation of removing the aqueous layer from the organic layer, adding 88 mL of water to the organic layer and stirring to remove the aqueous layer from the organic layer was repeated three times, and adding 88 mL of saturated brine to the organic layer and stirring to remove the aqueous layer from the organic layer The obtained organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off. Subsequently, silica gel chromatography was performed using hexane and chloroform as developing solvents, and the solvent was distilled off and dried under reduced pressure to obtain 15.87 g of a white solid. Under an inert atmosphere, 6.89 g of the solid, 1.50 g of catechol, and 100 mL of toluene were added to a reaction vessel equipped with a Dean Stark, and the mixture was stirred for 8 hours while dehydrating and refluxing at 100 ° C. The mixture was cooled to room temperature and concentrated to dryness to obtain 7.93 g of a solid. The solid was recrystallized once from hexane and acetonitrile, recrystallized twice from chloroform and acetonitrile, recrystallized once from hexane, and 3.30 g (yield 22.7%) of the target compound 5. LC surface percentage: 99.6%).

(Compound 5)

（化合物６−１）

[Synthesis Example 7]
<Synthesis of Compound 6-1>
To the reaction vessel, 200.0 g (0.855 mol) of 4-iodoanisole, 441.0 g (2.56 mol) of 4-bromoaniline and 5.60 g (0.031 mol) of 1,10-phenanthroline were added. The inside was replaced with argon gas, and 545 mL of toluene was added. To this, 3.08 g (0.031 mol) of cuprous chloride, 374.9 g (6.68 mol) of potassium hydroxide and 11 mL of toluene were added, and the mixture was stirred at 125 ° C. for 2 hours. After cooling to room temperature, 545 mL of chloroform was added and filtered, the filtrate was washed with 2N hydrochloric acid and distilled water, and the organic layer was concentrated to dryness to obtain 141.8 g of a dark purple substance. The dark purple substance 14.9 g was purified by silica gel column chromatography (developing solvent hexane / chloroform 1: 3), and the eluate was concentrated to dryness and vacuum dried to obtain 4.4 g of the intended compound 6-1. (Yield 18%) was obtained.
LC-MS (APPI / posi): 278 [M + H ⁺ ]

(Compound 6-1)

（化合物６−２）

<Synthesis of Compound 6-2>
10.00 g (36.0 mmol) of the above compound 6-1 in a reaction vessel, p-diiodobenzene 35.58 g (108 mmol), 1,10-phenanthroline 0.24 g (1.3 mmol). In addition, the inside of the container was replaced with argon gas, and 206 mL of toluene was added. Thereto were added cupric chloride (0.13 g, 1.3 mmol), potassium hydroxide (15.77 g, 281 mmol), and toluene (4 mL), and the mixture was stirred at 125 ° C. for 7 hours. After cooling to room temperature, 206 mL of chloroform was added and filtered, and the filtrate was concentrated to dryness. The concentrate was dissolved in chloroform, and methanol was added dropwise to precipitate a precipitate. The precipitate was removed by filtration, and the filtrate was concentrated to obtain a solid. Subsequently, the residue was purified by silica gel column chromatography (developing solvent hexane / chloroform 3: 1), and the eluate was concentrated to dryness and vacuum dried to obtain 12.57 g (yield 73%) of the target compound 6-2. )Obtained.
LC-MS (APPI / posi): 480 [M + H ⁺ ]

(Compound 6-2)

（化合物６−３）


<Synthesis of Compound 6-3>
2.26 g (4.7 mmol) of the above compound 6-2 was added to the reaction vessel, the inside of the vessel was replaced with argon gas, and 40 mL of tetrahydrofuran was added. Next, 3.50 mL (7.0 mmol) of a 2 mol / L isopropylmagnesium chloride tetrahydrofuran solution was added dropwise at room temperature over 10 minutes, and stirring was continued for 1 hour. After stirring, the reaction solution was cooled to −45 ° C., and 1.60 mL (14 mmol) of trimethoxyborane was added dropwise over 10 minutes, stirred at −45 ° C. for 30 minutes, and further stirred at room temperature for 30 minutes. The reaction solution was added dropwise to 25 mL of 2N hydrochloric acid, toluene was added and stirred, and then the aqueous layer was removed from the organic layer. Organic layer 2N hydrochloric acid is added and stirred to remove the aqueous layer from the organic layer, saturated brine is added to the organic layer to remove the aqueous layer from the organic layer, and the organic layer is dried over anhydrous magnesium sulfate and concentrated to dryness. As a result, an oily substance was obtained. The oily substance was dissolved in chloroform and subjected to silica gel column chromatography (developing solvent: chloroform). Subsequently, 90 mL of toluene and 0.56 g (4.7 mmol) of pinacol were added, and the mixture was stirred at 125 ° C. for 2 hours. After cooling to room temperature, adding water and stirring, the aqueous layer is removed from the organic layer, and the resulting organic layer is dried over anhydrous magnesium sulfate, concentrated to dryness, and dried under reduced pressure to give the desired compound 6- 0.64 g (yield 28%) of 3 was obtained as an oily substance.
LC-MS (APPI / posi): 480 [M + H ⁺ ]

(Compound 6-3)

（化合物７−１） [Synthesis Example 8]
<Synthesis of Compound 7-1>
Under an inert gas atmosphere, 1.56 g (6.98 mmol) of palladium acetate, 2.8 g (13.96 mmol) of tri-t-butylphosphine and 1.6 L of xylene were added to the reaction vessel, and the mixture was stirred at 28 ° C. for 1 hour. Carbazole 128.4 g (768 mmol), 1-bromo-4-butyloxybenzene 160.0 g (698 mmol) and xylene 1.6 L were added and stirred. Next, 80.0 g (838 mmol) of sodium-tert-butoxide and 0.8 L of xylene were added at 80 ° C., and the mixture was stirred at 130 ° C. overnight. The reaction solution was cooled to room temperature, filtered through a filter packed with celite, concentrated to dryness, and then subjected to silica gel column chromatography to obtain 150.6 g (yield 66%) of the desired compound 7-1. Obtained.

(Compound 7-1)

（化合物７−２）
<Synthesis of Compound 7-2>
In an inert gas atmosphere, 130.0 g (412 mmol) of Compound 7-1 and 2.5 L of N, N-dimethylformamide were added to the reaction vessel, and 143.8 g (808 mmol) of N-bromosuccinimide was added at 4 ° C. And stirred overnight at room temperature. Next, 2 kg of ice was added to the reaction solution and stirred, and then the precipitated solid was filtered, washed with n-hexane, and dried under reduced pressure. Subsequently, silica gel column chromatography was performed, and then recrystallization was performed from toluene and n-hexane to obtain 159.2 g (yield 81%) of the target compound 7-2.
GC-MS (EI): 473
¹ H-NMR: 1.02 (t, 3H), 1.55 (m, 2H), 1.84 (m, 2H), 4.06 (t, 2H), 7.09 (2H, d), 7.17 (d, 2H), 7.36 (d, 2H), 7.50 (d, 2H), 8.18 (s, 2H)

(Compound 7-2)

（化合物７−３）
<Synthesis of Compound 7-3>
In an inert gas atmosphere, 60.0 g (127 mmol) of compound 7-2, 19.3 g (76 mmol) of pinacol diborane, 37.3 g (380 mmol) of potassium acetate, 600 mL of dehydrated 1,4-dioxane, dichloro [1, 1′-bis (diphenylphosphino) ferrocene] palladium (3.1 g, 3.8 mmol) was added, and the mixture was stirred at 50 ° C. for 4 hours. After cooling to room temperature, the mixture was filtered through a filter packed with celite and concentrated to dryness. Next, the work of dissolving in toluene, adding water and stirring to remove the aqueous layer from the organic layer was performed twice. The organic layer was dehydrated with anhydrous magnesium sulfate, and after removing the anhydrous magnesium sulfate, the organic layer was concentrated and dried. Solidified. Subsequently, purification was performed by silica gel column chromatography to obtain 11.7 g (yield 18%) of the intended compound 7-3.
LC-MS (APPI / posi): 519 [M ^+. ]
¹ H-NMR: 1.02 (t, 3H), 1.40 (s, 12H), 1.55 (m, 2H), 1.84 (m, 2H) 4.06 (t, 2H), 7 .09 (d, 2H), 7.16 (d, 1H), 7.28 (d, 1H), 7.38 (d, 2H), 7.46 (dd, 1H), 7.86 (d, 1H), 8.28 (d, 1H), 8.59 (s, 1H)

(Compound 7-3)

（二価の基３）
[Example 7]
<Synthesis of Block Copolymer 4>
In a 100 mL two-necked flask, 0.250 g (0.43 mmol) of the above compound 5 was charged, and the inside of the flask was replaced with argon gas. Next, 1.90 mg (0.009 mmol) of 4-t-butylbromobenzene and 8.9 mL of toluene were charged and Ar bubbling was performed, followed by stirring at 45 ° C. for 5 minutes. Next, 0.59 mg (0.0006 mmol) of tris (dibenzylideneacetone) dipalladium, 1.80 mg (0.0051 mmol) of tris (2-methoxyphenyl) phosphine and 1.0 mL of toluene were added, and the mixture was stirred at 45 ° C. for 10 minutes. 1.9 mL of a 33 wt% aqueous cesium carbonate solution was added. Next, the mixture was stirred at 114 ° C. for 30 minutes, and disappearance of compound 5 was confirmed by high performance liquid chromatography. The molecular weight of the peak top in SEC of the polymer compound at this time was confirmed to be 8.6 × 10 ⁴ . . Next, 0.307 g (0.58 mmol) of the above compound 3 and 2 mL of toluene were added, 0.78 mg (0.0009 mmol) of tris (dibenzylideneacetone) dipalladium and 2.41 mg of tris (2-methoxyphenyl) phosphine ( 0.0068 mmol), 1.0 mL of toluene, and 2.6 mL of a 33 wt% aqueous cesium carbonate solution were added, and the mixture was stirred at 114 ° C for 7 hours. Next, 0.73 mg (0.0008 mmol) of tris (dibenzylideneacetone) dipalladium, 2.24 mg (0.0064 mmol) of tris (2-methoxyphenyl) phosphine and 1.0 mL of toluene were added, and the mixture was stirred at 114 ° C. for 7 hours 30 hours. Stir for minutes. Next, 0.86 mg (0.0009 mmol) of tris (dibenzylideneacetone) dipalladium, 2.70 mg (0.0077 mmol) of tris (2-methoxyphenyl) phosphine and 1.0 mL of toluene were added, and the mixture was stirred at 114 ° C. for 7 hours. Then, the disappearance of compound 3 was confirmed by high performance liquid chromatography, and the molecular weight at the peak top in SEC of the polymer compound at this time was 9.9 × 10 ⁴ , and it was confirmed that the molecular weight was increased by copolymerization. . Subsequently, 0.062 g (0.28 mmol) of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene and 2 mL of toluene were added, and tris (dibenzylideneacetone) diethyl was added. Add 0.32 mg (0.0003 mmol) of palladium and 0.97 mg (0.003 mmol) of tris (2-methoxyphenyl) phosphine, 1.0 mL of toluene and 1.1 mL of 33 wt% aqueous cesium carbonate solution at 114 ° C. for 4 hours. Stir. After cooling to room temperature, the aqueous layer of the reaction solution was removed from the organic layer, and the precipitate obtained by dropping the organic layer into 90 mL of methanol was filtered and dried to obtain a yellow solid. The yellow solid was dissolved in 30 mL of toluene, subjected to column chromatography on silica gel and activated alumina, and the eluate was concentrated. The concentrated solution was added dropwise to methanol, and the deposited precipitate was filtered and dried to obtain 0.25 g of a solid. An operation of dissolving 0.21 g of the solid in tetrahydrofuran and dropping the solution into acetone and filtering and drying the resulting precipitate was carried out three times to obtain 0.17 g of the target block copolymer 4. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 7.7 × 10 ⁴ and Mw = 1.3 × 10 ⁵ , respectively. From the result of elemental analysis of the block copolymer, the molar ratio of the following divalent group 3 to the divalent group 2 was 55:45. Accordingly, the block copolymer 4 comprises a block having a divalent group 3 as a constituent unit and two blocks having a divalent group 2 as a constituent unit, and the chemical formula weight of the divalent group 3 and the divalent group 2 Are 388.6 and 327.4, respectively. Therefore, the number average degree of polymerization of the block having the divalent group 3 as the structural unit is 109, and the number average degree of polymerization of the block having the divalent group 2 as the structural unit. Was 106.

(Divalent group 3)

（Ｘ１）

また、該ＨＭＱＣスペクトル上で、式（Ｘ２）においてＨ_C1およびＨ_D1で示されるプロトンは、それぞれ７．４４ｐｐｍ、７．０２ｐｐｍの位置にあり、式（Ｘ２）においてC_C1およびC_D1で示される炭素１３の化学シフトは、それぞれ１２７．１ｐｐｍ、１２０．１ｐｐｍの位置にあって、Ｈ_C1とC_C1、Ｈ_D1とC_D1で示されるプロトンと炭素の対に対してプロトン−炭素１３相関ピークが観測された。

（Ｘ２）

一方、該ＨＭＱＣスペクトル上で、式（Ｘ３）においてＨ_A2およびＨ_B2で示されるプロトンは、それぞれ７．６４ｐｐｍ、７．６９ｐｐｍの位置にあり、また式（Ｘ３）においてC_A2およびC_B2で示される炭素１３は、それぞれ１２５．８ｐｐｍ、１２１．４ｐｐｍの位置にあって、Ｈ_A2とC_A2、Ｈ_B2とC_B2で示されるプロトンと炭素の対に対してプロトン−炭素１３相関ピークが観測された。

また、該ＨＭＱＣスペクトル上で、式（Ｘ３）においてＨ_C2およびＨ_D2で示されるプロトンは、それぞれ７．５９ｐｐｍ、７．０８ｐｐｍの位置にあり、式（Ｘ３）においてC_C2およびC_D2で示される炭素１３の化学シフトは、それぞれ１２７．９ｐｐｍ、１２１．５ｐｐｍで、Ｈ_C2とC_C2、Ｈ_D2とC_D2で示されるプロトンと炭素の対に対してプロトン−炭素１３相関ピークが観測された。 さらに、ＮＯＥＳＹ測定を行ったところ、式（Ｘ３）においてＨ_B2およびＨ_C2で示されるプロトン間の交差ピークの出現位置、すなわち（Ｆ１軸、Ｆ２軸）＝（７．６９ｐｐｍ、７．５９ｐｐｍ）、および（Ｆ１軸、Ｆ２軸）＝（７．５９ｐｐｍ、７．６９ｐｐｍ）にＮＯＥピークが観測された。このことは、式（Ｘ３）においてＨ_B2およびＨ_C2で示されるプロトン間の距離が小さいことを示しており、式（Ｘ３）におけるＨ_B2およびＨ_C2の帰属が正しいことを明確に示している。
これらの知見を総合すると、ブロック共重合体４は、式（Ｘ１）で示されるブロックと、式（Ｘ２）で示されるブロックとを含み、さらに、式（Ｘ３）で示される連結部が存在することが確認された。 <NMR measurement of block copolymer 4>
The block copolymer 4 obtained above was used as a tetrahydrofuran-d ₈ solution, and ¹ H detection ¹ H- ¹³ C two-dimensional correlation spectrum (HMQC spectrum) and NOE correlation spectrum (NOESY spectrum) were measured at 30 ° C. The NMR apparatus was an Avance 600 nuclear magnetic resonance apparatus manufactured by Bruker.
When the HMQC spectrum was measured, the protons represented by H _A1 and H _B1 in the formula (X1) are at the positions of 7.75 ppm and 7.80 ppm, respectively, and in the formula (X1), the protons are C _A1 and C _B1 . The carbon 13 shown is at positions of 126.5 ppm and 121.6 ppm, respectively, and a proton-carbon 13 correlation peak is observed for the proton-carbon pair indicated by H _A1 and C _A1 and H _B1 and C _B1. It was done.

(X1)

In the HMQC spectrum, protons represented by H _C1 and H _D1 in the formula (X2) are at positions of 7.44 ppm and 7.02 ppm, respectively, and are represented by C _C1 and C _D1 in the formula (X2). The chemical shifts of carbon 13 are at positions of 127.1 ppm and 120.1 ppm, respectively, and proton-carbon 13 correlation peaks are present for proton-carbon pairs indicated by H _C1 and C _C1 and H _D1 and C _D1. Observed.

(X2)

On the other hand, on the HMQC spectrum, protons represented by H _A2 and H _B2 in the formula (X3) are at positions of 7.64 ppm and 7.69 ppm, respectively, and are represented by CA ₂ and C _B2 in the formula (X3). Carbon 13 is located at 125.8 ppm and 121.4 ppm, respectively, and proton-carbon 13 correlation peaks are observed for the proton-carbon pairs indicated by H _A2 and C _A2 and H _B2 and C _B2. It was.

On the HMQC spectrum, protons represented by H _C2 and H _D2 in the formula (X3) are at positions of 7.59 ppm and 7.08 ppm, respectively, and are represented by C _C2 and C _D2 in the formula (X3). The chemical shifts of carbon 13 were 127.9 ppm and 121.5 ppm, respectively, and proton-carbon 13 correlation peaks were observed for proton-carbon pairs represented by H _C2 and C _C2 and H _D2 and C _D2 . Furthermore, when NOESY measurement was performed, the appearance position of the cross peak between protons represented by H _B2 and H _C2 in formula (X3), that is, (F1 axis, F2 axis) = (7.69 ppm, 7.59 ppm), NOE peaks were observed at (F1 axis, F2 axis) = (7.59 ppm, 7.69 ppm). This shows that the distance between the proton indicated by H _B2 and H _C2 in formula (X3) is small, clearly shows that the assignments of H _B2 and H _C2 in formula (X3) is correct .
Summing up these findings, the block copolymer 4 includes a block represented by the formula (X1) and a block represented by the formula (X2), and further has a connecting portion represented by the formula (X3). It was confirmed.

[Example 8]
<Preparation of polymer light-emitting device using block copolymer 4>
Preparation of Solution The block copolymer 4 obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.6% by weight.
Production of EL device An EL device was produced in exactly the same manner as in Example 6 except that the xylene solution of the block copolymer 4 obtained above was used instead of the xylene solution of the block copolymer 2. The rotation speed during spin coating was 3000 rpm, and the film thickness after film formation was about 79 nm.
EL device performance By applying a voltage to the obtained device, EL light emission having a peak at 430 nm was obtained from this device. The EL emission color at a luminance of 100 cd / m 2 is represented by C.I. I. E. In terms of color coordinate values, x = 0.162 and y = 0.066. The intensity of EL emission was almost proportional to the current density. The driving voltage at 100 cd / m 2 was 6.0V. The device started to emit light from 4.3 V, and the maximum light emission efficiency was 0.30 cd / A.

（二価の基４）

[Example 9]
<Synthesis of Block Copolymer 5>
In a 100 mL two-necked flask, 0.250 g (0.43 mmol) of the above compound 5 was charged, and the inside of the flask was replaced with argon gas. Next, 1.90 mg (0.009 mmol) of 4-t-butylbromobenzene and 8.9 mL of toluene were charged and stirred at 45 ° C. for 5 minutes. Next, 0.58 mg (0.0006 mmol) of tris (dibenzylideneacetone) dipalladium, 1.83 mg (0.0052 mmol) of tris (2-methoxyphenyl) phosphine and 1.0 mL of toluene were added, and the mixture was stirred at 45 ° C. for 10 minutes. 1.9 mL of a 33 wt% aqueous cesium carbonate solution was added. Next, the mixture was stirred at 114 ° C. for 30 minutes, and disappearance of compound 5 was confirmed by high performance liquid chromatography. The molecular weight of the peak top in SEC of the polymer compound at this time was confirmed to be 7.6 × 10 ⁴ . . Then, 0.279 g (0.58 mmol) of the above compound 6-3 and 2 mL of toluene were added, 0.79 mg (0.0009 mmol) of tris (dibenzylideneacetone) dipalladium and tris (2-methoxyphenyl) phosphine. 37 mg (0.0067 mmol), 1.0 mL of toluene, and 2.6 mL of a 33 wt% aqueous cesium carbonate solution were added, and the mixture was stirred at 114 ° C. for 3 hours. Next, 0.83 mg (0.0009 mmol) of tris (dibenzylideneacetone) dipalladium, 2.75 mg (0.0078 mmol) of tris (2-methoxyphenyl) phosphine and 1.0 mL of toluene were added, and the mixture was stirred at 114 ° C. for 7 hours 30 hours. Stir for minutes. Next, 0.81 mg (0.0009 mmol) of tris (dibenzylideneacetone) dipalladium, 2.32 mg (0.0066 mmol) of tris (2-methoxyphenyl) phosphine and 1.0 mL of toluene were added, and the mixture was stirred at 114 ° C. for 9 hours. did. Next, 0.78 mg (0.0009 mmol) of tris (dibenzylideneacetone) dipalladium, 2.31 mg (0.0066 mmol) of tris (2-methoxyphenyl) phosphine and 1.0 mL of toluene were added, and the mixture was stirred at 114 ° C. for 17 hours. did. The disappearance of compound 6-3 was confirmed by high performance liquid chromatography, and the molecular weight of the peak top in SEC of the polymer compound at this time was 8.9 × 10 ⁴ , and it was confirmed that the molecular weight was increased by copolymerization. . Next, 0.057 g (0.26 mmol) of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene and 2 mL of toluene were added, and tris (dibenzylideneacetone) diethyl was added. Add 0.37 mg (0.0004 mmol) of palladium and 0.99 mg (0.003 mmol) of tris (2-methoxyphenyl) phosphine, 1.0 mL of toluene, and 1.1 mL of 33 wt% aqueous cesium carbonate solution at 114 ° C. for 2 hours. Stir for 30 minutes. After cooling to room temperature, the aqueous layer of the reaction solution was removed from the organic layer, and the precipitate obtained by dropping the organic layer into 120 mL of methanol was filtered and dried to obtain a yellow solid. To the yellow solid, 27 mL of toluene was added, and silica gel and activated alumina column chromatography was performed, and the eluate was concentrated. The concentrated solution was added dropwise to methanol, and the deposited precipitate was filtered and dried to obtain 0.16 g of a solid. An operation of dissolving 0.13 g of the solid in toluene and dropping the solution into methanol and filtering and drying the resulting precipitate was carried out twice to obtain 0.12 g of the target block copolymer 5. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 5.3 × 10 ⁴ and Mw = 1.1 × 10 ⁵ , respectively. From the result of elemental analysis of the block copolymer, the molar ratio of the divalent group 3 to the divalent group 4 shown below was 64:36. Accordingly, the block copolymer 5 comprises a block having a divalent group 3 as a constituent unit and two blocks having a divalent group 4 as a constituent unit, and the chemical formula weight of the divalent group 3 and the divalent group 4 is Since the number is 388.6 and 273.3 respectively, the number average degree of polymerization of the block having the divalent group 3 as the structural unit is 87, and the number average degree of polymerization of the block having the divalent group 4 as the structural unit is 70.

(Divalent group 4)

また、該ＨＭＱＣスペクトル上で、式（Ｙ２）においてＨ_C1およびＨ_D1で示されるプロトンは、それぞれ７．４７ｐｐｍ、７．０８ｐｐｍの位置にあり、式（Ｙ２）においてC_C1およびC_D1で示される炭素１３の化学シフトは、それぞれ１２７．３ｐｐｍ、１２３．２ｐｐｍの位置にあって、Ｈ_C1とC_C1、Ｈ_D1とC_D1で示されるプロトンと炭素の対に対してプロトン−炭素１３相関ピークが観測された。

（Ｙ２）


一方、該ＨＭＱＣスペクトル上で、式（Ｙ３）においてＨ_A2およびＨ_B2で示されるプロトンは、それぞれ７．６３ｐｐｍ、７．６８ｐｐｍの位置にあり、また式（Ｙ３）においてC_A2およびC_B2で示される炭素１３は、それぞれ１２５．９ｐｐｍ、１２１．２ｐｐｍの位置にあって、Ｈ_A2とC_A2、Ｈ_B2とC_B2で示されるプロトンと炭素の対に対してプロトン−炭素１３相関ピークが観測された。

また、該ＨＭＱＣスペクトル上で、式（Ｙ３）においてＨ_C2およびＨ_D2で示されるプロトンは、それぞれ７．６１ｐｐｍ、７．１４ｐｐｍの位置にあり、式（Ｙ３）においてC_C2およびC_D2で示される炭素１３の化学シフトは、それぞれ１２７．９ｐｐｍ、１２４．８ｐｐｍで、Ｈ_C2とC_C2、Ｈ_D2とC_D2で示されるプロトンと炭素の対に対してプロトン−炭素１３相関ピークが観測された。
さらに、ＮＯＥＳＹ測定を行ったところ、式（Ｙ３）においてＨ_B2およびＨ_C2で示されるプロトン間の交差ピークの出現位置、すなわち（Ｆ１軸、Ｆ２軸）＝（７．６８ｐｐｍ、７．６１ｐｐｍ）、および（Ｆ１軸、Ｆ２軸）＝（７．６１ｐｐｍ、７．６８ｐｐｍ）にＮＯＥピークが観測された。このことは、式（Ｙ３）においてＨ_B2およびＨ_C2で示されるプロトン間の距離が小さいことを示しており、式（Ｙ３）におけるＨ_B2およびＨ_C2の帰属が正しいことを明確に示している。
これらの知見を総合すると、ブロック共重合体５は、式（Ｙ１）で示されるブロックと、式（Ｙ２）で示されるブロックとを含み、さらに、式（Ｙ３）で示される連結部が存在することが確認された。
<NMR measurement of block copolymer 5>
The block copolymer 5 and tetrahydrofuran -d ₈ solution, ¹ H detection ¹ H- ¹³ C two-dimensional correlation spectrum at 30 ° C. (HMQC spectrum) and NOE correlation spectra (NOESY spectra) were measured. The NMR apparatus was an Avance 600 nuclear magnetic resonance apparatus manufactured by Bruker.
When the HMQC spectrum was measured, the protons represented by H _A1 and H _B1 in the formula (Y1) were at the positions of 7.75 ppm and 7.80 ppm, respectively. In the formula (Y1), the protons were represented by C _A1 and C _B1 . The carbon 13 shown is at positions of 126.5 ppm and 121.6 ppm, respectively, and a proton-carbon 13 correlation peak is observed for the proton-carbon pair indicated by H _A1 and C _A1 and H _B1 and C _B1. It was done.

On the HMQC spectrum, protons represented by H _C1 and H _D1 in the formula (Y2) are at positions of 7.47 ppm and 7.08 ppm, respectively, and are represented by C _C1 and C _D1 in the formula (Y2). The chemical shifts of carbon 13 are at positions of 127.3 ppm and 123.2 ppm, respectively, and proton-carbon 13 correlation peaks are present for the proton-carbon pairs indicated by H _C1 and C _C1 and H _D1 and C _D1. Observed.

(Y2)


On the other hand, on the HMQC spectrum, proton indicated by H _A2 and H _B2 in the formula (Y3), respectively 7.63Ppm, in a position of 7.68 ppm, also shown in equation (Y3) in C _A2 and C _B2 Carbon 13 is located at the positions of 125.9 ppm and 121.2 ppm, respectively, and proton-carbon 13 correlation peaks are observed for the proton-carbon pairs indicated by H _A2 and C _A2 and H _B2 and C _B2. It was.

On the HMQC spectrum, protons represented by H _C2 and H _D2 in the formula (Y3) are at positions of 7.61 ppm and 7.14 ppm, respectively, and are represented by C _C2 and C _D2 in the formula (Y3). The chemical shifts of carbon 13 were 127.9 ppm and 124.8 ppm, respectively, and proton-carbon 13 correlation peaks were observed for proton-carbon pairs represented by H _C2 and C _C2 and H _D2 and C _D2 .
Furthermore, when NOESY measurement was performed, the appearance position of the cross peak between protons represented by H _B2 and H _C2 in formula (Y3), that is, (F1 axis, F2 axis) = (7.68 ppm, 7.61 ppm), NOE peaks were observed at (F1 axis, F2 axis) = (7.61 ppm, 7.68 ppm). This shows that the distance between the proton indicated by H _B2 and H _C2 in formula (Y3) is small, clearly shows that the assignments of H _B2 and H _C2 in formula (Y3) is correct .
Summing up these findings, the block copolymer 5 includes a block represented by the formula (Y1) and a block represented by the formula (Y2), and further includes a connecting portion represented by the formula (Y3). It was confirmed.

[Example 10]
<Preparation of Polymer Light-Emitting Device Using Block Copolymer 5>
Preparation of Solution The block copolymer 5 obtained above was dissolved in chloroform to prepare a chloroform solution having a polymer concentration of 0.5% by weight.
Production of EL device An EL device was produced in the same manner as in Example 6 except that the chloroform solution of the block copolymer 5 obtained above was used instead of the xylene solution of the block copolymer 2. The rotation speed during spin coating was 3600 rpm, and the film thickness after film formation was about 90 nm.
EL device performance By applying a voltage to the obtained device, EL light emission having a peak at 445 nm was obtained from this device. The EL emission color at a luminance of 100 cd / m 2 is represented by C.I. I. E. In terms of color coordinate values, x = 0.181 and y = 0.134. The intensity of EL emission was almost proportional to the current density. The driving voltage at 100 cd / m 2 was 8.0V. The device started to emit light from 5.7 V, and the maximum light emission efficiency was 0.14 cd / A.

（二価の基５）

[Example 11]
<Synthesis of Block Copolymer 6>
In a 200 mL three-necked flask, 0.600 g (1.02 mmol) of the above compound 5 was charged, and the inside of the flask was replaced with argon gas. Next, 4.53 mg (0.021 mmol) of 4-t-butylbromobenzene and 22.0 mL of toluene were charged and stirred at 45 ° C. for 5 minutes. Next, 1.46 mg (0.0016 mmol) of tris (dibenzylideneacetone) dipalladium, 4.44 mg (0.013 mmol) of tris (2-methoxyphenyl) phosphine and 2.0 mL of toluene were added, and the mixture was stirred at 45 ° C. for 10 minutes. Then, 4.7 mL of 33 wt% aqueous cesium carbonate solution was added. Next, the mixture was stirred at 114 ° C. for 30 minutes, and disappearance of compound 5 was confirmed by high performance liquid chromatography. It was confirmed that the molecular weight of the peak top in SEC of the polymer compound at this time was 6.9 × 10 ⁴ . . Next, 0.718 g (1.38 mmol) of Compound 7-3 and 5 mL of toluene were added, and 1.84 mg (0.0020 mmol) of tris (dibenzylideneacetone) dipalladium and 5.61 mg of tris (2-methoxyphenyl) phosphine. (0.016 mmol), 2.0 mL of toluene, and 6.5 mL of 33 wt% aqueous cesium carbonate solution were added, and the mixture was stirred at 114 ° C for 3 hours. Then, 1.94 mg (0.0021 mmol) of tris (dibenzylideneacetone) dipalladium, 6.00 mg (0.017 mmol) of tris (2-methoxyphenyl) phosphine, and 2.0 mL of toluene were added. Next, the mixture was stirred at 114 ° C. for 19 hours and 30 minutes, and disappearance of compound 7-3 was confirmed by high performance liquid chromatography. The molecular weight of the peak top in SEC of the polymer compound at this time was 8.4 × 10 ⁴ . It was confirmed that the molecular weight was increased by copolymerization. Next, 0.138 g (0.63 mmol) of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene and 4.8 mL of toluene were added, and tris (dibenzylideneacetone) was added. ) 0.80 mg (0.0009 mmol) of dipalladium and 2.57 mg (0.0073 mmol) of tris (2-methoxyphenyl) phosphine, 1.0 mL of toluene, and 3.0 mL of 33 wt% aqueous cesium carbonate solution were added at 114 ° C. Stir for 1 hour 30 minutes. After cooling to room temperature, the aqueous layer of the reaction solution was removed from the organic layer, and the precipitate obtained by dropping the organic layer into 194 mL of methanol was filtered and dried to obtain a yellow solid. To the yellow solid, 81 mL of toluene was added, and silica gel and activated alumina column chromatography was performed, and the eluate was concentrated. The concentrated solution was added dropwise to methanol, and the deposited precipitate was filtered and dried to obtain 0.52 g of a solid. 0.52 g of the solid was dissolved in tetrahydrofuran, the insoluble part was removed by filtration, and the filtrate was concentrated to dryness. This was dissolved in toluene, and the precipitate obtained by dropping the solution into methanol was filtered and dried. This was dissolved in tetrahydrofuran, and the precipitate obtained by dropping the solution into acetone was filtered and dried three times. Further, the solid was dissolved in toluene, the solution was dropped into methanol and the precipitate was filtered and dried. As a result, 0.17 g of the target block copolymer 6 was obtained. The number-average molecular weight and weight-average molecular weight in terms of polystyrene were Mn = 7.3 × 10 ⁴ and Mw = 1.2 × 10 ⁵ , respectively. From the result of elemental analysis of the block copolymer, the molar ratio of the divalent group 3 to the divalent group 5 was 92: 8. Accordingly, the block copolymer 6 comprises a block having a divalent group 3 as a structural unit and two blocks having a divalent group 5 as a structural unit. The chemical formula weight of the divalent group 3 and the divalent group 5 Are 388.6 and 313.4, respectively, so that the number average degree of polymerization of a block having a divalent group 3 as a constituent unit is 173, and the number average degree of polymerization of a block having a divalent group 5 as a constituent unit is Was 19.

(Divalent group 5)

[Example 12]
<Preparation of polymer light-emitting device using block copolymer 6>
Preparation of Solution The block copolymer 6 obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.6% by weight.
Production of EL device An EL device was produced in exactly the same manner as in Example 6 except that the xylene solution of block copolymer 6 obtained above was used instead of the xylene solution of block copolymer 2. The rotation speed during spin coating was 3000 rpm, and the film thickness after film formation was about 78 nm.
EL device performance By applying a voltage to the obtained device, EL light emission having a peak at 430 nm was obtained from this device. The EL emission color at a luminance of 100 cd / m 2 is represented by C.I. I. E. In terms of color coordinate values, x = 0.170 and y = 0.108. The intensity of EL emission was almost proportional to the current density. The driving voltage at 100 cd / m 2 was 6.4V. The device started to emit light from 4.9 V, and the maximum light emission efficiency was 1.02 cd / A.

[Example 13]
<Synthesis of Block Copolymer 7>
In a 200 mL three-necked flask, 0.650 g (1.01 mmol) of the above compound 1 was charged, and the inside of the flask was replaced with argon gas. Next, 4.52 mg (0.021 mmol) of 4-t-butylbromobenzene and 21.5 mL of toluene were charged and stirred at 45 ° C. for 5 minutes. Next, 1.43 mg (0.0016 mmol) of tris (dibenzylideneacetone) dipalladium, 4.40 mg (0.013 mmol) of tris (2-methoxyphenyl) phosphine and 2.0 mL of toluene were added, and the mixture was stirred at 45 ° C. for 10 minutes. Then, 4.6 mL of 33 wt% aqueous cesium carbonate solution was added. Next, the mixture was stirred at 114 ° C. for 2 hours, and disappearance of compound 1 was confirmed by high performance liquid chromatography. The molecular weight of the peak top in SEC of the polymer compound at this time was 6.6 × 10 ⁴ , and the molecular weight was determined by copolymerization Confirmed that the increase. . Next, 0.799 g (1.36 mmol) of the above compound 5 and 4.7 mL of toluene were added, and 1.95 mg (0.0021 mmol) of tris (dibenzylideneacetone) dipalladium and tris (2-methoxyphenyl) phosphine 6. 15 mg (0.018 mmol), 2.0 mL of toluene, and 6.2 mL of a 33 wt% aqueous cesium carbonate solution were added. Next, the mixture was stirred at 114 ° C. for 1 hour and 40 minutes, and disappearance of compound 5 was confirmed by high performance liquid chromatography. The molecular weight at the peak top in SEC of the polymer compound at this time was 9.1 × 10 ^4. It was confirmed. Next, 0.726 g (1.36 mmol) of the above compound 3 and 4.7 mL of toluene were added, and 1.84 mg (0.0020 mmol) of tris (dibenzylideneacetone) dipalladium and tris (2-methoxyphenyl) phosphine 5. 58 mg (0.016 mmol), 2.0 mL of toluene, and 6.2 mL of a 33 wt% aqueous cesium carbonate solution were added. Next, the mixture was stirred at 114 ° C. for 19 hours and 50 minutes, and the disappearance of compound 3 was confirmed by high performance liquid chromatography. The molecular weight of the peak top in SEC of the polymer compound at this time was 1.0 × 10 ⁵ , It was confirmed that the molecular weight was increased by copolymerization. Then, 0.133 g (0.61 mmol) of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene and 4.7 mL of toluene were added, and tris (dibenzylideneacetone ) Add 0.88 mg (0.001 mmol) of dipalladium and 2.78 mg (0.0079 mmol) of tris (2-methoxyphenyl) phosphine, 1.0 mL of toluene, and 2.8 mL of 33 wt% aqueous cesium carbonate solution at 114 ° C. Stir for 2 hours. After cooling to room temperature, the aqueous layer of the reaction solution was removed from the organic layer, and the precipitate obtained by dropping the organic layer into 300 mL of methanol was filtered and dried to obtain a yellow solid. The yellow solid was dissolved in 133 mL of toluene, subjected to column chromatography on silica gel and activated alumina, and the eluate was concentrated. The concentrated solution was added dropwise to methanol, and the deposited precipitate was filtered and dried to obtain 1.13 g of a solid. The solid obtained by dissolving 1.13 g of the solid in tetrahydrofuran and dropping the solution into acetone was filtered and dried three times. Further, the solid was dissolved in toluene, and the solution was dropped into methanol and precipitated. Was filtered and dried to obtain 0.97 g of the target block copolymer 7. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 8.0 × 10 ⁴ and Mw = 1.5 × 10 ⁵ , respectively. From the result of the following NMR measurement of the block copolymer, the molar ratio of the divalent group 1, the divalent group 3, and the divalent group 2 was 27:41:32. Accordingly, the block copolymer 7 comprises a block having a divalent group 1 as a constituent unit, a block having a divalent group 3 as a constituent unit, and three blocks having a divalent group 2 as a constituent unit. Since the chemical formula amounts of the group 1, divalent group 3 and divalent group 2 are 438.7, 388.6 and 327.4, respectively, the number average polymerization of blocks having the divalent group 1 as a constituent unit The number average degree of polymerization of the block having the divalent group 3 as the structural unit was 84, and the number average degree of polymerization of the block having the divalent group 2 as the structural unit was 78.

<NMR measurement of block copolymer 7>
The NMR measurement was performed at 30 ° C. using an Avance 600 nuclear magnetic resonance apparatus manufactured by Bruker as a polymer solution of about 1% deuterated tetrahydrofuran.

When ¹ H-NMR measurement of the block copolymer 6 was performed, protons represented by H ₍₁₎ and H ₍₂₎ in the formula (ZW1) representing the divalent group 1 on the ¹ H-NMR spectrum were obtained. The chemical shifts of the peaks were 9.10 ppm and 8.67 ppm, respectively.

On the ¹ H-NMR spectrum, the chemical shifts of the proton peaks represented by H ₍₈₎ , H ₍₉₎ and H ₍₁₀₎ in the formula (ZW2) representing the divalent group 2 are 7 respectively. .45 ppm, 7.23 ppm, and 7.04 ppm.

On the ¹ H-NMR spectrum, the integrated intensity of peaks of H ₍₁₎ , H ₍₂₎ , H ₍₈₎ , H ₍₉₎ , H ₍₁₀₎ is obtained and contained in one divalent group. Table 1 shows the results of normalization taking into account the number of equivalent protons.

In the ¹ H-NMR spectrum, the proton peak represented by H ₍₁₁₎ , H ₍₁₂₎ , H ₍₁₃₎ in the formula (ZW3) representing the divalent group 3 is 7.53 ppm to 8 It was observed in the range of 0.09 ppm. Furthermore, in this range, proton peaks represented by protons H ₍₃₎ , H ₍₄₎ , H ₍₅₎ , H ₍₆₎ , H ₍₇₎ in the formula (ZW1) were also observed.

The integral intensities of protons H ₍₃₎ , H ₍₄₎ , H ₍₅₎ , H ₍₆₎ , and H ₍₇₎ are the same as the above-mentioned (YY1) with protons H ₍₃₎ , H ₍₄₎ , H ₍ It was calculated as 4798.7 (b3_7) by multiplying 5 which is the number of protons of ₅₎ , H ₍₆₎ and H ₍₇₎ . Therefore, the integral intensities of protons H ₍₁₁₎ , H ₍₁₂₎ and H ₍₁₃₎ are values from 13657.2, which are actually measured values of the integral intensities from 7.53 ppm to 8.09 ppm on the ¹ H-NMR spectrum. By subtracting (b3_7), it was calculated as 8588.5 (b11_13). Further, protons H _(11), protons H ₍₁₂₎ and H ₍₁₃₎ normalized integrated intensity of the (YY3) proton values _{(b11_13) H (11),} H (12) and H ₍₁₃₎ By dividing the number by 6, it was calculated as 1476.4 (YY3).

  From the above, the molar ratio of the three types of divalent groups constituting the block copolymer 6 is determined by using the standardized integral intensities YY1, YY2, and YY3 (divalent group 1) :( Divalent group 2): (Divalent group 3) = Formula (ZW1): Formula (ZW2): Formula (ZW3) = 959.7: 1168.6: 1476.4 = 27: 32: 41 I understood.

[Example 14]
<Preparation of polymer light-emitting device from block copolymer 7>
Preparation of Solution The block copolymer 7 obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.5% by weight.
Production of EL device An EL device was produced in exactly the same manner as in Example 6 except that the xylene solution of block copolymer 7 obtained above was used instead of the xylene solution of block copolymer 2. The rotation speed during spin coating was 3000 rpm, and the film thickness after film formation was about 77 nm.
EL device performance By applying a voltage to the obtained device, EL light emission having a peak at 450 nm was obtained from this device. The EL emission color at a luminance of 100 cd / m 2 is represented by C.I. I. E. In terms of color coordinate values, x = 0.151 and y = 0.105. The intensity of EL emission was almost proportional to the current density. The driving voltage at 100 cd / m 2 was 5.4V. The device started to emit light from 4.1 V, and the maximum light emission efficiency was 1.33 cd / A.

[Example 15]
<Synthesis of Block Copolymer 8>
The reaction vessel was charged with 0.650 g (1.01 mmol) of the above compound 1, and the inside of the flask was replaced with argon gas. Next, 4.51 mg (0.021 mmol) of 4-t-butylbromobenzene and 21.5 mL of toluene were charged, and the mixture was stirred at 45 ° C. for 5 minutes. Next, 1.34 mg (0.0015 mmol) of tris (dibenzylideneacetone) dipalladium, 4.14 mg (0.012 mmol) of tris (2-methoxyphenyl) phosphine and 2.0 mL of toluene were added, and the mixture was stirred at 45 ° C. for 10 minutes. Then, 4.6 mL of 33 wt% aqueous cesium carbonate solution was added. Next, the mixture was stirred at 114 ° C. for 2 hours, and disappearance of Compound 1 was confirmed by high performance liquid chromatography. The molecular weight of the peak top in SEC of the polymer compound at this time was confirmed to be 6.2 × 10 ⁴ . . Next, 0.799 g (1.36 mmol) of the above compound 5 and 4.7 mL of toluene were added, and 1.93 mg (0.0021 mmol) of tris (dibenzylideneacetone) dipalladium and tris (2-methoxyphenyl) phosphine 5. 84 mg (0.017 mmol), toluene 2.0 mL, and 33 wt% aqueous cesium carbonate solution 6.2 mL were added. Next, the mixture was stirred at 114 ° C. for 1 hour, and disappearance of compound 5 was confirmed by high performance liquid chromatography. The molecular weight of the peak top in SEC of the polymer compound at this time was confirmed to be 1.0 × 10 ^5. did. Next, 0.727 g (1.36 mmol) of the above compound 3 and 4.7 mL of toluene were added, and 1.99 mg (0.0022 mmol) of tris (dibenzylideneacetone) dipalladium and tris (2-methoxyphenyl) phosphine 6. 07 mg (0.017 mmol), 2.0 mL of toluene, and 6.2 mL of a 33 wt% aqueous cesium carbonate solution were added. Next, the mixture was stirred at 114 ° C. for 9 hours, and disappearance of compound 3 was confirmed by high performance liquid chromatography. The molecular weight of the peak top in SEC of the polymer compound at this time was 1.1 × 10 ⁵ , and copolymerization It was confirmed that the molecular weight increased. Next, 0.709 g (1.36 mmol) of the above compound 7-3 and 4.7 mL of toluene were added, and 1.81 mg (0.0020 mmol) of tris (dibenzylideneacetone) dipalladium and tris (2-methoxyphenyl) phosphine 5.49 mg (0.016 mmol), 2.0 mL of toluene, and 6.2 mL of 33 wt% aqueous cesium carbonate solution were added, and the mixture was stirred at 114 ° C. for 7 hours. Subsequently, 1.90 mg (0.0021 mmol) of tris (dibenzylideneacetone) dipalladium, 5.83 mg (0.017 mmol) of tris (2-methoxyphenyl) phosphine, and 2.0 mL of toluene were added. Next, the mixture was stirred at 114 ° C. for 15 hours, and disappearance of compound 7-3 was confirmed by high performance liquid chromatography. The molecular weight of the peak top in SEC of the polymer compound at this time was 1.2 × 10 ⁵ , It was confirmed that the molecular weight was increased by copolymerization. Subsequently, 0.134 g (0.61 mmol) of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene and 4.7 mL of toluene were added, and tris (dibenzylideneacetone) was added. ) 0.78 mg (0.0009 mmol) of dipalladium and 2.35 mg (0.0067 mmol) of tris (2-methoxyphenyl) phosphine, 1.0 mL of toluene, and 2.7 mL of 33 wt% aqueous cesium carbonate solution were added at 114 ° C. Stir for 2 hours. After cooling to room temperature, the aqueous layer of the reaction solution was removed from the organic layer, and the precipitate obtained by dropping the organic layer into 385 mL of methanol was filtered and dried to obtain a yellow solid. The yellow solid was dissolved in tetrahydrofuran, the insoluble part was removed by filtration, the filtrate was concentrated, and the precipitate obtained by adding the solution dropwise to acetone was filtered and dried. This was dissolved in 119 mL of toluene, concentrated by silica gel and activated alumina column chromatography. The concentrated solution was added dropwise to methanol, and the deposited precipitate was filtered and dried to obtain 1.03 g of a solid. The solid obtained by dissolving 1.03 g of the solid in tetrahydrofuran and dropping the solution into acetone was filtered and dried twice. Further, the solid was dissolved in toluene, and the solution was dropped into methanol to precipitate. Was filtered and dried to obtain 0.89 g of the target block copolymer 8. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 9.4 × 10 ⁴ and Mw = 1.8 × 10 ⁵ , respectively. As a result of the following NMR measurement, the molar ratio of the divalent group 1, the divalent group 3, the divalent group 2 and the divalent group 5 was 26: 36: 31: 6. Accordingly, the block copolymer 8 comprises a block having a divalent group 1 as a constituent unit, a block having a divalent group 3 as a constituent unit, a block having a divalent group 2 as a constituent unit, and a divalent group 5. It consists of four blocks as structural units, and the chemical formula weights of the divalent group 1, the divalent group 3, the divalent group 2 and the divalent group 5 are 438.7, 388.6, 327.4 and Therefore, the number average degree of polymerization of the block having the divalent group 1 as a structural unit is 56, and the number average degree of polymerization of the block having the divalent group 3 as a structural unit is 87. The number average degree of polymerization of the block having the valent group 2 as the structural unit was 89, and the number average degree of polymerization of the block having the divalent group 5 as the structural unit was 18.

<NMR measurement of block copolymer 8>
The NMR measurement was performed at 30 ° C. using an Avance 600 nuclear magnetic resonance apparatus manufactured by Bruker, Inc. with the block copolymer 8 as an approximately 1% solution of deuterated tetrahydrofuran.

When ¹ H-NMR measurement of the block copolymer 8 was performed, the chemical shift of the proton peak represented by H ₍₁₄₎ in the formula (Z5) representing the divalent group 1 on the ¹ H-NMR spectrum is 9.10 ppm.

On the ¹ H-NMR spectrum, the chemical shifts of the proton peaks represented by H ₍₂₀₎ and H ₍₂₁₎ in the formula (Z6) representing the divalent group 2 are 2.08 ppm and 1. It was 38 ppm.

Further, on the ¹ H-NMR spectrum, the chemical shift of the proton peak represented by H ₍₂₅₎ in the formula (Z7) representing the divalent group 5 was 4.03 ppm.

また、該¹Ｈ-NMRスペクトル上で、二価の基３を表す式（Ｚ９）においてＨ₍₃₁₎、Ｈ₍₃₂₎、Ｈ₍₃₃₎で示されるプロトンのピークは、６．８０ｐｐｍから８．０７ｐｐｍの範囲に観測された。さらにこの範囲には、式（Ｚ５）においてＨ₍₁₅₎、Ｈ₍₁₆₎、Ｈ₍₁₇₎ 、Ｈ₍₁₈₎、Ｈ₍₁₉₎で示されるプロトンのピークと、式（Ｚ６）においてＨ₍₂₂₎、Ｈ₍₂₃₎、Ｈ₍₂₄₎で示されるプロトンのピークと、式（Ｚ７）においてＨ₍₂₆₎、Ｈ₍₂₇₎、Ｈ₍₂₈₎ 、Ｈ₍₂₉₎、Ｈ₍₃₀₎で示されるプロトンのピークが観測された。

On the ¹ H-NMR spectrum, the integrated intensity of the peaks of H ₍₁₄₎ , H ₍₂₀₎ , H ₍₂₁₎ , H ₍₂₅₎ is obtained, and the number of equivalent protons contained in one divalent group Table 2 shows the results of normalization taking this into consideration.

Further, on the ¹ H-NMR spectrum, the proton peak represented by H ₍₃₁₎ , H ₍₃₂₎ , H ₍₃₃₎ in the formula (Z9) representing the divalent group 3 is from 6.80 ppm to 8 It was observed in the range of 0.07 ppm. More this range, H ₍₁₅₎ In the formula _{(Z5), H (16)} , H (17), and proton peak indicated by _{H (18), H (19} ), in the formula (Z6) H _{( 22)} , proton peaks represented by H ₍₂₃₎ and H ₍₂₄₎ and H ₍₂₆₎ , H ₍₂₇₎ , H ₍₂₈₎ , H ₍₂₉₎ and H ₍₃₀₎ in the formula (Z7) The indicated proton peak was observed.

Protons H ₍₁₅₎ , H ₍₁₆₎ , H ₍₁₇₎ , H ₍₁₈₎ , and H ₍₁₉₎ are observed in the range of 6.80 ppm to 8.07 ppm on the ¹ H-NMR spectrum. The integral intensity and the integral intensity of protons H ₍₂₂₎ , H ₍₂₃₎ , and H ₍₂₄₎ and the protons H ₍₂₆₎ , H ₍₂₇₎ , H ₍₂₈₎ , H ₍₂₉₎ , and H ₍₃₀ Table 3 shows the results of calculating the integral intensity of ₎ using Y4, Y5, and Y6 described above.

Therefore, the integral intensity of protons H ₍₃₁₎ , H ₍₃₂₎ and H ₍₃₃₎ is a value (b15 — 19) from the actually measured value 27487.8 of the integrated intensity from 6.80 ppm to 8.07 ppm on the ¹ H-NMR spectrum. ), (B22_24) and (b26_30) were subtracted to calculate 8442.7 (b31_33). Further, protons H _(31), protons H ₍₃₂₎ and H ₍₃₃₎ normalized integrated intensity of the (Y7) proton values _{(b31_33) H (31),} H (32) and H ₍₃₃₎ By dividing by 6 which is the number, 1407.1 (Y7) was calculated.

  From the above, the molar ratio of the four types of divalent groups constituting the block copolymer 8 is determined by using standardized integrated intensities Y4, Y5, Y6, and Y7 (divalent group 1): (Divalent group 2): (Divalent group 5): (Divalent group 3) = Formula (Z5): Formula (Z6): Formula (Z7): Formula (Z9) = 1016.5: 1200. 5: 244.7: 1407.1 = 26: 31: 6: 36.

It is a figure which shows the voltage-current characteristic of the light emitting element of Example 6, and the light emitting element of the comparative example 3. FIG. It is a figure which shows the voltage-luminance characteristic of the light emitting element of Example 6, and the light emitting element of the comparative example 3. FIG.

Claims (38)

A block copolymer comprising two or more blocks represented by the following formula (1),

(In the formula (1), Ar represents a conjugated divalent group, represents the same divalent group in the same block, m represents the number average degree of polymerization of Ar present in one block, Represents a number.)
At least two of m present in the copolymer represent a number of 5 or more, Ar in two adjacent blocks of the copolymer are different from each other, and the copolymer is represented by the formula (1) In the case of consisting of two blocks represented by the formula (1), two types of Ar are contained. A block copolymer comprising four or more types of Ar when the block consists of four or more blocks. The block copolymer according to claim 1, wherein the conjugated divalent group is a group represented by the following formula (2).

(2)


(In the formula (2), A ¹ , A ² , A ³ , A ⁴ and A ⁵ each independently represent an arylene group or a divalent heterocyclic group which may be substituted. B ¹ , B ² , B ³ and B ⁴ are each ^{independently, -BR 1 -, - NR 2} -, - SiR 3 R 4 -, - PR 5 -, - C≡C -, - have a CR ^b = N-or a substituent R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^b each independently represents a hydrogen atom or a substituent, a ¹ , a ² , a ³ , a ⁴ and a ⁵ represents an integer of 0 to 3 and represents an integer satisfying 1 ≦ a ¹ + a ² + a ³ + a ⁴ + a ⁵ ≦ 15, b ¹ , b ² , b ³ and b ⁴ are each independently 0 Or represents 1.) The block copolymer according to claim 1 or 2, wherein Ar in different blocks all represent different divalent groups. The group represented by the formula (2) is represented by the following formulas (C-1), (C-11), (C-15), (D-9), (D-10-1), (D-11), It is a group selected from the group consisting of (D-13), (D-16), (D-17), (G-1), (G-2), (G-3) and (G-4). The block copolymer according to any one of claims 1 to 3.

(The above formulas (C-1), (C-11), (C-15), (D-9), (D-10-1), (D-11), (D-13), (D- 16), (D-17), (G-1), (G-2), (G-3) and (G-4), R ^a and R ^c each independently represent a hydrogen atom or a substituent. A plurality of R ^c may be the same or different from each other.) The block copolymer according to any one of claims 1 to 4, wherein at least two of a plurality of m represent a number of 5 to 1 x 10 ⁴ . The block copolymer according to any one of claims 1 to 5, comprising 2 to 100 blocks represented by the formula (1). It represents with following formula (5), The block copolymer in any one of Claims 1-6 characterized by the above-mentioned.

(5)

(In the formula (5), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ and Ar ¹⁰ each independently represents a conjugated divalent group; In the same block, the same divalent group is represented, and two adjacent blocks represent different divalent groups, R ^X and R ^Y each independently represent a terminal group, or R ^X and R ^Y A single bond is formed and bonded at the two ends of the block copolymer to form a cyclic structure: m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , m ⁷ , m ⁸ , m ⁹ and m ¹⁰ each represent the number average degree of polymerization of Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ and Ar ¹⁰ , and each independently represents a number of 0 or more. Represents at ^{least one} of m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , m ⁷ , m ⁸ , m ⁹ and m ^10. 2 represents a number equal to or greater than 5. If m ¹ ≧ 5 and m ² ≧ 5 and m ³ = m ⁴ = m ⁵ = m ⁶ = m ⁷ = m ⁸ = m ⁹ = m ¹⁰ = 0, then Ar ¹ and Ar ² each represent a divalent group different from each other, each of m ¹ , m ² and m ³ is a number of 1 or more, and at least two of m ¹ , m ² and m ³ are a number of 5 or more. And when m ⁴ = m ⁵ = m ⁶ = m ⁷ = m ⁸ = m ⁹ = m ¹⁰ = 0, Ar ¹ and Ar ² represent different divalent groups, Ar ² and Ar ³ are Each represents a divalent group different from each other, and Ar ¹ and Ar ³ may be the same or different from each other, m ¹ , m ² , m ³ , m ⁴ , m ⁵ , m ⁶ , m ⁷ , m ⁸ , m ⁹ And at least 4 of m ¹⁰ represent a number of 1 or more and at least 2 represents a number of 5 or more, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ and Ar ¹⁰ represent four or more divalent groups.) The block copolymer according to any one of claims 1 to 7, which is represented by the following formula (5-A).

(In the formula (5-A), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent a conjugated divalent group, and each represents a different divalent group. R ^X and R ^Y each represent Each independently represents a terminal group, or R ^X and R ^Y form a single bond and are bonded at two ends of the block copolymer to form a cyclic structure: m ¹ , m ² , m ³ and m ⁴ represents the number average degree of polymerization of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ , each independently represents a number of 1 or more, and at least two of m ¹ , m ² , m ³ and m ⁴ are 5 (The above number is expressed.) Ar ¹ and Ar ² are each independently a divalent group represented by the above formula (C-11) or (C-15), and Ar ³ and Ar ⁴ are each independently the above formula (D-10-1). ), (D-16), (G-1), (G-2), (G-3) or (G-4). The block copolymer as described. It represents with following formula (6), The block copolymer in any one of Claims 1-7 characterized by the above-mentioned.

(In the formula (6), Ar ¹ , Ar ² and Ar ³ each independently represent a conjugated divalent group, Ar ¹ and Ar ² are different from each other, Ar ² and Ar ³ are different from each other, Ar ¹ and Ar ³ may be the same as or different from each other, R ^X and R ^Y each independently represent a terminal group, or R ^X and R ^Y form a single bond between the two ends of the block copolymer. And m ¹ , m ² and m ³ each represent the number average degree of polymerization of Ar ¹ , Ar ² and Ar ³ , each independently represents a number of 1 or more, m ¹ , m ² And at least two of m ³ represent a number of 5 or more.) Ar ¹ is a divalent group represented by the above formula (C-11) or (C-15), and Ar ³ is the above formula (D-10-1), (D-16), (G-1 The block copolymer according to claim 10, which is a divalent group represented by (G-2), (G-3), or (G-4). It represents with following formula (7), The block copolymer in any one of Claims 1-7 characterized by the above-mentioned.

(In Formula (7), Ar ¹ and Ar ² each independently represent a conjugated divalent group, Ar ¹ and Ar ² are different from each other, and R ^X and R ^Y each independently represent a terminal group, Alternatively, R ^X and R ^Y form a single bond and are bonded to each other at two ends of the block copolymer to form a cyclic structure, where m ¹ and m ² are the number average degree of polymerization of Ar ¹ and Ar ² , respectively. And each independently represents a number of 5 or more.) Ar ¹ is a divalent group represented by the above formula (C-11) or (C-15), and Ar ² is the above formula (D-10-1), (D-16), (G-1 ), (G-2), (G-3) or (G-4), which is a divalent group represented by the block copolymer according to claim 12. The block copolymer according to any one of claims 1 to 13, which is obtained by condensation polymerization of two or more monomers represented by the following general formula (b).

(In the formula (b), Ar represents the same divalent group as the divalent group represented by Ar in the formula (1). X ¹ represents a halogen atom, a sulfonate group represented by the formula (c), or a methoxy group. M ¹ represents a borate group, a boric acid group, a group represented by the formula (d), a group represented by the formula (e), or a group represented by the formula (f).

(In formula (c), R ^P represents an optionally substituted alkyl group or aryl group.)

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

(In the formula (f), R ^Q , R ^R and R ^S each independently represents an alkyl group or an aryl group.) Two or more types of monomers in which X ^{1 in the} formula (b) is a halogen atom or a sulfonate group represented by the formula (c), and M ¹ is a borate group or a borate group, The block copolymer according to claim 14, which is obtained by condensation polymerization in the presence of a ligand. The block copolymer according to claim 15, wherein the palladium complex is [tris (dibenzylideneacetone)] dipalladium or palladium acetate. The block copolymer according to claim 15 or 16, wherein the ligand is tris (2-methylphenyl) phosphine or tris (2-methoxyphenyl) phosphine. The number average molecular weight of polystyrene conversion is 1 * 10 < ³ > -1 * 10 < ⁷ >, The block copolymer in any one of Claims 1-17 characterized by the above-mentioned.   A polymer composition comprising at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material, and the block copolymer according to any one of claims 1 to 18. object.   A solution comprising the block copolymer according to claim 1.   A solution comprising the polymer composition according to claim 19.   The solution according to claim 20 or 21, comprising two or more organic solvents.   The solution according to any one of claims 20 to 22, which has a viscosity of 1 to 20 mPa · s at 25 ° C.   The luminescent thin film containing the block copolymer in any one of Claims 1-18, or the polymer composition of Claim 19.   The luminescent thin film according to claim 24, wherein the quantum yield of fluorescence is 50% or more.   The electroconductive thin film containing the block copolymer in any one of Claims 1-18, or the polymer composition of Claim 19.   The organic-semiconductor thin film containing the block copolymer in any one of Claims 1-18, or the polymer composition of Claim 19.   An organic transistor comprising the organic semiconductor thin film according to claim 27.   The method for forming a thin film according to any one of claims 24 to 27, wherein an inkjet method is used.   It has an organic layer between the electrodes which consist of an anode and a cathode, and this organic layer contains the block copolymer as described in any one of Claims 1-18, or the polymer composition as described in Claim 19. A polymer light emitting device characterized by that.   The polymer light emitting device according to claim 30, wherein the organic layer is a light emitting layer.   32. The polymer light emitting device according to claim 31, wherein the light emitting layer further contains a hole transport material, an electron transport material or a light emitting material.   A block copolymer according to any one of claims 1 to 18, or a polymer according to claim 19 having a light emitting layer and a charge transport layer between electrodes comprising an anode and a cathode. The polymer light-emitting device according to claim 30, comprising a composition.   A light-emitting layer and a charge transport layer are provided between electrodes composed of an anode and a cathode, a charge injection layer is provided between the charge transport layer and the electrode, and the charge injection layer is any one of claims 1 to 18. The polymer light-emitting device according to claim 30, comprising the block copolymer according to claim 20 or the polymer composition according to claim 19.   A planar light source using the polymer light emitting device according to any one of claims 30 to 34.   A segment display device comprising the polymer light emitting device according to any one of claims 30 to 34.   A dot matrix display using the polymer light emitting device according to any one of claims 30 to 34. 35. A liquid crystal display device comprising the polymer light-emitting element according to claim 30 as a backlight.

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