JP2006077171A - Benzotriazole structure-containing polymer, method for producing the same and charge transport material and organic electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer to be an n type organic semiconductor material and having excellent electron attracting properties. <P>SOLUTION: The polymer is obtained by including a structure represented by formula (1) (wherein, R<SP>1</SP>to R<SP>3</SP>denote each independently a hydrogen atom or a monovalent substituent) as a repeating unit. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel polymer containing a benzotriazole structure and a method for producing the same, and further, a charge transporting material containing the polymer and excellent in n-type semiconductor characteristics, and an organic electronic device using the charge transporting material About.

  A π-electron conjugated polymer having a π-electron conjugated double bond in the main chain is oxidized by the addition of an electron-donating substance, and a p-type organic semiconductor in which holes play a main role in electrical conduction, and an electron-accepting substance. There are n-type organic semiconductors that are reduced by addition and electrons play a major role in electrical conduction. There are many examples of the former, such as poly (2,5-thienylene), poly (2,5-pyrrolylene), and polyparaphenylene vinylene, but the latter is extremely rare.

  An n-type organic semiconductor that can be an electron conductor can be used for an electron transport layer such as an organic EL element, an organic photoconductor electrode, and an organic transistor, and for a wide variety of other uses.

  Poly (2,5-pyridinediyl) described in Non-Patent Document 1 is one of the few n-type organic semiconductors having an electron-withdrawing pyridine structure as a repeating unit as a π-electron conjugated polymer. However, the pyridine structure has a weak electron withdrawing property and is insufficient in terms of stability as an n-type organic semiconductor, and a new material has been demanded.

  On the other hand, the benzotriazole structure contains more electron-withdrawing groups -C = N- than the pyridine structure, and the π-conjugated planar structure can be expanded by controlling the orientation, so that the charge transport property is high. Expected to be a semiconductor.

  Non-Patent Document 2 reports the synthesis of a polymer having a benzotriazole skeleton introduced into the side chain of polythiophene and its spectroscopic properties.

Synthetic Metals, Vol. 25, 1988, p. 103-107 Macromolecules, Vol. 34, 2001, p. 2522

  However, according to the study by the present inventors, the polymer described in Non-Patent Document 2 has not been sufficiently attracted by electrons to be used as an n-type organic semiconductor material. Accordingly, there has been a demand for a new polymer that can be an n-type organic semiconductor material and has excellent electron withdrawing properties.

The present invention has been made in view of the above-described problems.
That is, an object of the present invention is to provide a novel polymer excellent in electron withdrawing property and a method for producing the same, which can be an n-type organic semiconductor material with few reported examples.
Another object of the present invention is to provide a charge transport material comprising the polymer.
Furthermore, an object of the present invention is to provide an organic device using the charge transport material.

  As a result of intensive studies in view of the above problems, the present inventors have found that a novel polymer having a benzotriazole ring structure in the main chain is excellent in electron withdrawing properties and is suitable for use as an n-type organic semiconductor, such as a charge transport material. As a result, the present invention has been completed.

（式（１）中、Ｒ¹〜Ｒ³はそれぞれ独立に水素原子又は１価の置換基を表わす。）
ここで、式（１）で表わされる繰り返し単位と、下記式（２）で表わされる繰り返し単位とが交互に結合した部分を少なくとも有することが好ましい（請求項２）。

（式（２）中、Ａｒは、π共役構造を有する２価の有機基を示す。）
また、本発明の別の趣旨は、請求項１又は請求項２に記載のベンゾトリアゾール構造含有高分子を製造する方法であって、少なくとも下記式（３）で表わされる化合物を用いて、金属錯体の存在下で重合させることを特徴とする、ベンゾトリアゾール構造含有高分子の製造方法に存する（請求項３）。

（式（３）中、Ｒ¹〜Ｒ³は、式（１）の同じ符号と同様の基を表わす。Ｘは、ハロゲン原子を表わす。）
ここで、上記金属錯体としては、パラジウム及び／又はニッケル錯体を用いることが好ましい（請求項４）。
また、本発明の別の趣旨は、上述のベンゾトリアゾール構造含有高分子を含有することを特徴とする、電荷輸送材料に存する（請求項５）。
また、本発明の別の趣旨は、上述の電荷輸送材料を用いたことを特徴とする、有機電子デバイスに存する（請求項６）。
ここで、上記有機電子デバイスとしては、発光素子、スイッチング素子、光電変換素子、光センサー、又は太陽電池であることが好ましい（請求項７〜１１）。 That is, the gist of the present invention resides in a benzotriazole structure-containing polymer characterized by containing a structure represented by the following formula (1) as a repeating unit (claim 1).

(In formula (1), R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent substituent.)
Here, it is preferable to have at least a portion in which the repeating unit represented by the formula (1) and the repeating unit represented by the following formula (2) are alternately bonded.

(In the formula (2), Ar represents a divalent organic group having a π-conjugated structure.)
Another aspect of the present invention is a method for producing a benzotriazole structure-containing polymer according to claim 1 or 2, wherein at least a compound represented by the following formula (3) is used to form a metal complex: The present invention resides in a method for producing a benzotriazole structure-containing polymer, characterized in that the polymerization is carried out in the presence of (Claim 3).

(In formula (3), R ^{1 to} R ³ represent the same groups as those in formula (1). X represents a halogen atom.)
Here, it is preferable to use a palladium and / or nickel complex as the metal complex.
Another object of the present invention resides in a charge transport material characterized by containing the above-mentioned benzotriazole structure-containing polymer (claim 5).
Another object of the present invention resides in an organic electronic device using the above-described charge transport material (claim 6).
Here, the organic electronic device is preferably a light emitting element, a switching element, a photoelectric conversion element, an optical sensor, or a solar cell (claims 7 to 11).

The benzotriazole structure-containing polymer of the present invention is excellent in electron withdrawing properties and exhibits characteristics as an n-type semiconductor. Therefore, it can be suitably used for applications such as charge transport materials.
Moreover, according to the method for producing a benzotriazole structure-containing polymer of the present invention, the above-described benzotriazole structure-containing polymer of the present invention can be efficiently produced.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

[I. Polymer containing benzotriazole structure)
First, the benzotriazole structure-containing polymer of the present invention will be described.
The benzotriazole structure-containing polymer of the present invention (hereinafter sometimes abbreviated as “polymer of the present invention”) contains a structure represented by the following formula (1) (benzotriazole structure) as a repeating unit. Features.

In formula (1), R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent substituent. Here, “independently” means not only that all of R ^{1 to} R ³ are independent from each other in each benzotriazole structure, but also a plurality of benzoates present in the polymer of the present invention. It also shows that the triazole structures are independent from each other. That is, for example, when any Rα (α is an integer of 1 to 3) in any benzotriazole structure in the polymer is a methyl group, a methyl group may be used for Rα that is a similar position in another benzotriazole structure. This indicates that the substituent may be other than the methyl group. Therefore, when m benzotriazole structures are present in one polymer, it is indicated that any Rα is an independent substituent in each of the m benzotriazole structures.

Hereinafter, first, R ¹ will be specifically described.
When R ¹ is a monovalent substituent, the type thereof is not particularly limited as long as it does not depart from the spirit of the present invention. Examples thereof include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.); a nitro group; A cyano group; a carbonyloxy group; a carboxyl group; a sulfonic acid group; an amino group; and a monovalent organic group. Examples of the monovalent organic group include an alkyl group; an alkenyl group; an alkynyl group; an aryl group; a heterocyclic group; an alkoxy group; an aryloxy group; an alkylthio group; an arylthio group; a carboxylic acid ester group; And / or aryl-substituted silyl group; alkyl and / or aryl-substituted amino group; amide group and the like. When R ¹ is an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, or an alkynyl group, or a group containing these aliphatic hydrocarbon groups in its structure, the aliphatic hydrocarbon group is linear It may have any of a branched structure and a ring structure.

  These exemplified groups may further have another substituent. The type of the substituent is not particularly limited as long as it does not depart from the gist of the present invention. Examples include halogen atom; nitro group; cyano group; sulfonic acid group; carbonyloxy group; carboxyl group; amino group; An alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxylic acid ester group, a sulfonic acid ester group, an alkyl and / or aryl-substituted silyl group, an alkyl and / or Aryl-substituted amino group; amide group and the like. When the substituent is an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, or an alkynyl group, or a group containing these aliphatic hydrocarbon groups in the structure, the aliphatic hydrocarbon group is a straight chain It may have any structure of a shape, a branch shape, and a ring shape.

In the case where R ¹ is an organic group, the number of carbon atoms is usually 20 or less, preferably 10 or less, in terms of the value of the entire R ¹ including the substituent when it has the above-mentioned further substituent. .

Specifically, examples of when R ¹ is an alkyl group include a methyl group, an ethyl group, a propyl group (n-propyl group, i-propyl group), a butyl group (n-butyl group, t-butyl group, isobutyl). Group, s-butyl group), pentyl group (n-butyl group etc.), hexyl group (n-hexyl group etc.), decyl group, dodecyl group, hexadecyl group etc. linear or branched alkyl group; cyclopentyl group And a cyclic alkyl group such as a cyclohexyl group. Examples of substituted alkyl groups include halogen-substituted alkyl groups such as trifluoromethyl groups; alkoxyalkyl groups such as 2-methoxyethyl groups; nitro-substituted alkyl groups such as 2-nitroethyl groups; cyano groups such as cyanomethyl groups Substituted alkyl groups; alkoxycarbonyl group-substituted alkyl groups such as 3-methoxycarbonylpropyl group; metal-containing substituted alkyl groups such as —CH ₂ SO ₃ Na and —CH ₂ CH ₂ COOK, and the like.

Examples of when R ¹ is an alkenyl group include ethenyl group, 2-propenyl group, 1,3-butadienyl group and the like. Examples of substituted alkenyl groups include alkoxyalkenyl groups such as 4-methoxy-2-butenyl group.

Examples of when R ¹ is an alkynyl group include an ethynyl group and a 2-propynyl group.

Examples of when R ¹ is an aryl group include a phenyl group and a naphthyl group. Examples of the substituted aryl group include alkoxyaryl groups such as 4-methoxyphenyl group; halogen-substituted alkoxyaryl groups such as 3-trifluoromethylphenyl group.

Examples of when R ¹ is a heterocyclic group include sulfur-containing heterocyclic groups such as thienyl groups; oxygen-containing heterocyclic groups such as furyl groups and pyranyl groups; nitrogen-containing heterocyclic groups such as pyrrolyl groups and pyridyl groups; A selenium-containing heterocyclic group such as a group; a heterocyclic group containing a heterohetero atom such as an isothiazoyl group, and the like. Examples of the substituted heterocyclic group include alkyl-substituted heterocyclic groups such as a 3-methylthienyl group.

When R ¹ is an unsubstituted or substituted alkoxy group, examples thereof include various alkoxy groups obtained by bonding the above-described various unsubstituted or substituted alkyl groups to an oxygen atom.

When R ¹ is an unsubstituted or substituted aryloxy group, examples thereof include various aryloxy groups obtained by bonding the various unsubstituted or substituted aryl groups exemplified above to an oxygen atom.

When R ¹ is an unsubstituted or substituted alkylthio group, examples thereof include various alkylthio groups obtained by bonding various unsubstituted or substituted alkyl groups exemplified above to a sulfur atom.

When R ¹ is an unsubstituted or substituted arylthio group, examples thereof include various arylthio groups obtained by bonding various unsubstituted or substituted aryl groups exemplified above to a sulfur atom.

When R ¹ is an alkyl and / or aryl-substituted silyl group, examples thereof are obtained by bonding 1 to 3 of the above-mentioned various unsubstituted or substituted alkyl groups and / or aryl groups to a silicon atom. And various substituted silyl groups.

When R ¹ is a carboxylic acid ester group, examples thereof include various carboxylic acids obtained by substituting various unsubstituted or substituted alkyl groups or aryl groups exemplified above with a hydrogen atom of a carboxylic acid group —COOH. An acid ester group is mentioned.

In the case where R ¹ is a sulfonic acid ester group, as an example, various unsubstituted or substituted alkyl groups or aryl groups exemplified above are substituted with a hydrogen atom of a sulfonic acid group —S (═O) ₂ —OH. And various sulfonic acid ester groups obtained in this manner.

When R ¹ is an alkyl and / or aryl-substituted amino group, examples thereof include one or two of the various unsubstituted or substituted alkyl groups and / or aryl groups exemplified above bonded to a nitrogen atom. The various substituted amino groups obtained are mentioned.

When R ¹ is an amide group, examples thereof are obtained by substituting various unsubstituted or substituted alkyl groups and / or aryl groups exemplified above with a hydrogen atom at the terminal of the formamide group —NH—COH. Various amide groups can be mentioned.

Subsequently, R ² and R ³ will be specifically described. In the following description, for convenience, they are collectively described as “R ² · R ³ ”. However, as described above, R ² and R ³ are independent and may be the same or different from each other. good.

In the case where R ² and R ³ are monovalent substituents, the type thereof is not particularly limited as long as it does not depart from the gist of the present invention, but examples include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.); A nitro group; a cyano group; a carbonyloxy group; a carboxyl group; a sulfonic acid group; an amino group; and a monovalent organic group. Examples of the monovalent organic group include an alkyl group; an alkenyl group; an alkynyl group; an aryl group; a heterocyclic group; an alkoxy group; an aryloxy group; an alkylthio group; an arylthio group; a carboxylic acid ester group; And / or aryl-substituted silyl group; alkyl and / or aryl-substituted amino group; amide group and the like. In addition, when R ² · R ³ is an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, an alkynyl group, or a group containing these aliphatic hydrocarbon groups in its structure, the aliphatic hydrocarbon group is It may have any of linear, branched and cyclic structures.

  These exemplified groups may further have another substituent. The type of the substituent is not particularly limited as long as it does not depart from the gist of the present invention. Examples include halogen atom; nitro group; cyano group; sulfonic acid group; carbonyloxy group; carboxyl group; amino group; An alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxylic acid ester group, a sulfonic acid ester group, an alkyl and / or aryl-substituted silyl group, an alkyl and / or Aryl-substituted amino group; amide group and the like. When the substituent is an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, or an alkynyl group, or a group containing these aliphatic hydrocarbon groups in the structure, the aliphatic hydrocarbon group is a straight chain It may have any structure of a shape, a branch shape, and a ring shape.

If R ² · R ³ is an organic group, the number of carbon atoms is the R ² · R ³ total value including the substituents if they have further substituents described above, usually 20 or less, preferably The range is 10 or less.

Specifically, examples of the case where R ² and R ³ are alkyl groups include methyl group, ethyl group, propyl group (n-propyl group, i-propyl group), butyl group (n-butyl group, t-butyl group). Group, isobutyl group, s-butyl group), pentyl group (n-butyl group, etc.), hexyl group (n-hexyl group, etc.), decyl group, dodecyl group, hexadecyl group, etc., linear or branched alkyl group A cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group; Examples of substituted alkyl groups include halogen-substituted alkyl groups such as trifluoromethyl groups; alkoxyalkyl groups such as 2-methoxyethyl groups; nitro-substituted alkyl groups such as 2-nitroethyl groups; cyano groups such as cyanomethyl groups Substituted alkyl groups; alkoxycarbonyl group-substituted alkyl groups such as 3-methoxycarbonylpropyl group; metal-containing substituted alkyl groups such as —CH ₂ SO ₃ Na and —CH ₂ CH ₂ COOK, and the like.

Examples of the case where R ² and R ³ are alkenyl groups include ethenyl group, 2-propenyl group, 1,3-butadienyl group and the like. Examples of substituted alkenyl groups include alkoxyalkenyl groups such as 4-methoxy-2-butenyl group.

Examples of the case where R ² and R ³ are an alkynyl group include an ethynyl group and a 2-propynyl group.

Examples of the case where R ² and R ³ are aryl groups include a phenyl group and a naphthyl group. Examples of the substituted aryl group include alkoxyaryl groups such as 4-methoxyphenyl group; halogen-substituted alkoxyaryl groups such as 3-trifluoromethylphenyl group.

Examples of the case where R ² and R ³ are heterocyclic groups include sulfur-containing heterocyclic groups such as thienyl groups; oxygen-containing heterocyclic groups such as furyl groups and pyranyl groups; nitrogen-containing heterocyclic rings such as pyrrolyl groups and pyridyl groups A selenium-containing heterocyclic group such as a selenoyl group; a heterocyclic group containing a heterohetero atom such as an isothiazoyl group, and the like. Examples of the substituted heterocyclic group include alkyl-substituted heterocyclic groups such as a 3-methylthienyl group.

When R ² and R ³ are unsubstituted or substituted alkoxy groups, examples thereof include various alkoxy groups obtained by bonding the various unsubstituted or substituted alkyl groups exemplified above to oxygen atoms. .

In the case where R ² and R ³ are unsubstituted or substituted aryloxy groups, examples thereof include various aryloxy groups obtained by bonding various unsubstituted or substituted aryl groups exemplified above to oxygen atoms. Can be mentioned.

When R ² and R ³ are unsubstituted or substituted alkylthio groups, examples thereof include various alkylthio groups obtained by bonding various unsubstituted or substituted alkyl groups exemplified above to a sulfur atom. .

In the case where R ² and R ³ are unsubstituted or substituted arylthio groups, examples thereof include various arylthio groups obtained by bonding various unsubstituted or substituted aryl groups exemplified above to a sulfur atom. .

When R ² and R ³ are alkyl and / or aryl-substituted silyl groups, examples thereof include 1 to 3 of the above-mentioned various unsubstituted or substituted alkyl groups and / or aryl groups bonded to a silicon atom. And various substituted silyl groups obtained in this manner.

When R ² and R ³ are carboxylic acid ester groups, examples thereof are obtained by substituting various unsubstituted or substituted alkyl groups or aryl groups exemplified above with a hydrogen atom of a carboxylic acid group —COOH. Various carboxylic ester groups are mentioned.

When R ² · R ³ is a sulfonic acid ester group, examples thereof include various unsubstituted or substituted alkyl groups or aryl groups exemplified above as hydrogen of a sulfonic acid group —S (═O) ₂ —OH. Examples include various sulfonic acid ester groups obtained by substituting atoms.

In the case where R ² and R ³ are alkyl and / or aryl-substituted amino groups, examples thereof include one or two of the various unsubstituted or substituted alkyl groups and / or aryl groups exemplified above, and a nitrogen atom. Examples include various substituted amino groups obtained by bonding.

In the case where R ² and R ³ are amide groups, for example, the above-mentioned various unsubstituted or substituted alkyl groups and / or aryl groups are substituted with the terminal hydrogen atom of the formamide group —NH—COH. And various amide groups obtained.

Among the above examples, R ^{1 to} R ³ are each independently preferably a hydrogen atom, an electron-withdrawing substituent, or a hydrocarbon group or a substituent containing the same.

In particular, from the viewpoint of improving the characteristics of the polymer as an n-type semiconductor, it is preferable to use an electron-withdrawing substituent as at least one of R ^{1 to} R ³ . Examples of the electron-withdrawing substituent include a halogen atom, a nitro group, a cyano group, a halogen-substituted alkyl group, a carboxylic acid group and a salt thereof, a sulfonic acid group and a salt thereof, a carboxylic acid ester group, and a sulfonic acid ester group. Among these, a halogen atom, a nitro group, a cyano group, a halogen-substituted alkyl group, a carboxylic acid group and a salt thereof, a sulfonic acid group and a salt thereof, and a sulfonic acid ester group are preferable. Specifically, the halogen atom is preferably a fluorine atom. The halogen-substituted alkyl group is preferably a fluorine-substituted alkyl group (fluoroalkyl group), particularly preferably a trifluoromethyl group. When these groups are introduced into R ^{1 to} R ³ that are the side chains of the polymer, the electron withdrawing property of the polymer is increased, and the n-type semiconductor properties of the polymer are improved.

Further, from the viewpoint of improving the solubility of the polymer in the solvent, as at least one of R ¹ to R ^3, it is preferable to use a hydrocarbon group or a substituted group containing a. Examples of the hydrocarbon group or a substituent containing the same include an unsubstituted or substituted alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkyl and / or aryl-substituted silyl group, alkyl and / or An aryl substituted amino group etc. are mentioned. Among them, an unsubstituted or substituted alkyl group or aryl group is preferable, and an alkyl group or a fluorine-substituted alkyl group (fluoroalkyl group) is particularly preferable. When these groups are introduced into R ^{1 to} R ³ which are the side chains of the polymer, the electron withdrawing property of the polymer may be slightly lowered, but the solubility in a solvent is increased and the processability of the polymer is improved. The

  Specific examples of the repeating unit of the formula (1) include those included in the following groups (A) to (C). However, these are merely examples, and the repeating unit of the formula (1) applicable to the polymer of the present invention is not limited to those included in these groups (A) to (C).

・ Group (A):
In the formula (1), a group consisting of a structure in which R ^{1 to} R ³ are each independently any of the following groups.
H-,
F-,
CH ₃₋ ,
CH ₃ (CH ₂ ) _n — (n represents an integer of 1 to 23),
CH ₃ (CH ₂ ) _n (CF ₂ ) _m — (n, m each independently represents an integer of 1 to 23. Further, a bond of n (CH ₂ ) and m (CF ₂ ) The order is arbitrary.),
CF ₃ −,
CF ₃ (CF ₂ ) _n — (n represents an integer of 1 to 23),
CF ₃ (CH _{2) n} (CF _{2) m} -. (N and m each independently represent an integer of 1 to 23 The coupling of n (CH ₂₎ and m of (CF ₂₎ The order is arbitrary.)

・ Group (B):
In the formula (1), a group consisting of a structure in which R ^{1 to} R ³ are each independently any of the groups listed in Table 1 below.

・ Group (C):
In the formula (1), a group consisting of a structure in which R ^{1 to} R ³ are each independently any of the groups listed in Table 2 below.

  If the polymer of this invention has a repeating unit of Formula (1), there will be no other restriction | limiting. For example, the homopolymer which consists of one type of repeating unit of Formula (1) may be sufficient, and the copolymer which consists of two or more types of repeating units of Formula (1) may be sufficient. Furthermore, the copolymer which consists of one type or two or more types of repeating units of Formula (1) and one type or two or more types of other repeating units may be sufficient.

  The ratio of the repeating unit of the formula (1) in the polymer is not particularly limited, but is a certain high ratio from the viewpoint of imparting sufficient electron withdrawing property to the polymer and exhibiting properties as an n-type semiconductor. Is preferred. Specifically, the weight ratio of the monomer corresponding to the repeating unit of the formula (1) with respect to the whole raw material monomer at the time of polymer production is usually 1% by weight or more, preferably 10% by weight or more. On the other hand, the upper limit is usually 100% by weight or less, preferably 90% by weight or less.

  When the polymer of the present invention has other repeating units in addition to the repeating unit of the formula (1), the structure of the other repeating units is not particularly limited, but a preferable structure is represented by the following formula (2). Things.

上記式（２）中、Ａｒは、π共役構造を有する２価の有機基を表わす。ここで「π共役構造」は、多重結合が単結合と交互に連なった構造を表わす。高分子中にこのようなπ共役構造を有する有機基が存在することによって、高分子のπ共役平面が広がり、トリアゾール骨格の電子吸引性がより高くなり、ｎ型半導体としての特性がより向上する。

In the above formula (2), Ar represents a divalent organic group having a π-conjugated structure. Here, the “π conjugate structure” represents a structure in which multiple bonds are alternately connected to single bonds. By the presence of an organic group having such a π-conjugated structure in the polymer, the π-conjugated plane of the polymer is expanded, the electron withdrawing property of the triazole skeleton is increased, and the characteristics as an n-type semiconductor are further improved. .

  Examples of Ar include structures represented by the following formulas (I) to (XII). However, these are merely examples, and Ar applicable to the polymer of the present invention is not limited to the structures of the following formulas (I) to (XII).

  In the above formulas (I) to (XII), the definitions of the respective symbols are as follows.

R ^{4 to} R ⁷⁰ are each independently
H,
F,
CH ₃₋ ,
CH ₃ (CH ₂ ) _n — (n represents an integer of 1 to 23),
CH ₃ (CH ₂ ) _n (CF ₂ ) _m — (n and m each independently represents an integer of 1 to 23),
CF ₃ −,
CF ₃ (CF ₂ ) _n — (n represents an integer of 1 to 23),
CF ₃ (CH ₂ ) _n (CF ₂ ) _m — (n and m each independently represents an integer of 1 to 23),
Phenyl group,
Nitro group,
An amino group,
A cyano group,
Carboxyl group,
Sulfonic acid groups,
Represents a hydroxyl group or an alkoxy group.

A ^{3 to} A ³⁰ each independently represents a carbon atom or a nitrogen atom. In the case of a nitrogen atom, R ^{4 to} R ⁷⁰ corresponding thereto do not exist.

Q ^{1 to} Q ⁶ each independently represent —CR ⁷¹ R ⁷² —, —NR ⁷³ —, —S—, —SiR ⁷⁴ R ⁷⁵ —, or —Se— (R ^{71 to} R ⁷⁵ are each independently A hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 23 carbon atoms, a fluorine-substituted alkyl group in which the alkyl group is substituted with 1 or 2 or more fluorine atoms, or an aromatic ring group Represent.)

を表わす。 E ¹ is a nitrogen atom or

Represents.

n ¹ represents an integer of 0 or more and 6 or less.
n ² represents an integer of 1 to 6.
n ³ and n ⁴ each independently represents an integer of 1 or more and 8 or less.
n ⁵ and n ¹⁰ each independently represents an integer of 1 or more and 10 or less.
n ⁶ ~n ⁹ and n ¹¹ ~n ¹⁴ each independently represent an integer of 0 to 10.

  When the polymer of the present invention has the repeating unit (Ar) of the formula (2) in addition to the repeating unit of the formula (1), the content of the repeating unit of the formula (2) in the polymer is not particularly limited. All of the units other than the repeating unit of the formula (1) may be occupied by the repeating unit of the formula (2), and further other repeating units may be contained. Further, the repeating unit of the formula (2) contained in the polymer may be only one type or two or more types.

  Moreover, the presence state of the repeating unit of the formula (1) and the formula (2) in the polymer is not particularly limited. The repeating units of formula (1) and formula (2) may be present alternately, the repeating units of formula (1) and formula (2) may be present at random, and the repeating unit of formula (1) The unit and the repeating unit of the formula (2) may be separately assembled and exist in a block shape. However, it is preferable that the repeating units of the formula (1) and the formula (2) are alternately present in at least a part of the polymer. This is because the electron-withdrawing property of the triazole skeleton works between molecules, causing inter-molecule stacking to facilitate orientation.

  The polymer structure of the present invention has a nuclear magnetic resonance (hereinafter abbreviated as “NMR”) spectrum, infrared (hereinafter abbreviated as “IR”) spectrum, elemental analysis method, mass spectrometry (hereinafter referred to as “MS”). It can be analyzed and identified by a method such as

  As an example, the polymer of the present invention is separated from the organic electronic device containing the polymer of the present invention by a method such as washing, and is further abbreviated as thermogravimetric analysis-mass spectrometry (hereinafter “TG-MS”). ) Method to identify the benzotriazole structure of formula (1) from the structure of the decomposition product, to quantify the elemental composition ratio by elemental analysis, and to identify the binding state by NMR spectrum measurement or IR spectrum measurement, etc. It is possible to identify the benzotriazole structure of formula (1). Specific examples include Polymer Journal, Vol. 32, No. 11, 2000, p. It can carry out by the method similar to the measurement by poly- nitropyridine of 991-994.

  There is no restriction | limiting in particular as molecular weight of the polymer | macromolecule of this invention, What is necessary is just to select so that it may become a suitable range according to the use. For example, when the polymer of the present invention is used as a charge transport layer for an organic electronic device or the like to be described later, usually, a method of coating the polymer by dissolving it in a solvent is performed to form the film. In this case, the higher the molecular weight of the polymer, the more excellent the film strength and uniformity after film formation can be obtained. On the other hand, if the molecular weight of the polymer is too high, it may be difficult to dissolve in a solvent, which is not preferable. Accordingly, the optimum molecular weight of the polymer of the present invention varies depending on its processability, application, etc., and it is preferable to use them individually. In general, the weight average molecular weight obtained by molecular weight measurement by GPC is usually 300 or more, preferably 1000 or more. The upper limit is not particularly limited, but is usually 100,000 or less.

  The molecular weight of the polymer of the present invention can be measured by liquid chromatography such as gel permeation chromatography (hereinafter abbreviated as “GPC”). Specifically, for example, as in the measurement with poly-nitropyridine described in Polymer Journal, Vol. 32, No. 11, p. 991-994, 2000, a solvent such as dimethylformamide, chloroform, trifluoroacetic acid or the like. And can be measured by GPC.

  The polymer of the present invention described above contains a benzotriazole structure in its main chain, is excellent in electron withdrawing properties, and exhibits properties as an n-type semiconductor. As described above, the polymer structure of a polymer containing a benzotriazole structure in the side chain is described in Ahn, S .; H. As described in Non-Patent Document 2 above, sufficient electrical characteristics were not obtained only by introducing a benzotriazole structure into the side chain. On the other hand, introduction of a benzotriazole structure into the main chain of the polymer has been very difficult due to poor reactivity of benzotriazole itself. On the other hand, the polymer of the present invention is excellent in electron withdrawing properties, exhibits properties as an n-type organic semiconductor, and can be efficiently manufactured by, for example, a manufacturing method described later.

In addition, it can confirm by the oxidation-reduction potential measurement that the polymer of this invention is an n-type conductor excellent in electron withdrawing property. Specifically, when a solution containing a polymer is prepared, the polymer is electrochemically reduced, and measured using an electrode such as Ag ⁺ / Ag, a reduction wave of about 0.5 V to −2 V is obtained. It can be confirmed by showing.

  Moreover, it can be confirmed by electrical conductivity measurement that the polymer of the present invention is a semiconductor. Specifically, it can be confirmed by measuring the conductivity of the optically or electrochemically reduced sample. In addition, there are other methods such as analyzing the operation behavior of the field effect transistor, measuring the Hall effect, measuring the thermoelectromotive force, and measuring the photoconductivity.

[II. Method for producing polymer containing benzotriazole structure]
The method for producing the polymer of the present invention is not particularly limited, but usually one kind or two or more kinds of monomers corresponding to the repeating unit of the above formula (1) may be used as needed. Or it can manufacture by the method of superposing | polymerizing or copolymerizing in the presence of a metal complex with 2 or more types of monomers. Hereinafter, this production method (method for producing the benzotriazole structure-containing polymer of the present invention) will be described.

  As the monomer corresponding to the repeating unit of the formula (1), a compound represented by the following formula (3) is usually used.

In formula (3), R ^{1 to} R ³ represent the same groups as those in formula (1).
X represents a halogen atom. Among these, a bromine atom, a chlorine atom, and an iodine atom are preferable, and a bromine atom is particularly preferable.

  In addition, the manufacturing method in particular of the compound of Formula (3) is not restrict | limited, Various well-known methods can be arbitrarily selected as a manufacturing method of a general benzotriazole structure compound. For example, it is described in Liebigs Annalen der Chemie (1994).

  As the monomer, one of the compounds of formula (3) is used alone, or two or more thereof are used in combination. When two or more kinds are used in combination, the ratio is not particularly limited, and may be appropriately adjusted according to the structure of the target polymer.

  Moreover, when manufacturing the polymer containing repeating units other than Formula (1), in addition to the compound of Formula (3), the aromatic compound which has a 2 or more halogen atom is used as another monomer. The term “aromatic compound having two or more halogen atoms” as used herein is not particularly limited in terms of the type thereof, provided that two or more hydrogen atoms at any position in the aromatic ring are substituted with halogen atoms. Instead, an appropriate one may be selected according to the structure of the target repeating unit. Specific examples include p-dibromobenzene, 2,5-dibromothiophene, 2,5-dibromopyridine, 2,6-dibromopyridine and the like.

  As for other monomers, one kind may be used alone, or two or more kinds may be used in any combination. Further, the use ratio is not particularly limited, and may be appropriately adjusted according to the structure of the target polymer.

  The type of the metal complex is not particularly limited, and can be arbitrarily selected from various known metal complexes for polymerization. Examples include reduction catalysts such as copper complexes, nickel complexes, and palladium complexes. Of these, nickel complexes and palladium complexes are preferred.

  Examples of the nickel complex include bis (1,5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, dichloro (2,2'-bipyridine) nickel and the like. Among them, a nickel (zero-valent) complex such as bis (1,5-cyclooctadiene) nickel is preferable because it has a high polymerization ability for the compound of formula (3). In addition, a nickel complex may be used individually by 1 type, and may use 2 or more types by arbitrary compositions and combinations. Further, dichloro (2,2′-bipyridine) nickel (divalent) and magnesium or zinc as a dehalogenating agent can be used in combination.

  Examples of the palladium complex include tetrakis (triphenylphosphine) palladium and dichloro {1,3-bis (diphenylphosphine) propane} palladium. Among these, tetrakis (triphenylphosphine) palladium is preferable because it has a high polymerization ability with respect to the compound of formula (3). In addition, any one of these palladium complexes may be used alone, or two or more thereof may be used in any composition and combination. Moreover, you may use together 1 type, or 2 or more types of palladium complexes with 1 type, or 2 or more types of nickel complexes, and arbitrary combinations.

When used as a catalyst, the metal complex is used in a molar ratio with respect to all monomers as a raw material, and is usually in the range of 5 × 10 ⁻³ times or more and 5 × 10 ⁻² times or less. Further, when the compound itself acts as a reactant, such as a zero-valent nickel complex, the molar ratio with respect to all monomers as a raw material is usually in the range of 1 to 2 times.

  The polymerization procedure is not particularly limited, but usually the monomer is dissolved or dispersed in a solvent in a reaction vessel, and a catalyst is added thereto to start the reaction.

  The type of the solvent is not particularly limited as long as it can dissolve or disperse the monomer suitably and does not cause an undesirable reaction with the monomer or polymer. Examples include N, N-dimethylformamide, tetrahydrofuran, toluene and the like. In addition, a solvent may be used individually by 1 type and may mix and use 2 or more types by arbitrary combinations.

  Although the atmosphere during the polymerization reaction is not particularly limited, it is usually carried out in air or under an inert atmosphere, preferably under an inert atmosphere. Examples of the inert atmosphere include an argon gas or nitrogen gas atmosphere.

Although there is no restriction | limiting in particular in the temperature at the time of a polymerization reaction, Usually, 20 degreeC or more, Preferably it is 40 degreeC or more, and is 100 degrees C or less normally, Preferably it is the range of 80 degrees C or less.
Although there is no restriction | limiting in particular also in the pressure at the time of a polymerization reaction, Usually, it carries out at a normal pressure.

  The polymerization reaction time varies depending on the type of monomer and catalyst used, the temperature and pressure during polymerization, etc., but is usually 1 hour or more, preferably 5 hours or more, and usually 20 hours or less, preferably 10 hours or less. It is a range.

  After completion of the polymerization reaction, the obtained polymer is recovered by an arbitrary method, and post-treatment is performed as necessary. Examples of a method for recovering the polymer from the reaction solution include a method such as reprecipitation. Examples of the post-treatment include removal of the metal complex by washing with a chelating agent or the like.

[III. Charge transport material)
Next, the charge transport material of the present invention will be described.
The charge transport material of the present invention is characterized by containing at least the polymer of the present invention described above. Any one of the polymers of the present invention may be contained alone, or two or more may be contained in any combination. Moreover, although it may consist only of the polymer of the present invention, it may contain other components (for example, other polymers, monomers, various additives, etc.).

The type of the polymer of the present invention contained in the charge transporting material is not particularly limited, but for reasons such as solubility in an organic solvent and excellent processability, among R ^{1 to} R ^{3 in} formula (1) It is preferable that at least one is a hydrocarbon group or a substituent containing the same. From the viewpoint of high electron-withdrawing properties and excellent n-type semiconductor properties, at least one of R ^{1 to} R ³ in formula (1) is an electron-withdrawing substituent, or formula (1) What contains the repeating unit of Formula (2) other than the repeating unit of is preferable.

  The charge transport material of the present invention is suitable for a charge transport layer of an organic electronic device described later as one of its uses. In that case, the charge transporting material is preferably used after being formed into a film, and the physical properties such as the above-described solubility in an organic solvent and excellent workability appear as preferred points. Details of the use as the charge transport layer of the organic electronic device will be described in the section of the organic electronic device.

Although the charge transport material of the present invention can sufficiently function as a material for a charge transport layer of an organic electronic device, it can be used by mixing and / or laminating with other charge transport materials. Other charge transport materials that can be used in combination with the charge transport material of the present invention include known charge transport materials such as quinolinol derivative metal complexes such as trisaluminum quinolinol (hereinafter abbreviated as “Alq ₃ ”), oxadiazine derivatives, triazine derivatives, and the like. Examples of the material include, but are not limited to, materials.

[IV. Organic electronic devices)
Next, the organic electronic device of the present invention will be described.
The organic electronic device of the present invention is formed using the above-described charge transport material of the present invention. As long as the charge transport material of the present invention can be applied, the type of the organic electronic device is not particularly limited. Examples include a light emitting element, a switching element, a photoelectric conversion element, a photosensor utilizing photoelectric conductivity, a solar cell, and the like.

  Examples of the light emitting element include various light emitting elements used for display devices. Specific examples include a liquid crystal display element, a polymer dispersion type liquid crystal display element, an electrophoretic display element, an electroluminescent element, an electrochromic element, and the like.

  Specific examples of the switching element include a diode (pn junction diode, Schottky diode, MOS diode, etc.), a transistor (bipolar transistor, field effect transistor (FET), etc.), a thyristor, and a composite element thereof (for example, TTL). Etc.).

  Specific examples of the photoelectric conversion element include a charge coupled device (CCD), a photomultiplier tube, and a photocoupler. Moreover, what utilized these photoelectric conversion elements is mentioned as an optical sensor using photoelectric conductivity.

  Which part of the organic electronic device the charge transport material of the present invention is used is not particularly limited, and can be used for any part as long as it can take advantage of the characteristics as an n-type semiconductor. Usually used in charge transport layers of organic electronic devices.

The type of the charge transport material of the present invention to be used is not particularly limited, but at least one of R ^{1 to} R ^{3 in} the formula (1) is carbonized for reasons such as solubility in an organic solvent and excellent workability. A charge transport material containing a polymer which is a hydrogen group or a substituent containing the hydrogen group is preferred. From the viewpoint of high electron-withdrawing properties and excellent n-type semiconductor properties, a polymer in which at least one of R ^{1 to} R ³ in formula (1) is an electron-withdrawing substituent, or formula (1 The charge transporting material containing a polymer containing the repeating unit of the formula (2) in addition to the repeating unit of

  As an example of the organic electronic device of the present invention, a field effect transistor (FET) which is a kind of switching element will be described. FIGS. 1 to 3 each schematically illustrate a configuration example of a field effect transistor (hereinafter, may be abbreviated as “the field effect transistor of the present invention” or “the FET of the present invention”) which is a kind of the organic electronic device of the present invention. FIG. As shown in FIGS. 1 to 3, the basic structure of the field effect transistor of the present invention is that an insulating layer 3, a gate electrode 2 isolated by the insulating layer 3, and a charge transport property are provided on a support substrate 1. The layer 4 has a source electrode 5 and a drain electrode 6 provided so as to be in contact with the charge transporting layer 4. The order in which the layers are stacked is not particularly limited, and may be stacked in any order of FIGS. Furthermore, the field effect transistor of the present invention is not limited to the field effect transistor having the structure shown in FIGS. 1 to 3, and layers other than those shown in FIGS. 1 to 3 may be formed.

  When the charge transport material of the present invention is used in an organic electronic device, it is appropriate to form a film on a substrate or the like and use it as a charge transport film.

  The material of the substrate to be deposited is not particularly limited as long as it can support a field effect transistor and a display element, a display panel, or the like manufactured thereon. Examples include an inorganic substrate such as glass and a plastic substrate made of a polymer. Among them, preferably selected from the group consisting of polyester, polycarbonate, polyimide, polyether sulfone, amorphous polyolefin, epoxy resin, polyamide, polybenzoxazole, polybenzothiazole, vinyl polymer, polyparabanic acid, polysilsesquioxane, and siloxane. A plastic substrate is preferred. Further, general-purpose resins such as polyesters such as polyethylene terephthalate and polyethylene naphthalate and polycarbonate are preferred from the viewpoint of strength and cost, and condensation polymers such as polyimide, polyamide, polybenzoxazole, polybenzothiazole, polyparabanic acid, etc. A crosslinked product such as polyvinylphenol that can be insolubilized by heat treatment or the like is preferable from the viewpoint of heat resistance and solvent resistance. As a constituent material of the support substrate, polyester, polycarbonate, polyimide, and polybenzoxazole are particularly preferable, and polyester and polyimide such as polyethylene terephthalate and polyethylene naphthalate are most preferable.

  A method for forming the charge transport material is not particularly limited, and the film can be formed using a known method. For example, a coating process using a solution in which a charge transport material is dissolved in an organic solvent is suitable for easily producing a multilayer structure element.

  Application methods include casting, spin coating, dip coating, blade coating, wire bar coating, spray coating, and other coating methods, ink jet printing, screen printing, offset printing, letterpress printing, etc. A printing lithography method, a soft lithography method such as a microcontact printing method, and a combination of these methods can be used. Furthermore, as a technique similar to coating, the Langmuir-Blodgett method, in which a monomolecular film formed on the water surface is transferred to a substrate and laminated, the liquid crystal or melt state is sandwiched between two substrates or introduced between the substrates by capillary action. And the like.

  The thickness of the charge transport film is not particularly limited. In the case of the field effect transistor exemplified above, the characteristics of the element do not depend on the film thickness as long as it is greater than the required film thickness. As the film thickness increases, the leakage current often increases. Therefore, the preferable film thickness is usually 1 nm or more, preferably 10 nm or more. Further, it is usually 10 μm or less, and preferably 500 nm or less. In addition, the charge transport material of the present invention can be used alone, but can also be used by mixing with other materials, and can also be used in a laminated structure with other layers.

  The produced charge transport film can be improved in properties by post-treatment. For example, the heat treatment can relieve distortion in the film generated during film formation, and can improve and stabilize characteristics. Furthermore, a change in characteristics due to oxidation or reduction can be induced by exposure to an oxidizing or reducing gas or liquid such as oxygen or hydrogen. This can be used for the purpose of increasing or decreasing the carrier density in the film, for example.

For the electrodes and wirings for producing organic electronic devices, gold, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium, sodium, and other metals, InO ₂ , SnO ₂ , ITO, etc. Conductive polymers such as conductive oxides, polyaniline, polypyrrole, polythiophene, polyacetylene, polydiacetylene, and acids such as hydrochloric acid, sulfuric acid, sulfonic acid, Lewis acids such as PF ₆ , AsF ₅ , FeCl ₃ , iodine, etc. Dispersed doped materials such as halogen atoms, metal atoms such as sodium potassium, semiconductors such as silicon, germanium, gallium arsenide and the like, carbon materials such as fullerenes, carbon nanotubes, graphite, and metal particles Conductive materials such as conductive composite materials It is needed. As a method for forming them, a vacuum deposition method, a sputtering method, a coating method, a printing method, a sol-gel method, or the like can be used. The patterning method is also a photolithography method combining photoresist patterning and etching with an etchant or reactive plasma, ink-jet printing, screen printing, offset printing, letterpress printing and other printing methods, micro-contact printing method, etc. The soft lithography method and a combination of these methods can be used. In addition, it is also possible to use a direct pattern production by irradiating an energy beam such as a laser or an electron beam to remove the material or change the conductivity of the material.

  A protective film can be formed on the surface of the formed charge transport film, electrode, wiring or the like in order to minimize the influence of outside air. Examples thereof include polymer films such as epoxy resin, acrylic resin, polyurethane, polyimide, and polyvinyl alcohol, inorganic oxide films such as silicon oxide, silicon nitride, and aluminum oxide, and nitride films. Examples of the method for forming the polymer film include a method in which a polymer solution is applied and dried, and a method in which a monomer is applied or vapor-deposited for polymerization. Furthermore, it is possible to perform a crosslinking treatment or to form a multilayer film. For the formation of the inorganic film, a formation method using a vacuum process such as a sputtering method or a vapor deposition method, or a formation method using a solution process typified by a sol-gel method can be used.

  The organic electronic device of this invention can be used for arbitrary uses according to the kind. For example, the field effect transistor using the charge transport material of the present invention can be used as a switching element of an active matrix of a display. This utilizes the fact that the current between the source and drain can be switched by the voltage applied to the gate, so that the switch is turned on only when a voltage is applied to or supplied to a certain display element, and the circuit is disconnected at other times. By doing so, a high-speed, high-contrast display is performed. Further, as an alternative to the conventional active matrix, it is advantageous as an element capable of an energy saving process and a low cost process.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these Examples, unless the summary is exceeded. In the present specification, “part” represents “part by weight” unless otherwise specified, and “wt%” represents “wt%”. “T-Bu” represents a tert-butyl group, “Hex” represents a hexyl group, and “Ph” represents a phenyl group.

[Evaluation method]
<Method for Measuring Redox Potential of Charge Transport Material>
The oxidation-reduction potential of the charge transport material was measured by a cyclic voltammetry measurement “Electrochemical Analyzer 650A” manufactured by BAS. The sweep rate was 100 mV / sec and the sample concentration was 1 mM. Ferrocene / ferrocenium (Fc / Fc ⁺ ) was used as an internal standard.

<Measurement of electric conductivity of charge transport layer>
Using a shadow mask with a width of 1 mm on a Pyrex (registered trademark) substrate (manufactured by Furuuchi Chemical Co., Ltd.) of 2.5 cm × 2.5 cm, a vacuum vapor deposition machine EX-400 (vacuum degree: 1.3 × 10 ^{− 4} Pa), an aluminum electrode having a thickness of 1000 mm (100 nm) was deposited. On this electrode-attached substrate, a sample having a concentration of 0.5 wt% was spin-coated at a rotation speed of 1000 rpm to produce a film having a thickness of 4000 mm (400 nm). Thickness of this film was measured with a vacuum mask EX-400 (vacuum degree: 1.3 × 10 ⁻⁴ Pa) manufactured by ULVAC, using a shadow mask with a width of 1 mm so that it was crossed against the electrode. A 1000 mm (100 nm) aluminum electrode was deposited. The space between the electrodes was measured with a semiconductor parameter analyzer 4155 manufactured by Agilent, a voltage-current curve was obtained, and the electrical conductivity was calculated.

上記反応式（１）に従って合成を行なった。具体的には以下の通りである。 [Synthesis Example 1: Synthesis 1 of 4,7-dibromo-2-hexyl-1,2,3-benzotriazole]

Synthesis was performed according to the above reaction formula (1). Specifically, it is as follows.

<Step 1-1>
In a 300 mL flask, methanol (100 mL), 1,2,3-benzotriazole (5.0 g, 42 mmol), potassium-t-butoxide (5.0 g, 44 mmol), 1-bromohexane (8.2 g, 49 mmol) And stirred at room temperature for 96 hours. Thereafter, the solvent was removed by an evaporator, and the residue was washed with two layers of water-chloroform and then extracted with chloroform. This was purified using silica gel column chromatography (solvent: chloroform) to obtain 5.5 g of a transparent oily product.

The obtained product was subjected to elemental analysis and proton nuclear magnetic resonance spectrum ( ¹ H-NMR) measurement. The results are shown below.
Elemental analysis: predicted for C ₁₂ H ₁₇ N ₃ : C, 70.90; H, 8.43; N, 20.67% .Found: C, 71.10; H, 8.34; N, 20.36%.
・¹ H-NMR (400MHz, CDCl ₃ ): δ = 7.85 (m, 2H, aromatic), 7.38 (m, 2H, aromatic), 4.72 (m, 2H, CH ₂ α), 2.11 (m, 2H, CH ₂ β), 1.33 (br, 6H, (CH ₂ ) ₃ ), 0.87 (m, 3H, CH ₃ ).

From this result, it was confirmed that the main product was 2-hexylbenzotriazole (compound (1a) in the above reaction formula (1)). The yield was 51%. In addition, the presence of 45% of 1-hexylbenzotriazole (compound (1b) in the above reaction formula (1)) was confirmed as a by-product.
The mixed product was purified by column chromatography to obtain 2-hexylbenzotriazole as the main product.

<Step 1-2>
4.8 g of the obtained 2-hexylbenzotriazole was added to 20 mL of a 5.8 M aqueous hydrobromic acid solution, stirred at 100 ° C. for 1 hour, bromine (7.8 g, 48 mmol) was added, and further at 135 ° C. Stir for hours. Thereafter, the mixture was cooled to room temperature, and sodium hydrogen carbonate was added to neutralize the reaction solution. The product in the reaction solution was washed with two layers of chloroform-water and extracted with chloroform. This was purified by silica gel column chromatography (chloroform) to obtain 6.0 g of a brown oily product.

The obtained product was subjected to elemental analysis and proton nuclear magnetic resonance spectrum ( ¹ H-NMR) measurement. The results are shown below.
Elemental analysis: predicted for C ₁₂ H ₁₅ Br ₂ N ₃ : C, 39.92; H, 4.19; N, 11.64% .Found: C, 39.71; H, 4.19; N, 12.00%.
・¹ H-NMR (400MHz, CDCl ₃ ): δ = 7.42 (br, 2H, aromatic), 4.75 (m, 2H, CH ₂ α), 2.14 (br, 2H, CH ₂ β), 1.33 (br, 6H , (CH ₂ ) ₃ ), 0.86 (m, 3H, CH ₃ ).

  From this result, it was confirmed that the product was 4,7-dibromo-2-hexyl-1,2,3-benzotriazole (compound (2) in the above reaction formula (1)). The yield based on 2-hexylbenzotriazole was 75%.

上記反応式（２）に従って合成を行なった。具体的には以下の通りである。 [Synthesis Example 2: Synthesis 2 of 4,7-dibromo-2-hexyl-1,2,3-benzotriazole]

Synthesis was performed according to the above reaction formula (2). Specifically, it is as follows.

<Step 2-1>
While stirring 1,2-diamino-3,6-dibromobenzene (0.80 g, 3.0 mmol) and acetic acid (12 mL) in Schlenk, NaNO ₂ (0.30 g, 3.3 mmol) was added to 6 mL of water. The solution dissolved in was added. After stirring for 20 minutes, the reaction solution was filtered to recover a solid. The obtained solid was washed with water and filtered again to obtain 0.66 g of a pink powder product.

The obtained product was subjected to elemental analysis and proton nuclear magnetic resonance spectrum ( ¹ H-NMR) measurement. The results are shown below.
Elemental analysis: predicted for C ₆ H ₃ Br ₂ N ₃ : C, 26.02; H, 1.09; N, 15.17%. Found: C, 25.84; H, 0.88; N, 15.17%.
・¹ H-NMR (400MHz, CF ₃ COOD): δ = 7.56 (s, 2H, aromatic).

  From the results, it was confirmed that the product was 4,7-dibromo-1,2,3-benzotriazole. The yield was 80%.

<Step 2-2>
The obtained 4,7-dibromo-1,2,3-benzotriazole is hexylated in the same manner as in <Step 1-1> of [Synthesis Example 1] to give 4,7-dibromo-2. -Hexyl-1,2,3-benzotriazole was obtained. The yield based on 4,7-dibromo-1,2,3-benzotriazole was 24%.

[Example 1: Polymerization of polymer 1 [P (BTz)]
Ni (cod) ₂ (2.1 g, 7.6 mmol), 1,5-cyclooctadiene (0.95 mL, 7.6 mmol), 2,2′-bipyridyl (1.2 g, 7.6 mmol), [synthesis The 7,4-dibromo-2-hexyl-1,2,3-benzotriazole (1.1 g, 2.9 mmol) obtained in Example 1] was placed in Schlenk, and the inside was purged with nitrogen, followed by stirring at 60 ° C. . After stirring for 96 hours, the reaction solution was poured into methanol to reprecipitate the produced polymer. The obtained polymer was recovered by filtration, and washed with an aqueous ammonia solution, an aqueous Na ₂ -EDTA solution, distilled water, a methanol solution of dimethylglyoxime, diluted hydrochloric acid, and methanol in this order. Finally, vacuum drying was performed to obtain a red powder product.

The obtained product was subjected to elemental analysis and proton nuclear magnetic resonance spectrum ( ¹ H-NMR) measurement. The results are shown below.
・ Elemental analysis: predicted for H (C ₁₂ H ₁₅ N ₃・ 7H ₂ O) ₁₆ H: C, 68.87; H, 7.71; N, 20.08%; Mn = 3200. Found: C, 68.89; H, 7.37; N , 19.26%; Mn = 3000 (by ¹ H-NMR).
・¹ H-NMR (400MHz, CF ₃ COOD): δ = 8.0-8.4 (br, 2H, aromatic), 5.07 (s, 2H, CH ₂ α), 2.29 (s, 2H, CH ₂ β), 1.46 ( br, 6H, (CH ₂ ) ₃ ), 0.99 (s, 3H, CH ₃ ).

  From the above results, it was confirmed that this product was a polymer [P (BTz)] having a repeating unit represented by the following formula. The yield was 96%.

（上記式中、ｎは整数を表わす。）
また、ＧＰＣ法による測定で平均繰り返し数を求めたところ、ｎ＝１５であった。

(In the above formula, n represents an integer.)
Moreover, it was n = 15 when the average repeating number was calculated | required by the measurement by GPC method.

When the redox potential was measured for the obtained P (BTz), a reversible peak was observed in the vicinity of −2 V for the first reduction potential, suggesting the possibility of becoming an n-type conductor. In addition, electrical conductivity was measured. The sample solution was a trifluoroacetic acid solution. As a result, the electric conductivity was in the 10 ⁻⁸ S / cm range, indicating the electric conductivity of the semiconductor region.

[Example 2: Polymerization of polymer 2 [P (PTz-AE)]]
4,7-Dibromo-2-hexyl-1,2,3-benzotriazole (0.36 g, 1.0 mmol), 2,5-diethynyl-1,4-dihexyloxy obtained in [Synthesis Example 1] Benzene (0.32 g, 1.0 mmol), toluene 20 mL, triethylamine 8 mL, Pd (PPh ₃ ) ₄ (0.052 g, 4.5 × 10 ⁻² mmol), copper iodide (CuI) (1.2 × 10 ^-2 g, 6.0 × 10 ^-2 mmol) was placed in a Schlenk, and the inside was replaced with nitrogen, followed by stirring at room temperature. When heated to 60 ° C., a solid precipitated in the reaction solution in about 30 minutes. For this reason, after pouring the reaction solution into methanol and reprecipitating the produced polymer, the polymer was recovered by filtration. Since the obtained polymer was almost soluble in chloroform, it was dissolved in chloroform, added again to methanol for reprecipitation, and the polymer was recovered by filtration. Finally, vacuum drying was performed to obtain a yellow powdery product (near brown).

The obtained product was subjected to elemental analysis and proton nuclear magnetic resonance spectrum ( ¹ H-NMR) measurement. The results are shown below.
Elemental analysis: predicted for Br (C ₃₄ H ₄₃ N ₃ O ₂ ) ₆ Br: C, 73.93; H, 7.85; N, 7.61; Br, 4.82%; Mn = 3300. Found: C, 74.71; H, 7.54 ; N, 5.59; Br, 4.30%; Mn = 3100 (by GPC analysis).
・¹ H-NMR (400MHz, CDCl ₃ ): δ = 7.56 (s, 2H, aromatic), 7.11 (m, 2H, aromatic), 4.79 (s, 2H, BTz-CH ₂ α), 4.04 (m, 4H , AE-CH ₂ α), 2.19 (s, 2H, BTz-CH ₂ β), 1.90 (m, 4H, AE-CH ₂ β), 1.40 (m, 18H, Alkyl), 0.90 (m, 9H, CH ₃ ).

  From the above results, it was confirmed that this product was a polymer [P (PTz-AE)] having a repeating unit represented by the following formula. The yield was 89%.

（上記式中、ｎは整数を表わす。）
また、ＧＰＣ法による測定で平均繰り返し数を求めたところ、ｎ＝６であった。

(In the above formula, n represents an integer.)
Moreover, it was n = 6 when the average repeating number was calculated | required by the measurement by GPC method.

When the obtained polymer [P (PTz-AE)] was subjected to redox potential measurement, a reversible peak was observed in the vicinity of -2 V, and the first reduction potential could be an n-type conductor. It was suggested. In addition, electrical conductivity was measured. The sample solution was a chloroform solution. As a result, the electric conductivity was in the 10 ⁻⁸ S / cm range, indicating the electric conductivity of the semiconductor region.

[Example 3: Polymerization of polymer 3 [P (BTz-F)]]
4,7-Dibromo-2-hexyl-1,2,3-benzotriazole (0.36 g, 1.0 mmol) obtained in [Synthesis Example 1], 9,9′-dihexylfluorene-2,7-bis (Trimethylene borate) (0.47 g, 1.0 mmol), Pd (PPh ₃ ) ₄ (0.047 g, 4.1 × 10 ⁻² mmol), toluene 20 mL, sodium carbonate aqueous solution (2.0 M) 5 mL, methanol 5 mL was put into Schlenk and the inside was replaced with nitrogen, followed by stirring at 80 ° C. After stirring for 60 hours, the reaction solution was poured into methanol to reprecipitate the polymer. The obtained polymer was dissolved in chloroform and added to hexane for reprecipitation, and then the obtained polymer was recovered. This was vacuum-dried to obtain a yellow powdery product.

The obtained product was subjected to elemental analysis and proton nuclear magnetic resonance spectrum ( ¹ H-NMR) measurement. The results are shown below.
Elemental analysis: predicted for (HO) ₂ B (C ₃₇ H ₄₇ N ₃ ) ₁₄ Br: C, 81.89; H, 8.76; N, 7.74; Br, 1.05%; Mn = 7598. Found: C, 80.62; H , 8.77; N, 7.76; Br, 1.34%; Mn = 7400 (by GPC analysis).
1H-NMR (400 MHz, CDCl3): δ = 8.18-7.79 (m, 8H, aromatic), 4.86 (s, 2H, BTz-CH2α), 2.25 (br, 4H, F-CH ₂ α), 2.15 (br , 2H, BTz-CH ₂ β), 1.52 (br, 4H, F-CH ₂ γ), 1.41 (br, 6H, BTz- (CH ₂ ) ₃ ), 1.15 (s, 12H, F- (CH ₂ ) ₃ ), 0.95-0.79 (br, 13H, F-CH ₂ β and CH ₃ )

  From the above results, it was confirmed that this product was a polymer [P (BTz-F)] having a repeating unit represented by the following formula. The yield was 88%.

（上記式中、ｎは整数を表わす。）
また、ＧＰＣ法による測定で平均繰り返し数を求めたところ、ｎ＝１４であった。

(In the above formula, n represents an integer.)
Moreover, it was n = 14 when the average number of repetitions was calculated | required by the measurement by GPC method.

When the obtained polymer [P (PTz-AE)] was subjected to redox potential measurement, a reversible peak was observed in the vicinity of -2 V, and the first reduction potential could be an n-type conductor. It was suggested. In addition, electrical conductivity was measured. The sample solution was a chloroform solution. As a result, the electric conductivity was in the 10 ⁻⁸ S / cm range, indicating the electric conductivity of the semiconductor region.

  The benzotriazole structure-containing polymer of the present invention is excellent in electron withdrawing properties and has properties as an n-type organic semiconductor. Therefore, the benzotriazole structure-containing polymer of the present invention can be suitably used for various applications such as an organic electronic device as a charge transport material (particularly an electron transport material), and is extremely useful.

It is sectional drawing which shows the structural example of the field effect transistor which is 1 type of the organic electronic device of this invention. It is sectional drawing which shows another structural example of the field effect transistor which is 1 type of the organic electronic device of this invention. It is sectional drawing which shows another structural example of the field effect transistor which is 1 type of the organic electronic device of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support substrate 2 Gate electrode 3 Insulator layer 4 Charge transport layer 5 Source electrode 6 Drain electrode

Claims (11)

A benzotriazole structure-containing polymer comprising a structure represented by the following formula (1) as a repeating unit.

(In formula (1), R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent substituent.) 2. The benzotriazole structure-containing polymer according to claim 1, comprising at least a portion in which the repeating unit represented by the formula (1) and the repeating unit represented by the following formula (2) are alternately bonded.

(In the formula (2), Ar represents a divalent organic group having a π-conjugated structure.) A method for producing the benzotriazole structure-containing polymer according to claim 1 or 2,
A method for producing a benzotriazole structure-containing polymer, comprising polymerizing at least a compound represented by the following formula (3) in the presence of a metal complex.

(In formula (3), R ^{1 to} R ³ represent the same groups as those in formula (1), and X represents a halogen atom.) The method for producing a benzotriazole structure-containing polymer according to claim 3, wherein a nickel complex and / or a palladium complex is used as the metal complex. A charge transport material comprising the benzotriazole structure-containing polymer according to claim 1 or 2. An organic electronic device using the charge transport material according to claim 5. The organic electronic device according to claim 6, wherein the organic electronic device is a light emitting element. The organic electronic device according to claim 6, wherein the organic electronic device is a switching element. The organic electronic device according to claim 6, wherein the organic electronic device is a photoelectric conversion element. The organic electronic device according to claim 6, wherein the organic electronic device is a photosensor using photoelectric conductivity. The organic electronic device according to claim 6, wherein the organic electronic device is a solar cell.

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